CN110357836B - Ethylene oxide production method - Google Patents

Ethylene oxide production method Download PDF

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CN110357836B
CN110357836B CN201810252748.9A CN201810252748A CN110357836B CN 110357836 B CN110357836 B CN 110357836B CN 201810252748 A CN201810252748 A CN 201810252748A CN 110357836 B CN110357836 B CN 110357836B
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reaction
preset value
silver catalyst
catalyst
ethylene oxide
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CN110357836A (en
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蒋军
代武军
林伟
李旻旭
蒋文贞
薛茜
王淑娟
汤之强
李金兵
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • 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

Abstract

The invention belongs to the field of catalysts, and particularly relates to a method for producing ethylene oxide, which comprises the following steps: (1) the reaction gas containing ethylene and oxygen is contacted with a silver catalyst for reaction under the conventional ethylene epoxidation reaction condition; (2) when the selectivity of the catalyst is lower than a first preset value, the reaction conditions are adjusted to ensure that the space velocity is 6000-10000h‑1The space-time yield is 270-450Kg EO/h/m3-cat, continuing the reaction; (3) when the selectivity of the catalyst is higher than a second preset value, the conventional ethylene epoxidation reaction condition is recovered, and the reaction is continued; (4) optionally repeating steps (2) - (3); the second preset value is higher than the first preset value. The method of the invention can improve the selectivity of the silver catalyst, in particular the silver catalyst containing rhenium with large specific surface area, so that the silver catalyst has better application prospect and improves the economical efficiency of the production of the ethylene oxide.

Description

Ethylene oxide production method
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a method for producing ethylene oxide.
Background
Ethylene oxide is an important petrochemical product and an organic synthesis intermediate, is mainly produced by ethylene gas-solid phase catalytic epoxidation reaction at present, and is an alpha-alumina supported metal silver catalyst. As an important petrochemical catalyst, silver catalysts have been the only effective catalyst for ethylene epoxidation to ethylene oxide.
In a gas-solid phase ethylene catalytic epoxidation reaction system, the main reaction is (1) the reaction of selective oxidation of ethylene to Ethylene Oxide (EO), and the main side reactions are (2) the reaction of complete oxidation of ethylene to carbon dioxide and water and (3) the reaction of deep (complete) oxidation of EO to carbon dioxide and water; all three reactions are irreversible exothermic reactions. EO is the target product of the reaction system, and the selectivity of EO generation largely determines the economy of the whole production process, so that the development of silver catalysts with higher selectivity is the main direction of research. At present, the highest selectivity of ethylene catalytic epoxidation reaction reaches about 90%, and the used silver catalyst mainly has two types: (1) a rhenium-containing silver catalyst; (2) a rhenium-free silver catalyst with a nitrogen oxide gas promoter added.
The catalyst system added with the nitrogen oxide gas auxiliary agent and not containing rhenium and silver produces more byproducts due to the introduction of the gas auxiliary agent, and has the main defect that the treatment process is complex after the reaction, so that the economical efficiency is reduced. Compared with the prior art, the rhenium-containing silver catalyst can achieve the highest selectivity of about 90 percent, and the reaction process and subsequent treatment are simpler, so the rhenium-containing silver catalyst is widely applied in industry.
As the ethylene epoxidation reaction system is a strong exothermic reaction, in order to avoid the reduction of the EO generation selectivity in the transfer process (mass transfer and heat transfer process), the industrial silver catalyst should be selected with a specific surface area of 1.0m2Alpha-alumina carrier with low specific surface area of about/g for supporting metallic silver ((1) Gates B.C. catalytic Chemistry, New York: John Wiley&Sons,Inc.1992:392-396；(2)Mao C F,Vannice M A.High surface area α-aluminas III.Oxidation of ethylene,ethylene oxide,and acetaldehyde over silver dispersed on high surface areaα-alumina[J]Applied Catalysis A: General,1995,122(122): 61-76). The specific surface area of the industrial silver catalyst and the carrier is mostly not higher than 1.6m2/g。
When the specific surface areas of the carrier and the silver catalyst are larger, the silver catalyst shows the phenomena of higher activity and lower selectivity due to smaller sizes of the pore passages in the catalyst and the loaded metal silver particles, so that the ethylene material consumption is high, the economical efficiency of EO production is reduced, and the application of the catalyst is limited. This problem is also present with rhenium-containing highly selective silver catalysts.
Therefore, how to increase the specific surface area (especially, the specific surface area is more than or equal to 2.0 m)2Above/g) selectivity of rhenium-containing silver catalysts is an important technical problem. Has important significance for improving the economy of EO production.
Disclosure of Invention
Based on the above-mentioned prior art circumstances, the inventors of the present invention have found, through extensive experimental studies, that the selectivity of a silver catalyst, particularly a rhenium-containing silver catalyst having a large specific surface area, can be improved by regulating the reaction process conditions, thereby finding a practical and practical method for producing EO.
Specifically, the invention provides an ethylene oxide production method, which comprises the following steps:
(1) the reaction gas containing ethylene and oxygen is contacted with a silver catalyst for reaction under the conventional ethylene epoxidation reaction condition;
(2) when the selectivity of the catalyst is lower than a first preset value, the reaction conditions are adjusted to ensure that the space velocity is 6000-10000h-1The space-time yield is 270-450Kg EO/h/m3Cat, preferably 290 and 420Kg of EO/h/m3-cat, continuing the reaction;
(3) when the selectivity of the catalyst is higher than a second preset value, the conventional ethylene epoxidation reaction condition is recovered, and the reaction is continued;
(4) optionally repeating steps (2) - (3);
the second preset value is higher than the first preset value.
According to the process of the present invention, space velocity and space-time yield are increased at lower catalyst selectivity, and the catalyst selectivity is improved by recovering the conventional ethylene epoxidation reaction conditions after the catalyst selectivity is increased, and performing the reaction once or more. Wherein the above effects can be achieved by increasing the space velocity and space-time yield at lower catalyst selectivity and by restoring the conventional ethylene epoxidation reaction conditions at higher catalyst selectivity. Therefore, the first preset value and the second preset value of the catalyst selectivity can be set as required as long as the second preset value is higher than the first preset value.
In actual industrial production, in order to obtain ideal catalyst selectivity and save energy and reduce consumption as much as possible, the first preset value and the second preset value preferably have a certain large difference, preferably, the catalyst selectivity is calculated by percentage, and the second preset value is higher than the first preset value by more than one percentage point, preferably, the second preset value is higher than the first preset value by more than two percentage points.
Particularly preferably, the first preset value is 82% -86%, and the second preset value is 84% -92%; further preferably, the first preset value is 83% -85%, and the second preset value is 86% -92%.
In the invention, the method for measuring the selectivity of the catalyst comprises the following steps: under certain technological conditions, when the reaction is stabilized and the set reaction conditions are reached, the gas compositions at the inlet and the outlet of the reactor are continuously measured. The measurement results were corrected for volume shrinkage, and the selectivity (S) was calculated according to the following formula:
Figure BDA0001608215830000031
wherein, Delta EO is the concentration difference of ethylene oxide in outlet gas and inlet gas of the reactor, Delta CO2Is the difference in carbon dioxide concentration between the outlet gas and the inlet gas of the reactor. Multiple (e.g., more than ten) sets of reaction data are taken each day, and the average is taken as the reaction temperature and selectivity data for that day.
The method of the present invention is not limited to the above-described method of calculating selectivity. The first preset value and the second preset value can be calculated in a unified mode.
In the method of the present invention, the steps (2) - (3) can be repeated and the number of repetitions can be determined according to actual needs. When repeating steps (2) - (3), the repeated first preset value is the same as or different from the previous first preset value; the repeated second preset value is the same as or different from the previous second preset value. The first preset value and the second preset value can be flexibly determined according to actual needs, as long as the second preset value is higher than the first preset value or the difference value is preferably met.
The time for the contact reaction in step (1) is not particularly limited in the present invention, and may even be 0, that is, the reaction is carried out at a high space velocity and space-time yield from the beginning, and depending on the specific production situation, the time for the contact reaction in step (1) may be generally 0 to 200 days, preferably 0.1 to 130 days, and in one embodiment, preferably 3 to 40 days; the reaction may be continued in step (2) for a period of 5 to 150 days, and in one embodiment, the reaction is continued for a period of preferably 7 to 60 days. The method of the invention can select to adjust the reaction within the time, and the specific adjusting time point can be determined according to the standard and combined with the actual production requirement.
According to the present invention, the conventional ethylene epoxidation reaction conditions may be various conventional ethylene epoxidation reaction conditions in the art, and generally, the conventional ethylene epoxidation reaction conditions include: the reaction temperature is 200-280 ℃, the system pressure is 1-3MPa, and the space velocity is 2500-6000h-1The space-time yield is 145-260Kg EO/h/m3-cat。
The composition of the reaction gas in the process of the present invention is not particularly limited, and may be a composition conventional in the art, and generally, the ethylene content of the reaction gas is 10 vol% to 40 vol% and the oxygen content is 5 vol% to 10 vol%, based on the total volume of the reaction gas. In addition, the reaction gas may also contain carbon dioxide, an inhibitor, typically a chlorinated alkane, and an equilibrium gas, typically nitrogen. In the reaction gas, the content of carbon dioxide can be 0mol percent to 2.0mol percent, the content of inhibitor can be 0.2 ppmv to 2.0ppmv, and the balance gas is used.
According to the present invention, in step (3), when both the space-time yield and the space velocity need to be reduced, said reversion to conventional ethylene epoxidation reaction conditions is preferably effected stepwise: the space-time yield is reduced (preferably by reducing the EO concentration) and then the space velocity. Thereby improving the operation safety and reducing the temperature runaway phenomenon caused by the heat effect.
In the context of the present invention, increasing or decreasing the space-time yield is preferably achieved by adjusting the outlet EO concentration.
The restoration to the conventional ethylene epoxidation reaction conditions in step (3) does not mean the restoration to the conditions consistent with step (1), as long as the restoration is within the range of the conventional ethylene epoxidation reaction conditions.
The method of the invention is suitable for various silver catalysts, and is especially suitable for large specific surface (more than or equal to 2.0 m)2A/g) silver catalyst, is particularly suitable for large specific surface (more than or equal to 2.0 m)2A/g), high rhenium element content silver catalyst, can significantly improve the selectivity of such catalysts.
Particularly preferably, the silver catalyst comprises an alpha-alumina carrier and silver loaded on the carrier, and an alkali metal, an alkaline earth metal, a rhenium promoter and an optional rhenium synergistic promoter; the content of rhenium element is 300-2000ppmw, preferably 400-1800ppmw, further preferably 500-1500ppmw, and more preferably 600-1200ppmw based on the total weight of the silver catalyst; the specific surface area of the silver catalyst is 2.0-4.0m2A/g, preferably from 2.1 to 3.5m2/g。
Further, the silver catalyst also preferably has at least one of the following characteristics:
-the silver catalyst has an average pore diameter of 0.5-3.0 μm, preferably 0.6-2.0 μm;
-the silver content is from 10 to 40 wt%, based on the total weight of the silver catalyst;
-the alkali metal is selected from at least one of lithium, sodium, potassium, rubidium and cesium in an amount of 10-2000ppmw, preferably 100-1600ppmw, based on the total weight of the silver catalyst;
-said alkaline earth metal is selected from at least one of magnesium, calcium, strontium and barium in an amount of from 10 to 10000ppmw, preferably from 10 to 4000ppmw, based on the total weight of the silver catalyst;
-said rhenium co-promoter is selected from at least one of boron, fluorine, sulphur, cerium, chromium, molybdenum, tungsten, titanium, zirconium, cobalt, nickel, copper and zinc in an amount of from 10 to 2000ppmw, preferably from 20 to 1500ppmw, based on the total weight of the silver catalyst.
The content of each metal component of the catalyst is calculated by metal elements.
The above catalysts are commercially available or may be prepared by methods conventional in the art. The preparation method comprises the following steps: soaking an alpha-alumina carrier in a solution of a silver compound, an organic amine compound and an auxiliary agent, and then filtering and activating heat treatment to prepare the catalyst; the promoter includes an alkali metal, an alkaline earth metal, a rhenium promoter, and optionally a rhenium co-promoter. Wherein, the rhenium auxiliary agent is soluble rhenium salt, preferably potassium perrhenate and/or ammonium perrhenate.
The method of the invention can improve the selectivity of the silver catalyst, in particular the silver catalyst containing rhenium with large specific surface area, so that the silver catalyst has better application prospect and improves the economical efficiency of the production of the ethylene oxide.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below.
In the following examples and comparative examples, the evaluation of catalytic reaction performance was carried out in a microreactor of stainless steel tubular type having an inner diameter of about 4mm and filled with 1mL of 12 to 22 mesh crushed and sieved catalyst. During the reaction, a certain amount of reaction gas passes through a heated reactor, the gas composition of the raw material gas and the reaction tail gas is analyzed by mass spectrometry in a quantitative mode, the content of a target product EO is taken as a target, and the temperature of a heating furnace is controlled in a cascade mode.
In the following examples and comparative examples, conventional reaction conditions include:
Figure BDA0001608215830000061
composition of reaction gas (mol%):
Figure BDA0001608215830000062
under certain technological conditions, when the reaction is stabilized and the set reaction conditions are reached, the gas compositions at the inlet and the outlet of the reactor are continuously measured. The measurement results were corrected for volume shrinkage, and the selectivity (S) was calculated according to the following formula:
Figure BDA0001608215830000063
wherein, Delta EO is the concentration difference of ethylene oxide in outlet gas and inlet gas of the reactor, Delta CO2Is the difference in carbon dioxide concentration between the outlet gas and the inlet gas of the reactor. More than ten groups of reaction data are selected every day, and the average value is taken as the reaction temperature and selectivity data of the day.
In the following examples and comparative examples, the specific surface area (S) of the catalystBET) The average pore diameter of the catalyst is 4V/S determined by a standard nitrogen physical adsorption BET methodBETCalculated (V is the pore volume, mercury intrusion method). The content of silver in the catalyst is determined by X-ray fluorescence analysis (XRF), and the content of other elements is determined by inductively coupled plasma atomic emission spectrometry (ICP-AES).
The silver catalyst can be prepared by the following conventional preparation method of the silver catalyst:
(1) adding a certain amount of ethylenediamine and/or ethanolamine and deionized water into a glass flask with a stirrer to obtain a mixed solution; slowly adding a certain amount of powdery silver oxalate into the mixed solution while stirring, and keeping the temperature of the solution at 0-15 ℃ to completely dissolve the silver oxalate. Adding cesium, strontium, rhenium and a synergistic additive of one or more rhenium selected from boron, fluorine, sulfur, cerium, chromium, molybdenum, tungsten, titanium, zirconium, cobalt, nickel, copper and zinc, and uniformly mixing the obtained solution to obtain a silver-containing impregnation solution;
(2) taking a certain amount of porous alpha-alumina carrier (specific surface area is 1.8-3.5 m)2/g) immersing in the solution obtained aboveSoaking for 30min under the condition of vacuum pumping;
(3) the excess solution was leached off and thermally decomposed in a stream of air at 250 ℃ for 5 min.
Repeating the steps (1) to (3) to obtain the silver catalyst with required component content.
Comparative example 1
1mL (about 0.8g) of the silver catalyst CAT1 was weighed and charged into a microreactor having an inner diameter of 0.4mm, and the catalytic reaction was carried out under conventional reaction conditions by using the reaction procedures shown in Table 1. The results of the catalytic reaction performance evaluation are shown in Table 1.
The silver catalyst CAT1 is an alpha-alumina carrier supported silver catalyst, and is based on the total weight of the silver catalyst CAT1, wherein the silver content is 35 wt%, the rhenium content is 660ppmw, the cesium content is 360ppmw, the alkaline earth metal content is 2300ppmw, the titanium content is 260ppmw, and the specific surface area of the catalyst is 2.1m2(iv)/g, average pore diameter 1.30. mu.m.
Example 1
The silver catalyst CAT1 described in comparative example 1 was used to perform catalytic reaction under the same reaction conditions and reaction gas compositions as in comparative example 1, using the reaction process shown in Table 1, and the evaluation results of catalytic reaction performance are shown in Table 1.
TABLE 1
Figure BDA0001608215830000081
As can be seen from Table 1, by using the reaction process of the present invention, example 1 exhibited a selectivity as high as 88.5% compared to comparative example 1, and the selectivity remained above 88% after 180 days of reduced space velocity.
Example 2
1mL (0.80g) of the silver catalyst CAT2 was weighed and charged into a microreactor having an inner diameter of 0.4mm, and the catalytic reaction was carried out by the reaction process shown in Table 2. The results of the reaction property evaluations are shown in Table 2.
The silver catalyst CAT2 is an alpha-alumina carrier supported silver catalyst, and the total weight of the silver catalyst CAT2 is used as a reference, wherein the metallic silver containsIn an amount of 36 wt%, a rhenium content of 386ppmw, an alkali metal cesium content of 520ppmw, an alkaline earth metal content of 2060ppmw, a nickel content of 310ppmw, and a specific surface area of 3.1m2In terms of a/g, the average pore diameter was 0.65. mu.m.
Comparative example 2
The silver catalyst CAT2 of example 2 was used to catalyze the reaction under the same reaction conditions and reaction gas compositions as those of example 2 by the reaction process shown in table 2, and the results of the evaluation of the reaction properties are shown in table 2.
Example 3
1mL (0.80g) of the silver catalyst CAT3 was weighed and charged into a microreactor having an inner diameter of 0.4mm, and a catalytic reaction was carried out by the reaction process shown in Table 2, and the other reaction conditions and the reaction gas composition were the same as those in example 2.
The silver catalyst CAT3 is an alpha-alumina carrier supported silver catalyst, and is based on the total weight of the silver catalyst CAT3, wherein the content of metallic silver is 36.1 wt%, the content of rhenium is 722ppmw, the content of alkali metal cesium is 560ppmw, the content of alkaline earth metal is 2430ppmw, the content of nickel is 321ppmw, and the specific surface area of the silver catalyst is 3.2m2In terms of a/g, the average pore diameter was 0.62. mu.m. The results of the reaction property evaluations are shown in Table 2.
TABLE 2
Figure BDA0001608215830000101
Figure BDA0001608215830000111
As can be seen from Table 2, the selectivity of example 2 using the process of the present invention is higher than that of comparative example 2, indicating that the process of the present invention can improve the silver catalyst, especially the silver catalyst with large specific surface area (e.g., 2.0-4.0 m)2Selectivity in/g).
Example 3 showed a significant selectivity increase 16 days after the first increase in space velocity and EO concentration and a high selectivity up to 88% after the second adjustmentAnd excellent catalytic reaction performance is shown. It can be seen that the process of the present invention facilitates a large specific surface area (e.g. 2.0-4.0 m)2The silver catalyst has more obvious effect of rapidly reaching a high selectivity state at a high rhenium content (such as more than 400 ppmw), so that the silver catalyst has higher practical value.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (12)

1. A process for the production of ethylene oxide comprising the steps of:
(1) the reaction gas containing ethylene and oxygen is contacted with a silver catalyst for reaction under the conventional ethylene epoxidation reaction condition;
(2) when the selectivity of the catalyst is lower than a first preset value, the reaction conditions are adjusted to ensure that the space velocity is 6000-10000h-1The space-time yield is 270-450Kg EO/h/m3-cat, continuing the reaction;
(3) when the selectivity of the catalyst is higher than a second preset value, the conventional ethylene epoxidation reaction condition is recovered, and the reaction is continued;
(4) optionally repeating steps (2) - (3);
the second preset value is higher than the first preset value;
the silver catalyst comprises an alpha-alumina carrier and silver loaded on the carrier, and an alkali metal, an alkaline earth metal, a rhenium promoter and an optional rhenium synergistic promoter; the rhenium element content was 300-2000ppmw, based on the total weight of the silver catalyst; the specific surface area of the silver catalyst is 2.0-4.0m2/g；
The first preset value is 82% -86%, and the second preset value is 84% -92%;
the conventional ethylene epoxidation reaction conditions include: the reaction temperature is 200-280 ℃, the system pressure is 1-3MPa, and the space velocity is 2500-6000h-1The space-time yield is 145-260Kg EO/h/m3-cat。
2. The process for producing ethylene oxide as claimed in claim 1, wherein, in the step (2), the space-time yield is 290-420Kg EO/h/m3-cat。
3. The ethylene oxide production process according to claim 2, wherein the first preset value is 83% to 85% and the second preset value is 86% to 92%.
4. The ethylene oxide production process according to claim 1, wherein the first preset value at the time of repeating steps (2) to (3) is the same as or different from the previous first preset value; the second preset value when repeating steps (2) - (3) is the same as or different from the previous second preset value.
5. The ethylene oxide production process according to claim 1, wherein the contact reaction time in the step (1) is 0 to 200 days; the reaction is continued for 5 to 150 days in the step (2).
6. The ethylene oxide production process of claim 1, wherein the conventional ethylene epoxidation reaction conditions comprise: the reaction temperature is 200-280 ℃, the system pressure is 1-3MPa, and the space velocity is 2500-6000h-1The space-time yield is 145-260Kg EO/h/m3-cat。
7. The ethylene oxide production process according to claim 1, wherein the reaction gas has an ethylene content of 10 to 40 vol% and an oxygen content of 5 to 10 vol%, based on the total volume of the reaction gas.
8. Ethylene oxide production process according to claim 1, wherein in step (3) the reversion to conventional ethylene epoxidation reaction conditions is effected stepwise: the space-time yield is reduced first and then the space velocity is reduced.
9. The ethylene oxide production process of claim 1 wherein the silver catalyzesThe agent comprises an alpha-alumina carrier and silver loaded on the carrier, and an alkali metal, an alkaline earth metal, a rhenium promoter and an optional rhenium synergistic promoter; the content of rhenium element is 400-1800ppmw based on the total weight of the silver catalyst; the specific surface area of the silver catalyst is 2.1-3.5m2/g。
10. The ethylene oxide production process according to claim 9, wherein the rhenium element content is 500-1500ppmw, based on the total weight of the silver catalyst.
11. The ethylene oxide production process according to claim 9 or 10, wherein the silver catalyst has at least one of the following characteristics:
-the silver catalyst has an average pore diameter of 0.5-3.0 μm;
-the silver content is from 10 to 40 wt%, based on the total weight of the silver catalyst;
-the alkali metal is selected from at least one of lithium, sodium, potassium, rubidium, and cesium in an amount of 10-2000ppmw, based on the total weight of the silver catalyst;
-said alkaline earth metal is selected from at least one of magnesium, calcium, strontium and barium in an amount of 10 to 10000ppmw, based on the total weight of the silver catalyst;
-said rhenium co-promoter is selected from at least one of boron, fluorine, sulphur, cerium, chromium, molybdenum, tungsten, titanium, zirconium, cobalt, nickel, copper and zinc in an amount of from 10 to 2000ppmw, based on the total weight of the silver catalyst.
12. The ethylene oxide production process according to claim 11, wherein the average pore diameter of the silver catalyst is 0.6 to 2.0 μm.
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CN102421766A (en) * 2009-04-21 2012-04-18 陶氏技术投资有限公司 Methods for enhancing the efficiency of rhenium-promoted epoxidation catalysts and epoxidation methods utilizing these
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