(19) TZZ __¥_T (11) EP 2 821 137 A1 (12) EUROPEAN PATENT APPLICATION published in accordance with Art. 153(4) EPC (43) Date of publication: (51) Int Cl.: 07.01.2015 Bulletin 2015/02 B01J 31/40 (2006.01) B01J 38/00 (2006.01) C07C 41/58 (2006.01) C07C 43/06 (2006.01) (2006.01) (21) Application number: 13754170.2 C07F 5/02 (22) Date of filing: 01.03.2013 (86) International application number: PCT/JP2013/055731 (87) International publication number: WO 2013/129662 (06.09.2013 Gazette 2013/36) (84) Designated Contracting States: • MACHIDA, Masashi AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Chiba 2990192 (JP) GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO • SEKIGUCHI, Hiroki PL PT RO RS SE SI SK SM TR Chiba 2990293 (JP) Designated Extension States: • YOSHIDA, Yukio BA ME Chiba 2990293 (JP) • TSUBOUCHI, Toshiyuki (30) Priority: 02.03.2012 JP 2012047436 Chiba 2990293 (JP) (71) Applicant: Idemitsu Kosan Co., Ltd. (74) Representative: Hoffmann Eitle Chiyoda-ku Patent- und Rechtsanwälte PartmbB Tokyo 100-8321 (JP) Arabellastraße 30 81925 München (DE) (72) Inventors: • ODA, Sumihiro Chiba 2990293 (JP) (54) RECOVERY METHOD AND RECYCLING METHOD FOR BORON TRIFLUORIDE COMPLEX (57) In a reaction in which a boron trifluoride complex containing the boron trifluoride complex by separating is used as a catalyst, the expensive and harmful boron the boron trifluoride complex present in the reaction mix- trifluoride complex is separated from a reaction mixture ture by using a saturated hydrocarbon-based solvent. EP 2 821 137 A1 Printed by Jouve, 75001 PARIS (FR) 1 EP 2 821 137 A1 2 Description arate the boron trifluoride complex from the resulting re- action mixture. In order to separate the boron trifluoride TECHNICAL FIELD complex from the reaction mixture, there are usually adopted a method of washing the reaction mixture with [0001] The present invention relates to processes for 5 water after adding water to the reactionmixture to deac- the recovery and recycling of a boron trifluoride complex, tivate the boron trifluoride complex therein, a method of and more particularly, it relates to processes for the re- washing the reaction mixture with water after neutralizing covery of a boron trifluoride complex and reusing of the the reaction mixture solution by a basic aqueous solution boron trifluoride complex recovered, wherein the boron of ammonia, sodium hydroxide, lime or the like. trifluoride complex is used as a catalyst in a process for 10 [0006] However, in the above methods, a waste water producing compounds by alkylation, condensation reac- containing a hydrate of boron trifluoride or a neutralized tion of olefins, oligomerization reaction, polymerization product of boron trifluoride in a high concentration is dis- reaction, condensation reaction and isomerization reac- charged. Therefore, in recent years, there is a demand tion, and in a process for producing petroleum resins, for suitablemeasures to be taken for removal ofthe waste chroman, and indene-resins. 15 water containing fluorides or boron in consideration of the problem of environmental pollution. In particular, BACKGROUND ART since it is difficult to remove boron easily by a current technologyfor waste-water treatment, and since it is cost- [0002] Boron trifluoride and a boron trifluoride complex ly to remove boron completely, there is a demand for constituted of boron trifluoride and a complexing agent 20 removal of boron at low costs. Furthermore, since boron (ligand) are well known as a so-called Friedel-Crafts cat- trifluoride is expensive, there is a demand for recovery alyst, and the boron trifluoride complex has an excellent and reuse of the removed boron trifluoride or boron trif- catalyst performance of suppressing side reactions and luoride complex. promoting only main reactions effectively as compared [0007] However, for example, in the condensation re- 25 with AlCl3, FeCl3, sulfuric acid and the like. Therefore, action of olefins using the boron trifluoride complex as a various boron trifluoride complexes are industrially used catalyst, the boron trifluoride complex is almost dissolved widely as a catalyst in various chemical reactions such in the reaction mixture or forms an emulsion. Hence, even as alkylation, isomerization, polymerization, dimeriza- if the reaction mixture is allowed to stand, it is difficult to tion, condensation, addition, decomposition, dehydra- completely separate the reaction mixture and the boron tion, etc. 30 trifluoride complex catalyst from each other. Therefore, [0003] Main industrial use of the boron trifluoride or the boron trifluoride complex is removed from the reac- boron trifluoride complex includes, for example, a cata- tion mixture by washing the reaction mixture with water lyst in producing ethyl benzene by gas phase alkylation or the basic aqueous solution. However, if water or the from ethylene and benzene. The boron trifluoride or bo- basic aqueous solution is added to the boron trifluoride ron trifluoride complex is also used as a catalyst in the 35 complex, the boron trifluoride catalyst forms a water com- process for producing alkyl benzenes used for synthetic plex such as BF3(H2O)n or a boron trifluoride salt, and detergents or antioxidants by liquid phase alkylation re- cannot be repeatedly used as a catalyst as it is. Also, action of an olefin and an aromatic compound. there is known a method of separating a catalyst liquid [0004] Furthermore, the boron trifluoride or boron trif- layer from the reaction mixture using a complex of BF3 luoride complex is also used as a polymerization catalyst 40 with phosphoric acid, acetic acid or phenol (for example, in producing petroleum resins and chroman-indene res- refer to Patent Document 1). However, the above reac- ins which are widely used in the fields such as adhesives tion proceeds only slowly unless the catalyst concentra- and printing ink. When the boron trifluoride or boron trif- tion is 10% or more. Moreover, since the catalyst acts as luoride complex is used as the polymerization catalyst, a Broensted acid, side reactions such as isomerization it is possible to attain effects such as less deterioration 45 tend to occur, and consequently the aforementioned sep- in quality of a product and less corrosion of an equipment aration method cannot be adopted particularly for a con- used. As mentioned above, the boron trifluoride or boron densation dimerization reaction of olefins. trifluoride complex provides a catalyst that can be used [0008] Conventionally, there is known a method for the in various applications as a catalyst for production of var- recovery of boron trifluoride or a boron trifluoride com- ious products in chemical industries. 50 plex, wherein the reaction mixture solution containing the [0005] The boron trifluoride complex constituted of bo- boron trifluoride or boron trifluoride complex is contacted ron trifluoride and a complexing agent (ligand) is used, with calcium fluoride (CaF2) at a temperature of 200°C depending on the reaction as intended, in the form of a or lower, and the resulting calcium tetrafluoroborate complex in which various compounds are coordinated to (Ca(BF4)2) is heated at a temperature between 100°C boron trifluoride at an appropriate ratio. The boron triflu- 55 and 600°C, to obtain the boron trifluoride to be recovered oride complex acts as a catalyst in the reaction as intend- and calcium fluoride (for example, refer to Patent Docu- ed. It is general that the boron trifluoride complex is de- ment 2). activated after stopping the reaction as intended to sep- [0009] Similarly, there is known a method for the re- 2 3 EP 2 821 137 A1 4 covery of boron trifluoride by contacting a fluoride such CITATION LIST as lithium fluoride, strontium fluoride and barium fluoride with the reaction mixture solution containing the boron Patent Literature trifluoride or boron trifluoride complex to produce a tetrafluoroborate and heating the tetrafluoroborate at a 5 [0015] temperature between 100°C and 600°C (for example, refer to Patent Document 3, Patent Document 4 and Pat- Patent Document 1: JP 02-45429A ent Document 5). Patent Document 2: JP 2000-109313A [0010] However, in the reaction using the boron triflu- Patent Document 3: JP 2000-128522A oride or boron trifluoride complex as a catalyst, it is nec- 10 Patent Document 4: JP 2000-135402A essary to react at a low temperature below room temper- Patent Document 5: JP 2000-135403A ature in many cases. Moreover, when the temperature Patent Document 6: JP 2001-104805A is raised to about 100°C after stopping the reaction, at Patent Document 7: JP 2004-195360A which the tetrafluoroborate is synthesized advanta- Patent Document 8: JP 2004-141819A geously, a side reaction tends to occur, which results in 15 decrease in the yield of the reaction product as aimed or SUMMARY OF THE INVENTION deterioration in quality thereof. The tetrafluoroboric acid is hardly formed below room temperature. In addition, PROBLEM TO BE SOLVED BY THE INVENTION decomposition reaction by heating at high temperature is not desirable from the viewpoint of energy saving. 20 [0016] The prevent invention has been made in view [0011] Moreover, there is a problem that, when the re- of the above problems encountered in the conventional action mixture solution containing the boron trifluoride or art. An object of the present invention is to provide a boron trifluoride complex is viscous, much time and effort method of recovering a boron trifluoride complex in which are required in order to separate borates such as calcium the expensive and harmful boron trifluoride complex is tetrafluoroborate from the reaction mixture. 25 separated from a reaction mixture containing the boron [0012] There is also known a method for the recovery trifluoride complex in a facilitated manner, and a method of the boron trifluoride or boron trifluoride complex, of reusing the thus recovered boron trifluoride complex wherein the boron trifluoride or boron trifluoride complex in the reaction.