CA1300586C - Silver-deposited catalyst for production of ethylene oxide - Google Patents
Silver-deposited catalyst for production of ethylene oxideInfo
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- CA1300586C CA1300586C CA000536568A CA536568A CA1300586C CA 1300586 C CA1300586 C CA 1300586C CA 000536568 A CA000536568 A CA 000536568A CA 536568 A CA536568 A CA 536568A CA 1300586 C CA1300586 C CA 1300586C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
Abstract of the Disclosure A silver-deposited catalyst for production of ethylene oxide by oxidizing ethylene, having high selec-tivity and long life, is provided by this invention. The catalyst is characterized by a combination of (a) catalyst ingredients comprising silver and a cation component selected at least from sodium, potassium, rubidium and cesium, and (b) a carrier composed mainly of alpha-alumina, said carrier having a surface area of 0.6 to 2 m2/g, a water absorption of 20 to 50%, a silica content of 0.5 to 12% by weight, a silica content, per m2/g of sur-face area, of 0.5 to 12, preferably 1 to 8, and a sodium content of 0.08 to 2% by weight.
Description
~3V~S~36 This invention relates to a silver-deposited catalyst for producing ethylene oxide by vapor-phase oxidation of ethylene.
Annual world production of ethylene oxide amounts to as much as several million tons. In order to produce ethylene oxide efficiently, it has been strongly desired to develop improved catalysts having high selec-tivity and long active lives, a~d various methods have been proposed. Most of thes~ method~ are directed to lo optimization of the combination of silver as a main active ingredient with an additiv~ such as an alkali and the proportions o~ these ingredients, and to improvement of carriers for supporting these ingredients. One aim o~ the latter-mentioned type of methods would be to obtain high selectivity and long li~e by increasing the specific surface area of the carrier and thereby improving the dispersion of silver and enabling the resulting catalyst to be used at low temperatures. ~he desired effect, however, cannot be obtained by simply increasing the surface area o the carrier because diffusion of the inside of the carrier particles exerts an adverse effect and side reactions occur on the surface of the carrier.
Hence, such methods require further improvement.
~or example, in the technique disclosed in Japanese Laid-Open Patent Publication No. 89843/1981, an alpha~alumina carrier having a sodium con~ent of as low as 0.07% by weight or less is selected and used as a carrier having a surface area of O.S to 5 m~g, and by combining this carrier with S to 2S% by weight Qf silver and 0~001 to 0.05 gram-equivalen~ of at least one alkali metal selected from potassium, rubidium and cesium, a good catalyst is obtained-.- -The present inven ors have made extensive in-vestigations on a carrier having a high surface area in ~3~ 58~
Annual world production of ethylene oxide amounts to as much as several million tons. In order to produce ethylene oxide efficiently, it has been strongly desired to develop improved catalysts having high selec-tivity and long active lives, a~d various methods have been proposed. Most of thes~ method~ are directed to lo optimization of the combination of silver as a main active ingredient with an additiv~ such as an alkali and the proportions o~ these ingredients, and to improvement of carriers for supporting these ingredients. One aim o~ the latter-mentioned type of methods would be to obtain high selectivity and long li~e by increasing the specific surface area of the carrier and thereby improving the dispersion of silver and enabling the resulting catalyst to be used at low temperatures. ~he desired effect, however, cannot be obtained by simply increasing the surface area o the carrier because diffusion of the inside of the carrier particles exerts an adverse effect and side reactions occur on the surface of the carrier.
Hence, such methods require further improvement.
~or example, in the technique disclosed in Japanese Laid-Open Patent Publication No. 89843/1981, an alpha~alumina carrier having a sodium con~ent of as low as 0.07% by weight or less is selected and used as a carrier having a surface area of O.S to 5 m~g, and by combining this carrier with S to 2S% by weight Qf silver and 0~001 to 0.05 gram-equivalen~ of at least one alkali metal selected from potassium, rubidium and cesium, a good catalyst is obtained-.- -The present inven ors have made extensive in-vestigations on a carrier having a high surface area in ~3~ 58~
order to produce a catalyst having high selectivity and a lony life. These investigations have led to the discovery that to obtain a catalyst having high activity and high selectivity for the production of ethylene oxide, the combination of catalyst ingredients and a carrier is important, and a catalyst of such high performance can be obtained by combining a carrier having a silica content of a specific range which has not attracted attention previously, particularly a silica and a sodium content within specific ranges, with silver and a specific cation component as catalyst ingredients. It has particularly been found in accordance with this :Lnvention that the action of soclium added as the cation component is characteristic, and by combining it with at least one of potassium, rubidium and cesium, and preferably barium as well, a catalyst capable of exhibiting high performance can be obtained.
One aspect of the present invention provides a silver-deposited catalyst for production of ethylene oxide by oxidizing ethylene, comprising as catalyst ingredients silver and a cation component selected at least from sodium, potassium, rubidium and cesium, and a carrier composed mainly of alpha-alumina, the carrier having (1) a surface area of 0.6 to 2 m2/g, (2) a water absorption of 20 to 50%, (3~ a silica content of 0.5 to 12% by weight, ~4) a silica content, per m2/g of surface area, of 0.5 to 12, preferably 1 to 8, ~5) a sodium content of 0.08 to 2% by weight, (6) an acidity that can be detected by an indicator having a pKa of +4.8, and ~7) a crystal of S16Si2O13 which can be detected by X-ray diffraction analysis.
~3(~ 6 In a preferred embodiment, the cation component is composed of (A) sodium and (B~ at least one of potassium, rubidium and cesium.
In another preferred embodiment, ~he cation component is composed of IA) sodium, (B) at least one of potassium, rubidium and cesium and (C) barium.
In another preferred embodiment, the cation component has been deposited on the carrier from aqueous solution.
In yet another preferred embodiment, during production of the catalyst, silver and/or the cation component is impregnated in the carr:Ler and heat-treated in superheated steam at 130 to A second aspect of the present invention provides a process for producing the catalyst.
A third aspect of the present invention provides a method for production of ethylene oxide by oxidizing ethylene in the presence of the catalyst.
The reason for the hiyh performance of the catalyst of this invention is not entirely clear. It has been found that 1) X-ray diffraction shows that in the carrier used in this invention, A16Si2013 is for~ed besides alpha-Al203;
2) the carrier used in this invention has acidity that can be detected by an indicator having a pKa of t4.8 ~the acidity is measured in accordance with page 161 et seq. of Tanabe and Takeshita, "Acid Base Catalysts", published on Apri~ 26, 1966 by Sangyo Tosho K.K.); and 3) the acidity of the carrier disappears when Na2CO3 ~iL3~ 5~
3a 67566-1035 is deposited on it and basicity appears under which the color of Bromothymol Blue having pKb of ~7.0 is changed.
On the basis of these facts, it ls presumed that the carrier used in the catalyst of this inventi.on exhibits acidity which can be detected by an indicator haviny a p~a of ~4.8 as a result of containing silica, particularly silica and sodium in amounts within specified ranges, that the acidity is moderately controlled by the addition of the cation component as a catalysk ingredient, and that by the synergistic effect of these, the catalyst exhibits very hiyh performance.
The silver compound used to form silver as a catalytic ingredient in this invention may be any silver eompound which forms with an amine a complex soluble in an aqueous solvent and decomposes at a temperature of not more than 500C, preferably not more than 300C, more preferably not more than 260C, to deposit silver. Examples are silver oxide, silver nitrate, silver carbonate and silver carboxylates such as silver acetate and silver ~3(~S1~6 ~ 4 --oxalate. The amine as a complex-formin~ agent may be any amine which can solubilize the silver compound in an aqueous solvent. ~xamples are pyridine, acetonitrile, ammonia and amin s having 1 to 6 carbon atoms. Ammonia, pyridine, monoamines such as butylamine, alkanolamines such as ethanolamines, alkylenediamines having 2 to 4 carbon atoms, and polya~ines are preferred. Ethylene-diamine and l,3-propanediamine, particularly a mixture of both, are especially preferred.
lC For impregnation in the carrier, it is most practical to use the silver compound in the form of an aqueous amine solution. An aqueous solution containing an alcohol, for example, may also be used. The concentration o~ silver in the impregnating solution is selected so that 5 to 25% by weight of silver is deposited finally as a catalytic ingredient. The impregnating operation is carried out by an ordinary method. If required, pressure reduction, heating, spraying, etc. are also carried out.
The amine is added in an amount required to complex the silver compound (usually, two amino groups correspond to one silver ato~). Usually, it is sa~e to add it i~ an amount exceeding the~equivalent weight by 5 to 30%.
~ eat-treatment after the impregnation is carried out by selecting such a temperature and time as are re-quired to deposit silver on the carrier. It is mostdesirable to select such conditions as to allow silver to exist on the carrier a~ fine particles as uniformly as possible~ Generally, high temperatures and long periods of time are undesirable because they promote aggregation of the deposited silver particl~s. Preferably, calcina-tio~ is carried out for as short as S to 30 minutes by using air (or an inert gas such as nitrogen) heated at 120 to 300C or supe~heated steam. The calcination for a short period of time is also desirable since it shortens the time required ~or catalyst preparation. In parti-cular, the use of superheated steam is desirable as it ~3~15~j makes the distri~ution of silver on the carrier uniform.
The cation component as a catalytic ingredient is preferably added in the form of a compound soluble in an aqueous solvent in a soluble concentration. It may, however, remain partly insoluble. Examples of such com-pounds are inorganic salts such as nitrates, carbonates, bicarbonates, halides, hydroxides, nitrites and sulfates, and carboxylates such as formates. The halides as the cation component are preferably added so that 5 ppm to 10 Orl% by weight, preferably 7 ppm to 0.Q7% by weight, of a halogen such as chlorine, bromine or fluorine, particulary chlorine, is contained as a catalytic ingredient in the final catalyst. The cation component may be added to the silver impregnating solution and deposited (simultaneous impregnation). Or it may be impregnated before or a~ter deposition of the ~ilver. After-impregnation, however, is unsuitable in the case of sodium. An aqueous solution is preferred as the impregnating solution. The use of a solution containing an alcohol, for example, is not re-commendable from the standpoint of safety and simplifi-cation of process steps.
Sodium as a catalytic ingredient is preferably contained in an amount of 50 ppm to 1% by weight in the catalyst~ Its optimum amount varies depending upon the silica content. Advantageously, it is generally 500 to 4,000 ppm. It is especially preferred to apply it in the form of sodium carbonate or sodium bicarbonate.
The content of the alkali metal component selected from potassium, rubidium and cesium is preferably 10 to 2,000 ppm, particularly 75 to 30~ ppm for potassium, 160 to 650 ppm for rubidium and 250 to 1,000 ppm for cesium. Most preferably, the alkali metal component is i~pregnated si~ultaneously with the impregnation of the silver compound. Preferably, it is added partly or wholly as a halide such as a chloride, bromide or fluoride, particularly the chloride. Preferably, barium is added in ~3Q~
an amount o 30 to 1,000 ppm, preferably 40 to 650 ppm, to the catalyst. Suitably, it is added in the form of a nitrate or hydroxide, for example.
When the cation component as a catalytic in-gredient is added by ~ method other than the simultaneousimpregna~ion, it is preferably deposited on the carrier by drying it for 5 to 30 minutes with superheated steam at 110 to 200C. This operation enables the cation component to be uniformly dispersed in the carrier~
The carrier is preferably molded into the shape of a sphere, a pellet, a ring, etc~ having a size of about 3 to 10 mm. Preferably, it is composed mainly of alpha-alumina. The carrier further has a surface area of 0.6 to 2 m2/g, preferably 0.8 to 1.7 m~/g. The carrier advan-tageously has a water absorption of 20 to 50~, preferably 25 to 45%1 in order to retain strength and this specific surface area and facilitate the impregnating operation.
Pores having a size of less than 0.1 micrometer are un-desirable for production of ethylene oxide~ Good results cannot be obtained with average pore diameters of less than 0.9 micrometer, particularly less than 0.5 micro-meter. Too large an average pore diameter cannot give the required surface area. ~ence, the average pore diameter of the carrier used in the invention is preferably 0.9 to 3.5 micrometers, more preferably 1 to 3 micrometers.
The carrier contains 0.5 to 1 % by weight, preferably 1 to 12% by weigbt, more preferably 2 to 10% by weight, of silica. The inclusion of silica increases the strength of the carrier.
The silica content per m2/g of the surface area is considered to be one measure of the acid amount on the surface of the carrier. If it is too small, he acid amount on the surface is small, and the intended effect does not appearO On the other hand, if it is too large, it does not lead to an increase in the acid amount, but rather causes deleterious side effects such as the ~.~Vl;)5~
decrease of the surface area and strength of the carrier and the nonuniformity of the poresO ~enceJ it i5 advan-tageously 0.5 to 12, preferably 1 to 8, ~ by ~eight/m2/g~
There is no particular limitation on the content of sodium included initially in the c:arrier. It has been found however in accordance with thi~; invention that a carrier containing 0.08 to 2~ by weic~ht of sodium (as Na) in addition to silica and showing acidity that can be detected by an indica~or having a pKa of +4.8 is very effective for making a catalyst having high activity and high selectivity. Preferably, the sodium content of the carrier is 0.1 to 1.5% by weight, above all 0.12 to 1~ by weight as Na. It is disadvantageous to reduce the sodium content to 0.07~ by weight or less as described in Japanese Laid-Open Patent Publication No. 89843/1981.
The reaction of conver~ing ethylene into ethylene oxide with the catalyst of this invention can be carried out by a conventional operating method. Fo~
example, the reaction pressure is 1 to 35 kgJcm2, and the reaction temperature is 180 to 300C~ preferably 200 to 260C. Ethylene is used in an amount of 1 to 3Q% by volume, and oxygen, 1 to 20% by volume. Generally, the prese~ce of a predetermined amount, for example, up to 70 by volume, of a diluent such as methane is preferred.
Oxygen may be fed in the form of air or industrial oxygen.
By adding a reaction modifier such as ethylene dichloride, the formation of hot spots in the catalyst can be pre-vented and the performance of the catalyst, particularly its selectivity, can be greatly improved. The amount of the reaction modifier is preferably several to several tens of ppm~
The following Examples and Comparative ~xamples illustrate the present invention.
In each run, a catalyst was prepared by using an alpha-alumina carrier (a ring-like shape having a size of 13S~
8 0 x 3 0 x 8 ~; surface area 1 m2/g, pore volume 0.4 ml/g; average pore diameter 1.9 micrometers) having each of the different SiO2 and Na contents indicated in Table 1 by the following method.
Sodium carbonate ~13.2 9) was dissolved in 1 liter of water, and 1 kg of the carrier was immersed in it. The excess of the solution was removed from the carrier by dripping. The carrier was then dried for 15 minutes with superheated steam at 140C.
AgN03 (228 9) and 135 9 of potassium oxalate ~K2C204.H20) were dissolved each in 1 liter of water and then mixed~ The mixture was heated to 60C in a water bath to obtain a white precipitate of silver oxalate.
After filtration, the precipitate was washed with diso tilled water to remove potassium from it. Separately, 200 ml of an aqueous solukion was prepared by dissolving 19.8 g of 1,3-propanediamine and 72.2 g of ethylenediamine, and with ice cooling, added little by little to the silver oxalate precipitate to prepare a silver oxalate/amine complex solution. It was mixed with 40 ml of an aqueous solution containing 0.065 g of barium hydroxide and 0.720 g of cesium chloride. Water was added to adjust-the entire volume to 378 ml. The solution was then trans-ferred to a rotary evaporator. After impregnating ~a2~o3, all the previously prepared dry carrier was added. Im-pregnation was carried out at 50C while rotating the evaporator. In the early stage of the impregnating operation, the pressure was reduced to 100 mm~g, and 5 minutes after the pressure was returned to atmosp~eric pres~ure, the impregnated carrier was taken out. The carrier wa~ h ated with superheated steam at 200C for 10 minutes at a flow rate of 2 m/second to prepare a catalyst of this invention. The amounts of Ag, Na, Ba, Cs and Cl deposited were 12%, 0.2%, 50 ppm, 473 ppm and 126 ppm, respectively.
The catalyst so prepared was pulverized to a ~3q~ S~i si~e of 6 to 10 mesh, and 3 ml of it was charged in a steel reaction tube having an inside diameter of 7O5 mm.
A reaction gas composed of 30% by volume of ethylene, 8%
by volume of oxygen, 1.5 ppm of vinyl chloride and the balance being nitrogen was passed through the reaction tube under 18 kg/cm2-G at a SV o 4,000 h 1. The reaction temperature T40 (C, bath temperature) at which the con-version of oxygen became 40% after the lapse of one week and the selectivity S40 of ethylene oxide based on ethylene at the time when the conversion of oxygen reached 40% are shown in Table 1. It is seen from the t-~ble that the catalysts of the invention have higher activity and selectivity than the catalyst in the comparative e~ample which had a lower SiO2 content. It is also seen that the catalyst having an 5iO2 content o~ 12% ~Example 3) has sligh~ly inferior activity and selectivity to the cata-lysts having an SiO2 content of 3 and 6% ~Examples 1 and 2). X-ray di~fraotion analysis showed that only alpha-alumina crystals exist in the carrier of Comparative ~xample 1, but the carriers of Examples 1 to 3 contained Al~Si2O13 crystals exist in addition to alpha-alumina.
With Methyl Red having ~ pKa of +4.8, the carriers of Examples 1 to 3 showed an acidic color in toluene solvent; and by titration with n-butylamine, the 2S amount of acid on the carriers of Examples l to 3 was about 1 micromole~g. The carrier of Comparative Example 1, however, did not show an acidic color with the same dye. Carriers obtained by pre-impregnating the carriers used in the Examples with Na2CO3 and subsequent drying did 3~ not at all show an acidic color, and this clearly shows that the acid si~es of the carriers were masked by the deposition of sodium carbonate. It was found on the other hand that the deposition of sodium carbonate changed the color of Bromothy~ol Blue having a pKb of +7.1 and the carriers showed basicity (a carrier without Na deposited thereon had no basic site).
~3()q~5~
Table 1 _ _ Example SiO Silica Na T40 S~0 con~ent content content of the per sur- of the (&) ~%) carrier faoe area carrier (wt.~ ~ 6/m2~g) lwt.%~
_ _ _ .
1 3 3 ~.2~213 82.1 2 6 6 0.20213 81.9 3 12 12 ~.20217 81.6 OEx. 1 0.3 0~3 0.0~217.5 80.3 ~*) CEx.: Comparative Example.
A catalyst wa~ prepared by the following method using the carrier ~SiO2 content 3~ by weight, Na content 0.20% by weight) used in Example 1.
AgNO3 (217 g) and 129 g of potassium oxalate lR2C2O4.~2O) were eaah dissolved in 1 liter of water and then mixed. The mixture was heated to 6nc in a water bath to obtain a well crystallized precipitate of silver oxalate. After filtration, the precipitate was washed with distilled water to remove potassium f rom it. Separ-ately, 200 ml of an aqueous solution was prepared by dissolving 18.9 g of 1,3-propanediamine and 68.8 g of ethylenediamine, and with ice cooling, added little by little to the silver oxalate precipitate to prepar~ a silYer oxalate/amine complex solution. It was mixed with 40 ~1 of an aqueous solution containing 0.686 g of cesium chloride. Water was added to adjust the volume of the mixture to 400 ml. The mixture was then transferred to a rotary evaporator~ and 950:g of the carrier used in Example 1 ~not containing sodium carbonate deposited thereon) was added and impregnated at 50C while rotating the evaporator. In ~h~ early stage of ~he impregna~ing ~3~ 6 operation, the pressure was returned to 109 mm~g. Five minutes after the pressure was returned to atmospheric pressure, the impregnated carrier was transferred to a wire cage to remove the excess of the solution. Further-more, it was left to stand for 2 hours to re~ove thesolution, and then heated with superheated steam at 200C
for 10 minutes at a flow rate of 2 m/sec. The amounts of Ag, Cs and Cl deposited were 12~, 473 ppm and 126 ppm~
respectively. These values agreed with the amounts of these components deposited which had been calculated from the concentrations of Ag, Cs, Cl in the impregnating solution left after the above impregnation and the poro-sity of the catalyst.
The catalyst was pulverized to a size of 6 to 10 mesh, and used in the sa~ne reaction as in Example 1. T40 was 220C, and S40 was 81.2%.
A catalyst was prepared in the same way as in Example 1 except that barium was ~ot added. The amounts of Ag, Na, Cs and Cl deposited were 12%, 0.2%, 473 ppm and 126 ppm, respectively.
COMPARATIVE EXA~PLES 2-3 ..
Catalysts were prepa~ed in the same way as in Example 1 except that alpha-alumina carriers (a ring-like shape having a size of 8 0 x 3 0 x 8 mm; surface area 0.44 m2/g; pore volume 0.37 ml/g; average pore diameter 3.0 microme~ers) having different SiO2 contents and a ~urface area outside the scope of the invention were used, and the amounts of the cation componen~s charged were changed ~the amounts of the cation components charged were determined so as to give an optimum composition in these catalyst systems). The compositions of the catalysts are shown in Table 2.
Using the resulting catalysts, the same reaction as in Example 1 was carried out. The results are also xhown in Table 2. It is seen that the catalysts obtained 105l~i in these examples are inferior in activity and selectivity to the catalyst ob~ained in Example 1. Furthermorel in these catalyst systems, the effect of including SiO2 is not clearly seen.
. . . _ _ _ o ~ ~ oo 9! ~ ~ E; ' N
~ ~ r .~ ~ U) al ~ ;
~ ~ :
~ . ~ ..
~3(3~
Catalysts were prepared in the same way as in Example 1 except that alpha-alumina carriers ~a ring-like shape having a size of 8 0 x 3 0 x 8 mm; surface area 1 m2/g, pore volume 0.36 ml/g; average pore diameter 2.1 micrometers) having different SiO2 and Na conten~s in-dicated in Table 3 were used. The amounts of Ag, Na, Ba, Cs and Cl deposited were 12%, 0.2%, 50 ppm, 473 ppm and 126 ppm, respectively.
Each of the catalysts was pulverized to a size of 6 to 10 mesh, and filled in a steel reaction tube having an inside diameter of 3 ml. A reaction gas com-posed of 30% by volume of ethylene, 8.5% by volume of oxygen, 6~ by volume of carbon dioxide, 1.5 ppm.o vinyl chloride and the balance being nitrogen was pa~sed through the reaction tube under a pressure of 14.5 kg/cm -G at a : SV of 4,000 h 1 T40 and S40 are shown in Table 3. It is seen that the performances of the catalysts were nearly equivalents when the SiO2 content was 1 to 3% and th~ ~a content was 0.12 to 1~, but that when the SiO2 content was 0.6%, S40 was slightly lower.
A catalyst was prepared in the same way as-in Example 1 except that an alpha-alumina carrier having a SiO2 content of 0O3 ~by weight and a Na content of 0.26~
by weight (a ring-like shape having a size of 8 0 x 3 a x 8 mm; surface area 1 m2/g; pore volume 0.36 ml/g; average pore diameter 2.0 micrometers) was used. The amounts of Ag, ~a, Ba~ Cs and Cl deposited were 12%, 0 o2%~ 50 ppm, 473 ppm, and 126 ppm.
Using the catalyst, the same reaction as in Example 6 was carried out. The results are shown in Table 3. It is seen that the catalyst has higher activity, but much lower selectivity, than the catalyst of Example 8.
Catalysts were prepared in the same way as in 13~CJ58G
Example 1 except that alpha-alumina carriers ~a ring-like shape having a size of 8 0 x 3 0 x 8 mm; sur~ace area 1.3 m2/~; pore volume 0.4 ml~g; average pore diameter 1.5 micrometers; SiO2 content 3% by weight~ having different Na contents indicated in Table 4 were used. The amounts of Ag, Na, Ba, Cs and Cl deposited were 12%; 0.2%, 50 ppm, 473 ppm, and 126 ppm, respectively.
Using these catalysts, the same reaction as in Example 6 was carried out. The results are shown in Table 4. It is seen that the catalyst of Comparative Example 5 :: having a low Na content had much lower activity, and lower selectivity, than the catalyst of Example 10. The carrier used in Comparative Example 5 showed a stronger acidic color in toluene with Dimethyl Yellow having a pKa of +3.3 than the carrier used in Example 10. Although it is not entirely clear what brought about the difference in per-~ormance between the two catalysts, we assume that it is partly attributed to the difference in acidity between the carriers used.
Table 3 :
. Example Car ~ier T40 S40 SiONa content ~C) ~%) con2ent~wt.~) _ 6 0.6 ~.26 22579.5 7 1.5 0.12 22480.5 B 3 0.26 225~0.6 9 5.5 1.0 22580.2 CEx. 4 0.3 0.26 22077.7 ~3~5~
-- 16 ~
Table 4 __ _ _ _ Example Car rier T40 S40 SiONa content ~C) (~) con~en(wt . % ) _ , _ __ 3 O .35 21~ 8~ .3 CEx. 5 3 0.05 229 7903 . . . __
One aspect of the present invention provides a silver-deposited catalyst for production of ethylene oxide by oxidizing ethylene, comprising as catalyst ingredients silver and a cation component selected at least from sodium, potassium, rubidium and cesium, and a carrier composed mainly of alpha-alumina, the carrier having (1) a surface area of 0.6 to 2 m2/g, (2) a water absorption of 20 to 50%, (3~ a silica content of 0.5 to 12% by weight, ~4) a silica content, per m2/g of surface area, of 0.5 to 12, preferably 1 to 8, ~5) a sodium content of 0.08 to 2% by weight, (6) an acidity that can be detected by an indicator having a pKa of +4.8, and ~7) a crystal of S16Si2O13 which can be detected by X-ray diffraction analysis.
~3(~ 6 In a preferred embodiment, the cation component is composed of (A) sodium and (B~ at least one of potassium, rubidium and cesium.
In another preferred embodiment, ~he cation component is composed of IA) sodium, (B) at least one of potassium, rubidium and cesium and (C) barium.
In another preferred embodiment, the cation component has been deposited on the carrier from aqueous solution.
In yet another preferred embodiment, during production of the catalyst, silver and/or the cation component is impregnated in the carr:Ler and heat-treated in superheated steam at 130 to A second aspect of the present invention provides a process for producing the catalyst.
A third aspect of the present invention provides a method for production of ethylene oxide by oxidizing ethylene in the presence of the catalyst.
The reason for the hiyh performance of the catalyst of this invention is not entirely clear. It has been found that 1) X-ray diffraction shows that in the carrier used in this invention, A16Si2013 is for~ed besides alpha-Al203;
2) the carrier used in this invention has acidity that can be detected by an indicator having a pKa of t4.8 ~the acidity is measured in accordance with page 161 et seq. of Tanabe and Takeshita, "Acid Base Catalysts", published on Apri~ 26, 1966 by Sangyo Tosho K.K.); and 3) the acidity of the carrier disappears when Na2CO3 ~iL3~ 5~
3a 67566-1035 is deposited on it and basicity appears under which the color of Bromothymol Blue having pKb of ~7.0 is changed.
On the basis of these facts, it ls presumed that the carrier used in the catalyst of this inventi.on exhibits acidity which can be detected by an indicator haviny a p~a of ~4.8 as a result of containing silica, particularly silica and sodium in amounts within specified ranges, that the acidity is moderately controlled by the addition of the cation component as a catalysk ingredient, and that by the synergistic effect of these, the catalyst exhibits very hiyh performance.
The silver compound used to form silver as a catalytic ingredient in this invention may be any silver eompound which forms with an amine a complex soluble in an aqueous solvent and decomposes at a temperature of not more than 500C, preferably not more than 300C, more preferably not more than 260C, to deposit silver. Examples are silver oxide, silver nitrate, silver carbonate and silver carboxylates such as silver acetate and silver ~3(~S1~6 ~ 4 --oxalate. The amine as a complex-formin~ agent may be any amine which can solubilize the silver compound in an aqueous solvent. ~xamples are pyridine, acetonitrile, ammonia and amin s having 1 to 6 carbon atoms. Ammonia, pyridine, monoamines such as butylamine, alkanolamines such as ethanolamines, alkylenediamines having 2 to 4 carbon atoms, and polya~ines are preferred. Ethylene-diamine and l,3-propanediamine, particularly a mixture of both, are especially preferred.
lC For impregnation in the carrier, it is most practical to use the silver compound in the form of an aqueous amine solution. An aqueous solution containing an alcohol, for example, may also be used. The concentration o~ silver in the impregnating solution is selected so that 5 to 25% by weight of silver is deposited finally as a catalytic ingredient. The impregnating operation is carried out by an ordinary method. If required, pressure reduction, heating, spraying, etc. are also carried out.
The amine is added in an amount required to complex the silver compound (usually, two amino groups correspond to one silver ato~). Usually, it is sa~e to add it i~ an amount exceeding the~equivalent weight by 5 to 30%.
~ eat-treatment after the impregnation is carried out by selecting such a temperature and time as are re-quired to deposit silver on the carrier. It is mostdesirable to select such conditions as to allow silver to exist on the carrier a~ fine particles as uniformly as possible~ Generally, high temperatures and long periods of time are undesirable because they promote aggregation of the deposited silver particl~s. Preferably, calcina-tio~ is carried out for as short as S to 30 minutes by using air (or an inert gas such as nitrogen) heated at 120 to 300C or supe~heated steam. The calcination for a short period of time is also desirable since it shortens the time required ~or catalyst preparation. In parti-cular, the use of superheated steam is desirable as it ~3~15~j makes the distri~ution of silver on the carrier uniform.
The cation component as a catalytic ingredient is preferably added in the form of a compound soluble in an aqueous solvent in a soluble concentration. It may, however, remain partly insoluble. Examples of such com-pounds are inorganic salts such as nitrates, carbonates, bicarbonates, halides, hydroxides, nitrites and sulfates, and carboxylates such as formates. The halides as the cation component are preferably added so that 5 ppm to 10 Orl% by weight, preferably 7 ppm to 0.Q7% by weight, of a halogen such as chlorine, bromine or fluorine, particulary chlorine, is contained as a catalytic ingredient in the final catalyst. The cation component may be added to the silver impregnating solution and deposited (simultaneous impregnation). Or it may be impregnated before or a~ter deposition of the ~ilver. After-impregnation, however, is unsuitable in the case of sodium. An aqueous solution is preferred as the impregnating solution. The use of a solution containing an alcohol, for example, is not re-commendable from the standpoint of safety and simplifi-cation of process steps.
Sodium as a catalytic ingredient is preferably contained in an amount of 50 ppm to 1% by weight in the catalyst~ Its optimum amount varies depending upon the silica content. Advantageously, it is generally 500 to 4,000 ppm. It is especially preferred to apply it in the form of sodium carbonate or sodium bicarbonate.
The content of the alkali metal component selected from potassium, rubidium and cesium is preferably 10 to 2,000 ppm, particularly 75 to 30~ ppm for potassium, 160 to 650 ppm for rubidium and 250 to 1,000 ppm for cesium. Most preferably, the alkali metal component is i~pregnated si~ultaneously with the impregnation of the silver compound. Preferably, it is added partly or wholly as a halide such as a chloride, bromide or fluoride, particularly the chloride. Preferably, barium is added in ~3Q~
an amount o 30 to 1,000 ppm, preferably 40 to 650 ppm, to the catalyst. Suitably, it is added in the form of a nitrate or hydroxide, for example.
When the cation component as a catalytic in-gredient is added by ~ method other than the simultaneousimpregna~ion, it is preferably deposited on the carrier by drying it for 5 to 30 minutes with superheated steam at 110 to 200C. This operation enables the cation component to be uniformly dispersed in the carrier~
The carrier is preferably molded into the shape of a sphere, a pellet, a ring, etc~ having a size of about 3 to 10 mm. Preferably, it is composed mainly of alpha-alumina. The carrier further has a surface area of 0.6 to 2 m2/g, preferably 0.8 to 1.7 m~/g. The carrier advan-tageously has a water absorption of 20 to 50~, preferably 25 to 45%1 in order to retain strength and this specific surface area and facilitate the impregnating operation.
Pores having a size of less than 0.1 micrometer are un-desirable for production of ethylene oxide~ Good results cannot be obtained with average pore diameters of less than 0.9 micrometer, particularly less than 0.5 micro-meter. Too large an average pore diameter cannot give the required surface area. ~ence, the average pore diameter of the carrier used in the invention is preferably 0.9 to 3.5 micrometers, more preferably 1 to 3 micrometers.
The carrier contains 0.5 to 1 % by weight, preferably 1 to 12% by weigbt, more preferably 2 to 10% by weight, of silica. The inclusion of silica increases the strength of the carrier.
The silica content per m2/g of the surface area is considered to be one measure of the acid amount on the surface of the carrier. If it is too small, he acid amount on the surface is small, and the intended effect does not appearO On the other hand, if it is too large, it does not lead to an increase in the acid amount, but rather causes deleterious side effects such as the ~.~Vl;)5~
decrease of the surface area and strength of the carrier and the nonuniformity of the poresO ~enceJ it i5 advan-tageously 0.5 to 12, preferably 1 to 8, ~ by ~eight/m2/g~
There is no particular limitation on the content of sodium included initially in the c:arrier. It has been found however in accordance with thi~; invention that a carrier containing 0.08 to 2~ by weic~ht of sodium (as Na) in addition to silica and showing acidity that can be detected by an indica~or having a pKa of +4.8 is very effective for making a catalyst having high activity and high selectivity. Preferably, the sodium content of the carrier is 0.1 to 1.5% by weight, above all 0.12 to 1~ by weight as Na. It is disadvantageous to reduce the sodium content to 0.07~ by weight or less as described in Japanese Laid-Open Patent Publication No. 89843/1981.
The reaction of conver~ing ethylene into ethylene oxide with the catalyst of this invention can be carried out by a conventional operating method. Fo~
example, the reaction pressure is 1 to 35 kgJcm2, and the reaction temperature is 180 to 300C~ preferably 200 to 260C. Ethylene is used in an amount of 1 to 3Q% by volume, and oxygen, 1 to 20% by volume. Generally, the prese~ce of a predetermined amount, for example, up to 70 by volume, of a diluent such as methane is preferred.
Oxygen may be fed in the form of air or industrial oxygen.
By adding a reaction modifier such as ethylene dichloride, the formation of hot spots in the catalyst can be pre-vented and the performance of the catalyst, particularly its selectivity, can be greatly improved. The amount of the reaction modifier is preferably several to several tens of ppm~
The following Examples and Comparative ~xamples illustrate the present invention.
In each run, a catalyst was prepared by using an alpha-alumina carrier (a ring-like shape having a size of 13S~
8 0 x 3 0 x 8 ~; surface area 1 m2/g, pore volume 0.4 ml/g; average pore diameter 1.9 micrometers) having each of the different SiO2 and Na contents indicated in Table 1 by the following method.
Sodium carbonate ~13.2 9) was dissolved in 1 liter of water, and 1 kg of the carrier was immersed in it. The excess of the solution was removed from the carrier by dripping. The carrier was then dried for 15 minutes with superheated steam at 140C.
AgN03 (228 9) and 135 9 of potassium oxalate ~K2C204.H20) were dissolved each in 1 liter of water and then mixed~ The mixture was heated to 60C in a water bath to obtain a white precipitate of silver oxalate.
After filtration, the precipitate was washed with diso tilled water to remove potassium from it. Separately, 200 ml of an aqueous solukion was prepared by dissolving 19.8 g of 1,3-propanediamine and 72.2 g of ethylenediamine, and with ice cooling, added little by little to the silver oxalate precipitate to prepare a silver oxalate/amine complex solution. It was mixed with 40 ml of an aqueous solution containing 0.065 g of barium hydroxide and 0.720 g of cesium chloride. Water was added to adjust-the entire volume to 378 ml. The solution was then trans-ferred to a rotary evaporator. After impregnating ~a2~o3, all the previously prepared dry carrier was added. Im-pregnation was carried out at 50C while rotating the evaporator. In the early stage of the impregnating operation, the pressure was reduced to 100 mm~g, and 5 minutes after the pressure was returned to atmosp~eric pres~ure, the impregnated carrier was taken out. The carrier wa~ h ated with superheated steam at 200C for 10 minutes at a flow rate of 2 m/second to prepare a catalyst of this invention. The amounts of Ag, Na, Ba, Cs and Cl deposited were 12%, 0.2%, 50 ppm, 473 ppm and 126 ppm, respectively.
The catalyst so prepared was pulverized to a ~3q~ S~i si~e of 6 to 10 mesh, and 3 ml of it was charged in a steel reaction tube having an inside diameter of 7O5 mm.
A reaction gas composed of 30% by volume of ethylene, 8%
by volume of oxygen, 1.5 ppm of vinyl chloride and the balance being nitrogen was passed through the reaction tube under 18 kg/cm2-G at a SV o 4,000 h 1. The reaction temperature T40 (C, bath temperature) at which the con-version of oxygen became 40% after the lapse of one week and the selectivity S40 of ethylene oxide based on ethylene at the time when the conversion of oxygen reached 40% are shown in Table 1. It is seen from the t-~ble that the catalysts of the invention have higher activity and selectivity than the catalyst in the comparative e~ample which had a lower SiO2 content. It is also seen that the catalyst having an 5iO2 content o~ 12% ~Example 3) has sligh~ly inferior activity and selectivity to the cata-lysts having an SiO2 content of 3 and 6% ~Examples 1 and 2). X-ray di~fraotion analysis showed that only alpha-alumina crystals exist in the carrier of Comparative ~xample 1, but the carriers of Examples 1 to 3 contained Al~Si2O13 crystals exist in addition to alpha-alumina.
With Methyl Red having ~ pKa of +4.8, the carriers of Examples 1 to 3 showed an acidic color in toluene solvent; and by titration with n-butylamine, the 2S amount of acid on the carriers of Examples l to 3 was about 1 micromole~g. The carrier of Comparative Example 1, however, did not show an acidic color with the same dye. Carriers obtained by pre-impregnating the carriers used in the Examples with Na2CO3 and subsequent drying did 3~ not at all show an acidic color, and this clearly shows that the acid si~es of the carriers were masked by the deposition of sodium carbonate. It was found on the other hand that the deposition of sodium carbonate changed the color of Bromothy~ol Blue having a pKb of +7.1 and the carriers showed basicity (a carrier without Na deposited thereon had no basic site).
~3()q~5~
Table 1 _ _ Example SiO Silica Na T40 S~0 con~ent content content of the per sur- of the (&) ~%) carrier faoe area carrier (wt.~ ~ 6/m2~g) lwt.%~
_ _ _ .
1 3 3 ~.2~213 82.1 2 6 6 0.20213 81.9 3 12 12 ~.20217 81.6 OEx. 1 0.3 0~3 0.0~217.5 80.3 ~*) CEx.: Comparative Example.
A catalyst wa~ prepared by the following method using the carrier ~SiO2 content 3~ by weight, Na content 0.20% by weight) used in Example 1.
AgNO3 (217 g) and 129 g of potassium oxalate lR2C2O4.~2O) were eaah dissolved in 1 liter of water and then mixed. The mixture was heated to 6nc in a water bath to obtain a well crystallized precipitate of silver oxalate. After filtration, the precipitate was washed with distilled water to remove potassium f rom it. Separ-ately, 200 ml of an aqueous solution was prepared by dissolving 18.9 g of 1,3-propanediamine and 68.8 g of ethylenediamine, and with ice cooling, added little by little to the silver oxalate precipitate to prepar~ a silYer oxalate/amine complex solution. It was mixed with 40 ~1 of an aqueous solution containing 0.686 g of cesium chloride. Water was added to adjust the volume of the mixture to 400 ml. The mixture was then transferred to a rotary evaporator~ and 950:g of the carrier used in Example 1 ~not containing sodium carbonate deposited thereon) was added and impregnated at 50C while rotating the evaporator. In ~h~ early stage of ~he impregna~ing ~3~ 6 operation, the pressure was returned to 109 mm~g. Five minutes after the pressure was returned to atmospheric pressure, the impregnated carrier was transferred to a wire cage to remove the excess of the solution. Further-more, it was left to stand for 2 hours to re~ove thesolution, and then heated with superheated steam at 200C
for 10 minutes at a flow rate of 2 m/sec. The amounts of Ag, Cs and Cl deposited were 12~, 473 ppm and 126 ppm~
respectively. These values agreed with the amounts of these components deposited which had been calculated from the concentrations of Ag, Cs, Cl in the impregnating solution left after the above impregnation and the poro-sity of the catalyst.
The catalyst was pulverized to a size of 6 to 10 mesh, and used in the sa~ne reaction as in Example 1. T40 was 220C, and S40 was 81.2%.
A catalyst was prepared in the same way as in Example 1 except that barium was ~ot added. The amounts of Ag, Na, Cs and Cl deposited were 12%, 0.2%, 473 ppm and 126 ppm, respectively.
COMPARATIVE EXA~PLES 2-3 ..
Catalysts were prepa~ed in the same way as in Example 1 except that alpha-alumina carriers (a ring-like shape having a size of 8 0 x 3 0 x 8 mm; surface area 0.44 m2/g; pore volume 0.37 ml/g; average pore diameter 3.0 microme~ers) having different SiO2 contents and a ~urface area outside the scope of the invention were used, and the amounts of the cation componen~s charged were changed ~the amounts of the cation components charged were determined so as to give an optimum composition in these catalyst systems). The compositions of the catalysts are shown in Table 2.
Using the resulting catalysts, the same reaction as in Example 1 was carried out. The results are also xhown in Table 2. It is seen that the catalysts obtained 105l~i in these examples are inferior in activity and selectivity to the catalyst ob~ained in Example 1. Furthermorel in these catalyst systems, the effect of including SiO2 is not clearly seen.
. . . _ _ _ o ~ ~ oo 9! ~ ~ E; ' N
~ ~ r .~ ~ U) al ~ ;
~ ~ :
~ . ~ ..
~3(3~
Catalysts were prepared in the same way as in Example 1 except that alpha-alumina carriers ~a ring-like shape having a size of 8 0 x 3 0 x 8 mm; surface area 1 m2/g, pore volume 0.36 ml/g; average pore diameter 2.1 micrometers) having different SiO2 and Na conten~s in-dicated in Table 3 were used. The amounts of Ag, Na, Ba, Cs and Cl deposited were 12%, 0.2%, 50 ppm, 473 ppm and 126 ppm, respectively.
Each of the catalysts was pulverized to a size of 6 to 10 mesh, and filled in a steel reaction tube having an inside diameter of 3 ml. A reaction gas com-posed of 30% by volume of ethylene, 8.5% by volume of oxygen, 6~ by volume of carbon dioxide, 1.5 ppm.o vinyl chloride and the balance being nitrogen was pa~sed through the reaction tube under a pressure of 14.5 kg/cm -G at a : SV of 4,000 h 1 T40 and S40 are shown in Table 3. It is seen that the performances of the catalysts were nearly equivalents when the SiO2 content was 1 to 3% and th~ ~a content was 0.12 to 1~, but that when the SiO2 content was 0.6%, S40 was slightly lower.
A catalyst was prepared in the same way as-in Example 1 except that an alpha-alumina carrier having a SiO2 content of 0O3 ~by weight and a Na content of 0.26~
by weight (a ring-like shape having a size of 8 0 x 3 a x 8 mm; surface area 1 m2/g; pore volume 0.36 ml/g; average pore diameter 2.0 micrometers) was used. The amounts of Ag, ~a, Ba~ Cs and Cl deposited were 12%, 0 o2%~ 50 ppm, 473 ppm, and 126 ppm.
Using the catalyst, the same reaction as in Example 6 was carried out. The results are shown in Table 3. It is seen that the catalyst has higher activity, but much lower selectivity, than the catalyst of Example 8.
Catalysts were prepared in the same way as in 13~CJ58G
Example 1 except that alpha-alumina carriers ~a ring-like shape having a size of 8 0 x 3 0 x 8 mm; sur~ace area 1.3 m2/~; pore volume 0.4 ml~g; average pore diameter 1.5 micrometers; SiO2 content 3% by weight~ having different Na contents indicated in Table 4 were used. The amounts of Ag, Na, Ba, Cs and Cl deposited were 12%; 0.2%, 50 ppm, 473 ppm, and 126 ppm, respectively.
Using these catalysts, the same reaction as in Example 6 was carried out. The results are shown in Table 4. It is seen that the catalyst of Comparative Example 5 :: having a low Na content had much lower activity, and lower selectivity, than the catalyst of Example 10. The carrier used in Comparative Example 5 showed a stronger acidic color in toluene with Dimethyl Yellow having a pKa of +3.3 than the carrier used in Example 10. Although it is not entirely clear what brought about the difference in per-~ormance between the two catalysts, we assume that it is partly attributed to the difference in acidity between the carriers used.
Table 3 :
. Example Car ~ier T40 S40 SiONa content ~C) ~%) con2ent~wt.~) _ 6 0.6 ~.26 22579.5 7 1.5 0.12 22480.5 B 3 0.26 225~0.6 9 5.5 1.0 22580.2 CEx. 4 0.3 0.26 22077.7 ~3~5~
-- 16 ~
Table 4 __ _ _ _ Example Car rier T40 S40 SiONa content ~C) (~) con~en(wt . % ) _ , _ __ 3 O .35 21~ 8~ .3 CEx. 5 3 0.05 229 7903 . . . __
Claims (12)
1. A silver-deposited catalyst for production of ethylene oxide by oxidizing ethylene, the catalyst comprising as catalyst ingredients silver and a cation component selected at least from sodium, potassium, rubidium and cesium, and a carrier composed mainly of alpha-alumina, the carrier having:
(1) a surface area of 0.6 to 2 m2/g, (2) a water absorption of 20 to 50%, (3) a silica content of 0.5 to 12% by weight, (4) a silica content, per m2/g of surface area, of 0.5 to 12, (5) a sodium content of 0.08 to 2% by weight, (6) an acidity that can be detected by an indicator having a pKa of +4.8, and (7) a crystal of Al6Si2O13, which can be detected by X-ray diffraction analysis.
(1) a surface area of 0.6 to 2 m2/g, (2) a water absorption of 20 to 50%, (3) a silica content of 0.5 to 12% by weight, (4) a silica content, per m2/g of surface area, of 0.5 to 12, (5) a sodium content of 0.08 to 2% by weight, (6) an acidity that can be detected by an indicator having a pKa of +4.8, and (7) a crystal of Al6Si2O13, which can be detected by X-ray diffraction analysis.
2. The catalyst of claim 1 wherein the cation component is composed of (A) sodium and (B) at least one of potassium, rubidium and cesium.
3. The catalyst of claim 1 wherein the cation component is composed of (A) sodium, (B) at least one of potassium, rubidium and cesium and (C) barium.
4. The catalyst of claim 1 wherein the cation component has been deposited on the carrier from aqueous solution.
5. The catalyst of claim 1 wherein during production of the catalyst, silver or the cation component or both are impregnated in the carrier and heat-treated in superheated steam at 130 to 300°C.
6. The catalyst of any one of claims 1 to 5 wherein the carrier has a surface area of 0.8 to 1.7 m2/g.
7. The catalyst of any one of claims 1 to 5, wherein the carrier has an average pore diameter of 0.9 to 3.5 micrometers.
8. The catalyst of any one of claims 1 to 5 wherein the carrier has an average pore diameter of 0.9 to 3.5 micrometers, a silica (SiO2) content of 1 to 12% by weight and a sodium content (as Na) of 0.1 to 1.5% by weight.
9. A process for producing the catalyst as defined in any one of claims 1 to 5, which comprises:
impregnating the carrier with an aqueous solvent that contains (1) a silver-amine complex dissolved in the solvent, the complex being capable of decomposing at a temperature not more than 500°C to deposit silver and (2) the cation component in the form of a compound at least partially dissolved in the solvent, and heating the so-impregnated carrier at a temperature for a period of time sufficient to decompose the silver-amine complex and to deposit silver on the carrier.
impregnating the carrier with an aqueous solvent that contains (1) a silver-amine complex dissolved in the solvent, the complex being capable of decomposing at a temperature not more than 500°C to deposit silver and (2) the cation component in the form of a compound at least partially dissolved in the solvent, and heating the so-impregnated carrier at a temperature for a period of time sufficient to decompose the silver-amine complex and to deposit silver on the carrier.
10. The process according to claim 9, wherein the heating is carried out at a temperature of 120 to 300°C using air or superheated steam.
11. A method for production of ethylene oxide, which comprises oxidizing ethylene with oxygen in the presence of the catalyst as defined in any one of claims 1 to 5.
12. The method according to claim 11, wherein the reaction is carried out at a pressure of 1 to 35 kg/cm2 and a temperature of 180 to 300°C using a gaseous mixture comprising 1 to 30% by volume of ethylene, 1 to 20% by volume of oxygen and up to 70% by volume of diluent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP104,950/86 | 1986-05-09 | ||
| JP10495086 | 1986-05-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1300586C true CA1300586C (en) | 1992-05-12 |
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ID=14394375
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000536568A Expired - Lifetime CA1300586C (en) | 1986-05-09 | 1987-05-07 | Silver-deposited catalyst for production of ethylene oxide |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4812437A (en) |
| EP (1) | EP0247414B2 (en) |
| JP (1) | JPH084745B2 (en) |
| CA (1) | CA1300586C (en) |
| DE (1) | DE3773995D1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2277622A1 (en) | 2003-10-16 | 2011-01-26 | Dow Technology Investments LLC | Method for the preparation of catalysts having enhanced stability, efficiency and/or activity for alkylene oxide production |
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| US5057481A (en) * | 1987-02-20 | 1991-10-15 | Union Carbide Chemicals And Plastics Technology Corporation | Catalyst composition for oxidation of ethylene to ethylene oxide |
| US4908343A (en) * | 1987-02-20 | 1990-03-13 | Union Carbide Chemicals And Plastics Company Inc. | Catalyst composition for oxidation of ethylene to ethylene oxide |
| CN1009437B (en) * | 1988-02-03 | 1990-09-05 | 中国石油化工总公司 | High-efficiency silver catalyst for oxidizing ethylene into epoxy ethane |
| JP2637537B2 (en) * | 1989-01-24 | 1997-08-06 | 株式会社日本触媒 | Silver catalyst for producing ethylene oxide and method for producing the same |
| CA1337722C (en) * | 1989-04-18 | 1995-12-12 | Madan Mohan Bhasin | Alkylene oxide catalysts having enhanced activity and/or stability |
| US5187140A (en) * | 1989-10-18 | 1993-02-16 | Union Carbide Chemicals & Plastics Technology Corporation | Alkylene oxide catalysts containing high silver content |
| US5145824A (en) * | 1991-01-22 | 1992-09-08 | Shell Oil Company | Ethylene oxide catalyst |
| DE4106508A1 (en) * | 1991-03-01 | 1992-09-03 | Basf Ag | SILVER CATALYST |
| CA2089510C (en) * | 1992-02-27 | 1998-09-01 | Shinichi Nagase | Silver catalyst for production of ethylene oxide and method for production of the catalyst |
| ES2157987T3 (en) * | 1993-08-23 | 2001-09-01 | Shell Int Research | CATALYST FOR OBTAINING ETHYLENE OXIDE. |
| EP1002575B1 (en) | 1998-11-17 | 2005-03-30 | Nippon Shokubai Co., Ltd. | Catalyst carrier for use in production of ethylene oxide |
| US6908879B1 (en) | 1999-09-06 | 2005-06-21 | Nippon Shokubai Co., Ltd. | Ceramic article, carrier for catalyst, methods for production thereof, catalyst for producing ethylene oxide using the carrier, and method for producing ethylene oxide |
| ZA200200049B (en) * | 2001-01-25 | 2002-07-16 | Nippon Catalytic Chem Ind | Fixed-bed shell-and-tube reactor and its usage. |
| JP4726349B2 (en) * | 2001-08-03 | 2011-07-20 | 株式会社日本触媒 | Catalyst for producing ethylene oxide, method for producing the same, and method for producing ethylene oxide using the catalyst |
| US6831037B2 (en) * | 2002-02-25 | 2004-12-14 | Saint-Gobain Norpro Corporation | Catalyst carriers |
| US6750173B2 (en) | 2002-04-08 | 2004-06-15 | Scientific Design Company, Inc. | Ethylene oxide catalyst |
| US6846774B2 (en) | 2003-04-23 | 2005-01-25 | Scientific Design Co., Inc. | Ethylene oxide catalyst |
| EP1890807B1 (en) | 2005-06-07 | 2019-04-03 | Shell International Research Maatschappij B.V. | A catalyst, a process for preparing the catalyst, and a process for the production of an olefin oxide, a 1,2-diol, a 1,2-diol ether, or an alkanolamine |
| EP1901842B8 (en) * | 2005-06-07 | 2019-10-30 | Saint-Gobain Ceramics & Plastics, Inc. | A catalyst carrier |
| JP4978277B2 (en) * | 2006-04-10 | 2012-07-18 | 三菱化学株式会社 | Catalyst for producing ethylene oxide, method for producing the same, and method for producing ethylene oxide |
| CN101360562B (en) * | 2006-04-10 | 2013-02-06 | 三菱化学株式会社 | Catalyst for ethylene oxide production, method for producing the same, and method for producing ethylene oxide |
| WO2007116585A1 (en) | 2006-04-10 | 2007-10-18 | Mitsubishi Chemical Corporation | Catalyst for ethylene oxide production, method for producing the same, and method for producing ethylene oxide |
| JPWO2010001732A1 (en) | 2008-06-30 | 2011-12-15 | 株式会社日本触媒 | Packing method of solid particles in fixed bed multitubular reactor |
| JP5258485B2 (en) * | 2008-09-30 | 2013-08-07 | 株式会社日本触媒 | Catalyst for producing ethylene oxide and method for producing ethylene oxide using the catalyst |
| JP2011121048A (en) * | 2009-12-09 | 2011-06-23 | Rohm & Haas Co | Method for blending and loading solid catalyst material into tubular structure |
| JP5984593B2 (en) * | 2011-09-30 | 2016-09-06 | 株式会社日本触媒 | Catalyst for producing ethylene oxide and method for producing ethylene oxide using the same |
| US9162215B2 (en) | 2011-10-31 | 2015-10-20 | Dow Technology Investments Llc | Methods for producing epoxidation catalysts and epoxidation methods utilizing these |
| CN104759279B (en) * | 2014-01-03 | 2017-09-26 | 中国石油化工股份有限公司 | A kind of alkene epoxidation silver catalyst and preparation method thereof |
| JP7269174B2 (en) | 2017-01-05 | 2023-05-08 | サイエンティフィック・デザイン・カンパニー・インコーポレーテッド | Carrier, catalyst, method for producing them, and method for producing ethylene oxide |
| WO2019245859A1 (en) | 2018-06-21 | 2019-12-26 | The J. David Gladstone Institutes | Generation of a population of hindbrain cells and hindbrain-like organoids from pluripotent stem cells |
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| US4207210A (en) * | 1973-10-26 | 1980-06-10 | Shell Oil Company | Process for preparing an ethylene oxide catalyst |
| EP0002045B1 (en) * | 1977-11-19 | 1981-09-02 | BASF Aktiengesellschaft | Process for preparing an ethylene oxide catalyst |
| DE2925625C2 (en) * | 1979-06-26 | 1981-10-01 | Chemische Werke Hüls AG, 4370 Marl | Process for increasing the activity and for extending the service life with high selectivity of silver-supported catalysts for use in the synthesis of ethylene oxide |
| US4419276A (en) * | 1981-09-30 | 1983-12-06 | Union Carbide Corporation | Silver catalyst for the manufacture of ethylene oxide and a process for preparing the catalyst |
| DE3310685A1 (en) * | 1982-07-24 | 1984-02-09 | Hoechst Ag, 6230 Frankfurt | SILVER CATALYSTS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF ETHYLENE OXIDE |
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1987
- 1987-05-01 JP JP62108099A patent/JPH084745B2/en not_active Expired - Lifetime
- 1987-05-05 US US07/046,177 patent/US4812437A/en not_active Expired - Lifetime
- 1987-05-07 CA CA000536568A patent/CA1300586C/en not_active Expired - Lifetime
- 1987-05-08 DE DE8787106704T patent/DE3773995D1/en not_active Expired - Lifetime
- 1987-05-08 EP EP87106704A patent/EP0247414B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2277622A1 (en) | 2003-10-16 | 2011-01-26 | Dow Technology Investments LLC | Method for the preparation of catalysts having enhanced stability, efficiency and/or activity for alkylene oxide production |
| US8513156B2 (en) | 2003-10-16 | 2013-08-20 | Dow Technology Investments Llc | Catalysts having enhanced stability, efficiency and/or activity for alkylene oxide production |
| US8765630B2 (en) | 2003-10-16 | 2014-07-01 | Dow Technology Investments Llc | Catalysts having enhanced stability, efficiency and/or activity for alkylene oxide production |
Also Published As
| Publication number | Publication date |
|---|---|
| US4812437A (en) | 1989-03-14 |
| JPH084745B2 (en) | 1996-01-24 |
| JPS63116743A (en) | 1988-05-21 |
| EP0247414B2 (en) | 1996-07-03 |
| EP0247414B1 (en) | 1991-10-23 |
| DE3773995D1 (en) | 1991-11-28 |
| EP0247414A2 (en) | 1987-12-02 |
| EP0247414A3 (en) | 1989-05-31 |
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