US007 173160B2
(12) United States Patent (10) Patent No.: US 7,173,160 B2 Maesen et al. (45) Date of Patent: Feb. 6, 2007
(54) PROCESSES FOR CONCENTRATING 5,306,851 A 4, 1994 Wu et al. HIGHER DAMONDOIDS 5,334,368 A 8, 1994 Becket al. 5,414,189 A 5/1995 Chen et al. (75) Inventors: Theo Maesen, Point Richmond, CA 5.439,860 A 8, 1995 Habib et al. (US); Robert M. Carlson, Petaluma, 5,468.372 A 11/1995 Seamans et al. CA (US); Jeremy E. Dahl, Palo Alto, 5,495,283 A 2f1996 Cowe CA (US); Shenggao Liu, Hercules, CA 5,498,812 A 3, 1996 Bradway et al. (US); Hye Kyung C. Timken, Albany, 5,925,235 A 7/1999 Habib CA (US); Waqar R. Qureshi, San 6,013,239 A 1/2000 Chen et al. - s 6,179,995 B1 1/2001 Cash et al. Francisco, CA (US) 6,534,437 B2 3/2003 Eijsbouts et al. 6,743,290 B2 6/2004 Dahl et al. (73) Assignee: stron U.S.A. Inc., San Ramon, CA 2002/0134301 A1 9, 2002 Dahl et al. 2002.0137976 A1 9, 2002 Dahl et al. (*) Notice: Subject to any disclaimer, the term of this S.E. A. 1939: R past l S; listed under 35 2002/0147373 A1 10, 2002 Dahl et al. .S.C. 154(b) by ayS. 2002/0177743 A1 11, 2002 Dahl et al. 2002fO1881 63 A1 12/2002 Dahl et al. (21) Appl. No.: 10/622,185 2002fO193648 A1 12/2002 Dahl et al. 2003/OO97032 A1 5/2003 Dahl et al. (22) Filed: Jul. 16, 2003 2003. O100808 A1 5.2003 Dahl et al. (65) Prior Publication Data US 2004/0054243 A1 Mar. 18, 2004 FOREIGN PATENT DOCUMENTS FR 1547516 11, 1968 Related U.S. Application Data WO OO 14811 A1 T 2000 (60) Provisional application No. 60/396.991, filed on Jul. WO OOf 41810 A1 7, 2000 18, 2002. WO OO 42124 A1 T 2000 s WO OO 42125 A1 T 2000 (51) Int. Cl WO OO 42126 A1 T 2000 we WO OO/42127 A1 T 2000 C. 12 3.08: WO OO 42128 A1 T 2000 C07C 7700 (2006.015 WO O1/45071 A2 6, 2001 CIOG 47/00 (2006.01) (52) U.S. Cl...... 585/352:585/258; 585/800; OTHER PUBLICATIONS 208/142: 208/107; 208/108; 208/109; 208/110; 208/112:208/143; 208/144; 208/145; 208/49; International Search Report from PCT/US03/22527 mailed Dec. 2, 208/78; 208/111.01 Fort,2003. Jr., et al.,al. AdAdamantane. Consequences ofof theth Diamondoidoid (58) Field of so S. 107.16. fi. Structure, Chem. Rev 64, 277-300 (1964). 208/112 143. 49 144 78 145 111 of Sandia National Laboratories (2000), World's First Diamond See application file fors completes - s search. . . history.. . www.Sandia.gov.Micromachines Created at Sandia, Press Release, (Feb. 22, 2000) (56) References Cited Lin, et al., Natural Occurrence of Tetramantane (CHs), Pentamantane (CH) and Hexamantane (CoH) in a Deep U.S. PATENT DOCUMENTS Petroleum Reservoir, Fuel 74, (10): 1512-1521 (1995). Dahl, et al., Diamondoid Hydrocarbons as Indicators of Natural Oil 3,852,207 A 12/1974 Stangeland et al. Cracking, Nature, 54-57 (1999). 4,347,121 A 8/1982 Mayer et al. 4,401,556 A 8, 1983 Bezman et al. (Continued) 4,534,852 A 8, 1985 Washecheck et al. 4,556,646 A 12/1985 Bezman Primary Examiner Elizabeth D. Wood 4,820,402 A 4/1989 Partridge et al. (74) Attorney, Agent, or Firm—Buchanan Ingersoll & 4,913,799 A 4, 1990 Gortsema et al. Rooney PC 4.956,747 A 9, 1990 Beer et al. 4.956,748 A 9, 1990 Yamamoto (57) ABSTRACT 4.956,749 A 9/1990 Chang 4,982,049 A 1/1991 Alexander et al. 5,019,665 A 5/1991 Partridge et al. Hydroprocessing such as hydrocracking is advantageously 5,059,567 A 10, 1991 Linsten et al. employed in processes for the recovery and purification of 5,073,530 A 12/1991 Bezman et al. higher diamondoids from petroleum feedstocks. Hydroc 5,080,776 A 1/1992 Partridge et al. racking and other hydroprocesses degrade nondiamondoid 5,114,563 A 5, 1992 Lok et al. contaminants. 5, 120,899 A 6, 1992 Chen et al. 5, 198,203 A 3/1993 Kresge et al. 5,246,689 A 9, 1993 Beck et al. 31 Claims, 10 Drawing Sheets US 7,173,160 B2 Page 2
OTHER PUBLICATIONS Handbook of Petroleum Refining Processes, Second Edition, Robert McKervey, Synthetic Approaches to Large Diamondoid Hydrocar A. Myers, Editor, McGraw Hill (1997) 7.1 “MAK bons, Tetrahedron 36, 971-992 (1980). Moderate—Pressure Hydrocracking” by M.C. Hunter, et al, no Chung et al., Recent Development in High-Energy Density Liquid month. Fuels, Energy and Fuels 13, 641-649 (1999). Handbook of Petroleum Refining Processes, Second Edition, Robert Balaban et al., Systematic Classification and Nomenclature of Diamond Hydrocarbons-I, Tetrahedron 34, 3599-3606 (1978). A. Myers, Editor, McGraw Hill (1997) 7.2 “Chevron Rollman et al. Adamantane for Petroleum with Zeolites, Abstracts, Isocracking-Hydrocracking for Superior Fuel and Lubes Produc 210" ACS National Meeting, Chicago, IL. Aug. 20-24, 1995 Fuel, tion” by Alan C. Bridge, no month. pp. 1012-1017. Wingert, G.C.-M.S. Analysis of Diamondoid Hydrocarbons in Handbook of Petroleum Refining Processes, Second Edition, Robert Smackover Petroleums, Fuel 71, 38 (Jan. 1992). A. Myers, Editor, McGraw Hill (1997) 7.3 “UOP Unicracking U.S. Appl. No. 10/012,545 “Compositions Comprising Process for Hydrocracking” by Mark Reno, no month. Tetramantanes and Processes for Their Separation', filed Dec. 12, Handbook of Petroleum Refining Proceeses, Second Edition, Robert 2001, Inventors Dahl, et al. Beck, J.S., et al., “A New Family of Mesoporous Molecular Sieves A. Myers, Editor, McGraw Hill (1997) 8.1 “Chevron RDS/VRDS Prepared with Liquid Crystal Templates'. J. Am. Chem. Soc. Hydrotreating” by David N. Brossard, no month. 114: 10834-10843 (1992), no month. Handbook of Petroleum Refining Processes, Second Edition, Robert Inoue, Yoshimasa, et al., “Improved Ni-Mo HDN Catalysts through Increased Dispersion and Intrinsic Activity of the Active Phase'. A. Myers, Editor, McGraw Hill (1997) 8.4 “UOP RCD Unionfining Science and Technology in Catalysis, Kodansha Ltd., Tokyo, Japan, Process” by Gregory J. Thompson, no month. pp. 415-418 (1998), no month. Kresge, et al., Nature 359:710 (1992), no month. U.S. Patent Feb. 6, 2007 Sheet 1 of 10 US 7,173,160 B2
Figure 1
100 Make-Up /16 Hydrogen 28
Product Gas - 38 Fresh Feed
/ 12 Recycle Fraction 1 10 -1 Gas / 26 24 Fraction 2 14N - / / Fraction 3 22 - Fraction 4
20 1. *
18 30 Fraction 5 U.S. Patent Feb. 6, 2007 Sheet 2 of 10 US 7,173,160 B2
Figure 2 /1 200
16 Make-UpHydrogen / Make-Up Hydrogen /50 --> Recycle
16 N Product Gas
Fresh Feed -28
10 u-12 Sycle Fraction 1
42
/ Fraction 2 32 40 14 Fraction 3 (
N Fraction 4
First-Stage Second-Stage Product N Product 64 U.S. Patent Feb. 6, 2007 Sheet 3 of 10 US 7,173,160 B2
Figure 3
/1 300
Make-Up Hyd 74 ake-Up Hydrogen / - 28 Product 1 Gas 16 10 Fresh Feed \ -2 -Ha
Hydrocracking Recycle 16 Reactor Gas 4. Fraction 1 68 N. -12 42 / Fraction 2 / 14% 26 3 - 40Fraction 3
res N / - N 20 Fraction 4 / 18 34
Hydrotreating -72 M Reactor Here 30 -36 76 / / Fraction 5 Recycle U.S. Patent Feb. 6, 2007 Sheet 4 of 10 US 7,173,160 B2
Figure 4
400
Hydrogen
62 Feed - 22
40 20
30 U.S. Patent Feb. 6, 2007 Sheet S of 10 US 7,173,160 B2
Figure 5
T-2 2OOOOOO Feedstock for 16OOOOO HCR Reaction
12OOOOO
Crude Oil Contaminant 8OOOOO
4OOOOO
T-2
24OOOOO Light 2000000 Hydrocarbons Product of HCR Reaction at 800 F 16OOOOO Diamantane T-3
12OOOOO Triamantane Pentamantanes Crude Oil Contaminant
- - - 5.00 1000 1500 2000 2500 3000
T-2 28OOOOO Light 2400000 Hydrocarbons Product of HCR 2OOOOOO Diamantane -1 Reaction at 850 of 16OOOOO Triannantane T-3 Pentamantanes& 12OOOOO Cyclohexamantane 1OOOOOO 8OOOOO / Hexamantanes & 6OOOOO Cycloheptamantanes 4OOOOO -1 2OOOOO 5.OO 1000 1500 T2000 2500 30, OO GCMS Time (min.) --> U.S. Patent Feb. 6, 2007 Sheet 6 of 10 US 7,173,160 B2
Figure 6
50 -
45 -
35 -
we30 E. Feedstock igh 25 Fr 4 & 5 t (combined) 20
15 R Product HCR (a) 850 F
IBP - 150 - 250 - 350 - 450 - 550 - 650 - 750 - 850 - 950 - 150 250 350 450 550 650 750 850 950 1050 Distillation Cuts (F) U.S. Patent Feb. 6, 2007 Sheet 7 of 10 US 7,173,160 B2
Figure 7
4.00 12 hours 3.50 g 3.00 3) 24 hours | 2.50 1 23 2.00 48 hours 108 hours Te 150 Starting -- tr 3. 1.00
O.50
O.OO T - - - - - OOO 5.00 10.00 15.00 20.00 25.00 3OOO Tetramantanes | Hydrocarbon U.S. Patent Feb. 6, 2007 Sheet 8 of 10 US 7,173,160 B2
Figure 8
Tetramantanes Hydrocarbon impurities 121)
lo 500000 Ab FEED U 400000 300000 nC 200000
100000 O so too
Tetramantanes (1(2)3 (121
1300000 O 11OOOOO Ab U 900000 PRODUCT da Hydrocarbon impurities
700000 C e 5OOOOO 3OOOOO 100000 ---- ol 6.00 700 s.00 g.o.o. 10.001100 T 1200 1300 T 1400 T. GCMS Time (min.) --> U.S. Patent Feb. 6, 2007 Sheet 9 of 10 US 7,173,160 B2 Figure 9
FEED PRODUCT U.S. Patent Feb. 6, 2007 Sheet 10 of 10 US 7,173,160 B2
Figure 10
A Unwanted Hydrocarbon Impurities 15OOOO 130OOO 1 10000 Pentamantanes 90000 70000 50000 3OOOO
1 OOOO st-see-assessels--eeeeriapsical-axis. A Slissalse-jersease-as-areas O 13.OO 13.50 14.OO 1450 15.OO 1550 16.OO 16.50
65000
55OOO Pentannantanes Unwanted Hydrocarbon 45OOO Impurities
35000
25000
15000
5000
GCMS Time (min.) --> US 7,173,160 B2 1. 2 PROCESSES FOR CONCENTRATING U.S. Pat. No. 4,956,747 HIGHER DAMONDOIDS ?? U.S. Pat. No. 4,956,748 * U.S. Pat. No. 4,956,749 This application claims priority under 35 U.S.C. S 119 to * U.S. Pat. No. 4,982,049 U.S. Provisional Application No. 60/396.991 entitled Pro- 5 * U.S. Pat. No. 5,019,665 cesses for Concentrating Higher Diamondoids and filed on 2 U.S. Pat. No. 5,059,567 Jul. 18, 2002, the entire content of which is hereby incor 27 U.S. Pat. No. 5,073,530 porated by reference. * U.S. Pat. No. 5,080,776 U.S. Pat. No. 5,114,563 BACKGROUND OF THE INVENTION 10 U.S. Pat. No. 5,198,203 U.S. Pat. No. 5,246,689 1. Field of the Invention U.S. Pat. No. 5,306,851 This invention is directed to processes for the concentra U.S. Pat. No. 5,334,368 tion, recovery and at least partial purification of higher U.S. Pat. No. 5,414,189 diamondoid components from petroleum feedstocks. 15 U.S. Pat. No. 5,439,860 2. Background Information U.S. Pat. No. 5,468.372 The following publications and patents are provided as 7 U.S. Pat. No. 5,498,812 background and if cited herein may be identified by their U.S. Pat. No. 5,925,235 SuperScript numbers: U.S. Pat. No. 6,013,239 Fort, Jr., et al., Adamantane: Consequences of the Dia- 20 U.S. Pat. No. 6,179,995 mondoid Structure, Chem. Rev 64, 277-300 (1964) ' "Improved Ni Mo HDN catalysts through increased ° Sandia National Laboratories (2000), World 's First Dia dispersion and intrinsic activity of the active phase' mond Micromachines Created at Sandia, Press Release, Inoue, Yoshimasa, Uragami, Yuji, Takahashi, Yasuhito: (2/22/2000) www.Sandia.gov. Eijsbouts, Sonja. Nippon Ketjen Co., Ltd., Tokyo, Japan. Lin, et al., Natural Occurrence of Tetramantane (C.H.s), 25 Studies in Surface Science and Catalysis (1999), 121 Pentamantane (CH2) and Hexamantane (CoH) in a Science and Technology in Catalysis (1998) Deep Petroleum Reservoir, Fuel 74, (10): 1512–1521 All of the above publications and patents are herein (1995) incorporated by reference in their entirety to the same extent * Dahl, et al., Diamondoid Hydrocarbons as Indicators of as if each individual publication or patent was specifically Natural Oil Cracking, Nature, 54–57 (1999) 30 and individually indicated to be incorporated by reference in McKervey, Synthetic Approaches to Large Diamondoid its entirety. Hydrocarbons, Tetrahedron 36, 971-992 (1980) Diamondoids are cage-shaped hydrocarbon molecules Chung et al., Recent Development in High-Energy Density possessing amazingly rigid structures that are Superimpos Liquid Fuels, Energy and Fuels 13, 641–649 (1999) able fragments of the diamond crystal lattice. Adamantane, 7 Balaban et al., Systematic Classification and Nomenclature 35 a ten-carbon molecule, is the smallest member of the dia of Diamond Hydrocarbons-I, Tetrahedron 34, 3599–3606 mondoid series, consisting of one diamond crystal Subunit. (1978) Diamantane contains two face-fused diamond Subunits and Handbook of Petroleum Refining Processes, Second Edi triamantane three. Adamantane and diamantane and to a tion, Robert A. Myers, Editor, McGraw Hill (1997) lesser extent, triamantane, are well studied. They have been Chapters: 7.1 "MAK Moderate—Pressure Hydrocrack- 40 isolated from petroleum feedstocks and synthesized hereto ing” by M. C. Hunter, et al. fore. The art has come to refer to adamantane, diamantane, 7.2 "Chevron Isocracking—Hydrocracking for Supe triamantane and Substituted analogs thereof as “lower dia rior Fuel and Lubes Production” by Alan C. Bridge mondoids”. Tetramantane and larger diamondoids and Sub 7.3 "UOP Unicracking Process for Hydrocracking” by stituted analogs, which exists as multiple isomers are Mark Reno 45 referred as “higher diamondoids”. That nomenclature is 8.1 "Chevron RDS/VRDS Hydrotreating” by David N. used herein. Brossard, and Until recently, the higher diamondoids were only mini 8.4 "UOP RCD Unionfining Process” by Gregory J. mally described. Lin, et al. reported the natural occurrence Thompson of tetramantane, pentamantane and hexamantane in deep Rollman et al. Adamantane for Petroleum with Zeolites, 50 petroleum reservoirs. However, these workers were only Abstracts, 210" ACS National Meeting, Chicago, Ill., able to tentatively identify such compounds in ionized form Aug. 20–24, 1995 Fuel, pgs. 1012–1017 as part of mass spectroscopy analyses. ' Petrov et al., Saturated Tricyclic C11-C13 Hydrocarbons Partridge, et al.' disclosed a process for concentrating From (two Soviet) Crude Oils, Neftekhimiya 13 N3, diamondoid-containing hydrocarbon solvents. This process 345 351 (May-June 1973) 55 involved three steps. The first was providing a solvent ' Wingert, G. C. M.S. Analysis of Diamondoid Hydrocar mixture made up of at least 50% by weight normal or bons in Smackover Petroleums, Fuel 71, 38 (January slightly-branched Cs-Co paraffins having dissolved therein 1992) at least one diamondoid compound. In the second step, this 'J. Am. Chem. Soc. 114: 10834–10843 (1992) mixture is contacted with a shape-selected catalyst in the Kresge, et al., Nature 359:710 (1992) 60 presence of added hydrogen to convert at least a portion of U.S. Pat. No. 3,852,207 the normal or slightly branched paraffins to lower-boiling U.S. Pat. No. 4,347,121 aliplaties and to prevent the conversion of more than about U.S. Pat. No. 4,401,556 10% by weight of the diamondoid compounds. In the third 7 U.S. Pat. No. 4,534,852 step the lower-boiling aliplaties and the diamondoids are U.S. Pat. No. 4,556,646 65 separated from one another. U.S. Pat. No. 4,820,402 Chen, et al.' disclosed methods for isolating high purity U.S. Pat. No. 4,913,799 lower diamondoid fractions and components. The disclosed US 7,173,160 B2 3 4 methods involved distilling a diamondoid-containing feed doilds, being more stable, were pyrolyzed to a lesser extent. stock into five overhead components. These overhead com This increased the concentration of the higher diamondoids ponents included adamantane, diamantane and triamantane. in the pyrolysis product. Chen, et al. further recited that the pot material recovered While the pyrolysis step has proven advantageous in its after the distillation contained a major amount of substituted breaking down of nondiamondoid materials, typically it is triamantane and minor amounts of tetramantane and penta time consuming and often appears to reduce ultimate yields mantane. Again, the Chen et al. identifications were specu of the desired higher diamondoids. Accordingly, there is a lative, with no isolations or definitive characterizations. need for an improved process to assist in the concentration More recently, present co-inventors Dahl and Carlson and isolation and recovery of the higher diamondoids. filed a series of United States patent applications in which 10 As will be discussed below, the present invention employs they described the isolation, identification and characteriza hydroprocessing to treat higher-diamondoid-containing tion of a large number of individual higher diamondoids feedstocks and thus to facilitate the separation of higher ranging from all four possible tetramantanes through unde diamondoids from nondiamondoids. Hydroprocessing is Camantane. used in many petroleum processing settings. It involves 15 contacting a petroleum feedstock with hydrogen at elevated See for example: temperatures, most often with a solid phase catalyst. Sub U.S. Ser. No. 10/012,333, now U .S. Pat. No. 6,843,851, categories of hydroprocessing include “hydrotreating and issued Jan. 18, 1005; “hydrocracking”. “Hydrotreating is a hydroprocess carried U.S. Ser. No. 10/012,334, now U.S. Pat. No. 6,828,469, out under conditions to react or remove contaminants from issued Dec. 7, 2004; the feedstocks. Such contaminants include Sulfur-containing U.S. Ser. No. 10/012,335, now U.S. Pat. No. 7,094,937, contaminants (in which case the process may be referred to issued Aug. 22, 2006; as “hydrodesulfurization'), nitrogen-containing contami * U.S. Ser. No. 10/012,336, now U.S. Pat. No. 6,743,290, nants (“hydrodenitrification'), and metals, which can be in issued Jun. 1, 2004; the form of organometallic compounds, ("hydrodemetalla 25 tion'). Hydrotreating also can include hydrogenation of . Pat. No. 7,034,194, olefinic and aromatic unsaturation. 25, 2006; In "hydrocracking, petroleum feedstock is contacted . No. 10/012,545, now U.S. Pat. No. 6,815,569, with a catalyst at elevated temperatures in the presence of 9, 2004; hydrogen to crack or otherwise convert undesired compo . No. 10/012,546, now U.S. Pat. No. 6,831,202, 30 nents to more desirable species or to preferentially break issued Dec. 14, 2004; down undesired species. The first modern hydrocracking . No. 10/012,704, now U.S. Pat. No. 6,812,370, operation was placed on stream in the 1950s by the Stan . 2, 2004; dard Oil Company of California. Since the 1960s, hydro . No. 10/012,709, now U.S. Pat. No. 6,812,371, cracking has been used in many settings. These include the . 2, 2004; and 35 formation of liquefied petroleum gas (LPG) from naptha feedstocks, the preparation of high quality distillate fuels . No. 10/017,821, now U.S. Pat. No. 6,844,477, from gas oils and other heavy stocks, the formation of jet and . 18, 2005; all filed on Dec. 12, 2001; and diesel fuels from vacuum gas oils and the processing of * U.S. Ser. No. 10/046,486, filed Jan. 16, 2002, now U.S. heavy feedstreams such as residuums to fuels and lubricat Pat. No. 6,858,700, issued Feb. 22, 2005; and 40 ing oils. U.S. Ser. No. 10/052,636 filed on Jan. 17, 2002, now U.S. In many settings, hydroprocessing involves a combination Pat. No. 6,861,569, issued Mar. 1, 2005, and all incorpo of several of these reactions taking place simultaneously in rated herein by reference. These patent applications the same reaction Zone or sequentially in serial Zones. As describe how the higher diamondoids were isolated from conditions such as temperature, pressure, space Velocity and petroleum feedstocks such as deep reservoired oils and 45 catalysts are altered, the relative impact of the various gas condensates. The concentrations of higher diamon reactions can change. doids in these feedstocks were reported to be quite low, generally in the parts per thousand to parts per billion SUMMARY OF THE INVENTION range. In addition, the relative concentrations of the various higher diamondoids were found to decrease rap 50 We have now found improved processes for providing idly as the size of the diamondoids increased. The other compositions enriched in higher diamondoids from petro components of the feedstocks included nondiamondoids leum feedstocks or fractions thereof which contain recov including nondiamondoid hydrocarbons, Sulfur-contain erable amounts of these higher diamondoids in admixture ing materials and metal-containing materials and lower with nondiamondoids. diamondoids. 55 We have found that hydroprocessing such admixtures A variety of methods to concentrate and isolate the higher efficiently reacts and breaks down a significant proportion of diamondoids were taught in the Dahl and Carlson patent the nondiamondoids to materials which are easily separated filings. Fractionation procedures, both atmospheric and from the higher diamondoids, and also removes undesired vacuum, were disclosed and isolated fractions enriched in Substitutions on higher diamondoid-based compounds to one or more of the desired higher diamondoids relative to the 60 provide higher diamondoids free of such substitutions, thus distillation feedstock were described. Thermal treatment yielding a product significantly enriched in the desired (pyrolysis) was taught as a desirable process step. In this higher diamondoids. In particular, hydroprocessing can be step the feedstock or a feedstock distillation fraction was used to break down and hydrogenate nondiamondoid hydro heated in a Parr reactor at about 400–500° C. for up to about carbons and desulfurize higher diamondoids containing Sul 20 hours. This pyrolysis step preferentially broke down the 65 fur functional groups. nondiamondoid materials to lower molecular weight mate In one general aspect, the invention provides a process for rials such as gases which were easily removed. The diamon concentrating higher diamondoids from petroleum mixtures US 7,173,160 B2 5 6 containing higher diamondoids in admixture with nondia In another aspect, the feedstock may contain higher mondoid materials. This process involves treating the petro diamondoid-based compounds such as alkyl higher diamon leum mixture under hydroprocessing conditions to hydroc doids, or higher diamondoids linked together through a rack or otherwise break down or convert at least a portion of Sulfur or carrying a Sulfur functional group. This may be a the nondiamondoid materials to more easily separated mate 5 naturally-occurring feedstock or a synthetic reaction prod rials. This produces a hydrocracked product containing uct. In this aspect, hydroprocessing may be used to convert higher diamondoids and modified nondiamondoid materials. the higher diamondoid-based compounds to higher diamon The hydrocracked product is then separated into fractions. doids themselves. At least one fraction is concentrated in higher diamondoids. One or more of the fractions concentrated in higher diamon 10 It will also be understood by those skilled in the process doids is recovered. ing and refining of petroleum feedstocks that some variation The hydroprocess can be carried out on relatively unproc of the order of the hydrocracking and Some pretreating steps essed petroleum feedstocks. The hydroprocessing can also may be desirable. Such variation is within the scope of the involve hydrocracking processes carried out on petroleum present invention. based feedstreams that are the result of hydrotreating steps 15 Such as, for example, hydrodemetallation, hydrodenitrifica BRIEF DESCRIPTION OF THE DRAWINGS tion and/or hydrodesulfurization and/or the result of frac tionation, or other refining processes. The hydrocracking This invention will be further described with reference and hydrotreating can be carried out simultaneously, if being made to the drawings in which: desired, as well. FIG. 1 is a schematic illustration of a representative Other hydrocarbon processing procedures that provide process flow diagram for a single stage hydroprocess of this broken down products can also be employed in place of or invention. in conjunction with hydroprocessing. Such procedures FIG. 2 is a schematic illustration of the process flow in a include, for example, fluid catalytic cracking, slurry cata representative two stage hydroprocess of this invention. lytic cracking, plasma cracking, and the like. Each of these 25 FIG. 3 is a schematic illustration of the process flow in a procedures is well known in the art. representative recycle hydrotreating and hydrocracking pro In this aspect, the invention provides processes for con cess of this invention. centrating higher diamondoids from petroleum mixtures FIG. 4 is a schematic illustration of an overall higher containing desired higher diamondoids, nondiamondoids, 30 diamondoid recovery process showing the incorporation of lower diamondoids and optionally Sulfur-containing mate the hydroprocessing of this invention. rials including diamondoid sulfides and Sulfur-linked dia mondoid polymers and dimers, nitrogen-containing materi FIG. 5 provides three representative gas chromato als, metal-containing materials and the like. In these graphic-mass spectrometric (GCMS) total ion chromato processes, the petroleum mixture may be subjected to one or grams (TIC) of (A) a higher diamondoid-containing fraction more pretreatment steps including distillation to form dis 35 of a petroleum feed stock before hydroprocessing under tillation fractions containing desired higher diamondoids conditions favoring hydrocracking and (B) and (C) the and having materials boiling above and/or below the desired products of this hydroprocessing of the fraction at two higher diamondoids. This pretreatment product contains the different reaction temperatures. These chromatograms show desired higher diamondoids in admixture with nondiamon that nondiamondoid components have been preferentially doids and is subjected to hydroprocessing including hydro 40 cracked and that tetramantanes, pentamantanes, hexaman cracking. The hydroprocessed product contains the desired tanes and heptamantanes have become concentrated and higher diamondoids and hydrocracked nondiamondoid available for isolation. materials. The product is separated into fractions. At least FIG. 6 is a bar graph showing yields of various distillate one fraction is enriched in the desired higher diamondoids. fractions determined by simulated distillation. Data are This latter fraction (or fractions) is recovered. This use of shown for both the hydroprocessing feedstock and the hydroprocessing can, in Some cases, lead to a simplification product produced at 850°F. reaction temperature. The graph or even elimination of Some Subsequent higher diamondoid shows the shift from higher boiling to lower boiling frac isolation and recovery steps. tions brought about by the hydroprocessing reactions. Other hydroprocessing reactions in addition to hydroc FIG. 7 is a graph showing how the degree of conversion racking can be carried out prior to, simultaneous with or 50 of nondiamondoids can be varied but how the change in after the hydrocracking. These other processing steps are conversion can have an effect on the extent of destruction of generally selected from hydrotreating steps and can include higher diamondoids, as well. hydrodemetallization to remove or convert metal-containing FIG. 8 provides GCMS selected ion chromatograms of a compounds, hydrodesulfurization to break down sulfur tetramantanes-containing fraction of a petroleum feedstock containing compounds including Sulfur-linked diamondoid 55 (A) before hydroprocessing under conditions leading to (as especially higher diamondoid)-containing dimers; and hydrocracking in combination with other hydroprocesses hydrodealkylation to remove alkyl substituents from alkyl and (B) after Such hydroprocessing. Substituted higher diamondoids. FIG. 9 is a black and white photo of feed and product The higher diamondoid-containing fractions resulting 60 samples illustrating that the product of the hydroprocessing from the hydroprocessing and Subsequent separation may be has a very colorless appearance while the feed is deeply further processed such as by further distillation, chromatog colored, indicative of aromatic compounds. raphy or like processes to further concentrate and isolate the FIG. 10 provides GCMS selected ion chromatograms of higher diamondoids they contain. a pentamantanes-containing fraction of a petroleum feed Overall processes involving one or more hydroprocessing 65 stock (A) before hydroprocessing and (B) after hydropro steps in combination with the further processing constitute cessing under conditions leading to hydrocracking and other additional aspects of this invention. hydroprocesses. US 7,173,160 B2 7 8 DETAILED DESCRIPTION OF THE molecular weight forms of these components and including INVENTION isomers of these forms. Substituted diamondoids preferably comprise from 1 to 10 and more preferably 1 to 4 alkyl This invention is directed to the application of hydropro substituents. “Diamondoids' include “lower diamondoids' cessing generally (and especially hydrocracking) to pro and “higher diamondoids”. cesses for the recovery and purification of higher diamon The term “lower diamondoids' or “adamantane, diaman doids from petroleum feedstocks. tane and triamantace' refers to any and/or all unsubstituted This detailed description of the invention is organized as and Substituted derivatives of adamantane, diamantane and follows. triamantane. The unsubstituted lower diamondoids show no Feedstocks representative feedstocks for the process are 10 isomers and are readily synthesized, distinguishing them described. from the “higher diamondoids”. Hydroprocessing Flow Schemes and Conditions—three The term “higher diamondoids' refers to any and/or all hydroprocessing process flow schemes are described Substituted and unsubstituted tetramantanes; to any and/or together with conditions—representative conditions favor all Substituted and unsubstituted pentamantanes; to any ing hydrocracking and various hydrotreating reactions. 15 and/or all Substituted and unsubstituted hexamantanes; to Catalysts—suitable catalysts are described. any and/or all Substituted and unsubstituted heptamantanes; Overall Process Schemes—representative overall process to any and/or all Substituted and unsubstituted octamantanes; schemes for recovering higher diamondoids incorporating to any and/or all Substituted and unsubstituted nonaman hydroprocessing are described. tanes; to any and/or all Substituted and unsubstituted deca This is followed by a series of Examples. mantanes; to any and/or all Substituted and unsubstituted undecamantanes; as well as mixtures of the above as well as Feedstocks isomers and stereoisomers. The terms “feedstock”. “hydrocarbonaceous feedstock” In the processes of this invention, a feedstock is selected and “petroleum feedstock’ all refer to hydrocarbonaceous that contains recoverable amounts of one or more selected materials comprising recoverable amounts of higher dia 25 higher diamondoids. Preferably, such feedstock comprises at mondoils. Preferably, Such feedstocks include oil, gas con least about 1 ppb of one or more higher diamondoids, more densates, refinery streams, oils derived from reservoir rocks, preferably, at least about 25 ppb and still more preferably at oil shale, tar Sands, and Source rocks, and the like. Feed least about 100 ppb. It is understood, of course, that feed stocks often contain significant quantities of Sulfur most stocks having higher concentrations of higher diamondoids commonly as organic Sulfur compounds. Sulfur-linked 30 facilitate recovery of these components. dimers and even trimers of diamondoids including higher Preferred feedstocks include, for example, natural gas diamondoids are often present in feedstocks. Feedstocks condensates and refinery streams having high concentrations typically include one or more lower diamondoids as well as of higher diamondoids. With regard to the latter, such nondiamondoid components. The latter are typically char refinery streams include hydrocarbonaceous streams recov acterized as comprising nondiamondoid-structure organic 35 erable from cracking processes, distillations, coking and the compounds having boiling points within the range of boiling like. Particularly preferred feedstocks include gas conden points of the higher diamondoids. Aromatics can be signifi sate feedstocks recovered from the Norphlet Formation in cant nondiamondoid materials whose removal can be par the Gulf of Mexico and from the LeDuc Formation in ticularly advantageous. Typical feedstocks may also contain Canada. impurities such as sediment, metals including nickel and, 40 In one embodiment, the feedstocks used in the processes Vanadium and other inorganics. They may also include of this invention typically comprise nondiamondoid com nondiamondoid-heteromolecules containing Sulfur, nitrogen ponents and diamondoid dimers. Such as lower diamondoid and the like. All of these nondiamondoid materials are dimers having a Sulfide linkage, all having boiling points included in "nondiamondoid components' as that term is within the range of the higher diamondoids selected for used herein. As will be described below, a feedstock may be 45 recovery as well as one or more lower diamondoid compo fractionated; demetallized, denitrified and/or desulfurized nents. These feedstocks will usually contain a mixture of Such as by hydrotreating; and/or otherwise treated prior to higher diamondoids. being hydrocracked or otherwise hydroprocessed. In Such feedstocks, higher diamondoid components often Suitable feedstocks may also include recycled materials cannot be effectively recovered directly from the feedstock containing recoverable amounts of higher diamondoids. An 50 because of their low concentrations. Accordingly, the pro example of a process providing Such a recycle-containing cesses of this invention may entail pretreatment steps to feedstock is illustrated in FIG. 3. Feedstocks can include remove a Sufficient amount of nondiamondoids and lower materials containing higher diamondoid and obtained from diamondoids from the feedstock under conditions to provide incomplete or undesired reactions of higher diamondoids to a treated feedstock from which the selected higher diamon form functionalized higher diamondoids. In the latter case, 55 doid components can be recovered. compositions containing materials having undesired func In one embodiment, the removal of these materials tionalization, for example, thiol, amino, nitro and similar includes a first distillation of the feedstock to remove functionalization of diamondoids, may be desirably used as nondiamondoid components as well as lower diamondoid feedstocks wherein the Subsequent hydroprocesses conve components as overhead and leave a higher diamondoid niently remove such functionality thereby regenerating the 60 enriched first bottoms. higher diamondoid free of such substitution. A second distillation can be operated to fractionate the The term "diamondoid’ refers to substituted and unsub first bottoms and provide several cuts in a temperature range stituted caged compounds of the adamantane series includ of interest enriched in the selected higher diamondoids or ing Substituted and unsubstituted adamantane, diamantane, groups of selected higher diamondoids. The cuts, which are triamantane, tetramantane, pentamantane, hexamantane, 65 enriched in one or more selected higher diamondoids or a heptamantane, octamantane, nonamantane, decamantane, particular higher diamondoid of interest, are retained and undecamantane, and the like and also including various typically require further purification such as by the hydro US 7,173,160 B2 10 processes of the present invention. The following Table 1 Hydroprocessing Flow Schemes and Conditions illustrates representative fractionation points (atmospheric In hydroprocessing a feedstream is contacted with hydro equivalent boiling points) that may be used to enrich various gen at an elevated temperature most commonly in the higher diamondoids in overheads. In practice it may be presence of a suitable base metal or noble metal containing advantageous to make wider temperature range cuts which catalyst to bring about hydrocracking and/or hydrotreating would often contain groups of higher diamondoids which (including hydrogenation of unsaturation, hydrodemetalli could be separated in Subsequent separation steps. zation, hydrodesulfurization and/or hydrodenitrification). While these various conversion steps have been accorded TABLE 1. separate names, it will be appreciated that, depending upon 10 the materials present in the feedstock and the reaction Fractionation Points conditions imposed, a single treatment in a single reaction Most Preferred Preferred Zone can result in combinations of these reactions taking place simultaneously or sequentially. Lower Cut Higher Cut Lower Cut Higher Cut Higher Temperature Temperature Temperature Temperature The severity of the hydroprocessing conditions is adjusted 15 depending on the feedstock and the process objectives. In Diamondoid (° C.) (° C.) (° C.) (° C.) general, more strenuous conditions provide higher degrees Tetramantanes 349 382 330 400 of cracking of nondiamondoid but also may lead to some Pentamantanes 385 427 360 450 Cyclohexa- 393 466 365 500 breaking down of desired higher diamondoids, as well. maintanes Hydrocracking reduces the size of the nondiamodoid hydro Hexamantanes 393 466 365 500 carbon molecules and often is accompanied by same hydro Heptamantanes 432 SO4 395 S4O genation of olefinic and aromatic unsaturation. Desulfuriza Octamantanes 454 527 420 S60 Nonamantanes 463 S49 425 590 tion and denitrification of the feedstock will also usually Decamantanes 472 571 435 610 occur to Some extent. The hydroprocessed product is then Undeca- 499 588 455 625 separated into various boiling range fractions. The separa maintanes 25 tion is typically conducted by fractional distillation preceded by one or more vapor-liquid separators to remove hydrogen Useful and/or other gases. Lower Cut Higher Cut Generally, in hydrotreating operations, cracking of the Higher Temperature Temperature hydrocarbon molecules is less pronounced and the unsatur Diamondoid (° C.) (° C.) 30 ated hydrocarbons are either fully or partially hydrogenated. Tetramantanes 300 430 This generally calls for conditions, somewhat less severe Pentamantanes 330 490 than those used for cracking. In all cases, however, the Cyclohexa- 330 550 conditions are selected with consideration for optimizing the maintanes recovery and yield of desired higher diamondoids. Hexamantanes 330 550 Heptamantanes 350 600 35 Hydroprocessing conditions useful in this invention Octamantanes 375 610 include temperatures in the range of from about 300 to about Nonamantanes 380 6SO 950° F (150 to 510° C.) arid preferably 400 to 925° F (204 Decamantanes 390 660 to 495°C.). In the experiments shown in the examples, base Undeca- 400 675 maintanes metal containing catalysts gave best results at temperatures 40 in the range of 600-875° F and especially 675-850° F. and noble metal catalysts gave best results attemperatures in the Other pretreatment processes for the removal of lower range of 625–925° F. and especially 700–925° F. diamondoids, and/or hydrocarbonaceous nondiamondoid Total pressure (added hydrogen plus feedstock pressure) components include, by way of example only, size separa is in the range of 200 to 4000 psi and preferably 500 to 3500 tion techniques, evaporation either under normal or reduced 45 psi and especially 900 to 3000 psi. pressure, crystallization, chromatography, well head sepa Hydrocarbon feed rates expressed as reactor space veloci rators, reduced pressure and the like. For example, lower ties (or liquid hourly space velocities “LHSVs) of about diamondoids can be preferentially removed from feedstocks 0.02 to 20 hrs', preferably 0.04 to 5 hrs' and especially using a variety of techniques such as are described in 0.05 to 4 hrs are employed. commonly-owned copending patent application U.S. Ser. 50 Hydrogen circulation rates (H/liquid ratios) are generally No. 10/017,821. Adamantane and diamantane dissolved in in the range of from about 200 standard cubic feet (scf) per deep gases may crystallize during commercial gas and barrel to about 20,000 scf/bbl and preferably 400 to 10,000 petroleum liquid production due to a drop in pressure. Scf/bbl. Commercially-available well head separators effectively As shown in FIG. 1, hydroprocessing Such as hydroc remove lower diamondoids from such feedstocks to avoid 55 racking is usually carried out as a continuous process in Scaling problems in oil and gas production equipment. Other which a higher diamondoid-containing feedstock is passed removal processes can utilize the larger sizes of the higher through line 10 to reactor 12 which contains bed(s) 14 of diamondoids to effect separation of lower diamondoids hydroprocessing (hydrocracking) catalyst. Gaseous hydro therefrom. For example, size separation techniques using gen is fed under pressure to reactor 12 via line 16. Such membranes will allow a feedstock retained in the membrane 60 hydrogen streams originate from, for example, a hydrogen to selectively pass lower diamondoids across the membrane plant or, a reforming reactor, or as hydrogen recycled from barrier provided that the pore size of the membrane barrier hydrocracker effluent. Purity of the gaseous stream will is selected to differentiate between compounds having the depend on a number of factors, but will generally be greater size of higher diamondoid components as compared to lower than 50% hydrogen, and often greater than about 90% diamondoid components. The pore size of molecular sieves 65 hydrogen or higher. The reactor temperature, pressure and such as zeolites and the like can also be used to effect size space Velocity are all controlled to provide conditions under separations. which nondiamondoid components of the feedstock are US 7,173,160 B2 11 12 broken down or modified. The hydrocrackate is removed reactor 68 are chosen to treat the feed and remove or react from reactor 12 via line 18 typically to a liquid/gas separator one or more contaminants such as metals (hydrodemetalli 20 where a gas stream containing unreacted hydrogen and Zation), Sulfur (hydrodesulfurization), or nitrogen-contain gaseous breakdown products such as hydrogen Sulfide and ing materials (hydrodenitrification). Hydrotreated product is gaseous alkanes and the like is taken off overhead via line 22 removed via line 72 and charged as feed to hydrocracking either to vent or recovery via line 24 or to recycle via lines reactor 12. The hydrocracking proceeds as described in FIG. 26 and/or 28. Preferably, hydrocracking is continued for a 1 with the following changes. Generally the hydrogen Sufficient period and at a sufficiently high temperature to required for hydrocracking in reactor 12 is provided at least crack, hydrogenate or otherwise convert at least about 10% in part as recycle gas from separator 20 via line 28. Recycle of the nondiamondoid components (more preferably at least 10 gas containing hydrogen can also be recycled to reactor 68 about 50% and even more preferably at least about 75%) via line 74. Also, the bottoms fraction taken off of fraction from the hydrocracker feedstock based on the total weight of ator 32, which generally is rich in higher diamondoids, may the nondiamondoid components in the feedstock prior to be removed as product via line 36 but more commonly is in hydrocracking. A liquid phase product made up of higher part recycled to hydrotreating reactor 68 via line 76. diamondoids and liquid cracked nondiamondoids as well as 15 These three hydroprocessing flow schemes are represen other materials is taken off as a bottoms via line 30 to a tative. Although processes providing at least a degree of fractionator 32 where it is split into two or more fractions— hydrocracking have proven very helpful, one could employ some of Which are rich in higher diamondoids (typically the hydrotreating alone. Also, one could separate the hydroc higher boiling fractions such as represented by fractions 4 racking and hydrotreating stage in the overall process and 5 removed via lines 34 and 36) and some of which are scheme. The number of reactors and fractionators and their rich in nondiamondoid cracking products (typically a gas locations in the process Scheme can also be varied. fraction represented by line 38 and lower boiling liquid fractions represented by lines 40, 42 and 44). Fractionator 32 Hydroprocessing Catalysts is most commonly one or more distillation columns. It Catalysts used in carrying out hydroprocessing operations would also be understood to those versed in the art that the 25 are well known in the art. See for example U.S. Pat. Nos. various process steps could also be run in a batch mode with 5,925,235, 5,439,860, 3,852,207, and 4,347,121', for intermediate storage. general descriptions of hydrotreating, hydrocracking, and Hydroprocessing (hydrocracking) can also be carried out typical catalysts used in Such processes. in two or more stages. FIG. 2 shows a representative Suitable catalysts include noble metals from Group VIII, multi-stage hydrocracker. The first stage is similar to the 30 Such as platinum, gold or palladium on an alumina or single stage unit depicted in FIG. 1. In the process shown in siliceous matrix. Another group of catalysts have Group VIII FIG. 2, the bottoms fraction from fractionator 32 is taken off and Group VIB nonnoble or base metals, such as nickel, via line 36 and if desired a portion of it can be removed via cobalt, molybdenum, and tungsten on an alumina or sili line 37. The remainder of the higher diamondoid-rich bot ceous matrix. More than one base metal may be used. For toms fraction is fed to second hydrocracking reactor 46 35 example, combinations of nickel-molybdenum, nickel-tung which contains bed(s) 48 of hydrocracking catalyst which Sten, or cobalt-molybdenum can be used. Nickel-tin can also may be the same or different than the catalyst used in the first be used. U.S. Pat. No. 5,468.372 describes a very suitable stage. Similarly, the reaction conditions may be the same as base metal (Ni/Mo) catalyst. U.S. Pat. No. 4,556,646 or varied from those present in the first stage. Hydrogen is describes a noble metal catalyst. Other suitable catalysts are added via line 50 and a second stage hydrocrackate is 40 described, for example, in U.S. Pat. No. 5,925.235 and removed via line 52 to separator 54 where a second gas U.S. Pat. No. 5,439,860 as well as U.S. Pat. No. 6,534, phase made up of hydrogen and gaseous cracking products 437 and WO's 0041810; 004181157 0042124; is taken off via line 56 and recycled to hydrocracker 46 via 0042125: 0042126, 0042127 and 0042128°. Excel lines 58 and/or 60. The liquid phase fraction of the hydro lent results may be achieved with the Akzo-Nobel “Stars' crackate is removed via line 62. A portion of this stream is 45 and “Nebula” commercial base metal catalysts. The base removed as product, line 64, and the remainder is recycled metals (such as nickel-molybdenum) are usually present in to fractionator 32 via line 66 so that light products can be the final catalyst composition as oxides, or as Sulfides. removed and the higher diamondoids can be concentrated in Preferred non-noble metal catalyst compositions contain high boiling fractions such as fractions 4 or 5. The product in excess of about 5 weight percent, preferably about 5 to from line 64 is also concentrated in higher diamondoids. 50 about 40 weight percent molybdenum and/or tungsten, and If desired, multiple hydroprocessing Zones operated at at least about 0.5, and generally about 1 to about 15 weight varied conditions to favor multiple cracking and treating percent of nickel and/or cobalt determined as the corre reactions may be used to facilitate the recovery of higher sponding oxides. The noble metal (such as platinum, gold or diamondoids in accord with this invention. FIG. 3 depicts a palladium) catalysts contain in excess of 0.01 percent noble processing scheme in which hydroprocessing under condi 55 metal, preferably between 0.1 and 1.0 percent metal. Com tions favoring hydrotreating and hydroprocessing under binations of noble metals may also be used, such as mixtures conditions favoring hydrocracking are carried out sequen of platinum, gold and palladium. Combinations of noble and tially with liquid recycle. In addition and as noted above, base metals may also be in the catalysts. other hydrocarbon processing procedures that provide The metal components (or compounds thereof) can be cracked products can also be employed in place of or in 60 incorporated into the overall catalyst composition by any conjunction with hydrocracking. Such procedures include, one of numerous procedures, including co-mulling, impreg for example, coking, catalytic cracking, fluid catalytic crack nation, or ion exchange and other techniques familiar to ing, slurry catalytic cracking, and the like. those versed in the art. Specifically, in FIG. 3, higher diamondoid-containing The matrix component can be of many types including feed is fed via line to hydrotreating reactor 68 which 65 Some that have acidic catalytic activity. Ones that have contains hydrotreating catalyst 70. Hydrogen is fed via line activity include amorphous silica-alumina, or a Zeolitic or 16 to reactor 68. The catalyst and reaction conditions in non-Zeolitic crystalline molecular sieve. Examples of Suit US 7,173,160 B2 13 14 able matrix molecular sieves include Zeolite Y. Zeolite X and cessing conversions desired. For example, relatively acidic the so called ultra stable Zeolite Y and high structural noble metal catalysts such as those on Zeolite clay or silica:alumina ratio Zeolite Y such as those described in U.S. amorphorus aluminasilicate Substrates can provide efficient Pat. Nos. 4,401,556, 4,820,402' and 5,059,567. Small cracking of high-boiling contaminants. They also may favor crystal size Zeolite Y, such as that described in U.S. Pat. No. dealkylating alkyl higher diamondoids which may be desir 5,073,530’, can also be used. Non-zeolitic molecular sieves able. which can be used include, for example, silicoaluminophos Some feeds contain large amounts (as much as 6-8% w) phates (SAPO), ferroaluminophosphate, titanium alumino Sulfur often linking diamondoids and higher diamondoids phosphate and the various ELAPO molecular sieves into dimers and the like. These high sulfur levels can described in U.S. Pat. No. 4.913,799 and the references 10 cited therein. Details regarding the preparation of various deactivate noble metal catalysts. Base metal catalysts are non-zeolite molecular sieves can be found in U.S. Pat. Nos. often more stable and retain activity better in the presence of 5,114,563’ (SAPO): 4,913,799 and the various references sulfur. cited-in U.S. Pat. No. 4.913,799'. Mesoporous molecular Overall Process Schemes sieves can also be used, for example the M41S family of 15 Hydroprocessing schemes such as those shown in FIGS. materials (J. Am. Chem. Soc. 114: 10834–10843(1992)), 1, 2 and 3 can be incorporated into overall process schemes MCM-41 (U.S. Pat. Nos. 5,246,689; 5,198.203; 5,334, for concentrating and recovering higher diamondoids. For 368), and MCM-48 (Kresge et al., Nature 359:710 example, FIG. 4 illustrates hydroprocessing scheme 100 of (1992)) FIG. 1 incorporated into such an overall process. Suitable matrix materials may also include synthetic or natural Substances as well as inorganic materials such as In FIG. 4, an overall diamondoid recovery process 400 is clay, silica and/or metal oxides such as alumina, silica shown. In this process, scheme 100 is preceded by a pair of alumina, Silica-magnesia, silica-Zirconia, Silica-thoria, distillation columns. It will be appreciated that scheme 100 silica-berylia, silica-titania as well as ternary compositions, could be scheme 200 or 300 of FIGS. 2 and 3, as well as Such as silica-alumina-thoria, silica-alumina-Zirconia, silica 25 other hydroprocessing configurations. Diamondoid-contain alumina-magnesia, and silica-magnesia-Zirconia. The latter ing feedstock is fed through line 40 to atmospheric distil may be either naturally occurring or in the form of gelati lation column 42 where light components are taken over nous precipitates or gels including mixtures of silica and head and removed via lines 44, 80 and 82. An atmospheric metal oxides. Naturally occurring clays which can be com residuum product containing the higher diamondoids as well posited with the catalyst include those of the montmorillo 30 as other heavy components is taken off via line 46 to vacuum nite and kaolin families. These clays can be used in the raw distillation column 48. In column 48 a variety of cuts are state as originally mined or initially subjected to calumnia taken represented by distillate lines 50, 52, 54, 56, 58 and tion, acid treatment or chemical modification. Syntheticlays bottoms line 60. Typically, the vacuum column can be such as are described in U.S. Pat. No. 5,495,283 and WO operated to give several distillate cuts containing higher 0146071 can also be employed. 35 diamondoids with the higher materials being higher boiling A particularly suitable noble metal catalyst comprises a and thus appearing in the higher boiling fractions such as Y-type zeolite, which has a unit cell size of about 24.35 A. represented by lines 56 and 58 and in residuum represented a SiO/Al2O ratio greater than 5.0, a Surface area greater by line 60. A representative higher-diamondoid containing than 500 m/g, and a sodium content of about 0.2 wt %. This cut removed via line 58 is used as feed for the hydropro Y-type Zeolite, which is stable in dry air to about 1000° C. 40 cessing unit, which operates as set forth in FIGS. 1, 2 and 3. may be used in the catalyst base. The ratio by weight of the By carrying out these optional distillation steps before amorphous inorganic oxide component to the Zeolite com hydrocracking, it is possible to separate the diamondoid ponent in the catalyst base is generally between 1:4 and 4:1, containing feed from Some metal-containing, Sulfur-contain preferably between 1:2 and 2:1. Such a catalyst, made up of ing and/or nitrogen containing species which are often 60% wt Y-type Zeolite and 40% alumina and carrying 0.5% 45 present in the crude feedstocks fed through line 40. The wt palladium was used in the present Example 1. materials may poison or deactivate the hydroprocessing Furthermore, more than one catalyst type may be used in catalyst in bed 14. These problems are reduced by the the reactor. The different catalyst types can be separated into pretreatment distillations. layers or mixed. For example, hydrotreating catalyst and As further shown in FIG. 4 one or more of the diamon hydrocracking catalyst can be layered or mixed in a single 50 doid-containing fractions taken off of column 32 via lines reactor. Examples of mixed and layered catalyst systems are 34, 42 and/or 44 can be passed to post-processing stage 62. described in U.S. Pat. Nos. 5,925,235 and 5,439,860. As described in detail in U.S. Ser. No. 10/059,636, post U.S. Pat. No. 4,534.852'7 describes a high-activity processing stage 62 can employ one or more chromato hydrotreating catalyst system. The upper bed consists of a graphic steps, including gas chromatography, high perfor catalyst containing from about 2–4 wt % nickel from about 55 mance liquid chromatography, crystallization, thermal 8–15 wt % molybdenum and from about 2–4 wt % phos diffusion techniques, Zone refining, progressive recrystaliza phorus Supported on a carrier consisting mostly of alumina. tion, size separation and the like to isolate and remove The lower bed consists of a high-activity, hydrodesulfuriza individual higher diamondoids. In Such a process, the recov tion catalyst Containing from about 2–4 wt % cobalt and/or ered feedstock may be first subjected to gravity column nickel, from about 8-15 wt % molybdenum and less than 60 chromatography using silver nitrate impregnated silica gel to about 0.5 wt % phosphorus Supported on a carrier consisting remove aromatics. In some cases, aromatic levels are so mostly of alumina. reduced in the product that this step can be eliminated. This These materials are merely representative of the many can be followed by HPLC using two different columns of hydrocracking and hydrotreating catalysts known in the field differing selectivities to isolate the target higher diamon of petroleum processing which can be used. 65 doids; and crystallization to provide crystals of pure target The choice of catalyst may be dictated at least in part by higher diamondoids. Where higher diamondoid concentra the nature of the feed being processed and the hydropro tions are not high enough for crystallization to occur, further US 7,173,160 B2 15 16 concentration by, for example, preparative capillary gas Step 2 GC/MS Assay chromatography, may be necessary. Feedstock A was analyzed using gas chromatography/ It will be appreciated that various sub-units of the process mass spectrometry to confirm the presence of target higher scheme can be operated in batch mode with intermediate diamondoids and to provide gas chromatographic retention Storage. times for these target materials. This information is used to Compositions and Utility track individual target higher diamondoids through Subse The above processes provide novel higher diamondoid quent isolation procedures. compositions. For example, in one embodiment, these pro cesses provide a composition comprising at least tetraman Step 3 Feedstock Atmospheric Distillation tane and pentamantane components wherein said composi 10 A sample of Feedstock B was distilled into a number of tion comprises at least about 10 weight percent tetramantane fractions based on boiling points to separate the lower components and at least about 0.5 weight percent pentam boiling point components (nondiamondoids and lower dia antane components based on the total amount of diamondoid mondoids) and for further concentration and enrichment of components present. These higher diamondoids are useful 15 particular higher diamondoids in various fractions. The for special polymers, in micro- and molecular-electronics yields of atmospheric distillate fractions of two separate and in nanotechnology applications. In particular, the rigid samples of Feedstock B are shown in Table 2, below and are ity, strength, stability, thermal conductivity, variety of struc contrasted to simulated distillation yields. As seen from tural forms and multiple attachment sites shown by these Table 2, the simulated distillation data are in agreement with molecules makes possible accurate construction of robust, the actual distillation data. The simulated distillation data durable, precision devices with nanometer dimensions. were used to plan Subsequent distillations. EXAMPLE 1. TABLE 2 This Example shows on overall process and has seven 25 Yields of Atmospheric Distillation Fractions from steps. Two Separate Runs of Feedstock B Step 1. Feedstock selection Step 2. GCMS assay Sim Dis Feedstock B (Run 2) Step 3. Feedstock atmospheric distillation Cut ( F.) Est. 'd Yields (Wt 9%) Yields (Wt 9%) Difference Step 4. Vacuum fractionation of atmospheric distillation To 349 8.0 7.6 0.4 residue 30 349 to 491 57.0 57.7 -O.7 Step 5. Hydroprocessing of selected fractions 491 to 643 31.0 30.6 0.4 Step 6. Removal of aromatic and polar nondiamondoid 643 and higher 4.0 4.1 -0.1 components Sim Dis Feedstock B (Run 1) Step 7. Multi-column HPLC isolation of higher diamon Cut ( F.) Est. 'd Yields (Wt 9%) Yields (Wt 9%) Difference 35 doids To 477 63.2 59.3 3.9 a) First column of first selectivity to provide fractions 477 to 515 4.8 7.3 -2.5 enriched in specific higher diamondoids. 515 to 649 28.5 31.2 -2.7 b) Second column of different selectivity to provide 649 and higher 3.5 2.1 1.4 isolated higher diamondoids. 40 Step 1 Feedstock Selection Suitable starting materials were obtained. These materials Step 4 Fractionation of Atmospheric Distillation Residue included a gas condensate, Feedstock A, and a gas conden by Vacuum Distillation sate containing petroleum components, Feedstock B. The resulting Feedstock B atmospheric residuum from Although other condensates, petroleums, or refinery cuts and 45 Step 3 (comprising 2–4 weight percent of the original products could have been used, these two materials were feedstock) was distilled into fractions containing higher chosen due to their high diamondoid concentration, approxi diamondoids). The feed to this high temperature distillation mately 0.3 weight percent higher diamondoids, as deter process was the atmospheric 650 F.--bottoms. Table 3 mined by GC and GC/MS. Both feedstocks were light illustrates the distillation reports for Feedstock B 650 colored and had API gravities between 19 and 20° API. F.+distillation bottoms.
TABLE 3 Distillation Report for Feedstock B-btims Feedstock B - Atmospheric distillation resid 650° F + bottoms Column Used: Sarnia HiVac
WAPORTEMP WEIGHT VOLUME API DENSITY WT WOL WT WOL CUT ST - END, F. G ml (a 60° F. 60/60 60° F. PCT PCT PCT PCT
1 601–656 666.4 639 4.1 1.0435 2012 19.38 2003 1940 2 656 702 666.9 646 S.6 1.0321 2014 19.59 2O.OS 19.62 3 702 752 334.3 330 8.3 1.0122 10.09 1O.O1 1O.OS 10.02 4 752 800 167.7 173 14.5 O.9692 S.O6 5.25 S.O4 5.25 5 800-852 167.3 181 21.7 O.9236 5.05 S.49 S.O.3 5.50 6 852-900 167.1 181 21.9 O.9224 5.05 S.49 S.O2 5.50 7 900-950 238.4 257 21.2 O.9267 7.25 7.79 7.17 7.8O 8 9SO 976 85.4 91 18.9 O.94.08 2.58 2.76 2.57 2.76 9 976-1OOO 80.8 85 18.2 O.9452 2.44 2.58 2.43 2.58 US 7,173,160 B2 17 18
TABLE 3-continued Distillation Report for Feedstock B-btims Feedstock B - Atmospheric distillation resid 650 F. + bottoms Column Used: Sarnia HiVac
10 1OOO-1026 93.8 98 16.9 0.9535 2.83 2.97 2.82 2.98 COL 4.0 4 3.4 1.0489 O.12 O.12 O.12 O.12 HOLDUP BTMS 1026+ 621.8 593 3.4 1.0489 18.78 17.98 1869 18.01 EORTRAPS 17.8 2O O54 O.61 O.S4 O.61 TOTALS 3311.7 3.298 1OOOO 100.00 99.56 100.15 LOSS 14.6 -5 0.44 -0.15 FEED 3326.3 3293 8.6 1.01OO 1OOOO 100.00 BACK CALCULATED API & 9.4 1.OO39 DENSITY
fraction of light hydrocarbons. These could be easily taken TABLE 4 overhead such as by separator 20 and/or by fractionator 32 in FIG. 1 to permit the recovery and isolation of the higher Elemental Composition of Feedstock B 2O diamondoids. Table 5 further describes the result of hydro Analyses on Feedstock B 650 + F Resid processing at 850 F. reaction temperature. Measured Value Nitrogen O.991 wt % TABLE 5 Sulfur O.863 wt % 25 Nickel 8.61 ppm Results of Successful Hydroprocessing Runs on Vanadium <0.2 ppm Higher-Diamondoid Containing Feeds Temp, F. 850 WHSV 1.69 Table 4 illustrates the partial elemental composition of Total. P. psig 1925 Feedstock B atmospheric distillation (650 F.) residue 30 Inlet H. P. psia 1824 including some of the identified impurities. Table 4 displays Gas Rate, SCFB S191. the Weight percent nitrogen, Sulfur, nickel and Vanadium in Conv < T, Wt % 79.82 Feedstock B atmospheric distillation residue. Subsequent Run Hour 676 steps remove these materials. No Loss Yields, Wt % 35 Methane O41 Step 5: Hydroprocessing of Isolated Fractions Ethane 2.03 A feed made by combining materials from distillate cuts Propane 4.17 4 and 5 (Table 3B) was prepared and analyzed for diamon I-Butane 1.43 doids and nondiamondoids using a gas chromatograph mass n-Butane 2.32 C5-180° F. 9.29 spectrometer (“GCMS). 18O-2SO F. 8.5 40 This distillate fraction contained tetramantanes, pentam 250 550 F. 38.88 antanes, and cyclohexamantane (and Small amounts of other 550 700°F. 1742 hexamantanes and certain heptamantanes) along with an 700°F.-- 1844 undesirable crude-oil material as indicated in the gas chro CS- 92.52 matogram shown in FIG. 5A. This distillate fraction was Mass Closure, Wt % 97.82 then Subjected to hydroprocessing in a laboratory scale 45 TPG Dist, by Wt 9% continuous flow hydroprocesser using a catalyst containing St S90 76.194 USY Zeolite, amorphous alumina and palladium at various 10.30% 232 358 temperatures, pressures, hydrogen flow rates and reactor SO% 487. space Velocities. 70,90% 640,755 In this hydroprocessing run, total pressure was maintained 95.99% 800,875 at 2300 psig, hydrogen flow rate at 5000 SCF/B, and reactor 50 space velocity at 1.0 hr', while the temperature was varied. FIGS. 5B and 5C are GCMS chromatograms of the liquid product from the hydroprocessing run. FIG. 5B is the data TABLE 6 from the product produced at 800° F. reaction temperature showing that the broad nondiamondoid hydrocarbon peak 55 Yields of Specific Higher Diamondoid Compounds in Feedstock and drops in intensity relative to the higher diamondoid com Hydroprocessing Product at Reaction Temperature 850 F. ponents when compared to the starting material (FIG. 5A). Weight % in Product The best conversions were found with the reaction tempera Weight % in 850 F. Reactor Percent ture at 850° F. as shown in FIG. 5C. At 850° F. nearly all of Higher Diamondoid Feedstock Temperature Yield the undesirable nondiamondoid hydrocarbons boiling in the 60 Methyltetramantane #1 O.26 O.S4 208 -750° F to -850° F have been converted and easily Tetramantane #1 0.27 O.71 264 removed lower molecular weight hydrocarbons. (FIG. 5C). Tetramantane #2 O.96 1.76 182 Tetramantane #3 O46 O.65 142 The shift from higher boiling to lower boiling material Methylpentamantane #1 O.20 O.17 85 shown in FIGS. 5A through 5C is further illustrated from Pentamantane #1 O.34 O.34 91 simulated distillation data shown in the bar graph in FIG. 6. 65 Pentamantane #2 O.29 0.27 94 As can be seen from FIGS. 5B and 5C, and the bar graph of FIG. 6 the hydroprocessed product contains a large US 7,173,160 B2 19 20 Step 6 Removal of Aromatic and Polar Nondiamondoid removal of undesirable non-higher diamondoid materials. Components However, measurable destruction of some of the higher The product produced in Step 5 was passed through a diamondoids was observed. silica-gel gravity chromatography column (using cyclohex A run at 730°F. at a LHSV of 0.25 hrs' showed removal ane clution solvent) to remove polar compounds and of the undesired specie but al less than full conversion. asphaltenes (Step 6). The use of a silver nitrate impregnated A run at 760–780° F. and a LHSV of 0.25 hrs' showed silica gel (10 weight percent AgNO) provides cleaner thorough conversion of nondiamondoids, particularly aro diamondoid-containing fractions by removing the free aro matics with lower levels of loss of desired higher diamon matic and polar components. While it is not necessary to use doids. The product was exceptionally clear (see FIG.9) and this chromatographic aromatic-separation method, it facili 10 free of coloration, carbon solids or tar. tates Subsequent steps. Additional optimization runs were carried out using the Table 6 shows good yields for the pentamantane compo 650 750° F. feed at 760° F., LHSV of 0.25 hrs, 5000 nents and that the specified tetramantanes are actually being produced from other components during the process. Representative higher diamondoids present in the feed 15 and product are listed in Table 7. Step 7 Multi-Column HPLC Isolation of Higher Diamon doids TABLE 7 An excellent method for isolating high-purity higher Yields of Specific Higher Diamondoid Compounds in Feedstock and diamondoids uses two or more HPLC columns of different Hydroprocessed Product selectivities in Succession. The first HPLC system consists of two whatman M20 Weight % in Percent Yield 10/50 ODS columns operated in series using acetone as Higher Weight % in Product (wt-% of mobile phase at 5.00 mL/min. A series of HPLC fractions Diamondoid Feedstock Bottoms feed) were taken. Fractions were combined and taken for further Methyltetramantane O.S6 1.OO 87 purification on a second HPLC system. 25 Tetramantane #1 1(2)3 O.66 1.32 96 Tetramantane #2 121 1.47 2.13 69 Further purification of this combined ODS HPLC fraction Tetramantane #3 (123 O41 O.61 72 is achieved using a Hypercarb stationary phase HPLC Pentamantane #1 O.OS O.10 93 column which has a different selectivity in the separation of *Bottoms equal 48 weight % of total hydroprocessed product. various higher diamondoids than the ODS column discussed 30 above. Isolated diamondoids are analyzed for purity by FIG. 7 illustrates the results of studies on optimizing GCMS and allowed to crystallize in a Super-saturated solu hydroprocessing conditions to destroy unwanted hydrocar tion in acetone. bon impurities while retaining higher diamondoids. 1(2)3 tetramantane shows higher stability to processing than 123 EXAMPLE 2 35 tetramantane. An increase in the ratio of 1(2)3 to 123 tetramantane indicates the destruction of 123 tetraman Steps 1, 2 and 3 of Example 1 were carried out. Atmo tanes relative to 1(2)3 tetramantane. Destruction of the spheric residium of step 3 was then processed in a pilot-scale unwanted hydrocarbon impurities is monitored using the wiped film evaporator (U1C model KDLS). ratio of the combined GCMS peak heights of the three In a first run, the step 3 residium was fed at a rate of 300 40 tetramantanes to the combined GCMS peak heights of three g/hr and a wiper speed of 300 rpm. Pressure was 0.004 selected impurities (9.20, 10.05 and 10.90 mins. FIG. 8). millitorr and the average evaporate temperature was 127.5° The goal of the hydroprocessing is to maintain a constant C. This leads to a distillate fraction (65% by wt) having a ratio of 123 to 1(2)3 tetramantane (no destruction of nominal atmospheric boiling range of 650–750 F. and a 123 relative to 1(2)3, as an indicator of minimal destruc residue (35% by wt) having a nominal boiling range at 750 45 tion of higher diamondoids), while maximizing removal of F. The distillate contained 0.83% w sulfur, 397 wt. ppm hydrocarbon impurities as shown by a significant increase in nitrogen and an API gravity of 11.3. The residue contained the tetramantanes to hydrocarbon impurity peak ratio. 2.71% w sulfur and had an API gravity of 12.3. The distillate GCMS analyses were performed on the feed and product of this run was used as “650–750° F. Feed” in this Example. of these hydroprocessing runs and are shown in FIG. 8. In a second run, the same step 3 residue was Subjected to 50 These GCMS plots illustrate destruction of unwanted hydro two stages of wiped film evaporation in the same evaporator carbon impurities with retention of tetramantanes and other and generally the same conditions. The first stage was higher diamondoids. Mass spectral ion m/z. 292 (the molecu carried out at an average temperature of 116° C. to yield a lar ion of the tetramantane isomers) is used to illustrate the first stage distillate of 35% and first stage residue of 65%. concentration of the tetramantane higher diamondoids. Mass 55 spectral ion m/z 57 (fragmention characteristic of a signifi This residue was sent through a second stage at 147 C. cant class of hydrocarbon impurities) is used as a measure of to yield a second distillate (19.3% by wit, basis first stage the concentration of unwanted impurities. FIG. 8A shows feed) having a nominal boiling range of 750-850 F. This relative concentrations of tetramantanes and hydrocarbon second distillate contained 6.92% w sulfur and had an API impurities in the starting material. The hydrocarbon impu gravity of 15.2. This second distillate was used as 60 rity peaks at 9.20, 10.05 and 10.90 minutes shown in FIGS. “750-850° Feed” in this Example. 8A and 8B were used to calculate parameters shown in FIG. The 650–750° F. Feed was hydroprocessed under the 7 which illustrate destruction of hydrocarbon impurities following conditions on a Akzo-Nobel “Stars KF848 base (M/S=57 fragment ion) with retention of desired tetraman metal catalyst. This feedstock contained high levels of tanes. aromatics and significant levels of Sulfur. 65 Additional runs were carried out using the 750-850° A total pressure of 2300 psi, LHSV of 1.0 hrs, H/oil of Feed. This material contained over 6% w sulfur. When it was 4000 scf/bbl and a temperature of 800° F. led to effective fed over the base metal catalyst under the general conditions US 7,173,160 B2 21 22 listed in this example, three advantageous findings were from to permit recovery of higher diamondoids from observed. This cut processed similarly to the 650–750° cut. the hydroprocessed feedstock; and Aromatics present in the 750-850 cut were removed. The c) fractionating the hydroprocessed feedstock into lower high sulfur content in the feed did not interfere with the boiling point fraction(s) enriched in converted nondia desired hydroprocessing reactions. One predictable anomaly 5 mondoid components and higher boiling fraction(s) was observed and is shown in the diamondoid peak sizes in enriched in higher diamondoids. FIGS. 10A and 10B. Six diamondoid peaks were observed 14. The process of claim 13 additionally comprising step in the feed (A) and product (B). The two peaks at about 13.5 d) minutes, the two at about 15.1 minutes and the peak at about d) recovering a fraction enriched in at least one higher 15.52 minutes were determined to correspond to the 5 10 diamondoid. pentamantanes while the 15.48 minute peak corresponded to cyclohexamantane. 15. A process for recovering a composition enriched in Cyclohexamantane has been previously observed to be higher diamondoids which process comprises: exceptionally stable. 10 shows that it appears to be broken a) selecting a feedstock comprising recoverable amounts down to a less pronounced degree than at least most of the 15 of higher diamondoids in admixture with nondiamon five pentamantanes. In all cases, however, the higher dia doid components; mondoids are present in greatly enhanced concentrations in b) fractionating the feedstock to provide a fraction com the hydroprocessing product, relative to similar-boiling prising recoverable amounts of higher diamondoids other components in the feed. and nondiamondoid components; and What is claimed is: c) contacting the feedstock fraction with hydrogen at a 1. A process for producing a composition enriched in temperature of about 300 to about 950 F. and at an higher diamondoids which process comprises: overall pressure of 200 to 4000 psi in the presence of a) selecting a feedstock comprising recoverable amounts a catalyst to react at least a portion of nondiamondoid of higher diamondoids in admixture with nondiamon components therein to facilitate recovery of higher doid components; 25 diamondoids from the reacted feedstock fraction. b) contacting the feedstock with hydrogen at a tempera 16. The process of claim 15 additionally comprising step ture of about 300 to about 950 F. and at an overall d) pressure of 200 to 4000 psi in the presence of a catalyst d) recovering higher diamondoid(s) from the reacted to preferencially react at least a portion of the nondia feedstock fraction. mondoid components therein to facilitate recovery of 30 17. The process of claim 15 wherein said contacting is higher diamondoids from the reacted feedstock. hydroprocessing. 2. The process of claim 1 additionally comprising step c) 18. The process of claim 15 wherein said contacting c) recovering higher diamondoid(s) from the reacted comprises hydrocracking. feedstock. 19. The process of claim 15 wherein said contacting 3. The process of claim 1 wherein said contacting is 35 comprises hydrotreating. hydroprocessing. 20. The process of claim 15 wherein said contacting is 4. The process of claim 3 additionally comprising step c) hydrotreating followed by hydrocracking. c) recovering higher diamondoid(s) from the reacted 21. The process of claim 15 wherein said contacting feedstock. comprises hydrotreating and simultaneous hydrocracking. 5. The process of claim 3 wherein said hydroprocessing 40 comprises hydrocracking. 22. The process of claim 15 wherein the feedstock frac 6. The process of claim 5 additionally comprising step c) tion is a distillation residue. c) recovering higher diamondoid(s) from the reacted 23. The process of claim 15 wherein the feedstock frac feedstock. tion is an overhead fraction. 7. The process of claim 3 wherein said hydroprocessing 45 24. The process of claim 15 wherein the process is a comprises hydrotreating. continuous process operating at space Velocity of from 0.02 8. The process of claim 7 additionally comprising step c) to 20 hrs'. c) recovering higher diamondoid(s) from the reacted 25. The process of claim 15 wherein the catalyst is a feedstock. heterogeneous catalyst. 9. The process of claim 1 wherein said contacting com 50 26. The process of claim 15 wherein the catalyst com prises hydrotreating followed by hydrocracking. prises noble metal. 10. The process of claim 9 additionally comprising step c) 27. The process of claim 15 wherein the catalyst com c) recovering higher diamondoid(s) from the reacted prises base metal. feedstock. 28. The process of claim 15 wherein the catalyst com 11. The process of claim 1 wherein said contacting 55 comprises hydrotreating and simultaneous hydrocracking. prises Zeolite. 12. The process of claim 11 additionally comprising step 29. The process of claim 15 wherein the catalyst com c) prises silica or alumina, or silica-alumina. c) recovering higher diamondoid(s) from the reacted 30. The process of claim 15 wherein the space velocity is feedstock. 60 from about 0.02 to 20 hrs' and the catalyst is a noble metal 13. A process for recovering a composition enriched in catalyst. higher diamondoids which process comprises: 31. The process of claim 15 wherein the space velocity is a) selecting a feedstock comprising recoverable amounts 0.02 to 2.0 hrs the hydrogen circulation rate is from 200 of higher diamondoids in admixture with nondiamon to 20,000 scf/bbl of feed and the catalyst is a base metal doid components; 65 catalyst. b) hydroprocessing the feedstock to convert at least a Sufficient amount of nondiamondoid components there