CN105618046B - Preparation method, silver catalyst and the method for producing ethylene oxide of silver catalyst - Google Patents
Preparation method, silver catalyst and the method for producing ethylene oxide of silver catalyst Download PDFInfo
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- CN105618046B CN105618046B CN201410610528.0A CN201410610528A CN105618046B CN 105618046 B CN105618046 B CN 105618046B CN 201410610528 A CN201410610528 A CN 201410610528A CN 105618046 B CN105618046 B CN 105618046B
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- 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
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Abstract
The present invention relates to a kind of preparation methods of silver catalyst, include the following steps：A) maceration extract is configured, maceration extract includes silver compound, organic amine, the chlorion and rhenium auxiliary agent that content is 0 50ppm；B) with the maceration extract impregnated carrier, and leaching；C) sample after leaching is placed in the atmosphere of chlorine-containing compound and is heat-treated, wherein the chlorinity in the atmosphere of the chlorine-containing compound is 0.1 10ppm, and the heat treatment temperature is 200 400 DEG C.The invention further relates to the silver catalysts being prepared by this method.The invention further relates to a kind of methods generating ethylene oxide using the silver catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of silver catalyst and silver catalysts.The silver is used the invention further relates to a kind of
Catalyst is come the method that generates ethylene oxide.
Background technology
Silver catalyst is to be commercially used for carrying out ethylene to produce the catalyst of ethylene oxide (EO).Characterization silver catalysis
The index of agent performance is activity, selectivity and the stability of silver catalyst.Activity refers to that process for ethylene oxide production reaches certain
React reaction temperature required when load；Reaction temperature is lower, and the activity of catalyst is higher.Selectivity refers to that ethylene turns in reaction
It is melted into the ratio between the overall reaction molal quantity of the molal quantity and ethylene of ethylene oxide.Stability is then the lower reduction of speed of activity and selectivity
The stability of rate, the smaller then catalyst of fall off rate is better.
The performance of silver catalyst is related with the preparation method of used carrier, the composition of catalyst and catalyst.
Improvement to carrier includes the variation etc. that other components, carrier physical property are added to carrier.It is added to carrier
Component includes alkali metal, fluoride, zirconium compound, silica, titanium dioxide, stannide and alkaline-earth metal etc.；And carrier
Pretreatment, impurity content control etc. in carrier, the method for also adjusting and improving carrier pore size distribution.
In addition to active component silver, also other auxiliary agents can play the role of improving catalyst performance in catalyst formulation, respectively
The co-catalyst that company refers to includes alkali metal, alkaline-earth metal, rhenium, molybdenum, tungsten, chromium, nickel and sulphur, phosphorus, boron, fluorine, chlorine, manganese, cobalt, thallium
Deng；The further promotion of catalyst performance is realized by coordinating auxiliary agent type and usage amount.
The preparation method of silver catalyst is that active component silver and various auxiliary agents are applied on carrier, main using dipping
Method, and activation process then can be carried out by heating.Classics dipping liquid making method such as Shell companies patent in 1972
Described in US3702259, argent-amine complex is generated using silver oxalate/ethylenediamine/ethanol amine.And when the condition being heat-treated and heat treatment
Used atmosphere has a major impact the performance of catalyst.Other than using air atmosphere, also have in the prior art a small amount of
Report uses the document containing inert gas atmosphere, for example, using inert gas atmosphere in patent CN1023076C.But at present
It is not yet reported that be heat-treated using the atmosphere of chlorine-containing compound, and the performance of silver catalyst in the prior art also has
Modified space.
From the thirties in last century, due to the importance of silver catalyst in the industrial production, each research institution is continuous
Ground has carried out numerous studies and improvement to silver catalyst.Since the commercial scale of production ethylene oxide is extremely huge, the choosing of reaction
Selecting property, which increases by 1%, can all save a large amount of raw material, generate huge economic benefit.Similarly, the service life of silver catalyst,
The improvement of stability also has significant economic benefit.Therefore, it is preferably silver-colored to catch at a kind of performance for a long time for this field
Catalyst is used for the production of ethylene oxide.
Invention content
Present inventors discovered unexpectedly that changing heat-treating atmosphere, catalyst in the preparation process of silver catalyst
Stability it is more preferable, be selectively substantially improved, reach the degree that can be used for industrialized production ethylene oxide, so as to obtain one
The kind better silver catalyst of performance.
It is an advantage of the invention to provide a kind of preparation methods of silver catalyst, are existed in the prior art with overcoming
The problem of.
To achieve the goals above, the present invention provides the following technical solutions：
A) maceration extract is configured, maceration extract includes silver compound, organic amine, the chlorion and rhenium that content is 0-50ppm
Auxiliary agent；
B) with the maceration extract impregnated carrier, and leaching；
C) sample after leaching is placed in the atmosphere of chlorine-containing compound and is heat-treated, wherein the chlorine-containing compound
Atmosphere in chlorinity be 0.1-10ppm, the heat treatment temperature be 200-400 DEG C.
Wherein, the example of the organic amine can be but be not limited only to pyridine, butylamine, ethylenediamine, 1,3- propane diamine or ethyl alcohol
It is one or more in amine.
The present inventor is by experiment it was unexpectedly observed that adding Micro Amounts of Chlorine in the atmosphere of the heat treatment in step c)
The selectivity of catalyst can be made to be significantly increased.The present inventor in maceration extract in step a) it has furthermore been found that be added
Trace chlorine can make selectivity be further enhanced.
Further include I A races metal promoted in the maceration extract described in step a) in the preferred embodiment of the present invention
It is one or more in the collaboration auxiliary agent of agent, II A races metal promoter and sulfur-bearing.
In the preferred embodiment of the present invention, impregnates described in step b) and carry out under vacuum.
In the preferred embodiment of the present invention, the carrier described in step b) is alumina support.
In another preferred embodiment of the present invention, to the product that step c) is obtained, institute in step b) can be used as
The carrier stated repeats step a) to c) or repeating step b) to c), finally obtaining the silver catalyst.
In the preferred embodiment of the present invention, the content of chlorion is less than 10ppm in the maceration extract.Chlorine contains
Measuring excessively high can cause precipitation silver-colored in maceration extract.
In some preferred embodiments of the present invention, the chlorine-containing compound in the atmosphere is selected from chloromethanes, chloroethene
Or mixtures thereof alkane, dichloroethanes, Bromofume, vinyl chloride.It is described in the particularly preferred embodiment of the present invention
Chlorine-containing compound in atmosphere is selected from chloroethanes.In some preferred embodiments of the present invention, chlorinity 0.1-
10ppm, preferably 0.1-5ppm, more preferably 0.1-1ppm, most preferably 0.5ppm, remaining is air.
In the preferred embodiment of the present invention, the heat treatment temperature is 230-300 DEG C.
In the preferred embodiment of the present invention, the heat treatment time is 2-30min.
In the preferred embodiment of the present invention, I A races metallic element of I A races metal promoter can be
It is one or more in lithium, sodium, potassium, rubidium, caesium and francium, it is preferably one or more in lithium, potassium and caesium.
In the preferred embodiment of the present invention, II A races metallic element of II A races metal promoter can be
It is one or more in beryllium, magnesium, calcium, strontium, barium and radium, preferably strontium and/or barium.
In the preferred embodiment of the present invention, the collaboration auxiliary agent of the sulfur-bearing is ammonium sulfate.
In the preferred embodiment of the present invention, silver-colored content is 10- in the maceration extract described in step a)
35wt%, preferably 18-30wt%.
It is a further object of the invention to provide a kind of silver catalyst made from above-mentioned method, the silver catalysis
Agent includes the carrier and rhenium of silver, load silver.
In the preferred embodiment of the present invention, the silver catalyst further includes I A races metal promoter, II A races gold
Belong to one or more in the collaboration auxiliary agent of auxiliary agent and sulfur-bearing.
In the preferred embodiment of the present invention, silver content is 10-30wt% in the catalyst, preferably
18-30wt%.
In the preferred embodiment of the present invention, the rhenium of 100-1000ppm is included in the catalyst.
In the preferred embodiment of the present invention, the I A races gold in the catalyst also comprising 100-2000ppm
Belong to.In the preferred embodiment of the present invention, the sulphur of 100-1000ppm is also included in the catalyst, preferably
The sulphur of 100-700ppm.Also include 100-1000ppm's in the preferred embodiment of the present invention, in the catalyst
II A races metal promoter.
In the preferred embodiment of the present invention, the carrier is solid oxidation alumina supporter, the solid oxidation
The specific surface area of alumina supporter is 0.5~3.0m2/ g, water absorption rate 50-70%, Kong Rongwei 0.5-0.8ml/g.
It is still another object of the present invention to provide a kind of method that ethylene generates ethylene oxide, the method packets
It includes using the silver catalyst being prepared according to the above method or uses above-mentioned silver catalyst.
In the preferred embodiment of the present invention, feed composition is：Ethylene (C2H4) it is 20-35mol%, oxygen
(O2) it is 5-10mol%, carbon dioxide (CO2) it is 0-3mol%, conditioning agent 0.3-2.0ppmv, remaining is the steady gas (N of cause2)。
In the preferred embodiment of the present invention, the reaction temperature of ethylene oxidation reactions is 200-260 DEG C, reaction
Pressure is 1.5-2.1MPa, Feed space velocities 3000-7000h-1；Reactor outlet tail gas ethylene oxide (EO) it is a concentration of
0.5-5%.
Beneficial effects of the present invention are：
The performance of silver catalyst made from method through the invention is more preferable, and especially selective higher, stability is more preferable,
Ethylene oxide is produced especially suitable for ethylene.It is identical in other reaction conditions, use side according to the present invention
Silver catalyst made from method improves the selectivity of product, has saved reaction raw materials, reduces byproduct of reaction；It extends and urges
The service life of agent, has saved cost；To more environment-friendly, in industrial production ethylene oxide, huge warp can be generated
Ji benefit.
Specific implementation mode
With reference to embodiment and comparative example, the invention will be further described.But it will be appreciated that the model of the present invention
It encloses and is not limited to the following example.Without departing from the scope and spirit of the present invention, various improvement can be carried out to it,
And element therein can be replaced with equivalent.
Carrier used in the following example is industrial solid alpha-alumina supports, and the specific surface area of the carrier is
1.24m2/ g, water absorption rate 52.5%, pore volume 0.64ml/g.
Every number (such as " 28 parts of ethylenediamines " " 10 parts of ethanol amines " and " 46 described in the following example and comparative example
Part deionized water " etc.), it is number by weight if without specified otherwise.
Embodiment
Embodiment 1
28 parts of ethylenediamines (by weight), 10 parts of ethanol amines and 46 parts of deionized waters are added in the reactor with stirring.
62 parts of the silver oxalate that silver content is 62.6wt% is slowly added in mixed liquor while stirring, keeps solution temperature 0~15
DEG C, silver oxalate forms argentamine liquid after all dissolving, and 0.08 part of rehenic acid ammonium is then added.It takes carrier 10g to be placed in container, uses
The argentamine liquid submergence carrier for stating preparation is kept for 30 minutes, and then leaching removes extra solution, then contains at 270 DEG C, in chlorine
Amount heats 5 minutes in the atmosphere for the chlorine-containing compound of 0.5ppm, and the chlorine-containing compound is chloroethanes, is prepared after cooling
Silver catalyst.Silver content is 20.2wt% in final catalyst, and rhenium content is 330ppm.
Embodiment 2
28 parts of ethylenediamines, 10 parts of ethanol amines and 46 parts of deionized waters are added in the reactor with stirring.While stirring
62 parts of the silver oxalate that silver content is 62.6wt% is slowly added in mixed liquor, keeps solution temperature at 0~15 DEG C, silver oxalate is complete
Portion dissolving after form argentamine liquid, then be added 0.10 part of cesium hydroxide, 0.04 part of potassium sulfate, 0.08 part of rehenic acid ammonium, 0.01 part
Ammonium sulfate, 0.08 part of strontium acetate.It takes carrier 10g to be placed in the container of vacuum-pumping, is evacuated to 10mmHg hereinafter, being matched with above-mentioned
The argentamine liquid of system submerges carrier, is kept for 30 minutes, and then leaching removes extra solution, then at 270 DEG C, chlorinity be
It is heated 5 minutes in the atmosphere of the chlorine-containing compound of 0.5ppm, the chlorine-containing compound is chloroethanes, and silver, which is prepared, after cooling urges
Agent, silver content is 21.2wt% in final catalyst, and rhenium content is 330ppm, and I A races metal promoter content is 760ppm, sulphur
Content is 220ppm, and II A races metal promoter content is 320ppm.
Embodiment 3
28 parts of ethylenediamines (by weight), 10 parts of ethanol amines and 46 parts of deionized waters are added in the reactor with stirring.
62 parts of the silver oxalate that silver content is 62.6wt% is slowly added in mixed liquor while stirring, keeps solution temperature 0~15
DEG C, silver oxalate forms argentamine liquid after all dissolving, then 0.08 part of rehenic acid ammonium of addition and 0.007 part of ammonium chloride, Cl in solution-1
A concentration of 47ppm.It takes carrier 10g to be placed in container, is kept for 30 minutes with the argentamine liquid submergence carrier of above-mentioned preparation, then dripped
Extra solution is filtered out, then is heated 5 minutes at 270 DEG C, in the atmosphere for the chlorine-containing compound that chlorinity is 0.5ppm, institute
It is chloroethanes to state chloride, and silver catalyst is prepared after cooling.Silver content is 20.6wt%, rhenium content in final catalyst
For 350ppm.
Embodiment 4
28 parts of ethylenediamines, 10 parts of ethanol amines and 46 parts of deionized waters are added in the reactor with stirring.While stirring
62 parts of the silver oxalate that silver content is 62.6wt% is slowly added in mixed liquor, keeps solution temperature at 0~15 DEG C, silver oxalate is complete
Portion dissolving after form argentamine liquid, then be added 0.10 part of cesium hydroxide, 0.04 part of potassium sulfate, 0.08 part of rehenic acid ammonium, 0.01 part
Ammonium sulfate, 0.08 part of strontium acetate, 0.001 part of ammonium chloride, Cl in solution-1A concentration of 7ppm.Carrier 10g is taken to be placed in vacuum-pumping
In container, 10mmHg is evacuated to hereinafter, being kept for 30 minutes with the argentamine liquid submergence carrier of above-mentioned preparation, then leaching removes
Extra solution, then 270 DEG C chlorinity be 0.5ppm chlorine-containing compound atmosphere in heat 5 minutes, the chloride containing
Object is chloroethanes, and silver catalyst is prepared after cooling, and silver content is 20.2wt% in final catalyst, and rhenium content is
312ppm, I A races auxiliary agent content are 752ppm, and sulfur content 209ppm, II A races auxiliary agent content is 320ppm.
Embodiment 5
28 parts of ethylenediamines, 10 parts of ethanol amines and 46 parts of deionized waters are added in the reactor with stirring.While stirring
62 parts of the silver oxalate that silver content is 62.6wt% is slowly added in mixed liquor, keeps solution temperature at 0~15 DEG C, silver oxalate is complete
Portion dissolving after form argentamine liquid, then be added 0.10 part of cesium hydroxide, 0.04 part of potassium sulfate, 0.08 part of rehenic acid ammonium, 0.01 part
Ammonium sulfate, 0.08 part of strontium acetate, 0.001 part of ammonium chloride, Cl in solution-1A concentration of 7ppm.Carrier 10g is taken to be placed in vacuum-pumping
In container, 10mmHg is evacuated to hereinafter, being kept for 30 minutes with the argentamine liquid submergence carrier of above-mentioned preparation, then leaching removes
Extra solution, then 200 DEG C chlorinity be 0.5ppm chlorine-containing compound atmosphere in heat 30 minutes, the chloride containing
Conjunction object is chloroethanes, and silver catalyst is prepared after cooling, and silver content is 20.1wt% in final catalyst, and rhenium content is
340ppm, I A races auxiliary agent content are 780ppm, and sulfur content 220ppm, II A races auxiliary agent content is 310ppm.
Embodiment 6
28 parts of ethylenediamines, 10 parts of ethanol amines and 46 parts of deionized waters are added in the reactor with stirring.While stirring
62 parts of the silver oxalate that silver content is 62.6wt% is slowly added in mixed liquor, keeps solution temperature at 0~15 DEG C, silver oxalate is complete
Portion dissolving after form argentamine liquid, then be added 0.10 part of cesium hydroxide, 0.04 part of potassium sulfate, 0.08 part of rehenic acid ammonium, 0.01 part
Ammonium sulfate, 0.08 part of strontium acetate, 0.0014 part of ammonium chloride, Cl in solution-1A concentration of 10ppm.Carrier 10g is taken to be placed in vacuum-pumping
Container in, be evacuated to 10mmHg hereinafter, being kept for 2 minutes with the argentamine liquid of above-mentioned preparation submergence carrier, then leaching removes
Remove extra solution, then 400 DEG C of chlorinity be 0.5ppm chlorine-containing compound atmosphere in heat 30 minutes, it is described containing chlorine
Compound is chloroethanes, and silver catalyst is prepared after cooling, and silver content is 20.7wt% in final catalyst, and rhenium content is
350ppm, I A races auxiliary agent content are 720ppm, and sulfur content 220ppm, II A races auxiliary agent content is 320ppm.
Embodiment 7
28 parts of ethylenediamines, 10 parts of ethanol amines and 46 parts of deionized waters are added in the reactor with stirring.While stirring
62 parts of the silver oxalate that silver content is 62.6wt% is slowly added in mixed liquor, keeps solution temperature at 0~15 DEG C, silver oxalate is complete
Portion dissolving after form argentamine liquid, then be added 0.10 part of cesium hydroxide, 0.04 part of potassium sulfate, 0.08 part of rehenic acid ammonium, 0.01 part
Ammonium sulfate, 0.08 part of barium acetate, 0.001 part of ammonium chloride, Cl in solution-1A concentration of 7ppm.Carrier 10g is taken to be placed in vacuum-pumping
In container, 10mmHg is evacuated to hereinafter, being kept for 30 minutes with the argentamine liquid submergence carrier of above-mentioned preparation, then leaching removes
Extra solution, then 230 DEG C of chlorinity be 5ppm chlorine-containing compound atmosphere in heat 5 minutes, chloride containing conjunction
Object is chloroethanes, and silver catalyst is prepared after cooling, and silver content is 20.5wt% in final catalyst, and rhenium content is
350ppm, I A races auxiliary agent content are 740ppm, and sulfur content 220ppm, II A races auxiliary agent content is 320ppm.
Embodiment 8
28 parts of ethylenediamines, 10 parts of ethanol amines and 46 parts of deionized waters are added in the reactor with stirring.While stirring
62 parts of the silver oxalate that silver content is 62.6wt% is slowly added in mixed liquor, keeps solution temperature at 0~15 DEG C, silver oxalate is complete
Portion dissolving after form argentamine liquid, then be added 0.10 part of cesium hydroxide, 0.04 part of potassium sulfate, 0.08 part of rehenic acid ammonium, 0.01 part
Ammonium sulfate, 0.08 part of strontium acetate, 0.001 part of ammonium chloride, Cl in solution-1A concentration of 7ppm.Carrier 10g is taken to be placed in vacuum-pumping
In container, 10mmHg is evacuated to hereinafter, being kept for 30 minutes with the argentamine liquid submergence carrier of above-mentioned preparation, then leaching removes
Extra solution, then 300 DEG C of chlorinity be 1ppm chlorine-containing compound atmosphere in heat 5 minutes, chloride containing conjunction
Object is chloroethanes, and silver catalyst is prepared after cooling, and silver content is 20.2wt% in final catalyst, and rhenium content is
350ppm, I A races auxiliary agent content are 730ppm, and sulfur content 220ppm, II A races auxiliary agent content is 320ppm.
Embodiment 9
28 parts of ethylenediamines, 10 parts of ethanol amines and 46 parts of deionized waters are added in the reactor with stirring.While stirring
62 parts of the silver oxalate that silver content is 62.6wt% is slowly added in mixed liquor, keeps solution temperature at 0~15 DEG C, silver oxalate is complete
Portion dissolving after form argentamine liquid, then be added 0.10 part of cesium hydroxide, 0.04 part of potassium sulfate, 0.08 part of rehenic acid ammonium, 0.01 part
Ammonium sulfate, 0.08 part of barium acetate, 0.001 part of ammonium chloride, Cl in solution-1A concentration of 7ppm.Carrier 10g is taken to be placed in vacuum-pumping
In container, 10mmHg is evacuated to hereinafter, being kept for 30 minutes with the argentamine liquid submergence carrier of above-mentioned preparation, then leaching removes
Extra solution, then 270 DEG C chlorinity be 0.1ppm chlorine-containing compound atmosphere in heat 5 minutes, the chloride containing
Conjunction object is chloroethanes, and silver catalyst is prepared after cooling, and silver content is 20.5wt% in final catalyst, and rhenium content is
350ppm, I A races auxiliary agent content are 740ppm, and sulfur content 220ppm, II A races auxiliary agent content is 320ppm.
Embodiment 10
28 parts of ethylenediamines, 10 parts of ethanol amines and 46 parts of deionized waters are added in the reactor with stirring.While stirring
62 parts of the silver oxalate that silver content is 62.6wt% is slowly added in mixed liquor, keeps solution temperature at 0~15 DEG C, silver oxalate is complete
Portion dissolving after form argentamine liquid, then be added 0.18 part of cesium hydroxide, 0.05 part of potassium sulfate, 0.02 part of lithium sulfate, 0.16 part
Rehenic acid ammonium, 0.01 part of ammonium sulfate, 0.08 part of strontium acetate, 0.08 part of barium acetate, 0.001 part of ammonium chloride, Cl in solution-1It is a concentration of
7ppm.It takes carrier 10g to be placed in the container of vacuum-pumping, is evacuated to 10mmHg hereinafter, being soaked with the argentamine liquid of above-mentioned preparation
Do not have carrier to be kept for 30 minutes, then leaching removes extra solution, then the chlorine-containing compound for being 10pm in 270 DEG C of chlorinity
It is heated 5 minutes in atmosphere, the chlorine-containing compound is chloroethanes, is prepared silver catalyst after cooling, silver in final catalyst
Content is 20.3wt%, and rhenium content is 820ppm, and I A races auxiliary agent content is 1530ppm, sulfur content 520ppm, II A races auxiliary agent
Content is 850ppm.
Embodiment 11
28 parts of ethylenediamines, 10 parts of ethanol amines and 46 parts of deionized waters are added in the reactor with stirring.While stirring
45 parts of the silver oxalate that silver content is 62.6wt% is slowly added in mixed liquor, keeps solution temperature at 0~15 DEG C, silver oxalate is complete
Portion dissolving after form argentamine liquid, then be added 0.02 part of cesium hydroxide, 0.01 part of potassium sulfate, 0.03 part of rehenic acid ammonium, 0.01 part
Ammonium sulfate, 0.02 part of strontium acetate, 0.01 part of barium acetate, 0.001 part of ammonium chloride, Cl in solution-1A concentration of 7ppm.Take carrier 10g
It is placed in the container of vacuum-pumping, is evacuated to 10mmHg hereinafter, being kept for 30 points with the argentamine liquid submergence carrier of above-mentioned preparation
Clock, then leaching remove extra solution, then 270 DEG C of chlorinity be 0.5ppm chlorine-containing compound atmosphere in heat 5
Minute, the chlorine-containing compound is chloroethanes, silver catalyst is prepared after cooling, silver content is in final catalyst
18.5wt%, rhenium content are 110ppm, and I A races auxiliary agent content is 120ppm, sulfur content 110ppm, and II A races auxiliary agent content is
120ppm。
Embodiment 12
28 parts of ethylenediamines, 10 parts of ethanol amines and 46 parts of deionized waters are added in the reactor with stirring.While stirring
82 parts of the silver oxalate that silver content is 62.6wt% is slowly added in mixed liquor, keeps solution temperature at 0~15 DEG C, silver oxalate is complete
Portion dissolving after form argentamine liquid, then be added 0.10 part of cesium hydroxide, 0.08 part of rehenic acid ammonium, 0.08 part of strontium acetate, 0.001 part
Ammonium chloride.It takes carrier 10g to be placed in container, is kept for 30 minutes with the argentamine liquid submergence carrier of above-mentioned preparation, then leaching removes
Remove extra solution, then 270 DEG C of chlorinity be 0.5ppm chlorine-containing compound atmosphere in heat 5 minutes, it is described containing chlorine
Compound is chloroethanes, and silver catalyst is prepared after cooling.Silver content is 26.5wt% in final catalyst, and rhenium content is
340ppm, I A races auxiliary agent content are 520ppm, and II A races auxiliary agent content is 320ppm.
Comparative example 1
Silver catalyst is prepared as described in Example 1, the difference is that, it is heat-treated in air atmosphere, rather than
It is heat-treated in the atmosphere in chlorine-containing compound.
Comparative example 2
Silver catalyst is prepared as described in Example 2, the difference is that, it is heat-treated in air atmosphere, rather than
It is heat-treated in the atmosphere of chlorine-containing compound.
Comparative example 3
Silver catalyst is prepared as described in Example 4, the difference is that, Cl in maceration extract-1Concentration is different, increases
Cl-10.01 part of ammonium chloride is added in concentration, Cl in solution-1A concentration of 70ppm.
Embodiment 13
Silver catalyst made from method in method and comparative example through the invention is tested it by following mode
Performance.Reaction pressure is 1.8MPa；Air speed is 6000h-1；A concentration of the 2.4% of reactor outlet tail gas ethylene oxide (EO).
It is tested respectively made from comparative example -3 and embodiment 1-11 with laboratory reactor (hereinafter referred to as " micro- anti-") evaluating apparatus
The performance of silver catalyst, the results are shown in Table 1.
Table 1
| Catalyst | S0(%) | T0(℃) | S50(%) | T50(℃) | △T(℃) |
| Comparative example 1 | 81.22 | 221.5 | 82.42 | 225.7 | 4.2 |
| Comparative example 2 | 82.03 | 222.9 | 83.25 | 227.0 | 4.1 |
| Embodiment 1 | 82.24 | 224.2 | 84.01 | 226.2 | 2.0 |
| Embodiment 2 | 84.03 | 230.3 | 86.06 | 231.5 | 1.2 |
| Embodiment 3 | 82.62 | 226.7 | 84.69 | 228.4 | 1.7 |
| Embodiment 4 | 84.25 | 231.5 | 86.12 | 232.2 | 0.7 |
| Embodiment 5 | 84.10 | 230.7 | 86.02 | 233.4 | 2.7 |
| Embodiment 6 | 84.01 | 231.4 | 86.11 | 234.2 | 2.8 |
| Embodiment 7 | 83.76 | 230.5 | 85.69 | 233.2 | 2.7 |
| Embodiment 8 | 82.83 | 224.2 | 84.01 | 227.2 | 3.0 |
| Embodiment 9 | 83.55 | 233.4 | 85.12 | 236.5 | 3.1 |
| Embodiment 10 | 84.05 | 232.4 | 86.07 | 235.4 | 3.0 |
| Embodiment 11 | 82.52 | 225.9 | 83.97 | 228.8 | 2.9 |
| Embodiment 12 | 82.78 | 226.1 | 84.22 | 229.5 | 3.4 |
| Comparative example 3 | 80.12 | 238.1 | 80.01 | 240.2 | 6.1 |
Wherein, S0And T0The selectivity and reaction temperature of catalyst when respectively catalysis reaction originates, and S50And T50Point
It Wei be catalyzed the selectivity and reaction temperature of the catalyst after reaction occurs 50 days, △ T are anti-with catalysis when being catalysis reaction starting
The reaction temperature that should occur after 50 days is poor.△ T are smaller, then the stability of catalyst is better.
Heat treatment process does not use chlorine-containing compound in comparative example 1 and comparative example 2, in maceration extract also without using chlorine from
The selectivity that the catalyst after occurring 50 days is reacted in son, the initial stage selectivity of catalyst and catalysis is relatively low, and stability is poor.Than
Compared with comparative example 1 and embodiment 1 or compared with comparative example 2 with embodiment 2 it is found that using chlorinity in this hair during heat treatment
Chlorine-containing compound within the scope of bright preferred content can make the performance of catalyst be greatly improved (to compare comparative example 1 and reality
For applying example 1, S0It is increased to 83.74%, S by 81.22%50By 82.42% it has been increased to 85.15%, i.e. silver catalyst
Selectivity is improved；△ T also drop to 2.1 by 4.2 simultaneously, i.e. the stability of silver catalyst is improved).Compare reality
Example 2 and embodiment 4 are applied it is found that can further improve catalysis using the chlorion within the scope of preferred content of the present invention in maceration extract
Performance (the S of agent0It is increased to 84.25%, S by 84.03%50It is increased to 86.12%, the i.e. choosing of silver catalyst by 86.06%
Selecting property is improved；△ T also drop to 0.7 by 1.7 simultaneously, i.e. the stability of silver catalyst is improved), embodiment 1
It is compared with embodiment 3 it is also seen that the catalyst performance that chlorine ion concentration is prepared within preferred 10ppm in maceration extract
Most preferably.Compared with comparative example 1 and comparative example 2, the selectivity of catalyst is greatly improved in embodiment 1~12, and
It is greatly lowered using △ T after 50 days, illustrates that the stability of catalyst is also improved.Therefore, the present invention provides one
Kind is used for the new preparation method of the silver catalyst of industrial production ethylene oxide, and silver catalyst has relatively made from the method
Better performance, especially better choice and stability.Meanwhile as can be known from the results of Table 1, chlorine is most in heat-treating atmosphere
Good usage amount is 0.5ppm, can not be added in the chlorion in maceration extract, or within 10ppm.
Comparing embodiment is with comparative example 3 it is found that the additive amount of chlorine-containing compound is preferably micro in the present invention, more than this hair
Dosage described in bright claim can reduce the performance of catalyst.
Claims (23)
1. a kind of preparation method of silver catalyst, includes the following steps：
A) maceration extract is configured, maceration extract includes that silver compound, organic amine, the chlorion that content is 7-50ppm and rhenium help
Agent；
B) with the maceration extract impregnated carrier, and leaching；
C) sample after leaching is placed in the atmosphere of chlorine-containing compound and is heat-treated, wherein the gas of the chlorine-containing compound
Chlorinity in atmosphere is 0.1-10ppm, and the heat treatment temperature is 200-400 DEG C, and the heat treatment time is 2-30min.
2. according to the method described in claim 1, it is characterized in that, further including I A races metal in maceration extract described in step a)
It is one or more in the collaboration auxiliary agent of auxiliary agent, II A races metal promoter and sulfur-bearing.
3. according to the method described in claim 2, being carried out under vacuum it is characterized in that, being impregnated described in step b).
4. according to the method described in claim 3, it is characterized in that, the carrier described in step b) is alumina support.
5. method as claimed in any of claims 1 to 4, which is characterized in that the product that step c) is obtained, can make
For the carrier described in step b), step a) is repeated to c) or repeating step b) to c), finally obtaining the silver catalyst.
6. method as claimed in any of claims 1 to 4, which is characterized in that chlorion contains in the maceration extract
Amount is less than 10ppm.
7. method as claimed in any of claims 1 to 4, which is characterized in that the chlorine-containing compound in the atmosphere
Selected from or mixtures thereof chloromethanes, chloroethanes, dichloroethanes, vinyl chloride, and chlorinity is 0.1-10ppm, remaining is air.
8. the method according to the description of claim 7 is characterized in that chlorine-containing compound in the atmosphere is chloroethanes, and
Chlorinity is 0.1-5ppm, remaining is air.
9. according to the method described in claim 8, it is characterized in that, chlorinity is 0.1-1ppm, remaining is air.
10. according to the method described in claim 9, it is characterized in that, chlorinity is 0.5ppm, remaining is air.
11. method as claimed in any of claims 1 to 4, which is characterized in that the heat treatment temperature is 230-
300℃。
12. method as claimed in any of claims 2 to 4, which is characterized in that I A races of I A races metal promoter
Metallic element is one or more in lithium, potassium and caesium.
13. method as claimed in any of claims 2 to 4, which is characterized in that II A of II A races metal promoter
Race's metallic element is one or more in strontium and barium.
14. method as claimed in any of claims 1 to 4, which is characterized in that in the maceration extract described in step a)
The content of silver is 10-35wt%.
15. according to the method for claim 14, which is characterized in that silver-colored content is in the maceration extract described in step a)
18-30wt%.
16. silver catalyst made from a kind of method according to any one of claim 1 to 15, which is characterized in that institute
State the carrier and rhenium that silver catalyst includes silver, load silver.
17. silver catalyst according to claim 16, which is characterized in that the silver catalyst further includes I A races metal promoted
It is one or more in the collaboration auxiliary agent of agent, II A races metal promoter and sulfur-bearing.
18. silver catalyst according to claim 16 or 17, which is characterized in that silver content is 10- in the catalyst
30wt%.
19. silver catalyst according to claim 18, which is characterized in that silver content is 18-30wt% in the catalyst.
20. silver catalyst according to claim 16 or 17, which is characterized in that include 100- in the catalyst
The rhenium of 1000ppm.
21. silver catalyst according to claim 16 or 17, which is characterized in that include 100- in the catalyst
II A races metal promoter of the I A races metal promoter of 2000ppm, the sulphur of 100-1000ppm and 100-1000ppm.
22. silver catalyst according to claim 16 or 17, which is characterized in that the carrier is solid oxidation alumina supporter,
The specific surface area of the solid oxidation alumina supporter is 0.5~3.0m2/ g, water absorption rate 50-70%, Kong Rongwei 0.5-0.8mL/g
。
23. a kind of method that ethylene generates ethylene oxide, which is characterized in that including using according in claim 1 to 15
The silver catalyst that method described in any one is prepared or the silver according to any one of claim 16 to 22
Catalyst.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4415476A (en) * | 1981-02-25 | 1983-11-15 | Mitsubishi Petrochemical Co. Ltd. | Silver-based catalyst containing chlorine as an anionic component for the production of ethylene oxide |
| CN1260787A (en) * | 1997-06-23 | 2000-07-19 | 阿科化学技术公司 | Propylene expoxidation using chloride-containing silver catalyst |
| CN1665797A (en) * | 2002-06-28 | 2005-09-07 | 国际壳牌研究有限公司 | Method for the start-up of an epoxidation process and a process for the epoxidation of an olefin |
| CN101534938A (en) * | 2006-11-01 | 2009-09-16 | 陶氏环球技术公司 | Shaped porous bodies of alpha-alumina and methods for the preparation thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4245191B2 (en) * | 1993-08-23 | 2009-03-25 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Ethylene oxide catalyst |
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2014
- 2014-11-03 CN CN201410610528.0A patent/CN105618046B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4415476A (en) * | 1981-02-25 | 1983-11-15 | Mitsubishi Petrochemical Co. Ltd. | Silver-based catalyst containing chlorine as an anionic component for the production of ethylene oxide |
| CN1260787A (en) * | 1997-06-23 | 2000-07-19 | 阿科化学技术公司 | Propylene expoxidation using chloride-containing silver catalyst |
| CN1665797A (en) * | 2002-06-28 | 2005-09-07 | 国际壳牌研究有限公司 | Method for the start-up of an epoxidation process and a process for the epoxidation of an olefin |
| CN101534938A (en) * | 2006-11-01 | 2009-09-16 | 陶氏环球技术公司 | Shaped porous bodies of alpha-alumina and methods for the preparation thereof |
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