Hydrogenation and Hydrogenolysis CORPORATION, LOUISVILLE,
KY.
T
HIS review summarizes significant information which has become available in the past decade about hydrogenation as a unit process. Coal hydrogenation, and reduction and alkylation of nitrogen compounds by hydrogenation have been the subject of recent reviews and are not covered in this paper (897,843, 966,967).
OIL AND FAT HARDENING The hardening of whale oil in England about 1902 was the first commercial application of catalytic hydrogenation (16). Since that time the economic importance of hardened glyceride oils has had an enormous growth, which was stimulated in part by the shortages of hard animal fats during World Wars I and I1 and in part by the development of products that were more acceptable to the consumer in terms of price, or quality, or both. Most hydrogenated oils are consumed in edible products such as shortenings and margarine. The most important hydrogenated raw materials for these products are derived from whale (in Europe), cottonseed, and soybean oils. Lard is hydrogenated to improve its consistency and stability. Whale and fish oils, grease, tallow and fatty acids are hydrogenated for industrial uses, such as soap making (17,111). Fish liver oils are hydrogenated in the production of tasteless and odorless vitamin concentrates (188). In 1940 oil hardening by hydrogenation was a well developed unit process which is described in a number of reviews and surveys (16,64, 77,109,111,166,974,880). A number of more recent reviews and sarveys give some knowledge of current 96,186, 160,170,836). practices (16,1Q, In the United States there appears to be a trend toward the use of simpler hydrogenation equipment (17,19). The develop ment of special turbine-type agitators has eliminated need for complicated circulating systems for oil and hydrogen and permits the use of less complicated and expensive auxiliary e q u i p ment (l7,19, 77,134,166, 811,880). Commercial hydrogenators have a capacity of 6 to 20 tons of oil per batch, are usually made from carbon steel, and can withstand 100 to 150 pounds’ pressure and full vacuum. Vessels to be operated with continuous venting and large volume of inlet gas require no mechanical agitation, or a t most only simple paddle-type agitators revolving a t a moderate speed to give sufficient stirring for heat transfer and hydrogen dispersion. In vessels to be operated “dead ended”i.e., with occasional venting or venting only a t the end uf the reaction-the vertical agitator shaft should be provided with a turboagitator near the bottom of the vessel with the outlets of the hydrogen inlet tubes beneath it, another near the surface of the oil, and in some designs, a third agitator near the center, so that the agitator suction will draw hydrogen downward and disperse it in the oil (17,19,186). A recent patent describes liquid into gas circulation of oil within the hydrogenator by means of an axial flow turbine in a vertical tube which projects a stream of oil into the vapor space of the reactor against a rapidly rotating disk, thus atomizing the oil and providing excellent contact between oil and hydrogen
(1141. In another device, which is claimed to give very fast hydrogenation even with recalcitrant materials like fish oil, oil is rapidly circulated from a feed tank under pressure through a high-capacity centrifugal pump and back into the feed tank while hydrogen is fed into the oil on the suction side of the pump
(886). Continuous glyceride oil hydrogenation has never been an importsnt factor in this country or elsewhere, with the possible exception of Russia and Great Britain (19,96, 166). A continuous process using a k e d catalyst bed was developed in England during the early twenties and it has been subject to some development since that time (166). The limited area per unit volume of the superficially activated, massive nickel catalysts used in this system preclude selective hydrogenation under conditions which would give high output and low capital costs. Continuous oil hardening with powdered catalyst was carried out on a plant scale in Russia as early as 1933,but no up-to-date information on the status of this operation is available (180, 849). Sustained interest in continuous oil hydrogenation processes is shown by the issuance of several patents on apparatus and processes for this type of operation (99, 167,878). One of these patents describes continuous hydrogenation and hydrolysis ($78). None of these processes is known to be in operation. Pilot plant runs, using a mechanically agitated heat exchanger as a continuous hydrogenator with a powdered catalyst, showed good selectivity in the hydrogenation of linoleates and linolenates to oleates and ieooleates in the partial hydrogenation of linseed oil (986). Hydrogenations in the m a n u f a c t u r e of edible p r o d u c t s a r e CooLlle COIL1 generelly carried out in the range 250” to 400” F. a t pressures ranging from 1 to 10 atmospheres, depending on the product being made, the type of equipment, and the nature and age of the OWRTWY OCNERAL AMCRIOAN TRANIIPORTATION OMPORATION catalyst (17,96, 936, 980). Catalyst dosages Turbo-Mixer Corporation H drogenusually run 0.05 to ator with Shrouded Turbo Agitators
P
1705
INDUSTRIA1 AND ENGINEERING CHEMISTRY
1706
0.20% nickel on the weight of oil, and the catalyst may be all fresh, all used, or a mixture of fresh and used depending, in part, at least, on the material being hydrogenated and the product desired (17, 19, 96, 836, 880). Refractive index determinations are most commonly used to follow the reaction and to determine the end point, while setting points, melting points, and iodine values may be used as supplementary controls. A quick penetration micromethod has been developed and proposed as a control in hydrogenation of fat products (82). A congeal point which is determined by a mechanical device is useful for the same purpose (1W.
LIQUID LEVEL GASED HEATING-STEAM COMINO-WATER
INLEt OUTLET
LIQUID LEVEL UNOASED
SECONDARY Ob3 INLET
FLAT BLADE TURBINES
SlABIL12INO RINO
PRIMARY GAS INLET
HEATINO-STEAM CONDENSATE -RAINS 00DLlNO-WATER INLET
COURTUIY YlXlNO EPUIPMENT COMPANY
Oil and
Fat Hydro enator with Unshrouded Lightnin furbo Agitators
An investigation of the process variables in the hydrogenation of cottonseed and peanut oils confirms conclusions about selectivity reached by earlier investigators (10). Selectivity in the sense of conversion of linoleate to oleate (mixed normal and iso), with a minimum formation of saturated esters, increases with temperature and amount of catalyst, and decreases with increase in pressure and intensity of agitation. Conditions favoring selectivity, in the sense defined above, also favor formation of h l e i c acid; the nature of the catalyst is another factor affecting this variable. By the use of spectrophotometric methods of analysis (ad), the relative reactivities in hydrogenation of the various unsaturated components of several vegetable oils have been determined (81). Under selective conditions (high temperature, low pressure), the relative reactivities are: oleio, 1; i m l e i c , 1; isolinoleic, 3; linoleic, 20; linolenic, 40. Under nonselective conditions (low temperature, high pressure) relative rater may change to: oleic, 1; isolinoleic, 3; linoleic, 5 ; linolenia, 10.
Vol. 42, No. 9
These data, along with the results of a study of the formation of isomeric linoleates in hydrogenation of linolenates (I&), have been used in formulating a theory which attributes selectivity-Le., greater reactivity of the common polyunsaturated fatty acid residues, to the presence of methylene groups which are activated because they are sandwiched between pairs of ethenoid groups. This concept explains the lack of selectivity and low rates of hydrogenation of marine oils, inasmuch as these oils contain much multiple unsaturation in which ethenoid structures are separated by pairs of methylene groups (115'). A recent reevaluation of data obtained in the hydrogenation of linseed oil gives the following relative reactivites: under selective conditions, oleic, 1; isolinoleic, 3.85; linoleic, 31; linolenic, 77; under nonselective conditions, oleic, 1; isolinoleic, 2.5; linoleic, 7.5; linolenic, 12.5 (18). Cottonseed and sesame oils did not hydrogenate selectively in a continuous system using a fixed bed of extruded nickel on kieselguhr catalyst, but some selectivity was shown with safflower oil in which the initial ratio of linoleic to oleic is 4 to 1 (15's). Wet reduced nickel, made by reducing nickel formate in oil under hydrogen pressure, is the catalyst most used for fat and oil hydrogenation (17, 10, 95, 116, 855). In order to obtain reduction a t low temperatures, oil hydrogenation catalysts sometimes contain small amounts of copper. Dry reduced nickel supported on kieselguhr enjoys some use, especially a relatively new type that is prepared by adsorption on kieselguhr of nickel hydroxide formed by anodic corrosion of nickel (17, 19, 96, 186, 228). Reduced nickel catalysts, protected from the atmosphere by hardened oil, are now made commercially in the form of flakes and granules (80). Availability of these easily handled catalysts has permitted many oil and fat processors to give up their expensive and troublesome catalyst manufacturing operations. Investigation of nickel-copper catalysts has continued (89, 18.9). A catalyst consisting of 4.5% nickel, 4.5% copper, and 90% kieselguhr gave a highly selective hydrogenation of olive oil a t 220' C. (179). A series of patents on oil bleaching by hydrogenation describes various complex catalysts such as barium and calcium modified copper chromites (187); copper or silver or mixed copper-silver with oxides of one or more of chromium, vanadium, tungsten, uranium( 186); ferrites of copper, silver, gold, nickel, cobalt, palladium, platinum, and mixtures of these ferrites (161,189); nickel chromate and chromite (66). The effect of addition of a fifth metal to nickel-cadmium-cobaltmanganese and nickel-copper-cobalt-zinc catalysts has been determined @SO). Low density metal catalysts are prepared by sudden complete vaporization of organic reduction media (248). Mineral oil is used as a medium for the wet reduction of nickel salts of organic acids and mixed nickel-copper carbonates (20,862). Continuation of work on promoters of nickel chromite catalysts indicates that, in addition to sulfur, tellurium, and selenium, small amounts of tungsten, molybdenum, cerium, and manganese increase the rate of hydrogenation of peanut oil and even higher rates are obtained by use of kiesleguhr as promoter (88). A lengthy investigation of the hydrogenation of herring oil showa that the presence of small amounts of aluminum in activated Raney nickel catalyst is necessary for maximum activity (816). In continuous hydrogenation of peanut oil, 20% nickel (from formate) on kieselguhr has its maximum activity a t 300" C. This catalyst is only half as active as the corresponding preparation from the carbonate (127). Further study of this hydrogenstion shows that in the nickel-kieselguhr system, in which the nickel is derived from the carbonate, a peak in activity is reached between 10 and 20'% nickel, a minimum s t about 50%, and the maximum a t 100%; the 100% nickel shows three times the activity of the 20% nickel catalyst (128). Soaps of potassium and sodium are anticatalysts for oil hydrogenation; calcium, magnesium, and barium maps show a weak retarding effert,; and aluminum and iron soaps are indifferent (HI).
September 1950
INDUSTRIAL AND ENGINEERING CHEMISTRY
Low price and wartime shortages of fats and oils stimulated work on the refinement of tall oil, a mixture of unsaturated fatty acids and rosin acids, which is a by-product of the paper industry. Hydrogenation of tall oil, its esters and soaps, was found to give products of improved color and odor which were suitable for use in soap manufacture (60, 69-71, 94,249). The separation of the fatty and rosin acids in tall oil by selective adsorption or crystallization is facilitated by hydrogenation (181, 918).
HYDROGENOLYSIS OF ACIDS AND ESTERS Alcohols derived from fat acids were first manufactured in Germany about 1928. Raw materials were fat acids or their esters and the reduction was accomplished by hydrogenolysis at high pressure and temperature over complex catalysts (98, 136). The long-chain alcohols thus produwd are intermediates for surface-active agents, and their commercial importance has followed the rapfd growth pattern of synthetic detergent and wetting agent usage (136, 171473, 863). In 1940, a plant for the production of ethylene glycol went into operation using a process in which the last step was the hydrogenolysis of hydroxyacetic acid or an ester of this acid to give the glycol (838). In that year, formaldehyde requirements of this process were nearly 16,000,000 pounds of 37% solution (933). In 1948, operations were begun in a full scale plant for the production of hydroabietyl alcohol by hydrogenolysis of methyl esters of rosin acids (167). The potential importance of complete hydrogenation of carboxyl groups to methyl is illustrated by the preparation of thymol and menthol by simultaneous hydrogenation and hydrogenolysis of o-hydroxycummic acid esters over copper, nickel, cobalt, or iron chromite (931),and by the British proposal during the past war that toluene be made by hydrogenolysis of phthalic anhydride in the vapor phase a t 300' to 450' C. a t over 100 atmospheres pressure, using vanadium, tungsten, or molybdenum oxides or sulfides as catalysts (93). Large scale hydrogenolysis of carboxy compounds has been commercialized by only a few companies and has been operated only a relatively short time, so that details of industrial operations have not become widely known. Surveys and reviews (e, 4 , g U l ) and the more recent literature (78,1U3,163,164,167, 819, 814, 878) indicate that the higher alcohols are made from fatty glycerides and rosin esters by both continuous and batchwise reaction in the liquid phase a t 275' to 375"C. and 200 to 300 atmospheres pressure using copper chromite, chromitesof copper and other metals, or mixed oxides of metals such as copper, chromium, and barium as catalysts. Patent disclosures indicate that methyl glycolate is reduced to ethylene glycol in a continuous operation by passing it over a chromite catalyst, such as copper chromite, a t relatively moderate temperatures and pressures in the neighborhood of 200" C. and 30 atmospheres (161,183,184); a large excess of hydrogen, on the order of 1500%, is used and the apace velocity is about 20,000. It is necessary to adjust the temperature and partial pressure of the glycolate so that no condensation occurs, because formation of the liquid phase deactivates the catalyst. Conversion per pass is 93% and yield on glycolate consumed is 100%. The plant for abietyl alcohol, which was mentioned above, may also represent current ideas on the best design for the production of fatty alcohols (167). In this plant, hydrogen a t 5500 pounds per square inch is diasolved in molten methyl abietate; the solution is then passed through a preheater and a heat exchanger which bring the temperature up to reaction level, then downward through a long, small-diameter, forged 304 stainlesa steel reactor containing a bed of catalyst, then through another heat exchanger and down through an identical reactor, and then to high and low pressure gas separators. The steam, methanol, methane, and excess hydrogen are vented to the atmosphere and the product is filtered and cooled. There are three reactors and
1?07
heat exchangers manifolded so that they can be operated twq a t li time in series, the second reactor holding the fresher catalyst and the reactor out of service being rerharged with fresh catalyst. The heat exchangers and reactor jackets are heated and cooled with liquid Dowtherm. No reaction temperatures are given. About 10 years ago production of fatty alcohols by an im proved sodium reduction process was started (106,181). Ma. terial costs in this process are higher than in catalytic hydrogen. olysis, but the much smaller plant investment required and the recovery of glycerol and caustic soda as by-products help to make it competitive. Choice between the two processes will depend mainly on the demand for glycerol and the value which can be assigned to the caustic soda. With present glycerol prices the sodium reduction appears to have the advantage when it is carried out at the same location as caustic-consuming soap making and detergent manufacture. Most of the basic patents relating to the manufacture of alcohols by hydrogenolysis have expired, but patent8 based on applications in 1931, allowing broad claims relating to the hydrogenolysis of acids, esters, and anhydrides to alcohols, were issued in 1943 (813). Catalysts mentioned in this patent include hydrogenating catalysts with activating compounds such as oxygen-containing compounds of metals of Groups I to VII. Reaction conditions are in the range of 120" to 300" C: and 30 to 400 atmospheres. A similar process for preparation of alcohols from resinous acide has been patented (814). The we of copper-aluminum alloy as a hydrogenolysis catalyst was reported in Russia (18) Soaps of lead, cadmium, nickel, copper, and chromium act a6 catalysts for the hydrogenolysis of carboxy acids and their estern and are themselves reduced to alcohols (76, 78, 197-199, 861 1. Soaps of t h e e metals and unsaturated fatty acids are reduced to unsaturated alcohols and esters. The cadmium soaps of unsaturated fatty acids lessen the tendency of copper chromite to saturate ethylenic bonds in fatty acids and their esters (906) Iron oxide catalyst for unsaturated alcohols from rice bran oil is activated by chromic oxide, alumina and to a lesser extenl by zinc oxide and cadmium oxide (143). Zinc and cadmium vanadates and copper-cadmium alloy are catalysts for COD. version of unsaturated acids to unsaturated alcohols (908, 866).
REDUCTION OF CARBONYL COMPOUNDS
Most current interest in carbon monoxide hydrogenation 1s directed toward the Fisher-Tropsoh hydrogenation-polymefiza tion for manufacture of higher hydrocarbons and alcohols. This synthesis is a unit process in itself and is outside the SCOW of this review. Comprehensive surveys of this process have been published recently (246-149, 863). The synthesis of methanol from carbon monoxide has been carried out in this country for over 20 years with few important changes in the process (907). A recent journal article describer an up-to-date methanol plant, including some details on ita operation (130). Recent patents on methanol synthesis describe the use of fluid catalyst ( M ) ,a two-stage catalytic system in which the gases contact copper first a t 200" to 325' C. and then sin0 oxide a t 300"to 450" C. (876),catalyst regeneration by means of carbon monoxide treatment to remove iron (359,and &t* nance of catalyst activity by removal of carbon dioxide from regular synthesis gas (40). Wood is being used as a source Of synthesis gas in France (66). A systematic study of zincchromium oxide catalysts was made in Russia (97). Research on the hydrogenation of carbon monoxide is being carried out in England in order to enable production of a rich fuel gas which can be liquefied for storage (139). Some consideration is being given to methane synthesis for future urn la this country for the same reaeons, and because a high B.t.u. gas could be economically distributed long distances from gaa plants located near coal mines (6,8,86).
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INDUSTRIAL A N D ENGINEERING CHEMISTRY
Several patents describe the synthesis of formaldehyde from hydrogen and carbon monoxide using reduced nickel catalysts promoted with cobalt, copper, silver, zinc, lead, manganese, nagnesium, iron, or silica (86,87). Catalytic hydrogenation is used commercially in the reduction and saturation of products of aldol-type condensations to produce compounds such as n-butyl alcohol, n-hexyl alcohol, 2ethylhexanol, 1,a-butylene glycol, and others (273). Ethyl, propyl, and butyl alcohols are now obtained by hydrogenation of aldehydes produced in the controlled oxidation of lower aliphatic hydrocarbons ( 9 ) . Streptomycin is hydrogenated to a dihydro derivative which has antibiotic activity and low toxicity (190). Continuous operations using nickel catalysts, especially Raney nickel, are common, with temperatures and pressures varying with the reactant and products derived but in general below 150' C. and 800 pounds per square inch (66, 99, 146,163, 168, 237). Products may be drawn off through porous filtering media which permit recycling of powdered catalysts with part of the reactants, or fixed beds of pelleted or granulated catalysts, such as superficially activated Raney nickel catalyst, may be used. Different products may be obtained in reductions of un-' saturated aldehydes and ketones by selection of proper reaction conditions. With Raney nickel, the use of temperatures below 80" C. (66, 67) and acid media (268) causes preferential saturation of ethylenic double bonds. Thus, crotonaldehyde, mesityl oxide, and methyl iso-octenyl ketone are saturated to give butyraldehyde, methyl isobutyl ketone, and methyl iso-octyl ketone. The use of copper chromite permits reduction of unsaturate$ aldehydes to unsaturated alcohols (209). One of the most interesting developments in this field is the large scale hydrogenation of glucose to sorbitol, a hexitol which is useful as a humectant and as an intermediate for surface-active agents, resins, and vitamin C (194). Sorbitol was fist produced commercially in the United States in 1937 by electrolytic reduction of glucose (246). Rapidly growing demand for the product necessitated expansion of plant capacity, first by addition of electrolytic cells, then by installation of a batch hydrogenation process, and then by installation of a continuous process. In this latest proceay refined corn sugar-catalyst slurry is made up batchwise in weigh tanks and pumped continuously through vertical reactor tubes through which hydrogen a t 125 atmospheres is bubbled, the catalyst is filtered off batchwise in pressure filters and the product is deionized, decolorized, and adjusted to 70% strength by evaporation. The catalyst is nickel supported on clay and is made in the plant starting with metallic nickel. Reaction conditions, other than pressure, have not been published, but it can be concluded from patent and other reference sources that the temperature is in the range 140' to 160' C. and sugar concentration about 50 to 60% (162, 808, 281 ). Ammonium acetate and alkaline earth metal acetates (195) and metallic magnesium (83)promote the reaction. The hydrogenolysis of carbohydrates at high temperatures and pressures has been studied as a means of producing glycerol and glycols (74, 160, 176, 239-241). Capper catalysts are most effective and the main product is propylene glycol with a smaller yield of impure glycerol. At the present time, the process cannot compete with other sources of glycerol and propylene glycol (159). Small yiel& of ethylene glycol have been obtained from viood using an iron-containing nickel catalyst (la)). Recent developments in the chemistry of furan derivatives have made furfural an important intermediate for compounds having straight chains of 4 , 5 , 6 , and 7 carbon atoms (5'7). These new processes depend on the fact that tetrahydrofuran and tetrahydropyran rings are readily split to give products having functional groups on either end of the chain. The most important of these processes involves catalytic decarbonylation of furfural t o furan, hydrogenation of furan t o tetrahydrofuran, splitting the ring with hydrochloric acid to give 1,lklichloro-
Vol. 42, No. 9
butanol, and reaction with sodium cyanide to give adiponitrile which can be hydrogenated to hexamethylenediamine or hydrolyzed to adipic acid, which are monomers for the common form of nylon ( 1 4 ) . A review of reactions of furfural and its derivatives give conditions for the manufacture of furfuryl alcohol and tetrahydrofurfury1 alcohol (279). For furfuryl alcohol, hydrogenation is carried out a t 175" C. and lo00 to 1500 pounds per square inch with 1 to 270 copper chromite, and for tetrahydrofurfuryl alcohol, hydrogenation is carried out a t 170" to 180" C. and 1000 to 1500 pounds per square inch with a mixture of Raney nickel and copper chromite. Tetrahydrofurfuryl alcohol can be dehydrated snd rearranged to 2,3-dihydropyran, which can be hydrogenated, in the liquid phase in the presence of water, to 1,bpentanediol by using hydrogenolytic catalysts such as copperbarium chromite (34), and in the vapor phase in the presence of iron, nickel, or cobalt catalysts, to tetrahydropyran (32). At temperatures above 220 ' C. hydrogenolytic catalysts reduce furfural almost 100% to methyl furan (33, 41). Phenylmethylcarbinol (a-methylbeneyl alcohol) and substituted phenylmethylcarbinols, which may be used as intermediates for the manufacture of styrene and substituted styrenes, can be prepared by hydrogenation of the corresponding acetophenones using copper-chromium oxide catalysts with moderate temperatures and pressures on the order of 130' C. and 75 pounds per square inch (282). Divinylbenaene can be made by acetylating ethylbeneene, oxidizing the 4-ethylacetophenone to &acetyl acetophenone with air using chromic oxide on calcium carbonate as a catalyst, hydrogenating to 4hydroxyethylphenylcarbinol using copper chromite catalyst, and dehydrating to divinylbenzene over alumina (113). Acetyl cyanide, made by condensation of ketene and hydrogen cyanide, can be hydrogenated in vapor phase by passing it, with an equal volume of hydrogen, over a supported nickel catalyst a t 200" to 225' C. to give lactonitrile, which may be converted to acrylonitrile by dehydration (2OoW).
HYDROGENATION OF ALIPHATIC UNSATURATION Branched octanes obtained by hydrogenation of the dimer of isobutylene (2methylpropene) and the codimers from isobutylene and n-butenes are important components of high antiknock aviation gasoline. Processes for these hydrogenations were developed and put in operation about 1937 ( 174, 877). During the war, large quantities of octanes were produced by both high and low pressure vapor phase hydrogenation, using hydrogen made from steam and light hydrocarbons or recovered from other refining operations such as reforming (267,269). The high pressure process uses a fixed bed of sulfur-insensitive catalyst and operates at 3000 pounds per square inch and 450" to 675" F. (12). A similar German high pressure process which was operated a t 250 to 300 atmospheres used a nickel-tungsten catalyst containing 1570 nickel sulfide and 8570 tungsten sulfide (81, 116). The Germans also used a supported catalyst containing 3y0 nickel sulfide, 27% tungsten sulfide and 70% alumina for this operation (80). A Dutrh patent recommends limiting the tungsten content of this type of catalyst t o a maximum of 20% in order to prevent depolymerization of the hydrocarbon feed, giving as an example a catalyst containing 88.7% nickel sulfide and 11.3% tungsten sulfide (123). High pressure hydrogenations on sulfur-containing hydrocarbon feeds can be carried out with sulfur-sensitive nickel, cobalt, and iron catalysts, provided the ratio of hydrogen to hydrocarbon feed is adjusted with the sulfur content of the feed ($60). Typical operating conditions for the low pressure process are 80 pounds per square inch and 370" C. with a sulfur-sensitive nickel on porcelain catalyst (13). The olefin hydrocarbon feed must be low in sulfur and is pawed with part of the hydrogen stream through a bed of spent catalyst a t 400' C., which com-
INDUSTRIAL A N D ENGINEERING CHEMISTRY
September 1950
1709
I
3
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CONDENSER
OCTANE FEED
*..-...VUIANL
HOT OIL FURNACE
RECE~VER
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O D U R l U Y 8HEI.L DCVILOPMENT OWPAHI
Figure 4.
4
Low Pressure Petroleum Hydrogenation Process
pletes desulfurization, after which it is combined with the balance of the hydrogen flow and passed through the catalyst bed. The catalyst is'reactived in situ, and with two t o four reactivations a catalyst life of lo00 gallons of iso-octane (%methyl pentane) is not uncommon. Liquid space velocities of approximately 4 in vapor p k octene hydrogenation are claimed for a 62% nickel-28% kieselguhr catalyst with 60% excess hydrogen, pressures up to 200 pounds per square inch, and temperatures in the range 170" to 215" F. (124). A catalyst for olefin hydrogenation may be prepared by impregnating a refractory support, such aa alumina, with nickel sulfate, drying and then, a t 650' to 1200' F., alternately reducing with a mixture of ammonia and hydrogen, and oxidizing with moist air until the catalyst is sulfur-free (126). Selective hydrogenation of cracked aromatic aviation fuel-base stock was used extensively during the war to improve stability and leaded lean mixture octane rating ($69). Rugged sulfurresistant catalysts were used to eliminate olefinic unsaturation with a minimum of cracking and without hydrogenating the aromatic components. Operations were conducted at 3000 pounds per square inch with relatively pure hydrogen and a t 150 pounds per square inch using low purity hydrogen which was a by-product of other refinery operations. Selective hydrogenation of diolefins to olefins offers interesting possibilities in the purification of olefinic petroleum alkylation feed stocks and in the manufacture of intermediates. Cyclopentadiens can be converted to cyclopentene, which is an intermediate for glutaric acid (79, 16.4). Supported nickel sulfide catalysts are highly selective in this type of reaction (96). The rate-controlling step in the low pressure hydrogenation of iswctene on a commercial nickel catalyst has been found to be the rate of reaction of the olefin and hydrogen adsorbed on the catalytic surface (26,116). Thermodynamic conetants for a number of mono-olefins and m o n o o l e 5 hydrogenatione have been calculated using the best thermal data recently available (1%).
The recently announced manufacture of synthetic vitamin A involves partial hydrogenation of an acetylenic triple bond conjugated with an olefinic double bond (IO). Palladium on charcoal, sulfur-poisoned nickel, and Raney iron catalysts can be used in hydrogenations requiring this sort of selectivity (36, 61). Hydrogenation of a nonconjugated acetylenic bond to the ethylenic structure in other syntheses related to vitamin A preparation can be camed out with platinum black or palladium on barium sulfate (169,966). Selective hydrogenation of o l e h gas streams was developed during the war as a means of removing from butadiene small amounts of acetylenes which act as polymerization inhibitors (138, 86.4). Nickel, nickel-iron, -copper, -zinc, or -cobalt, and Raney iron are suitable catalysts ($6,91, 108). Presence of a trace of hydrogen sulfide in the feed renders chromium-nickeliron catalysts more selective (966). Ethylene, an important intermediate for synthetic rubber, resins, and chemicals in wartime Germany, was manufactured by selective hydrogenation of acetylene using a palladium on silica gel catalyst at 200' to 300' C. and atmospheric pressure (198). A 50% exoess of hydrogen was used, giving 50 t o 60% conversion to ethylene and only 6 to 8% of other hydrocarbons. The reaction temperature was raised as the catalyst aged and became less active and when 300' C. was reached, generally requiring 8 months, the catalyst was reactivated in situ by heating in air and steam a t 600' C. Three reactivations could be made before the catalyst wrta withdrawn from service for palladium recovery. Total monthly capacity was 6OOO tons of ethylene. The synthesis of ethylene by hydrogenation of acetylene over nickel and promoted nickel catalysts has been studied in Japan (178,177,246). The hydrogenation-polymerization of aoetylene to higher hydrocarbons has been the subject of research in Russia, Japan, and England (1.d,137,191,92&22.9). Butano-l,Pdiol, one of the intermediates in the Reppe process for butadiene, waa made by hydrogenating 1,4-butynediol a t 300 atmospheres, 70" to 140" C., over a silica gel-supported nickel-
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INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 42, No. 9 a t about 300" C. and 40 to 100 atmospheres with sulfurr e s i s t a n t catalysts such aa nickel sulfide and molybdenum oxide. C e r t a i n p o l y a l k y l phenols, such &g 2,4,6-tri-tertbutylphenol, are resistant to c o m p l e t e hydrogenation, so that cyclohexanones are easily obtained as the main hydrogenation products (869, 270). Hydrogenation of lignin yields hydroxy derivatives of alkyl cyclohexane (3,90, 166, 2% ,928, 834).
RESIN MODIFICATION Hydrogenated coumaroneindene r e s i n s a n d h y d r o genated rosin and its esters appeared on the market about 1940 ( 1 3 3 , 196). T h e s e Cobalt Molybdate Desulfurization Proceu products show superior resisb &nce to deterioration on excopper-manganese catalyst (83, 101). Butynediol was selecposure to light and air, and in the caae of the coumaronetively hydrogenated over an iron catalyst et 150 to 200 atmosindene resin, improved solubility in nonaromatic hydrocarbon pheres and 50" to 100O C. to give %butens1,4-diol. solvents. Other retJinousmaterials which are favorably modified by hydrogenation are dihydronaphthalene resins (81 7),condensation products of aromatic substances such as phenols, ethers, SATURATION OF A R O M A T I C RINGS and hydrocarbons with chlorinated aliphatics (98, 178), polyHydrogenated aromatics have been used commercially as acetal resins (106),copolymers of carbon monoxide and olefin solvents since World War I and in the past 10 years some of monomers (73, 122), cellulose ethers (88),polyallyl alcohol (11, these compounds, such as cyclohexanol, hove become important resins from condensation of aldehydes and cyclic olefin ketones intermediates for nylon, synthetic resins, and plasticizers. In (22), cyclo-aliphatic ketone resins (MI), a styreneethylbenzene the petroleum industry there is interest in the partial saturation condensate (m), terpene polymers (48, 44, 4 4 , cyclopentadiene of condensed aromatic compounds in catalytic cracking cycle polymers (63,238), indene polymers (66),rosin-phenol resine stocks to produce a product suitable for further cracking (58); ($lo), rosin-formaldehyde condensate (97), coal tar copolythis use of high pressure hydrogenation as a complementary mer resins (61)and alkyd resina (247). operation to catalytic cracking should prove economically feasible Commercial hydrogenated coumarone-indene resins are light at lower crude and fuel oil price levels than the over-all refining in color, color-stable, and soluble in nonaromatic petroleum solby hydrogenation operations which were initiated about 1931. vents a t low temperaturea (133). Saturation of the terminal Recent patents relate to continuous processes for hydrogenaolefinic groups stabilizes the initial light color (@), and hydrogenation of bensene using a bed of Raney nickel alloy granules which tion of the aromatic rings increases solubility in petroleum solare reactivated in situ (86.2)to vapor phase continuous hydrovents (64). Use of oxide-type catalysts, including chromites of genation of phenol and alkyl phenols (118) and to superficially copper, nickel, and iron, permits selective saturation of the Pctivated massive nickel, copper, and cobalt catalysts for hyterminal olefinic groups (4.9, 48-48) while nickel a t t a c h both drogenation of aromatics such as phenol (117, ,919). Other pattypes of unsaturation (66). Satisfsctory conditions for comsnts describe the USB of catalysts, activated by water-amine mercial hydrogenation appear t o be 200' C., approximately hydrolysis of alloys of nickel, cobalt, and iron with an easily lo00 pounds per square inch, and 5% Raney nickel on the resin oxidized metal such as magnesium, for the reduction of aniline content of a 70% solution in petroleum ether. A desulfurization $0cyclohexyl amine (104), and the use of alkali and alkaline earth pretreatment of the resin solution with bentonite clay or spent metals as nonsulfur-sensitive catalysts for the hydrogenation nickel catalyst should precede hydrogenation (49,466). Jf mononuclear aromatic and cycloaliphatic hydrocarbons a t Hydrogenation of rosin, rosin esters, and polymerized rosin high temperatures and pressures (d7, 671),ammonia acting as and its esters improves resistance of these products to oxidation an activator (879). Cyclohexanol waa produced in Germany for deterioration and discoloration (119, 120, 196). Recent patents use in polyamide fiber and reah ayntheeis by hydrogenation of describe the use of precious metal catalysts, such as platinum, phenol at 200" C., using a nickel on kieselyhr catalyst (102). organic solvents, and low temperatures for these hydrogenations Nickel on chromic oxide is a more active catalyst for saturating (14l,.l@, 178, 316). Goluene or xylene than nickel on asbestos or alumina (7). At stmospheric pressure pure nickel is more active in saturating SULFUR COMPOUNDS benaene thaa nickel containing small amounts of copper, cobalt, or iron; these catalysts showed maximum activity at 220' C. The catalytic hydrogenolysis of organic sulfur compounds, to convert the sulfur content into e a d y separable hydrogen aulfide, (6). Nickel causes saturation of naphthalene a t temperaturea between 123' and 200" C. (68). ia the basis of important methode of desulfurizing petroleum products and coal gas. An earlier unit process review on the Hydrogenation of anthracene in crude anthracene cake permits separation and purification of the contained anthracene, cargeneral subject of desulfu&ation has cited many references bszole, and phenanthrene by fractional distillation, extraction, relating to the hydrogenating phase, 80 this discurnion will be and dehydrogenation (83,1 4 ) . Hydrogenation ia carried out limited to a few of the more important publioationa (82).
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INDUSTRIAL AND ENGINEERING CHEMISTRY
September 1950
4
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C O 2 ABSOROER
P U R I F I E D H Y D R O G E N TO S T O R A G C
COP OUT
I
I
b
b
AMINE SOLUTION TO A 8 5 0 R B E R
m-
A
AMINE SOLUTION
3 R D STAGL
HEATER
COz.ABSORBER
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A M I N E SOLUTION
FROM- A b S O R B E R COURTE8Y OIRDLER CORCORATION
Flow Dirsnm of Stcrm=HydrocarbonHydrogen Plant A veraatile desulfurization process, applicable to all types of petroleum distillates normally encountered, based on the use of supported cobalt molybdate catalyst, was developed during the past decade (26, 31). Typical operating conditio- are 700" to 800" F., 450 pounds per square inch, and 600 standard cubic feet of hydrogen per barrel of coke still distillate, the sulfur being reduced from 4 t o 0.5oJ,. The bulk of the hydrogen sulfide is separated from the condensed stream as a gas, and the last traces by caustic and water scrubbing (11). Other processes developed during the war using catalysta such as nickel-tungsten sulfides or supported molybdenum oxide, require higher pressures in the range 720 to 1000 pounds per square inch and temperatures between 650" to 800" F. (69, 944, 968). A recent publication surveys in detail three processes being used in England for the desulfurization of coal gas, using nickel sulfide and nickel and copper thiomolybdate catalysts (198). A series of patents has been issued describing catalytic reduc-
tion of sulfur compounds and the thiolation of oxygen- and nitrw gen-containing compounds with mifur, sulfur compounds, and hydrogen (72,8.4,166,999,980). Another patent describes the hydrogenation of conjugated diene sulfone polymers to thiophenes using sulfur residant catalysts such as sulfides of molybdenum, cobalt, or tungsten (80).
HYDROGEN The steam-hydrocarbon process has been adapted to the production of the high purity hydrogen required for oil hardening and hydrogenation in the production of chemicals (110). Plants producing hydrogen from natural gas or propane are rapidly displacing the water-gas and the steam-iron plants which depend on coal as their basic raw material and which have, in the past, provided hydrogen for most large hydrogenation operations (808, 204). The steam-hydrocarbon reaction is carried out in vertical alloy steel tubes containing a nickel catalyst on a
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I N D U S T R I A L A N D E N G I1q E E R I N G C H E M I S T R Y
refractory support, the desulfurized hydrocarbon and steam passing downward through the tube, which is uniformly heated by a number of horizontal burners arranged a t various levels in the furnace, so as to provide uniform high heat input to support the endothermic reaction ($19). .Low hydrocarbon content in the product gas with no coking is obtained by the maintenance of high tube wall temperatures (1600” to 1700” F.), Essentially complete conversion of carbon monoxide to hydrogen and carbon dioxide is accomplished by reaction with steam over an iron catalyst at a relatively low temperature (700” to 850’ F.) in three stages, each stage being followed by amine scrubbing to remove carbon dioxide. The product coming from the final amine scrubbing is 99.97% pure hydrogen containing less than 0.01% carbon monoxide. The use in oil hardening of the hydrogen-nitrogen mixture obtained by catalytic dissociation of anhydrous ammonia has been shown to be eco?omically interesting where hydrogen requirements are moderate ($54). Hydrogen efficiencies comparable with those obtained in control runs with steam-iron hydrogen were obtained in hydrogenating cottonseed oil and lard, using continuous venting controlled by the density of the gas in the hydrogenator head space. Using the dissociated ammonia gas at 72 pounds per square inch and the steam-iron hydrogen a t 50 pounds per square inch, the former gave somewhat lower reaction rates. This last factor, in addition to the relatively high cost of ammonia as compared with natural gas, propane, or water gas, must be weighed against the very small capital investment involved in the ammonia dissociation plant in assaying the value of dissociated ammonia as a substitute for the purer types of hydrogen.
LITERATURE CITED (1) Adelson, D. E., and Grey, H. F., Jr. (to Shell Development Co.), U. S. Patent 2,414,578 (Jan. 21, 1947). (2) Adkina, H. B., “Reactions of Hydrogen with Organic Compounds over Copper, Chromium Oxide, and Nickel Catalysts,” Madison, Wis., University of Wisconsin Press, 1937. (3) Adkins, H., U. S. Patent 2,331,154 (Oct. 5, 1943). (4) Adkins, H., and Shriner, R. L., “Organic Chemistry,’’ pp. 779-834, New York, John Wiley & Sons, 1943. (5) Agliardi, N., Atli reale accad. sci. Torino. Classe sei. 8s. mat. ~ 2 . 77, . 82-96 (1941). (6) . , Akers, W. W.. and White, R. R., Chem. Eng. Prog~ess,44, NO.7, 553-66 (1948). (7) Akhmedli, M. K., J. Gen. Chem. (U.S.S.R.), 17, 224-30 (1947). ( 8 ) Anon.. Chem. Ena.. 54, No. 8. 105-6 (1947). i i j ma., 55, NO. 7, 136-9 (1948). (lo) Anon., Chem. Eng. News, 28, No. 7, 448 (1950). (11) Anon., Petroleum Refiner, 27, No. 9.2, 250-1 (1948) (12) Zbid., pp. 116-17. (13) Ibid., pp. 120-1. (14) Antsus, L. I., and Petrov, A. D., Petroleum Refiner, 23, 317-20 (1944). (15) Armstrong, E. F., and Williams, K. A,, Chemistry & Indwtry, 59,3-9 (1940). Bag, A, A,, and Egukov, T. I?., Uspekhi Khim., 14, No. 1, 56-64 (1945). Bailey, A. E., “Industrial Oil and Fat Products,” New York, Interscience Publishers, 1945. Bailey, A. E., J . A m . Oil Chemists’ SOC.,26, 644-8 (1949). Bailey, A. E., “Proceedings of a Short Six-Day Course in Vegetable Oils,” pp. 100-111, Urbana, Ill., University of Illinois, 1948. (20) . . Bailey, A. E., Feuge, R. O., and Smith, B. A,, Oil & Soap, 19, 169 (1942). (21) Bailey, A. E., and Fisher, G. S., Ibid., 23,14-18 (1946). (22) Ballard. S. A., and Haury, V. E. (to Shell Development Co.), U. S. Patent 2,380,142 (July 10, 1945). (23) Barr, F. T., and Campbell, D. L. (to Standard Oil Development Co.), Ibid., 2,266,161 (Dec. 16. 1942). (24) Beadle, B. W., Oil & Soap, 23,140-5 (1946). (25) Beckman, R. B., Pufahl, A. E., and Hougen, 0. A,, h”. ENG. CHEM.,35, 558-62 (1943). (26) Berg, C., el al., Chem. Eng. Progress, 43, No. 1. 1-12 (1947). (27) Bergstrom, F. W., and Carson, J. F., J . A m . Chem. SOC.,63, 2934-6 (1941).
Vol. 42, No. 9
(28) Blass, F., Heisel, Paul, Hendachel, Albert, and Nioodemus, Otto (to I. G. Farbenindustrie), U. S. Patent 2.193.327 . .
(March 12. 1940). (29) Borkowski, C. J., and Schille, J. L,, I W . , 2,320,063 (May 25, 1943). (30) Boyd, J. H., Jr., Ibid., 2,440,671 (May4, 1948). (31) Bradley, W. E., Byrns, A. C., and Lee, M. W., IND.ENG. CHEM.,35, 1160-7 (1943). (32) Bremner, J. G. M., Jones, D. G., Taylor, A. W. C., and Imperial Chemical IndustrieR, Ltd., Brit. Patent 565,175 (Oct. 31. 1944). (33) Bremner, J. G. M., and Keeys, R. K. F., J . Chem. Sac., 1947, 1068-80. (34) Bremner, J. G. M., and Starkey, F. (to Imperial Chemical Industries), U. S. Patent 2,440,929 (May 4, 1948). (35) Breuer, F. W. (to United Gas Improvement Co.), Zbid., 2,366,311 (Jan. 2,1945). (36) Zbid., 2,391,004 (Dec. 18, 1945). (37) Bried, E. A. (to Hercules Powder Co.), Ibid., 2,383,289 (Aug. 21.. 1945). ---, (38) Brown, E. L., Voorhies, A., and Smith, W. M., IND.ENO. CHEM., 38, 136-40 (1946). (39) Brown. R. L. (to Solvay Process Co.), U. S. Patent 2,276.921 (March 17, 1942). (40) Zbk?., 2,281,228 (April 28, 1942). (41) Burnette, L. W., Johns, I. B., Holdren, R. F., and Hixon, R. M., IND. ENG.CHEM.,40, 502-5 (1948). (42) Carmody, M. O., U. 8. Patent 2,249,112 (July 15,1941). ENG.CHEM.,34,768 (1942). (43) Carmody, W. H., IND. (44) Carmody, W. H., (to Carmody Research Laboratories), U. S. Patent 2,416,901 (March 4, 1947). (45) Zbid., 2,416,902 (March 4, 1947). (46) Zbid., 2,416,903 (March 4. 1947). (47) Ibid., 2,416,904 (March 4, 1947). (48) Ibid.,2,418,905 (March 4, 1947). (49) Carmody, W. H. (to Neville Co.), Ibid., 2,139,722 (Dec. 13 1939). (50) Ibid., 2,152,533 (March 28, 1939). (51) Ibid., 2,161,951 (June 13, 1939). (52) Ibid., 2,266,675 (Dec. 16, 1942).(53) Ibid., 2,293,277 (Aug. 18, 1943). (54) Carmody, W. H., and Kelly, H. E., IND.ENQ. CHEW..32, 771-5 (1940). (56) Carmody, W. H., Kelly, H. E., and Sheehan, W.,Zbid., 32, 684-92 (1940). (56) Casaus, P. L., Combustibles (Zaragoza), 7 , 151-62 (1947). (57) Case, 0. W . , , ~ N DENQ. . CHEM.,40,216-19 (1948). (58) Cerveny, W J., and Coraon, B. B., J . Am. C h m . SOC.,66, 2123-4 (1044). (59) Cole, R. M., and Davidson, D. D., IND.ENG. CEEM.,40, 2711-15 (1949). (60)Colgate-Palmolive-Peet Co., Brit. Patent 550,356 (Jan. 5, 1943). (61) CommercialSolvents Corp., Zbid., 695,459 (Dec. 5, 1947). (62) Copenhaver, J. W., and Bigelow, M. H., “Acetylene and Carbon Monoxide Chemistry,” New York, Reinhold Publishing Corp., 1949. (63) Coraon, B. B., and Detrick, R. 8. (to Koppers Co.), U. S. Patent 2,438,148 (March 23, 1948). (64) Dean, H. K., “Utilization of Fats,” New York, Chemical Publishing Co., 1938. (65) Delaunay, R., Chimie & industrie, 58, 33540 (1947). (66) Distillors Co., Ltd., Brit. Patent 595,941 (Dec. 23, 1947). (67) Doumani, T. F. (to Union Oil Co. of California), U. S. Patent 2,394,848 (Feb. 12, 1946). (68) Dow Chemical Co.. Brit. Patent 524,976 (Aug. 19, 1940). (69) Dressler, R. G., and Vivian, R. E., U. S. Patent 2,369,446 (Feb. 13, 1945). (70) Dressler, R. G., Vivian, R. E., and Hasselstrom, T., Ibid., 2,371,230 (March 13, 1945). (71) Ibid., 2,396,646 (April 19, 1946). (72) du Pont de Nemours & Co., E. I., Brit. Patent 577,279 (May 13, 1946). (73) Ibid., 598,145 (Feb. 11, 1948). (74) Du Puis, R. N. (to Association of American Soap and Glycerine Producers), U. S. Patent 2,282,603 (May 12, 1942). (76) Eckey, E. W., and Taylor, J. E., (to Procter and Gamble Co.), Zbid., 2,413,612 (Dec. 31, 1946). (76) Zbid., 2,413,613 (Dec. 31, 1946). (77) Ellis, C., “Hydrogenation of Organic Substances,” 3rd ed., New York, D. Van Nostrand Co., 1930. (78) Endres, R. (to Patchem A.-G.), U. S. Patent 2,235,702 (March 18, 1941). (79) Evans, T. W., Morris, R. C., and Shokal, E. C. (to Shell Development Co.), Zbid., 2,360,555 (Oct. 17. 1944).
INDUSTRIAL A N D ENGINEERING CHEMISTRY
September 1950
(80) Faragher, W. F., and Horne, W. A., U.9. Bur. Mines, Znfonn. Circ. 7368,2,3 (July 1946). (81) Ibid., pp. 33-4. Feuge, R. O., and Bailey, A. E., OiE & Soap, 21,78-84(1944). Flexser. L. A. (toHoffmann-La Roche). U. S. Patent 2.421.416 (June 3,1947); Fox. A. L. (to E. I. du Pont de Nemours & Co.),Zbid., 2,414,035 (Jan. 7, 1947). Foxwell, G. E., Am. Ges J.,167,lS (September 1947). Francon, J. (to Distillers Co.), Brit. Patent 517,740 (Feb. 7, 1940). Francon, J., and Distillers Co., Ltd., Ibid., 519,874 (April 9, 1940). Fraser, J. C. W., and Jackson, C. B., J. Am. Chem. SOC.,58, 950 (1936). Freed, M. L. (to Seymour Mfg. Co), U. 8. Patent 2,424,811 (June 29.1947). Freudenberg, K., and Lautsch, W., Ibid., 2,390,063 (Dec. 4, 1945). Frevel, L. K. (to Dow Chemical Co.), Ibid., 2,426,804(Sept. 2, 1947). Garber, H. J., IND. ENQ.CHEM.,40,1686-7 (1948). Gas Light & Coke Co., and Griffith, R. H., Brit. Paten6 677,816 (June 3, 1946). Gordon. E.. and Ranot. - . S.. Bull. mens. ITERG. 1948, NO. 4. 32-4. Goas, W. H., Oil & Soap, 23,241-4 (1946). Greensfelder, B. S., and Peterson, W. H. (to Shell Development Co.), U. 5. Patent 2,402,493(June 18, 1946). Grinevich, V. M., J . Applied Chm. (U.S.S.R.), 18, 90-6 (1945). Grundmann, C., and Burness, D. M., “New Methods of Preparative Organic Chemistry,” pp. 103-4, New York, Interscience Publishers, 1948. Gwynn, M. H., U. S. Patent 2,302,994(Nov. 24,1943). Hachihama, Y., Jodai, S., Ogawa, S., and Tomihiaa, K., J. SOC.Chem. Ind. Japan. 47,916-19 (1944). Haeneel, V., U. 5. Bur. Mines, Inform. Circ. 7375, 44 (August 1946). Zbid., p. 47. zbid.. p. 49. Hahn, J. H. (to Monsanto Chemical C o . ) . U. S. Patent 2,328,140 (Aug. 31, 1943). Hale, J. B. (to Eastman Kodak Co.), Ibid., 2,199,992 (May 7. 19401. Hansley, V. L., IND. ENG.CHEM.,39,55 (1947). Harrington, V. S.,Crist, F. B., Sells, A. A., and Jacob, W. A., Oil & Soap, 2’429-30 (1945). (108) Hebbard, G. M., and Hunt, W., U. 9. Patent 2,359,759 (Oct. 10,1944). (109) Hefter, G.. and Schonfeld, H., “Chimie und Teohnologie der Fette und Fettproducte,” Vol. 11, Vienna, Julius Springer, 1939. (110) Heineman, H., Petroleum Refiner, 23,35-6 (1944). (111)Hilditch, T. P., “Industrial Chemistry of the Fats and Waxes,” 2nd ed., New York, D. Van Nostrand Co., 1941. (112) Hilditch, T. P., Nature, 157,586 (1946). (113) Hochwalt, C. A. (to Mollsanto Chemical Co.), U. S. Patent 2,390,368(Dec. 4, 1945). (114) Holmboe, C. F., and Nordiske Fabriker De-No-Fa A/& Brit. Patent 820,043 (March 18,1949). (115) Holroyd, R., and Faragher, W. F., U. 8. Bur. Mines, Z n f m . Circ. 7375,27-8 (August 1946). (116) Hougen, 0. A., et al., Trans. Am. Inst. Chern. Eng~s.,42, 883-905 (1946). (117) Houghton, A. S. (to Allied Chemical and Dye Corp.), U. S. Patent 2,289,784(July 14, 1943). (118) Houghton, A. S.,and McNutt, H. E. (to Allied Chemical and Dye Corp.), Zbid., 2,328,719(Sept. 7, 1943). (119) Humphrey, I. W. (to Hercules Powder Co.), Brit. Patent 556,456 (Oct. 6, 1943). (120) Humphrey, I. W. (to Hercules Powder Co.), U. S. Patent 2,346,920-21 (April 18,1944). (121) I. G. Farbenindustrie. A.-G., Ger. Patent 711,888 (Aug. 11, 1941). (122) Imperial Chemical Industries, Ltd., Brit. Patent 583,172 (Deo. 12, 1946). (123) Internationrrle N. V. HydrogeneeringsoctrooienMaatschappij, Dutch Patent 61,702(Sept. 15, 1948). (124) Ipatieff, V. N., U.8. Patent 2,270,303(Jan. 20,1943). (125) Ipatieff, V. N., and Corson, B. B. (to Universal Oil Producta Co.), Ibid., 2,267,735(Dec. 30, 1942). (126) James, E. M.,“Cottonseed and Cottonseed Products,” Bailey, A. E., ed., pp. 711-19, New York, Interscience Publishers, 1943. ’
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(127) Jatkar, S. K. K., and Joglekar, R. V., J. lnddan C h a . SOC., Znd. & News Ed., 5 , P 7 (1942). (128)Zbid., pp. 8-10. (129) Jatkar, 9. K. K., and Joglekar, R. V., J. Zndian I?&.Sci., 23A, 139-57 (1941). (130) Kastens, M. L., Dudley, J. F., and Troeltzach, J., IND.ENQ. CHEM.,40,2230-40 (1948). (131) Kastens, M. L., and Peddicord, H., Ibid., 41,438 (1949). (132)Kellog, H. B., and Hineline, H. D., U. S. Patent 2,350,768 (June 6,1944). (133) Kenney, J. A.. “Protective and Decorative Coatings,” Mattiello, J. J., ed., p. 389,New York, John Wiley & Sons, 1941. (134) Kenyon, R. L., Stingley, D. V., and Young, H. P., IND. ENQ. CHEM.,42,202 (1950). (135) Killeffer, D. H.,Zbid., 25,138-40 (1933). (136) Kilpatrick, J. E., J. Research Natl. Bur. Standards, 36,659-1312 (1946). (137) Kimura, O.,J . Soe. Chem. Znd. Japan, 44,750-2 (1941). (138) King, C. C.,Trans. Am. Inst. Chem. Engre., 42,492 (1946). (139) King, J. G., Uaa World, 122,195200 (1945). (140) a k p a t r i c k , S.D.. Chem. Eng., 54, No. 4,100-1 (1947). (141) Kirkpatrick, W. J. (to Hercules Powder Co.), U. S. Patent 2,361,213 (Oct. 24, 1944). (142)Zbid., 2,367,287(Jan. 16, 1945). (143) Komori, S.,J. Soe. Chem. Znd. Japan 44,740 (1948). (144) Kosaka, Y., and Takashima, S., Ibid., 44, 261, Suppl. binding 23 (1941). (145)Kyrides, L. P. (to MQnsantQ Chemical co.),u. 8. Patent 2,368,366(Jan. 30, 1945). (146) Lane, J. C., and Weil, B. H., Petroleum Refiner, 25, No. 8, 356 (1946). (147) Zbid., 25,No. 9,423 (1946). (148)Ibid., 25,No. 10,493 (1946). (149)Ibid., 25,No. 11,587 (1946). (150) Langton, H. M., Food,15,117-18 (1946). (151) Larson, A. T., and E. I. du Pont de Nemours & Co., Brit. Patent 575,380(Feb. 15, 1946). (152) Lautsch, W.,and Freudenberg, K. (to Deutsche Revisionsund Treuhand A.-G.), Ger. Patent 741,686 (Sept. 30, 1943). (153) Lazier, W. A. (to E. I. du Pont de Nemours 8: Co.), U. 8. Patent 2,358,234(Sept. 12,1944). (154) Zbid., 2,358,235(Sept. 12,1944). (155) Lazier, W. A., “Twelfth Report of Committee on Catsly& National Research Council,” Chap. XII, New York, John Wiley & Sons, 1940. (156) Lazier, W. A., and Signaigo, F. K. (to E. I. du Pone de Nemours & co.), U.S. Patent 2,221,804(Nov. 19, 1940). (157) Lee, J.A., Chem. Em.,%, No. 11,131-2,158-61 (1948). (158) Lemon, H. W.,Can. J . Research, 22F,191 (1944). ENG.CHEM.,37, 152-7 (159) Lenth, C. W.,and Du Puis, R. N., IND. (1945). (160)Lenth, C. W., and Du Puis, R. N. (to Association of American Soap and Glycerine Producers), U. 5. Patent 2,290,439 (July 21, 1943). (161) Lever Brothers and Unilever Ltd., Brit. Patent 578,102 (June, 14, 1946). (162) Lolkema, J., Viugter. J. C., and van Western, H. A. (to N.V.. W.A. Scholten’s ChemischeFabrieken), Dutch Patent 80,685 (March 15, 1948). (163) Longley, R. I., Jr. (to Air Reduction Co.), U.5. Patent 2,433,614 (Dec. 30, 1947). (164) MaAlIister, 8. H., Anderson, J., Derr, E. L., and Peterson, W. H., IND. ENQ.CHEM.,40,2295-301 (1948). (165) Mac Lean, G. (to Turbo Mixer Corp.), U. S. Patent 2,313,664 (March 9,1943). 1 & Soap, 16,166(1939). (166) Manderstam, L. H., a (167) Manderstam, L. H., and Warner, L. W., U.S. Patent 2,410,670 (Nov. 5, 1946). (168) Metzger, F. J. (to Air Reduction Co.), Ibid., 2,419,!275 (April 22, 1947). (169) Milas, N. A. (to Research Corp.), Ibid., 2,415,834(Feb. 18, 1947). (170) Mitchell, R., Chem. Age (London),48,471-5,495-6(1943). (171) Mullin, C. E.,Soap, 14,No. 2,27-9,69 (1938). (172) Ibid., 15,NO.2,28-31,69-70(1939). (173) Ibid., 15,No. 3,2831 (1939). (174) Murphree, E. V., Brown, C. L., and G o b , E. J., IND. ENQ. CKEM., 32,1203-12 (1940). (175) Natta. G., Rigamonti, R., and Beati, E., Chimica e industn’a (Italy), 24,419-25 (1942). (176) Ohe, Hideo, J. Soc. Chem. Ind. Japan, 49,165-7 (1946). (177)Ibid., pp. 18591. (178) Otto, F. P., and Rieff, 0. M. (to Socony-Vacuum Oil Co.), U. S. Patent 2,394,560(Feb. 12, 1946). (179) Paleni, A., Chimica sinduatlda (Mi&), 24,3 (1943). (180) Panushev. A,, Maalobolnu-ghiroooe Delo., 11,466(1935).
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INDUSTRIAL AND ENGINEERING CHEMISTRY
(181)Papps, G., and Othmer, D. F., IND.ENQ.CHEM.,36, 430-4 (1944). ,182)Paquot, C., Demarcq, M., and Stroh, G., Bull. soc. chim. France, 1948,520-1. \183)Pardee, F. W.,Jr. (to E. I. du Pont de Nemours & Co.), U. 5. Patent 2,305,104(Dec. 15,1943). (184)Pardee, F. W.,Jr., and E. I. du Pont de Nemours & Co., Brit. Patent 566,240(Aug. 12,1943). (186)Pataraon, W. J. (to Lever Brothers Co.), U. S. Patent 2,123,342 (July 12,1938). (116)Ibid., 2,307,065(Jan. 6 , 1943). il87) Zbid., 2,410,102(oct. 29, 1946). (188)Zbdd., 2,437,706(March 16,1948). (189) Ibid.,2,437,706(March 16.1948). (lea) Peck, R.L., Hoffhine, C. E., and Folkers, K,, J . Am. C h m . SOC., 68,1391-2 (1946). (191)Petrov, A. D., Antsus, L. I., and Cheltsova, M. A,, Zmeat. Akad. NauR S.S.S.R. Otdel. Khim. Nsuk, 1947,363-74. 192) Pirie, J., Znd. Chemist., 24,231-9 (1948). ,193)Plant, J. H.G.,and Newling, W. B. S., “Catalytic Removal of Organio Sulfur Compounda from Coal Gas,” Publ. 344/157,London, Inst. Gas Engineera. 194) Porter, R. W., Chem. En& 54,NO. 11,114-17 (1947). (186)Power, J. T. (to Atlas Powder Go.), U. 8. Patent 2,280,975 (April 28, 1942). (196) Powers, P. O., “Protective and Decorative Coatings,” Mattiello, J. J., ed., Vol. I, P. 207, New York, John Wiley & Sons, 1941. (lw)Prooter and Gamble Co., Brit. Patent 670,957(June 31,1945). (198)IW., 584,939 (Jan. 27,1947). qge) Ibid., 585,219 (Feb. 3,1947). Quin, D. C., U. 8. Patent 2,386,507(Oct. 9,1945). (201)Ralston, A. W.,“Fatty Acids and Their Derivatives,” pp. 722-6, New York. John Wiley & Sow, 1948. 1202) Ray, G. C. (to Ph .pa Petroleum C0.h u. 8. Patent 2,396,201 (March 5,1946). (203)Reed, R. M., Trans. Am. Inat. them. E7WS., 41, 453-62 (1946). (2M)Ibid., 42,379-401 (1946). (206) Richardson, A. S. (to Procter and Gamble Go.), u. 5. Patent 2,376,496(May 8, 1945). (206) Rittmeister, W. (to American Hydsol Corp.), Zbid., 2,374,379 (April 24,1945). (207) Robell, J., and Demling, W. L. E., “Methanol Synthesis,” u. 6. Dept. Commerce, OTS Rept., P B 47864 (Aug. 1, 1946). (208)Rose, R. S.,Jr. (to Atlas Powder cos),u. 8. patent 2,292,293 (Aug. 4,1943). (209) Rummelsburg, A. L. (to Hercules Powder CO.), u. s. Patent 2,406,106(Aug. 20,1946). (210)zbid., 2,437,481(March 9, 1948). (211) Rubton, J. H.,IND. ENQ.CHEM.,37,422 (1945). (212) Babia, F. A. (to Allied Chemical and Dye Corp.), Can. Patent 413,473(June 29,1943). (213)Schmidt, 0.(tQ General Aniline and Film Corp.), U. S. Patents 2,323,095(June 15,1943). (214)Zbid., 2,392,952(1946). (215)Schmidt-Nielsen, S., and Spillurn, E.,ad. N o d e V&nskab. Selskabs, Fwh., 17,NO.31,122-6 (1944). (216) Schultz, E. D., and Shaefer, We E- (b Hercules Powder CO.), U.S. Patent 2,346,793(April 18, 1944). (217) Scott, N. D., and Walker, J. F., IND.ENG.CHEM.,32, 312 (1940). (218)Segessemam, E. (to National Oil Products CoJ, U. 9. Patent 2,400,607(May 21, 1945). (219) Shapleigh, J. H. (toHercules Powder Co.), U.S. Patent Reissue 21,521 (1940)of U. S. Patent 2,173,984(1939). (220) Sheridan, J., J. Chem. Soc., 1944,373-80. (291)Ibid., 1945,138-42. 22Z) Ibid., PP. 470-62 s ) Zbid., pp. 301-5. ,2%) Bherrard, E. C., and Harris, E. E., Brit. Patent 528,268 (Oct. 25,1940). 226) Sherrard, E. C., and Harris, E. E (to Secretary of Agriculture U.S.A.), U. 8.Patent 2,328,749(SW. 7, 19433. 226) SherrPrd, E. C., Hrrria, E. E., and Saeman, J. F. (to Secretary of Agriculture, U.S.A.), Ibid., 2,220.624(Nov. 5,1941). f.227)Sherwood, P. w., P e h k z b n Refiner, z8* No. 2*97-101 (1949); 29, No. 119-123; No* 2i ‘06-110; No* 39 150-154; No. 5,123; NO.6, 113 (1950). (2%) Sieck. W., U. 8. Patent 2,054,889(1936). (to E, 1. du Font de Nemours & Co.), Zba,, (22g) sigmig0, F. 2,230,390(Feb. 4, 1941). (230) Ibid., 2,400,410(Aug. 27,1946). (231) Ibid,, 2,419,093(April 15,1947). (232) Skeen, J. R., C h m . E w . , 56,357-8(1949).
i~@))
Vol. 42, No. 9
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