3,642,901 United States Patent Office Patented Feb. 15, 1972 2 converted to oxidation products, which are responsible for 3,642,901 . the eye-irritating, plant-damaging, and reduced visibility BORONTRFLUORDE, ETHERATEAMNE REACTION PRODUCTS characteristics of smog; that the intermediate product is Abraham M. Herbsman, 9721 3rd Ave., believed to break down to form ozone, which in turn may Los Angeles, Calif. 90305 further oxidize certain hydrocarbons, principally olefins; No Drawing. Application Sept. 13, 1968, Ser. No. 759,780, and that some of these intermediate products and the now Patent No. 3,488,169, dated Jan. 6, 1970, which is ozone itself are believed to comprise the high "oxidant' a continuation-in-part of application Ser. No. 283,550, content of the Los Angeles atmosphere. (Chemistry and May 27, 1963. Divided and this application July 31, Physiology of the Los Angeles Smog, Industrial and Engi 1969, Ser. No. 864,241 neering Chemistry 44, pp. 1342-6; 1952 and "Ozone For Int. CI. C07c35/00, 87/00, 87/06 O mation in Photochemical Oxidation of Organic Sub U.S. C. 260-583 A 4 Claims stances,” Industrial and Engineering Chemistry 45, pp. 2086-9; 1953). In a paper, entitled “Relative Reactivity of Various Hydrocarbons in Polluted Atmospheres' by ABSTRACT OF THE DISCLOSURE E. R. Stephens and W. E. Scott, presented May 17, 1962 A composition of matter, which is soluble in gasoline 5 to the American Petroleum Institute's Division of Refin and in liquid aliphatic hydrocarbons, and which consists ing, it is stated that irradiated "dilute mixtures of olefin of the product, produced by reacting boron trifluoride with nitrogen dioxide in air' produced most of the symp ethyl ether complex with an amine reagent, selected from toms of photochemical air pollution with eye irritant prod the group consisting of tertiary nonyl amine, a mixture of ucts, identified as formaldehyde, acrolein and peroxyacyl tertiary-alkyl primary amines, ranging from t-C12H25NH2 20 nitrates; and with plant damaging products, identified as to t-CH3NH2, a mixture of tertiary-alkyl primary ozone and peroxyacyl nitrates. amines, ranging from t-C18H3NH2 to t-C4H49NH2, and It is generally conceded that the major contaminant of primary alkyl aryl amines in which the alkyl radical is the air in Los Angeles is automobile exhaust. For the large enough to impart solubility to the reaction product efficient performance demanded, an automotive engine is in gasoline and liquid aliphatic hydrocarbons. 25 operated under "rich mixture' conditions with insufficient air for complete combustion. Because an internal com -cars... sees actres bustion engine acts as a "cracking' device with regard This application is a division of my prior copending to the fuel introduced therein, the major portion of the application Ser. No. 759,780, filed Sept. 13, 1968, and now exhaust hydrocarbons is unsaturated or olefinic in char U.S. Pat. 3,488,169, which is in turn a continuation-in-part 30 acter and, as such, is easily reacted upon in the atmos of my prior application Ser. No. 283,550, filed May 27, phere to produce Smog conditions. In their study of hy 1963, and now abandoned. drocarbon emission by automobile exhausts to the atmos The present invention relates to new compositions of phere, Magil et al. ("Hydrocarbon Constituents of Auto matter and method for treating internal combustion engine mobile Exhaust Gases,” Proceedings of the Second Na fuel gases, which consists in employing with the fuel or the 35 tional Air Pollution Symposium, Stanford Research In gases formed on combustion of the fuel a catalytic agent, stitute, pp. 71-83; 1952) concluded that the exhaust com capable of promoting polymerization and chemical con position is independent of the type of gasoline burned densation of organic compounds, such as unsaturated and stated, "The fact that the C5 to C olefin concentra hydrocarbons, olefins and aldehydes. This treatment has tion in the exhaust is the same for widely different types been found to inactivate and lessen the smog-inducing 40 of gasoline burned emphasizes that the olefinic material in components of the engine exhausts to a material degree, the gasoline does not contribute, except to a very small principally by decreasing the nitrogen oxides content and extent, to the olefinic material in the exhaust.' The Air increasing the molecular structure of the olefinic and Pollution Field Operations Manual by U.S. Department unsaturated hydrocarbons of the combustion gases. It also of Health, 1962, states that ethylene (present in auto has been found to inclusively improve combustion, effect mobile exhaust) causes severe damage to vegetation (page smoother engine performance and give better mileage, 3) and that the smog-forming potential is also dependent when the catalytic agent, as a catalytic composition, is on the ability of specific hydrocarbons to be oxidized added to automobile fuel. (page 32). According to certain aspects of my invention, the com It appears that the effort to overcome the problem of bustion engine gases are subjected to continuous intimate 50 emission of noxious gases by internal combustion engines gaseous admixture with the catalyst in a practically nas has been mainly confined to treatment of the gases at the cent vapor state. Thus, the most efficient means of cata muffler or tailpipe of the automobile in the design of lytic application is attained. Also of note, is the fact that chambers in which oxidation of the exhaust gas hydro the catalytic effect, herein employed, does not require the carbons might be completed. These adaptations are known injection of supplemental or secondary air into the 55 as an "afterburner' and a "catalytic converter.” Both exhaust, as demanded with the use of “afterburners' and adaptations demand the introduction of additional air to oxidation catalysts; and accordingly obviates the pollution complete the combustion. With the “afterburner, a pilot that results from the additional oxides of nitrogen, pro light or spark ignites the hydrocarbon-air mixture, and duced by such introduction of air. combustion is completed on a hot ceramic surface; while The untreated engine exhaust gases contain unsaturated 60 in a catalytic converter, oxidation is completed catalyti hydrocarbons, including olefins, which, accompanied by cally at a much lower temperature. The afterburner would oxides of nitrogen in the exhaust, readily react in the seem to present a hazard, due to the necessity of having atmosphere in the presence of sunlight to produce Smog high temperature and a flame or spark. The catalytic and irritating conditions. Also, expelled in the exhaust are converter has the drawbacks of back pressure and the aldehydic, ketonic and organic acid type compounds 65 necessary replacement or regeneration of the catalytic ("Nature of Smog' by W. L. Faith in Chemical Engineer pellet or otherwise arranged solid contact material. This ing Progress, 53, 406, August 1957). One of the most is explained by Thomas E. Corrigan in Chemical Engineer smog-afflicted areas is Los Angeles, California. As stated ing, January 1955, page 199; March 1955, page 197, of in Report No. 2 (1954) by the Los Angeles Air Pollution which the following excerpts are of note: “When a gas Foundation, Haagen-Smit shows that exhaust hydrocar 70 phase chemical reaction is promoted by a solid catalyst, bons in the presence of sunlight and nitrogen dioxide, are it has to be accompanied by adsorption. The reactants are 3,642,901 3. 4 adsorbed; the products are formed in an adsorbed con combustion, may also be treated in accordance with the dition and must be desorbed.” . "In many reactions present invention. there is a continual deposit upon the surface of the cat If desired, some of the components arising from the alyst which reduced its effectiveness. Even at a constant operation of this invention, can also be trapped and re flow rate the conversion in a flow reactor may continue 5 covered. The trap can be so designed as to take the place to decrease during a run. When the catalyst activity drops of the muffler and provided with a material to aid in the to a certain point it is removed and regenerated.” . “A coalescing of the vapor. Such materials may be in the material which vitiates the value of the catalyst is a form of coatings or loose packs or cartridges of water poison. A foreign material in the gas stream may either wettable (lyophillic) materials and hydrocarbon-oil wet combine permanently with the active centers or merely O table (hydrophobic) materials. Examples of lyophillic ma block the pore opening and hinder diffusion.' . “A terials include fiber glass, ceramics, pumice and silica gel reaction may be self-poisonous; if the adsorption of the and examples of hydrophobic materials include metallic product is so great that most of the active centers become sulfides, such as iron sulfide, amino or urea resins, and Occupied by product molecules. There would be no room metallic soaps. The incorporation in such a trap of polym for further adsorption of reactant molecules and the reac 5 erization catalysts such as fluorides of aluminum, cobalt, tion would cease.' Zinc and calcium or like metallic fluorides and metallic Of more significant concern, is the resultant increase soaps, such as the resinates or stearates of aluminum, cop of oxides of nitrogen, created by the mandatory use of per, calcium and magnesium, would serve the dual func Secondary air in both the “afterburner' and “oxidation tion of promoting both coalescence and additional polym catalytic converter.” Report No. 2 (1954) by the Los 20 erization capability. The lyophillic and hydrophobic ma Angeles Air Pollution Foundation states: “One of the terials are preferably intimately mixed, as for example: peculiarities of the Los Angeles atmosphere is its high (1) partial silicon-treated pumice, (2) partial silicon oZone content on Smoggy days.