CA1076095A - Olefin hydration process and catalyst - Google Patents
Olefin hydration process and catalystInfo
- Publication number
- CA1076095A CA1076095A CA277,445A CA277445A CA1076095A CA 1076095 A CA1076095 A CA 1076095A CA 277445 A CA277445 A CA 277445A CA 1076095 A CA1076095 A CA 1076095A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- phosphoric acid
- support
- organic filler
- filler material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT
A process and catalyst for hydrating olefins to form alcohols. The olefins are contacted with water vapor in the presence of an improved hydration catalyst comprising a predominantly siliceous support material calcined prior to impregnation with phosphoric acid.
The supported catalyst is prepared by forming a mixture of from 50-70 (wt.) % diatomaceous earth, from about 15-25 (wt.) % bentonite, and from about 5-35 (wt.) %
of a combustible organic filler material; calcining said mixture at a temperature of from about 1200°F, to about 1500°F.; and then impregnating the calcined support with phosphoric acid.
A process and catalyst for hydrating olefins to form alcohols. The olefins are contacted with water vapor in the presence of an improved hydration catalyst comprising a predominantly siliceous support material calcined prior to impregnation with phosphoric acid.
The supported catalyst is prepared by forming a mixture of from 50-70 (wt.) % diatomaceous earth, from about 15-25 (wt.) % bentonite, and from about 5-35 (wt.) %
of a combustible organic filler material; calcining said mixture at a temperature of from about 1200°F, to about 1500°F.; and then impregnating the calcined support with phosphoric acid.
Description
10,537 1076~95 BACKGROUND
This invention relates to an improvet process for hydrating olefins to form alcohols, and a catalyst composition useful for such process. More particularly, this invention relates to an olefin hydration process utilizing a phosphoric acid catalyst having ~ufficient mechanical strength to allow long-term operation while maintaining a relatiYely high-level of catalytic activity.
Processes for reacting olefins with water vapor at elevated pressures to form alcohols in the presence of suitable catalysts are well-known in the art. The pre-ferred catalysts for the reaction generally comprise phosphoric acid impregnated upon a predominantly siliceous carrier or support material. Typical of such support materials are the various forms of calcined diatomaceous earth which essentially consist of diatoms of silicon dioxide in intimate admixture with clay or clay-like materials which serve as bonding agents for the silica.
U. S. Patent Nos. 2,960,477 and 3,704,329, for example, are descriptive of such olefin hydration processes.
Although phosphoric acid catalysts of this type have gained general commercial acceptance, they, nevertheless, have certain disadvantages relating, pr~marily, to their relatively short operating life. This is due, in part, to the tendency of phosphoric acid to "drool" during normal operation, namely, the aqueous phosphoric acid tends to seep from the catalyst support and flow slowly through the catalyst bed. This adversely affects the physical integrity of the support to the extent that it begins to disintegrate and cake together in a relatively short period of time during operation. This ~'
This invention relates to an improvet process for hydrating olefins to form alcohols, and a catalyst composition useful for such process. More particularly, this invention relates to an olefin hydration process utilizing a phosphoric acid catalyst having ~ufficient mechanical strength to allow long-term operation while maintaining a relatiYely high-level of catalytic activity.
Processes for reacting olefins with water vapor at elevated pressures to form alcohols in the presence of suitable catalysts are well-known in the art. The pre-ferred catalysts for the reaction generally comprise phosphoric acid impregnated upon a predominantly siliceous carrier or support material. Typical of such support materials are the various forms of calcined diatomaceous earth which essentially consist of diatoms of silicon dioxide in intimate admixture with clay or clay-like materials which serve as bonding agents for the silica.
U. S. Patent Nos. 2,960,477 and 3,704,329, for example, are descriptive of such olefin hydration processes.
Although phosphoric acid catalysts of this type have gained general commercial acceptance, they, nevertheless, have certain disadvantages relating, pr~marily, to their relatively short operating life. This is due, in part, to the tendency of phosphoric acid to "drool" during normal operation, namely, the aqueous phosphoric acid tends to seep from the catalyst support and flow slowly through the catalyst bed. This adversely affects the physical integrity of the support to the extent that it begins to disintegrate and cake together in a relatively short period of time during operation. This ~'
2.
10 7 60 9 5 10,537 has the effect sf plugging up the bet of catalyst support thereby increasing the pressure drop of the gases flow-ing therethrough, decreasing the effective contact (or surface) area of the catalyst, and, in general, reducing catalyst efficiency.
U. S. Patent No. 3,686,334 describes a procedure for preparing supported catalysts by admixing a siliceous support material with phosphoric acid, and then calcining the resulting mixture to form a strengthened catalyst structure. The operating life of such a supported catalyst is generally limited by the resistance of the support to physical degradation resulting from the aforementioned "drool" of phosphoric acid. U. S, Patent No. 2,496,621, on the other hand, discloses a procedure wherein the catalyst support material is calcined at a temperature in the range of 800-1400C. prior to impregnation with the phosphoric acid catalyst. This results in an independently strong catalyst support capable of maintaining its physical integrity for a relatively long period of time.
Unfortunately, the catalyst is not sufficiently active to provide the level of olefin conversion required in a commercial hydration process, There remains, therefore, a need for an olefin hydration catalyst combining high catalytic activity with sufficient mechanical strength to withstand disintegration over relatively long periods of time under process conditions encountered during normal operation, SU~RY
This invention provides a process and ca~alyst for hydrating olefins to form alcohols. The olefins are lo s37 contacted with water vapor in the presence of a supported hydration catalyst comprising a pretominantly slliceous support material calcined prior to impregnation with phosphoric acid. The improved catalyst possesses mechanical strength which allows long-term operation without adversely affecting catalytic activity. It is prepared by mixing from about 50-70 (wt ) % diatomaceous earth, from about 15-25 (wt.) ~ bentonite, and from about 5-35 (wt.) ~ of a combustible organic filler material, and thereafter calcining the resulting mixture at a temperature of from about 1200F to about 1500F so as to provide an independently s~rong catalyst support capable of with-standing the loss of phosphoric acid from the catalyst support during normal process operation without a con-comitant loss of mechanical strength, The calcined support is thereafter impregnated with the phosphoric ` acid catalyst.
The present invention is predicated on the dis-covery that calcination of a siliceous catalyst support-form-~ng material, such as described above~at a temperature inthe range of about 1200F to 1500F is capable of bonding diatomaceous earth and bentonite, the primary constituents of the support material, so as to avoid the characteristic structural failure of prior art catalysts which occurs relatively quickly as a result of phosphoric acid "drool"
during normal operation; yet at the same time, avoid undue sintering of the support material and the accom-panying loss of active surface. Thus, the catalyst of the invention is capable of long-term process operation at a relatively high level of olefin conversion to alcohol.
1076095 lo, 537 DETAILED DESCRIPTION OF THE INVENTION
. _ . . .
The composition of the catalyst support employed in preparing the olefin hydration catalysts of the inven-tion i8 from about 50-70 percent by weight, diatomaceous earth, from about 15-25 percent by weight, bentonite and from about 5-35 percent, by weight, of a combust~ble organic filler material, the above percentages referring to the composition of the support prior to the calcina-tion step. A preferred composition ln terms of provid-ing an optimum balance of catalytic activity and mechanicalstrength is about 62 (wt.) % diatomaceous earth, about 21 (wt.) % bentonite and about 18 (wt.) % filler material.
During calcination, the organic filler material is burned out to provide a structure having sufficient porosity to ensure an even coating of phosphoric acid throughout the ; support during impregnation and to allow the reacting gases to readily contact the internal active sites of the support during operation. The combustible organic fil~er is preferably cornmea~ but powdered combustible materials such as wood, flour, starch, carbon black, and the like may also be used. To attain the desired porosity, the size of the filler materials admixed with the particles of di-atomaceous e æ th and bentonite should be within the range of about 500 to 2000 microns, and preferably about 1000 microns.
Diatomaceous earth, the main component of the catalyst support, is a naturally occurring form of silicon dioxide which serves to provide active sites for the form-ation of the reactive acid film. An especially desirable form of diatomaceous earth is manufactured by Johns-Manville Corporation and is designated as "Celite FC" possessing a 10,537 la76oss surface area o~ 20-30 meters2 /~ram. This material has the following average composi~ion:
omponentWeight Percent SiO2 86,7 Fe203 1.2 CaO 0.5 H2O, trace metal 8.3 ~x~des ~n~onite, ha~ing a preferred particle size dis,ribution such that about 90% of the particles are be~ow a size of about 74 microns, is admixed with the diatomaceous earth to provide mechanical strength to the catalyst support. Bentonite is a hydrated silicate having the following a~rerage composit~on:
- ComponentW~ht Percent ` SIQ2 49.0 A123 ~ 2aY~ 7~ .
F O ~ * ~ f J
Ca~ 1.8 - H2O, trace metal 24,7 oxides To prepare the catalyst support, diatomaceous earth, bentonite and cornmeal, in the proportions recited above,are admixed with water to form a paste which is dried and then calcined to burn out the organic filler and form a hardened support mater ~ typically in the form of a pellet about l/8~inch in diameter, The purpose of the drying step is to substantially reduce the moisture content o~ the pellet prior to calcination. This is conveniently accomplished by conveying the pellets over a belt-dryer at a - temperature in the range of about 150-340F. for a period of about 30 minùtes. Calcination may be effected at a 6.
1076095 lo, 537 temperature within the range of about 1200F to about 1500F depending somewhat upon the amount of filler in the support; the lower the percentage of filler material, the lower the desired temperature within the stated range.
For a support containing about 17 (wt.) % organic filler, the preferred calcination temperature is about 1350F.
The time required for calcination in, for example, a rotarykiln wherein uniform heating is provided may vary from about 10-30 minutes depending upon the temperature employed.
Thus, at a relati~ely high calcination temperature within the stated range, corresponding less calcination time is required.
Following calcination and prior to catalyst impregnation, the support material is preferably "washed"
in an acid solution to remove impurities, such, as, aluminum oxide, iron oxide and calcium oxide, which are soluble in phosphoric acid under normal operating condi-tions and may cause clogging of the pores with phosphate salts and ultimately, loss of catalyst activity. The acid wash is conveniently effected with any strong mineral acid;
hydrochloric acid (1:1) or phosphoric acid (85%) being preferred for this purpose. The catalyst support pellets are preferably refluxed with the acid for a period of from about 4-20 hours, and then washed with water at 90C for a period of about 2 hours until the support material is free of acid.
Impregnation of the calcined support material is carried out in an aqueous solution of phosphoric acid containing from about 40 to 80 percent, by weight, of phosphoric acid. The impregnation can be effected in any manner which will result in substantial saturation of the 10,537 -` 1076095 ~upport material with tlle acid c~alyst. Typically, the support material is soaked ~n an acid solution maintained at n temperature of about 30C for a period of time of from about 1/2 hour to 8 hours, Generally, a period o a~out 2 hours will suffice, The saturated support material is then freed of excess acid and dried at a temp- I, era~ure below 280~C to prevent sintering of the support i;~
material, Drying is conveniently carried out at a temp- !
~-ature o- about 180C in an inert atmosphere, The re- ¦
sulting impregnated catalyst contains from about 30 to 60 percent, by weight, orthophosphoric acid based on -the weight of the composite structure, i,e,, support material plus acid catalyst, Lower olefins, such as, ethylene, propylene and ~he butenes, may be directly hydrated to the corresponding alcohols by reacting the olefin starting material with ~ater vapor in the presence of a catalyst in accordance with the invention at a tem~erature within the range of about 220 to 300C,, a water vapor to olefin mole ~atio of about 0,3 to 1,0, and an operating pressure of about ', 500 to 1200 psig, Preferred operating conditions for - the conversion of, for example, ethylene to ethanol are a - temperature of about 270C,, a water vapor to olefin mole ratio of about 0.6, and a reaction pressure of about 1000 - psig, ~ower temperatures and higher pressures favor high equilibrium yields, Xowever, if temperatures are too low, reaction rates decrease, while unduly high pressures re-sult in relatively large amounts of polymeric material in the reaction products, Higher water vapor to olefin ~O~V~ 76 3U mole ratios result in improved ~-iel~3, but at the expense ~ of increased energy requirements or vaporization.
8.
- - 1076095 lo, 537 62 Parts by weight of "Celite FC" diatomaceous earth, 21 parts by weight of bentonite,(90% of the particles being below a size of about 74 microns) and 17 parts by weight of cornmeal (1000 microns), were admixed with water to form pellets which were 5/32" in diameter, The pellets were dried at a temperature of 350F, for 30 minutes to remove moisture and then calcined in air for 4U minutes at 1350F, Following calcination, the carrier was leached by refluxing with 1:1 hydrochloric acid for 4 hours to remove metallic impurities, then washed with water at 90C. for 2 hours. The leached carrier was then dried with an inert gas at 140C. for 18 hours and impregnated with 65% phosphoric acid at room temperature for 8 hours.
The excess acid was allowed to drain off and the catalyst , pellets were dried under inert conditions at llUC. for `i, 18 hours. The crush strength of the supported catalyst ~ was 20 lbs" radial; the porosity was 0.7 cc./gram.
' ` 20 A gaseous mixture of ethylene and steam in a lar ratio of 1,~:1 was passed through the supported catalyst of Example 1 at the rate of 2000 SCFH per cu, ft, of catalyst, The reactor pressure was 1000 psig.and the "~ temperature of the catalyst bed was maintained at 270C.
At the end of 1200 hours, ethanol production remained essentially unchanged at 9.2 lbs, per hour per cu, ft, of catalyst, The-effect of high temperature calcination, i.e., above the range of 12U0F.-150~F., was demonstrated by lU,5~7 1~76~)9S
preparlng catalyst support pelle~s of similar size snd composition to those d~scr~hed ~n Example 1. The pellets were dried ils accordance with ~:h~ procedure o~ Example 1, but werecalcined at a temperature o 180UF. Leaching, dry~ng, impregnation a~d final drying were then carried out as in Example 1. The r~sulting catalyst pellets were .
~rkedly harder tha~ those prepared acccrding to Example 1, ~nd had a crush strength gre~te~ than 72 lbs., radial.
Steam and ethylene were passed through a bed of this -10 catalyst under the process conditions described in Example ; 2, A~ter a~out 700 hours of operation, the e.hanol production rate was 4,3 lbs, per hour per cu. ft. of catalys~, less than 5U~o of the value measured in Example 2.
A gaseous mixture of propylene and steam in a molar - ratio of 2:1 was passed over the catalyst of Example 1 in a - backmixed reactor at the rate of 2000 SCFH per cu. ft. of ~;~ catalyst. This type of gradientless reactor was considered ideal for comparative analysis of the effects of operating variables or preparation conditions on the catalyst. Although production ratios are generally lower due to the backmixing, measurable effects of the reaction on catalyst properties could be obtained in a very short time. Under operating - conditions of 600 psig and 220C, isopropanol ~roduction - was found to be 7.2 lbs. per hour per cu. ft. of the catalyst at the end of 8 hours. No isopropyl ether or any impurities were detected. The analogous vapor phase hydration of ethylene to ethanol employing the same molar ratio in this equipment at 1000 psig and 270C, resulted in the production of 6.8 lbs. per hour of ethanol per cu. ft. of catalyst.
10.
10 7 60 9 5 10,537 has the effect sf plugging up the bet of catalyst support thereby increasing the pressure drop of the gases flow-ing therethrough, decreasing the effective contact (or surface) area of the catalyst, and, in general, reducing catalyst efficiency.
U. S. Patent No. 3,686,334 describes a procedure for preparing supported catalysts by admixing a siliceous support material with phosphoric acid, and then calcining the resulting mixture to form a strengthened catalyst structure. The operating life of such a supported catalyst is generally limited by the resistance of the support to physical degradation resulting from the aforementioned "drool" of phosphoric acid. U. S, Patent No. 2,496,621, on the other hand, discloses a procedure wherein the catalyst support material is calcined at a temperature in the range of 800-1400C. prior to impregnation with the phosphoric acid catalyst. This results in an independently strong catalyst support capable of maintaining its physical integrity for a relatively long period of time.
Unfortunately, the catalyst is not sufficiently active to provide the level of olefin conversion required in a commercial hydration process, There remains, therefore, a need for an olefin hydration catalyst combining high catalytic activity with sufficient mechanical strength to withstand disintegration over relatively long periods of time under process conditions encountered during normal operation, SU~RY
This invention provides a process and ca~alyst for hydrating olefins to form alcohols. The olefins are lo s37 contacted with water vapor in the presence of a supported hydration catalyst comprising a pretominantly slliceous support material calcined prior to impregnation with phosphoric acid. The improved catalyst possesses mechanical strength which allows long-term operation without adversely affecting catalytic activity. It is prepared by mixing from about 50-70 (wt ) % diatomaceous earth, from about 15-25 (wt.) ~ bentonite, and from about 5-35 (wt.) ~ of a combustible organic filler material, and thereafter calcining the resulting mixture at a temperature of from about 1200F to about 1500F so as to provide an independently s~rong catalyst support capable of with-standing the loss of phosphoric acid from the catalyst support during normal process operation without a con-comitant loss of mechanical strength, The calcined support is thereafter impregnated with the phosphoric ` acid catalyst.
The present invention is predicated on the dis-covery that calcination of a siliceous catalyst support-form-~ng material, such as described above~at a temperature inthe range of about 1200F to 1500F is capable of bonding diatomaceous earth and bentonite, the primary constituents of the support material, so as to avoid the characteristic structural failure of prior art catalysts which occurs relatively quickly as a result of phosphoric acid "drool"
during normal operation; yet at the same time, avoid undue sintering of the support material and the accom-panying loss of active surface. Thus, the catalyst of the invention is capable of long-term process operation at a relatively high level of olefin conversion to alcohol.
1076095 lo, 537 DETAILED DESCRIPTION OF THE INVENTION
. _ . . .
The composition of the catalyst support employed in preparing the olefin hydration catalysts of the inven-tion i8 from about 50-70 percent by weight, diatomaceous earth, from about 15-25 percent by weight, bentonite and from about 5-35 percent, by weight, of a combust~ble organic filler material, the above percentages referring to the composition of the support prior to the calcina-tion step. A preferred composition ln terms of provid-ing an optimum balance of catalytic activity and mechanicalstrength is about 62 (wt.) % diatomaceous earth, about 21 (wt.) % bentonite and about 18 (wt.) % filler material.
During calcination, the organic filler material is burned out to provide a structure having sufficient porosity to ensure an even coating of phosphoric acid throughout the ; support during impregnation and to allow the reacting gases to readily contact the internal active sites of the support during operation. The combustible organic fil~er is preferably cornmea~ but powdered combustible materials such as wood, flour, starch, carbon black, and the like may also be used. To attain the desired porosity, the size of the filler materials admixed with the particles of di-atomaceous e æ th and bentonite should be within the range of about 500 to 2000 microns, and preferably about 1000 microns.
Diatomaceous earth, the main component of the catalyst support, is a naturally occurring form of silicon dioxide which serves to provide active sites for the form-ation of the reactive acid film. An especially desirable form of diatomaceous earth is manufactured by Johns-Manville Corporation and is designated as "Celite FC" possessing a 10,537 la76oss surface area o~ 20-30 meters2 /~ram. This material has the following average composi~ion:
omponentWeight Percent SiO2 86,7 Fe203 1.2 CaO 0.5 H2O, trace metal 8.3 ~x~des ~n~onite, ha~ing a preferred particle size dis,ribution such that about 90% of the particles are be~ow a size of about 74 microns, is admixed with the diatomaceous earth to provide mechanical strength to the catalyst support. Bentonite is a hydrated silicate having the following a~rerage composit~on:
- ComponentW~ht Percent ` SIQ2 49.0 A123 ~ 2aY~ 7~ .
F O ~ * ~ f J
Ca~ 1.8 - H2O, trace metal 24,7 oxides To prepare the catalyst support, diatomaceous earth, bentonite and cornmeal, in the proportions recited above,are admixed with water to form a paste which is dried and then calcined to burn out the organic filler and form a hardened support mater ~ typically in the form of a pellet about l/8~inch in diameter, The purpose of the drying step is to substantially reduce the moisture content o~ the pellet prior to calcination. This is conveniently accomplished by conveying the pellets over a belt-dryer at a - temperature in the range of about 150-340F. for a period of about 30 minùtes. Calcination may be effected at a 6.
1076095 lo, 537 temperature within the range of about 1200F to about 1500F depending somewhat upon the amount of filler in the support; the lower the percentage of filler material, the lower the desired temperature within the stated range.
For a support containing about 17 (wt.) % organic filler, the preferred calcination temperature is about 1350F.
The time required for calcination in, for example, a rotarykiln wherein uniform heating is provided may vary from about 10-30 minutes depending upon the temperature employed.
Thus, at a relati~ely high calcination temperature within the stated range, corresponding less calcination time is required.
Following calcination and prior to catalyst impregnation, the support material is preferably "washed"
in an acid solution to remove impurities, such, as, aluminum oxide, iron oxide and calcium oxide, which are soluble in phosphoric acid under normal operating condi-tions and may cause clogging of the pores with phosphate salts and ultimately, loss of catalyst activity. The acid wash is conveniently effected with any strong mineral acid;
hydrochloric acid (1:1) or phosphoric acid (85%) being preferred for this purpose. The catalyst support pellets are preferably refluxed with the acid for a period of from about 4-20 hours, and then washed with water at 90C for a period of about 2 hours until the support material is free of acid.
Impregnation of the calcined support material is carried out in an aqueous solution of phosphoric acid containing from about 40 to 80 percent, by weight, of phosphoric acid. The impregnation can be effected in any manner which will result in substantial saturation of the 10,537 -` 1076095 ~upport material with tlle acid c~alyst. Typically, the support material is soaked ~n an acid solution maintained at n temperature of about 30C for a period of time of from about 1/2 hour to 8 hours, Generally, a period o a~out 2 hours will suffice, The saturated support material is then freed of excess acid and dried at a temp- I, era~ure below 280~C to prevent sintering of the support i;~
material, Drying is conveniently carried out at a temp- !
~-ature o- about 180C in an inert atmosphere, The re- ¦
sulting impregnated catalyst contains from about 30 to 60 percent, by weight, orthophosphoric acid based on -the weight of the composite structure, i,e,, support material plus acid catalyst, Lower olefins, such as, ethylene, propylene and ~he butenes, may be directly hydrated to the corresponding alcohols by reacting the olefin starting material with ~ater vapor in the presence of a catalyst in accordance with the invention at a tem~erature within the range of about 220 to 300C,, a water vapor to olefin mole ~atio of about 0,3 to 1,0, and an operating pressure of about ', 500 to 1200 psig, Preferred operating conditions for - the conversion of, for example, ethylene to ethanol are a - temperature of about 270C,, a water vapor to olefin mole ratio of about 0.6, and a reaction pressure of about 1000 - psig, ~ower temperatures and higher pressures favor high equilibrium yields, Xowever, if temperatures are too low, reaction rates decrease, while unduly high pressures re-sult in relatively large amounts of polymeric material in the reaction products, Higher water vapor to olefin ~O~V~ 76 3U mole ratios result in improved ~-iel~3, but at the expense ~ of increased energy requirements or vaporization.
8.
- - 1076095 lo, 537 62 Parts by weight of "Celite FC" diatomaceous earth, 21 parts by weight of bentonite,(90% of the particles being below a size of about 74 microns) and 17 parts by weight of cornmeal (1000 microns), were admixed with water to form pellets which were 5/32" in diameter, The pellets were dried at a temperature of 350F, for 30 minutes to remove moisture and then calcined in air for 4U minutes at 1350F, Following calcination, the carrier was leached by refluxing with 1:1 hydrochloric acid for 4 hours to remove metallic impurities, then washed with water at 90C. for 2 hours. The leached carrier was then dried with an inert gas at 140C. for 18 hours and impregnated with 65% phosphoric acid at room temperature for 8 hours.
The excess acid was allowed to drain off and the catalyst , pellets were dried under inert conditions at llUC. for `i, 18 hours. The crush strength of the supported catalyst ~ was 20 lbs" radial; the porosity was 0.7 cc./gram.
' ` 20 A gaseous mixture of ethylene and steam in a lar ratio of 1,~:1 was passed through the supported catalyst of Example 1 at the rate of 2000 SCFH per cu, ft, of catalyst, The reactor pressure was 1000 psig.and the "~ temperature of the catalyst bed was maintained at 270C.
At the end of 1200 hours, ethanol production remained essentially unchanged at 9.2 lbs, per hour per cu, ft, of catalyst, The-effect of high temperature calcination, i.e., above the range of 12U0F.-150~F., was demonstrated by lU,5~7 1~76~)9S
preparlng catalyst support pelle~s of similar size snd composition to those d~scr~hed ~n Example 1. The pellets were dried ils accordance with ~:h~ procedure o~ Example 1, but werecalcined at a temperature o 180UF. Leaching, dry~ng, impregnation a~d final drying were then carried out as in Example 1. The r~sulting catalyst pellets were .
~rkedly harder tha~ those prepared acccrding to Example 1, ~nd had a crush strength gre~te~ than 72 lbs., radial.
Steam and ethylene were passed through a bed of this -10 catalyst under the process conditions described in Example ; 2, A~ter a~out 700 hours of operation, the e.hanol production rate was 4,3 lbs, per hour per cu. ft. of catalys~, less than 5U~o of the value measured in Example 2.
A gaseous mixture of propylene and steam in a molar - ratio of 2:1 was passed over the catalyst of Example 1 in a - backmixed reactor at the rate of 2000 SCFH per cu. ft. of ~;~ catalyst. This type of gradientless reactor was considered ideal for comparative analysis of the effects of operating variables or preparation conditions on the catalyst. Although production ratios are generally lower due to the backmixing, measurable effects of the reaction on catalyst properties could be obtained in a very short time. Under operating - conditions of 600 psig and 220C, isopropanol ~roduction - was found to be 7.2 lbs. per hour per cu. ft. of the catalyst at the end of 8 hours. No isopropyl ether or any impurities were detected. The analogous vapor phase hydration of ethylene to ethanol employing the same molar ratio in this equipment at 1000 psig and 270C, resulted in the production of 6.8 lbs. per hour of ethanol per cu. ft. of catalyst.
10.
Claims (6)
1. In a process for hydrating olefins to form alcohols wherein said olefins are contacted with water vapor in the presence of a hydration catalyst comprising a predominantly siliceous support material impregnated with phosphoric acid, the improvement for enhancing the mechanical strength of the supported catalyst to allow long-term operation without adversely affecting catalytic activity which comprises forming a mixture comprising of from about 50-70 (wt.) % diatomaceous earth, from about 15-25 (wt.) % bentonite, and from about 5-35 (wt.) % of a combustible organic filler material; calcining said mixture prior to the addition of phosphoric acid at a temperature of from about 1200°F, to about 1500°F. so as to form an independently strong catalyst support; and thereafter impregnating said support with phosphoric acid to provide an active supported hydration catalyst capable of withstanding the loss of phosphoric acid from the catalyst support during normal process operation without a concomitant loss of mechanical strength.
2. The process of claim 1 wherein the composi-tion of said mixture comprises about 62 (wt.) % diatomaceous earth, about 21 (wt.) % bentonite and about 17 (wt.) % of a combustible organic filler material.
3. The process of claim 2 wherein said organic filler material is cornmeal,
4. A supported catalyst composition comprising a predominantly siliceous support material impregnated with phosphoric acid, said catalyst having been prepared 11.
10,537 by calcining the siliceous support material prior to the addition of phosphoric acid at a temperature of from about 1200°F. to about 1500°F, so as to provide an independently strong catalyst support capable of with-standing the loss of phosphoric acid therefrom without a concomitant loss of mechanical strength, the composition of said siliceous support material prior to calcination comprising of from about 50-70 (wt.) % diatomaceous earth, from about 15-25 (wt,) % bentonite, and from about 5-35 (wt.) % of a combustible organic filler material.
10,537 by calcining the siliceous support material prior to the addition of phosphoric acid at a temperature of from about 1200°F. to about 1500°F, so as to provide an independently strong catalyst support capable of with-standing the loss of phosphoric acid therefrom without a concomitant loss of mechanical strength, the composition of said siliceous support material prior to calcination comprising of from about 50-70 (wt.) % diatomaceous earth, from about 15-25 (wt,) % bentonite, and from about 5-35 (wt.) % of a combustible organic filler material.
5. The composition of claim 4 wherein the composition of said siliceous support material prior to calcination is comprised of about 62 (wt.) % diatomaceous earth, about 21 (wt.) % bentonite and about 17 (wt.) %
of a combustible organic filler material.
of a combustible organic filler material.
6. The composition of claim 5 wherein said organic filler material is cornmeal.
12.
12.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US72760076A | 1976-09-28 | 1976-09-28 | |
| US72758076A | 1976-09-28 | 1976-09-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1076095A true CA1076095A (en) | 1980-04-22 |
Family
ID=27111534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA277,445A Expired CA1076095A (en) | 1976-09-28 | 1977-04-29 | Olefin hydration process and catalyst |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5344504A (en) |
| CA (1) | CA1076095A (en) |
| DE (1) | DE2722616C3 (en) |
| ES (1) | ES458919A1 (en) |
| FR (1) | FR2365543A1 (en) |
| GB (1) | GB1576037A (en) |
| NL (1) | NL7705510A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1102777A (en) * | 1977-03-04 | 1981-06-09 | Percy R. Kavasmaneck | Low-metal content olefin hydration catalyst and related process |
| US4297241A (en) * | 1980-03-21 | 1981-10-27 | Union Carbide Corporation | Method of preparing an olefin hydration catalyst |
| FR2578448B1 (en) * | 1985-01-31 | 1990-11-16 | Manville Corp | PROCESS FOR PRODUCING CATALYST SUPPORTS AND PRODUCTS OBTAINED |
-
1977
- 1977-04-29 CA CA277,445A patent/CA1076095A/en not_active Expired
- 1977-05-18 DE DE2722616A patent/DE2722616C3/en not_active Expired
- 1977-05-18 ES ES458919A patent/ES458919A1/en not_active Expired
- 1977-05-18 FR FR7715375A patent/FR2365543A1/en not_active Withdrawn
- 1977-05-18 JP JP5649777A patent/JPS5344504A/en active Granted
- 1977-05-18 NL NL7705510A patent/NL7705510A/en not_active Application Discontinuation
- 1977-05-18 GB GB20812/77A patent/GB1576037A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5344504A (en) | 1978-04-21 |
| JPS5721250B2 (en) | 1982-05-06 |
| ES458919A1 (en) | 1978-02-16 |
| DE2722616A1 (en) | 1978-03-30 |
| DE2722616B2 (en) | 1979-01-18 |
| GB1576037A (en) | 1980-10-01 |
| FR2365543A1 (en) | 1978-04-21 |
| NL7705510A (en) | 1978-03-30 |
| DE2722616C3 (en) | 1981-09-24 |
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