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Home , Manganese dioxide

Patented Nov. 17, 1936 2,061,470

UNITED STATES 2,061,470PATENT OFFICE PRODUCTION OF METHANOL AND OTHER COMPOUNDS AND CATALYC AGENTs FoR USE THEREIN Alfred T. Larson, Wilmington, Del, assignor to E. I. du Pont de Nemours & Company, Wi mington, Del, a corporation of Delaware No Drawing. Application November 16, 1933, Serial No. 698,315 9 Claims. (CI. 260-156) This invention relates to chemical reactions in introduced at the proper temperature which may the gaseous phase and particularly to the pro be regulated and maintained in any desired way. duction of oxygenated hydrocarbons by The gaseous mixture containing the product of from gaseous mixtures. The present, application the reaction is withdrawn and cooled to effect is a continuation in part of my copending appli Condensation of the product or is treated other 5 cation Serial No. 426,442, filed February 6, 1930, Wise for the recovery thereof. Pat. No. 1,939,708, Dec. 19, 1933 which is a divi The catalysts are particularly well adapted for sion of application Ser. No. 202,165, filed June 28, the Synthesis of methanol from gaseous mixtures 1927. containing and . This 10 It is known that oxygenated hydrocarbons, and reaction may be conducted with the described cat O particularly methanol and its homologues, may alysts at various pressures and temperatures, but be prepared synthetically by passing a gaseous I prefer to carry out the synthesis of methanol mixture containing carbon monoxide and hydro at a pressure within the range of 400 to 1000 at gen under pressure over a catalyst. The Syn mospheres and at a temperature of 250° to 500° thesis depends upon reactions of which the foll C. The usefulness of the catalysts is not limited 5 lowing for methanol is characteristic: to the treatment of gaseous mixtures of any par ticular composition, it being possible to effect CO-2Has CH-OH the synthesis of methanol, for example, with the In my U. S. Patent No. 1,844,129 I have de improved catalysts by introducing gaseous mix scribed a process for manufacturing oxygenated tures containing hydrogen and carbon monoxide hydrocarbons and especially methanol, the proc in which the proportion of the latter is relatively 20 ess involving the use of catalysts prepared by fus low, for example, between 3 and 15%. If the ing and subsequently reducing a mixture of cop gaseous mixtures contain relatively higher pro per and Oxide. portions of carbon monoxide, the reaction pro It is the object of the present invention to ceeds more vigorously, greater quantities of heat 25 provide a further inprovement in the process de are evolved and corresponding provision must be scribed in the aforementioned patent. made, therefore, for the dissipation of heat so Other objects and advantages will be apparent that the catalysts may not be damaged by over as the invention is better understood by refer heating and undesirable side reactions, such as ence to the following specification in which its methanation, may be avoided. . 30 30 preferred embodiments are described. . . The following examples will serve to indicate I have discovered that improved results may the preferred procedure in preparing and utiliz be obtained in carrying out reactions in the gas ing catalysts such as are described herein, it be eous phase in the presence of a catalyst consist ing understood, however, that the invention is not ing of a reduction product of a fused mixture of limited to the details of operation or the par .35 oxide and manganese oxide, or copper ox ticular conditions as set forth. ide and zince oxide, if there is incorporated in Said Eacample 1-Prepare an intimate mixture of catalysts one or more of the elements magnesi seventy-five parts by weight of pure cupric oxide, um, aluminum, , , , twenty parts of pure manganese dioxide and 40 , , and ...... five parts of pure oxide. The mix The catalysts herein described exhibit an ac ture is fused, allowed to cool and crushed to suit tivity superior to that of a catalyst consisting of able size... The crushed-material is then reduced fused and reduced copper oxide and manganese. slowly at 150 to 350° C. and at atmospheric oxide alone; and also superior to that of any of pressure in a current of pure hydrogen. Since the the foregoing list of elements taken singly or in 45 combination with each other. The term "superior reduction process is exothermicit should becarried activity' is used to indicate that with a given out slowly, and with care so that the catalyst rate of gas flow the catalysts give a higher yield may not be damaged by excessive temperature. of product per hour or, correspondingly, to at The catalyst thus prepared may be employed for 50 tain a given hourly production a lower rate of gas the production of methanol by passing a gaseous flow may be maintained. - mixture containing hydrogen and carbon mon In carrying out the invention the prepared oxide in the volume ratio of twenty to one at a catalyst is disposed in a suitable receptacle adapt space velocity of 100,000 to 150,000, a pressure of ed to withstand the pressure at which the re 900 atmospheres and while maintaining a tem 55 action is conducted. The gaseous mixture is perature within the range of 250° to 400° C. The 55 2 2,061,470 principal product is methanol, which is associ I have no theory or explanation to offer for ated with Some of its higher homologues. any changes which may occur in the composition The following examples indicate the preferred of the catalysts, during either their reduction or proportions for preparing other catalysts includ actual use. It may be that in some cases the ed within the scope of the invention. These may reduction yields a lower and especially active s be prepared and employed in the synthesis of oxide which in conjunction with the activated methanol under the same conditions as are set copper with which it is associated forms a mass forth in Example 1. peculiarly adapted for the catalytic production Eaccomple 2-Eighty parts of pure cupric oxide, of oxygenated hydrocarbons. In any event, it is O fifteen parts df pure manganese dioxide and five to be understood that the term catalyst as em O parts of pure chromic oxide. ployed in the claims includes the contact mass Eacample 3-Eighty-seven parts of pure cupric in the form in which it may occur during its use. oxide, ten parts of pure manganese dioxide and It will be apparent from the foregoing that three parts of pure aluminum oxide. by providing new catalysts of superior activity 5 Eacample 4-Eighty-two parts of pure cupric and improved physical form, decreasing catalyst 5 Oxide, fifteen parts of pure manganese dioxide consumption and improving Smoothness of oper and three parts of pure zirconium oxide. ation, and by thus facilitating the production of Eacample 5-Eighty-five parts of pure cupric oxygenated hydrocarbons and other desirable oxide, ten parts of pure manganese dioxide and products of synthetic and other reactions, the 20 five parts of pure vanadium oxide. present invention represents a distinct advance 20 Eacample 6.-Eighty-seven parts of pure cupric in the art. While the invention has been de oxide, ten parts of pure manganese dioxide and scribed more particularly with reference to the three parts pure titanium oxide. synthesis of methanol, the improved Catalysts Eacample 7-Seventy-eight parts of pure Cl and the process may be utilized with similar pric oxide, twenty parts of pure manganese di advantages in conducting other reactions in the 25 oxide and two parts of pure thorium oxide. gaseous phase. r Eacample 8.-Seventy-five parts of pure cupric The various details of apparatus and pro Oxide, twenty, parts of pure manganese dioxide cedure may be modified to meet the particular and five parts bf. pure silica. w conditions of the reaction, the products being 30 Eacample 9. Seventy-nine parts of pure cupric recovered in any suitable or desirable way, it. 30 oxide, twenty parts of pure manganese dioxide being possible in the synthesis of methanol, for and one part of pure cerium oxide. example, at pressures above 200. atmospheres to Eacample 10-Eighty-seven parts of pure cop practically completely condense methanol from per oxide, ten parts of pure oxide, and three. the gases by cooling with water at ordinary tem 35 parts of aluminum oxide. perature. The methanol can be separated other 35 Eacample 11.-Eighty-five parts of copper oxide, wise and other products can be treated in the ten parts of , and five parts of vana manner best adapted to effect the separation dium oxide. thereof in an economical and satisfactory way. Eacample 12-Eighty parts copper oxide, fifteen Various changes may be made in the details 40 parts manganese oxide, 2.5 parts magnesium of operation hereinbefore described without de 40 Oxide, and 2.5 parts chromium oxide. parting from the invention or sacrificing any of Ecample 13-Seventy-five parts copper oxide, the advantages thereof. twenty parts of manganese oxide, 2.5 parts mag I. claim: 1. nesium oxide, and 2.5 parts vanadium oxide. 1. The improved catalyst for reactions in the 45 The catalysts described may be used in the gaseous phase comprising the reduction product 45 Synthesis of methanol and other oxygenated of a fused mixture containing from 1 to 5% of hydrocarbons and for conducting other reactions an oxide of an element of the group consisting . in the gaseous phase in a similar manner under of chronium, vanadium, zirconium, aluminum, conditions of pressure and temperature that may magnesium, titanium, thorium, silicon and 50 vary within a wide range, depending upon the cerium, and from 97 to 95% of copper oxide, and 50 particular nature of the desired reaction and of manganese oxide, the copper oxide being in the product to be prepared. A catalyst contain excess. ing two or more of the elements mentioned in 2. The improved catalyst for reactions in the combination with copper and manganese can be: gaseous phase comprising the reduction product 55 prepared similarly by combining the of of a fused mixture containing from 1 to 5% of 55. these elements. Such catalysts have the desir an oxide of an element of the group consisting able characteristics hereinbefore mentioned and of chromium, vanadium, zirconium, aluminum, may be utilized in effecting various reactions in smagnesiun, titanium, thorium, silicon and the gaseous phase including the production of cerium, and from 75 to 87% copper oxide and 60 oxygenated hydrocarbons such as methanol. from 20 to 10% manganese oxide. It is to be understood that while the gaseous 3. The improved catalyst for reactions in the mixtures employed need not be limited to those gaseous phase comprising the reduction product containing hydrogen and carbon monoxide ex cof a fused mixture containing 80% copper oxide, clusively, the gases should, nevertheless, be freed 15% manganese oxide, and 5% chromium oxide. 65 from impurities which are likely to deleteriously 4. The improved catalyst for reactions in the affect the catalyst, and of these the compounds gaseo phase comprising the reduction product of sulphur are the most commonly encountered. of a f :d mixture containing 82% copper oxide, The Sulphur compounds may be removed pre 15% manganese oxide, and 3% vanadium oxide. liminarily from the gases by suitable treatment 5. The improved catalyst for reactions in the . 70 thereof in accordance with the well understood gaseous phase comprising the reduction product 70 practice. In synthesizing methanol and the like, of a fused mixture containing 79% copper oxide, it is recommended that Suitable precautions be 20% manganese oxide, an Sycerium oxide: taken for avoiding the presence of metals of the 6. The process of synthesizing oxygenated or group (iron, , and ) in the ganic compounds which comprises Subjecting a 75 catalyst and in the gases that are to react. gaseous mixture containing hydrogen and an 75 a,081,470 . . . . . w 3 oxide of carbon to a catalyst at an elevated tem copper oxide and from 20 to 10% manganese perature and pressure, said catalyst comprising Oxide. the reduction product of a fused mixture con 8. The process of synthesizing oxygenated or taining from 1 to 5% of an oxide of an element ganic Compounds which comprises subjecting a of the group consisting of chromium, vanadium, gaseous mixture containing hydrogen and an zirconium, aluminum, magnesium, titanium, oxide of carbon to a catalyst at an elevated tem thorium, silicon, and cerium, and from 97 to 95% perature and pressure, said catalyst comprising of copper oxide and manganese oxide, the coppe the reduction product of a fused mixture, con Oxide being in excess. taining 80% copper oxide, 15% manganese oxide 7. The process of synthesizing oxygenated or and 5% chromium. ganic compounds which comprises subjecting a 9. The process of synthesizing oxygenated or gaseous mixture containing hydrogen and an ganic compounds which comprises subjecting a oxide of carbon to a catalyst at an elevated tem gaseous mixture containing hydrogen and an perature and pressure, said catalyst comprising - Oxide of carbon to a catalyst at an elevated tem the reduction product of a fused mixture con perature and pressure, said catalyst comprising taining from 1 to 5% of an oxide of an element the reduction product of a fused mixture contain of the group consisting of chromium, vanadium, ing 82% copper oxide, 15% manganese oxide and Zirconium, aluminum, magnesium, ... titanium, 3% Vanadium oxide. thorium, silicon, and cerium, and from 75 to 87% ALFRED T. LARSON.