This document describes a novel catalyst for the direct hydration of ethylene to ethyl alcohol. The catalyst comprises active synthetic silicon dioxide as a base with deposited natural kieselguhr and phosphoric acid. It provides enhanced mechanical strength, stability and resistance to deactivation compared to prior art catalysts. An example is given comparing the new catalyst to conventional catalysts under severe reaction conditions.
This document describes a novel catalyst for the direct hydration of ethylene to ethyl alcohol. The catalyst comprises active synthetic silicon dioxide as a base with deposited natural kieselguhr and phosphoric acid. It provides enhanced mechanical strength, stability and resistance to deactivation compared to prior art catalysts. An example is given comparing the new catalyst to conventional catalysts under severe reaction conditions.
This document describes a novel catalyst for the direct hydration of ethylene to ethyl alcohol. The catalyst comprises active synthetic silicon dioxide as a base with deposited natural kieselguhr and phosphoric acid. It provides enhanced mechanical strength, stability and resistance to deactivation compared to prior art catalysts. An example is given comparing the new catalyst to conventional catalysts under severe reaction conditions.
This document describes a novel catalyst for the direct hydration of ethylene to ethyl alcohol. The catalyst comprises active synthetic silicon dioxide as a base with deposited natural kieselguhr and phosphoric acid. It provides enhanced mechanical strength, stability and resistance to deactivation compared to prior art catalysts. An example is given comparing the new catalyst to conventional catalysts under severe reaction conditions.
54 CATALYST FOR DIRECT HYDRATION OF 56) References Cited ETHYLENE TO ETHYL ALCOHOL AND U.S. PATENT DOCUMENTS PROCESS FOR PREPARATION THEREOF 3,311,568 3/1967 Kumenko ............................ 252/.435 75) Inventors: Vlastimil Kadlec, Litvinov; Vojtéch 3,459,678 8/1969 Hagemeyer et al. ... 568/896 Grosser, Rudolice; Jakub Rosenthal, 4,038,2il 7/1977 Frampton ................. 252/.435 Meziboriu Litvinova, all of 4,297,241 10/1981 Kavasmaneck et al. ........... 252/435 Czechoslovakia 73) Assignee: Chemopetrol, koncernovy podnik, Primary Examiner-W. J. Shine Chemicke zavody 57 ABSTRACT ceskoslovenskosovetskeho pratelstvi, A novel catalyst for hydration of ethylene to ethyl Litvinov, Czechoslovakia alcohol comprises active synthetic silicon dioxide as a (21) Appl. No.: 255,221 base having deposited thereon natural kieselguhr and 22 Filed: Apr. 17, 1981 phosphoric acid. The catalyst is prepared by precipita (30) Foreign Application Priority Data tive silicon dioxide from sodium silicate with hydro chloric acid, filtering the precipitate, admixing it with Apr. 18, 1980 CS Czechoslovakia .................... 2734-80 natural kieselguhr and phosphoric acid and annealing 51) Int. Cl. ......................... B01J 21/08; B01J 27/16 the resultant composition. 52 U.S. Cl. ..................................... 252/.435; 568/896 58) Field of Search ......................... 252/435; 568/896 6 Claims, No Drawings 4,371,456 2 grams of ethyl alcohol in 1 liter of alcohol-aqueous CATALYST FOR DIRECT HYDRATION OF condensate. It is also considered advantageous to attain ETHYLENE TO ETHYLALCOHOL AND PROCESS high mechanical strength and resistance to deactivation FOR PREPARATION THEREOF to the extent that the catalyst is capable of being used for several cycles including regeneration for a time This invention relates to a novel catalyst for the di period of at least 10,000 hours. rect hydration of ethylene to ethyl alcohol and to a In accordance with the present invention, these ends method for the preparation thereof. More particularly, are effectively attained and the prior art limitations the present invention relates to a catalyst for the direct obviated by means of a novel combined catalyst evi hydration of ethylene to ethyl alcohol which evidences O dencing enhanced mechanical strength, stability and enhanced mechanical strength, stability and resistance resistance to deactivation which comprises a silicon to deactivation in the hydration process. dioxide base having deposited thereon active phos It has been recognized by those skilled in the art that phoric acid containing active synthetic silicon dioxide, catalysts capable of effecting the direct hydration of natural kieselguhr and phosphoric acid. The described ethylene to ethyl alcohol must evidence the prerequi 15 catalyst contains active synthetic silicon and natural sites of high efficiency, good mechanical properties and kieselguhr in a weight ratio ranging from 1:0.2 to 1:4 the ability, under standard conditions, to produce an with a general preference for a range of from 1:0.5 to alcohol-aqueous condensate having a high concentra 1:1, and from 20-50 weight percent phosphoric acid a tion of ethyl alcohol over a long time period. general preference being for a phosphoric acid weight Studies have revealed that catalysts meeting these 20 percentage of 30-40%. prerequisites include carriers comprising natural kiesel The described catalyst may conveniently be prepared guhr from various European and overseas sources. Un by reacting a sodium silicate solution with hydrochloric fortunately, such kieselguhrs typically contain varying acid in the presence of an electrolyte, thereby resulting amounts of foreign matter, namely, metal oxides, and it in the precipitation of a material which is filtered and has been customary to remove the oxides or substan 25 washed and either directly thereafter or following dur tially reduce the content thereof in accordance with ing drying is admixed with natural kieselguhr, water standard procedures. Typically, this end is attained by and a bonding agent. The resultant mixture now in a acid refining the kieselguhr at elevated temperatures plastic condition is then extruded to shape and either and either atmospheric or elevated pressure in the pres dried or directly pressed, annealed at a temperature in ence of inorganic acies. Following, the kieselguhr is 30 excess of 800° C., preferably 1000 to 1300° C., and then filtered, washed, dried, formed, thermally treated, satu saturated with phosphoric acid and dried. rated with phosphoric acid and re-dried. Although The resultant activated and stabilized catalyst is then hydration catalysts so prepared are capable of yielding suited for the direct hydration of ethylene to ethyl alco ethyl alcohol of high standards, the procedures em hol in a continuous reactor at a temperature less than ployed suffer from certain technical and economic limi 35 300 C. and a pressure of 7 to 8 MPa, the molecular ratio tations. Thus, from a technical standpoint, the produc of water to ethylene being 0.5 to 0.7. The described tion process is intricate and requires inconvenient catalyst has been found to be particularly effective at equipment specially prepared for the acid refining pro temperatures no higher than 280 C. with a molecular cess and the filtration step. Furthermore, the process is ratio of water to ethylene less than 0.6. not economical due to the demand for chemicals used in An example of the application of the novel catalyst the refining process and due to the inherent loss of the described herein is set forth below. It will be under most valuable fine kieselguhr particles during filtration. stood by those skilled in the art that the described em Accordingly, these prior art catalysts do not meet pres bodiment is solely for purposes of exposition and it is ent demands. not be construed as limiting. A second category of catalysts for effecting hydra 45 EXAMPLE tion of ethylene to ethyl alcohol is also known. This catalyst comprises as its active substance phosphoric Three types of catalysts were prepared for use in acid deposited upon a silica gel carrier. Under moderate synthesizing ethyl alcohol by the direct hydration of conditions over short time cycles the phosphoric acid ethylene, two of such catalysts being prepared in accor catalyst is presently used with some degree of success, 50 dance with the preparative technique of the invention the mechanical strength and resistance to deactivation and the third in accordance with conventional prior art being of lesser importance. However, this catalyst has a techniques. The characteristics of these catalysts are set limited life cycle. forth in the table which follows. Hydration of ethylene In the present industrial environment, the producer of to ethyl alcohol using these catalysts was effected under ethyl alcohol utilizing the direct hydration of ethylene 55 severe conditions in order to accentuate the differences process seeks to operate the production unit at a tem in their function. perature less than 300° C. with a yield in excess of 180 TABLE Catalyst No. 1 2 3 Type Conventional Invention Invention Comprising Comprising synthetic Comprising synthetic natural SiO2 and natural SiO2 and natural Kieselguhr Kieselguhr in ratio Kieselguhr in ratio of 1:1 of 1:4 Mode of By extruding, By extruding, By extruding, Preparation annealing at annealing at annealing at 150 C. 050 C. 200 C. Characteristics: H3PO4 weight % 38.5 35.20 37.2 4,371,456 TABLE-continued Catalyst No. 2 3 crushing strength N 26.4 68.5 64.5 bulk density g/1 840 730 752 Direct Hydration of Ethylene: pressure MPa. 8.0 7.5 7.4 temperature C. 290 280 280 ratio H2O:C2H4 0.6 0.58 0.59 test time hours 300 300 300 initial productivity 214 210 210 g/l final productivity 165 21 205 g/1 final carbon content 0.6 0.3 0.4 weight % Remark: "At the end of the test the content of phosphoric acid was 21%.
3. Catalyst in accordance with claim 1, wherein the
Analysis of the data set forth in the Table reveals that weight percent of phosphoric acid ranges from 30-40 catalysts prepared in accordance with the invention weight percent based on the weight of the final compo evidenced a significantly higher mechanical strength sition. and greater stability than the prior art catalyst, the latter 4. Process for the preparation of a catalyst in accor being evident from the difference in ethyl alcohol pro dance with claim 1 which comprises the steps of (a) ductivity at the start and end of the testing. Addition reacting a solution of sodium silicate with hydrochloric ally, the final carbon content at the end of testing is 25 acid in the presence of an electrolyte, so resulting in the indicative of higher resistance to deactivation than that formation of a precipitate, (b) filtering and washing said of the prior art catalyst. precipitate, (c) mixing said precipitate with natural kie What is claimed is: selguhr, water and a bonding agent, (d) extruding the 1. Catalyst for direct hydration of ethylene to ethyl resultant plastic composition and pressing, (e) annealing alcohol consisting of phosphoric acid on a silicon diox 30 said composition at a temperature in excess of 800 C., ide base characterized in that said catalyst consists of and (f) saturating said annealed composition with phos active synthetic silicon dioxide and natural kieselguhr in phoric acid and drying. a weight ratio ranging from 1:0.2 to 1:4, and phosphoric 5. Process in accordance with claim 4, wherein the acid in an amount ranging from 20-50 weight percent annealing temperature ranges from 1000 to 1300 C. based on the weight of the catalyst. 35 6. Process in accordance with claim 4, wherein said 2. Catalyst in accordance with claim 1, wherein the precipitate is dried prior to being mixed with natural weight ratio of silicon dioxide to kieselguhr ranges from kieselguhr, water and a bonding as a agent. 1:0.5 to 1:1.