CN101360562B - Catalyst for ethylene oxide production, method for producing the same, and method for producing ethylene oxide - Google Patents
Catalyst for ethylene oxide production, method for producing the same, and method for producing ethylene oxide Download PDFInfo
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- CN101360562B CN101360562B CN2007800017373A CN200780001737A CN101360562B CN 101360562 B CN101360562 B CN 101360562B CN 2007800017373 A CN2007800017373 A CN 2007800017373A CN 200780001737 A CN200780001737 A CN 200780001737A CN 101360562 B CN101360562 B CN 101360562B
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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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- 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
Disclosed is a catalyst for ethylene oxide production which is used for producing ethylene oxide from ethylene. This catalyst is composed of at least silver (Ag), caesium (Cs), rhenium (Re) and a carrier, and improved especially in selectivity. Specifically disclosed is a catalyst for ethylene oxide production, which is used for producing ethylene oxide from ethylene and composed of at least silver (Ag), caesium (Cs), rhenium (Re) and a carrier. If necessary, an alkali metal is loaded onto the carrier as a pretreatment, and then Ag, Cs and Re are loaded onto the carrier, thereby obtaining the catalyst. The carrier has a specific surface area of 0.6-3.0 m2/g, and a weight ratio between the silicon (Si) content and the sodium (Na) content in terms of SiO2/Na2O of 2-50. The Re content (based on the carrier) is 170-600 ppm per 1 m2/g of the specific surface area of the carrier, and the molar ratio Cs/Re is 0.3-19.
Description
Technical field
The present invention relates to the manufacture method of oxirane catalyst for producing and manufacture method thereof and oxirane.
Background technology
The main component that is used for making from ethene the catalyst of oxirane is silver (Ag), and silver loads on the carrier.Industrial, add the elements such as alkali metal, rhenium (Re) as co-catalyst for the Ag as the catalyst principal component, to improve catalyst performance (patent documentation 1).
About alkali-metal action effect, reported following effect: be present on the carrier, in and the effect of the Kα of carrier, perhaps be present in the effect that the catalytic action of Ag is adjusted on the Ag surface; But details it be unclear that.On the other hand, about Re, its having the site, is still not clear as the mechanism of action of co-catalyst in catalyst, but its must with alkali metal coexistence could play a role as co-catalyst (patent documentation 2).
Carrier generally is take Alpha-alumina as principal component, and Alpha-alumina carries out sintering to the mixture of material powder, adhesive, gas pore-forming agent and makes.The carrier of making like this contains the impurity such as silicon (Si), sodium (Na) usually as impurity, and wherein, Si content is with SiO
2Scaled value is counted 0.1～tens % by weight, Na content with Na
2The O scaled value is counted 0.01～several % by weight.
Have and report: the Si in the carrier, Na amount is for being made of Ag, alkali metal, carrier but the performance that does not contain the catalyst of Re has a significant impact (patent documentation 3 and 4).Therefore, be necessary to control Si, the Na amount in Alpha-alumina material powder, adhesive, the gas pore-forming agent, adjust Si, the Na amount in the carrier.In addition, containing aspect the Re catalyst, reporting Ag content is defined as catalyst (patent documentation 5 and 6) more than 20 % by weight.
Patent documentation 1: Unexamined Patent 9-150058 communique
Patent documentation 2: JP 63-126552 communique
Patent documentation 3: JP 63-116743 communique
Patent documentation 4: Unexamined Patent 1-123629 communique
Patent documentation 5: Unexamined Patent 3-207447 communique
Patent documentation 6:WO2005-097318 communique
Summary of the invention
The problem that the present invention will solve
The inventor etc. comprise Ag, Cs, Re and carrier at least to provide, and comprise at least that perhaps the improved oxirane catalyst for producing of Ag, Li, Cs, Re and carrier is target, conduct in-depth research, and the result has obtained following understanding.
(1) in the past, when catalyst by high surface area carrier, Ag, Cs, when Re consists of, the Si in the carrier, Na composition generally do not affect Re as the character of co-catalyst.Yet, if the Si composition in the carrier is limited to certain limit with the ratio that Na becomes to divide, unexpectedly unexpectedly can improve the promoting catalysis of Re, obtain the selective catalyst that significantly improves.
(2) by using the Li content in the large carrier of specific area and the raising catalyst, unexpectedly obtained the catalyst that keeps high selectivity and catalyst life significantly to improve.
The method of dealing with problems
Thereby finished the present invention based on above-mentioned cognition, the present invention includes one group of invention that is associated, the main points of each invention are as follows.
The 1st invention is based on above-mentioned understanding (1), and its main points are: a kind of oxirane catalyst for producing, this catalyst are used for making oxirane by ethene, and it comprises silver (Ag), caesium (Cs), rhenium (Re) and carrier at least; Wherein, as required, carrying alkali metal and then loads on Ag, Cs and Re on this carrier as pre-treatment on carrier, thereby obtains this catalyst, as described carrier, use be that specific area is 0.6～3.0m
2The weight ratio of the content of/g and Si and Na is with SiO
2/ Na
2The O scaled value is counted 2～50 carrier, with respect to every 1m of carrier
2The described specific area of/g, the content of described Re (take carrier as benchmark) is 170～600ppm, and the mol ratio of described Cs/Re is 0.3～19.
The 2nd invention is based on above-mentioned cognition (1) and the result that more furthers investigate, its main points are: a kind of oxirane catalyst for producing, it is used for making oxirane by ethene, and it comprises silver (Ag), caesium (Cs), rhenium (Re) and carrier at least; Wherein, as required, carrying alkali metal and then loads on Ag, Cs and Re on this carrier as pre-treatment on carrier, thereby obtains this catalyst, as described carrier, use be that specific area is 0.6～3.0m
2/ g and have the carrier of the following Kα of pKa5.0 is with respect to every 1m of carrier
2The described specific area of/g, the content of described Re (take carrier as benchmark) is 170～600ppm, and the mol ratio of described Cs/Re is 0.3～19.
Other main points of the present invention are: a kind of manufacture method of catalyst, the method is the manufacture method that comprises at least the 1st catalyst of inventing of silver (Ag), caesium (Cs), rhenium (Re) and carrier, wherein, the load operation of described Ag divides more than 2 times and carries out, and the Cs of at least a portion amount that contains in the catalyst and Re are loads when the last load operation of Ag.
Other main points of the present invention also are: a kind of manufacture method of catalyst, the method is the manufacture method that comprises at least the 2nd catalyst of inventing of silver (Ag), caesium (Cs), rhenium (Re) and carrier, wherein, the load operation of described Ag divides more than 2 times and carries out, and the Cs of at least a portion amount that contains in the catalyst and Re are loads when the last load operation of Ag.
Other main points of the present invention also are: a kind of manufacture method of oxirane, wherein, in the presence of the 1st catalyst of inventing, ethene is carried out oxidation.
Other main points of the present invention also are: a kind of manufacture method of oxirane, wherein, in the presence of the 2nd catalyst of inventing, ethene is carried out oxidation.
The 3rd invention is based on above-mentioned cognition (2), its main points are: a kind of oxirane catalyst for producing, this catalyst is used for making oxirane by ethene, and it comprises silver (Ag), lithium (Li), caesium (Cs), rhenium (Re) and carrier at least; Wherein, as described carrier, use be that specific area is 0.6～3.0m
2The carrier of/g, with respect to vehicle weight, Li content is 400～1000ppm.
Other main points of the present invention are: a kind of manufacture method of catalyst, the method is the manufacture method that comprises at least the 3rd catalyst of inventing of silver (Ag), lithium (Li), caesium (Cs), rhenium (Re) and carrier, wherein, the load operation of described Ag divides more than 2 times and carries out, and the Cs of at least a portion amount that contains in the catalyst and Re are loads when the last load operation of Ag.
Other main points of the present invention also are: a kind of manufacture method of oxirane, wherein, in the presence of the 3rd catalyst of inventing, ethene is carried out oxidation.
That is, the invention provides following technical scheme.
1. oxirane catalyst for producing, this catalyst are used for making oxirane by ethene, and it comprises silver (Ag), caesium (Cs), rhenium (Re) and carrier at least; Wherein,
As required, carrying alkali metal and then loads on Ag, Cs and Re on this carrier as pre-treatment on carrier, thereby obtains this catalyst,
As described carrier, use be that specific area is 0.6～3.0m
2The weight ratio of the content of/g and silicon (Si) and sodium (Na) is with SiO
2/ Na
2The O scaled value is counted 6～27 carrier,
Every 1m with respect to carrier
2The described specific area of/g, the content of described Re is 170～600ppm, and this content is take carrier as benchmark, and the mol ratio of described Cs/Re is 2.2～4.5, Cs in the mol ratio of described Cs/Re refers to post processing, is the Cs content that is carried in the processing of loaded Ag, Cs and Re on the catalyst.
2. above-mentioned 1 described catalyst, wherein, the principal component of carrier is Alpha-alumina.
3. above-mentioned 1 described catalyst, wherein, the Si content in the carrier is with SiO
2Scaled value is counted 0.5～7.0 % by weight.
4. above-mentioned 2 described catalyst, wherein, the Si content in the carrier is with SiO
2Scaled value is counted 0.5～7.0 % by weight.
5. above-mentioned 1 described catalyst, wherein, the Na content in the carrier is with Na
2The O scaled value is counted 0.05～0.50 % by weight.
6. above-mentioned 2 described catalyst, wherein, the Na content in the carrier is with Na
2The O scaled value is counted 0.05～0.50 % by weight.
7. above-mentioned 3 described catalyst, wherein, the Na content in the carrier is with Na
2The O scaled value is counted 0.05～0.50 % by weight.
8. above-mentioned 4 described catalyst, wherein, the Na content in the carrier is with Na
2The O scaled value is counted 0.05～0.50 % by weight.
9. each catalyst in above-mentioned 1～8, wherein, the alkali metal that is used for support pretreatment is lithium, the Li content after the pre-treatment in the carrier is 100～1000ppm.
10. each catalyst in above-mentioned 1～8, wherein, the alkali metal that is used for support pretreatment is caesium (Cs), the Cs content after the pre-treatment in the carrier is 100～1000ppm.
11. above-mentioned 9 described catalyst, wherein, the alkali metal that is used for support pretreatment also comprises caesium (Cs), and the Cs content after the pre-treatment in the carrier is 100～1000ppm.
12. each catalyst in above-mentioned 1～8, wherein, silver content accounts for 5～40 % by weight of total catalyst weight.
13. above-mentioned 9 described catalyst, wherein, silver content accounts for 5～40 % by weight of total catalyst weight.
14. above-mentioned 10 described catalyst, wherein, silver content accounts for 5～40 % by weight of total catalyst weight.
15. above-mentioned 11 described catalyst, wherein, silver content accounts for 5～40 % by weight of total catalyst weight.
16. the manufacture method of a catalyst, the method be comprise at least silver (Ag), caesium (Cs), rhenium (Re) and carrier above-mentioned 1～15 in the manufacture method of each described catalyst, wherein, the load operation of described Ag divides more than 2 times and carries out, and the Cs of at least a portion amount that contains in the catalyst and Re are loads when the last load operation of Ag.
17. the manufacture method of an oxirane, wherein, in above-mentioned 1～15 each described catalyst in the presence of, ethene is carried out oxidation.
The invention effect
Invent according to the 1st invention and the 2nd, provide comprise at least Ag, Cs, Re and carrier, selective improved oxirane catalyst for producing particularly.In addition, according to the 3rd invention, provide comprise at least Ag, Li, Cs, Re and carrier, the improved oxirane catalyst for producing of catalyst life particularly.
The specific embodiment
Below, the present invention is described in detail.
The catalyst of the＜the 1 invention 〉
The oxirane catalyst for producing of the 1st invention comprises Ag, Cs, Re and carrier at least, as optimal way, also contains Li.
As above-mentioned carrier, can list the porous refractories such as aluminium oxide, carborundum, titanium oxide, zirconia, magnesia, but that principal component is the material of Alpha-alumina is suitable especially.These porous refractories carry out sintering to the mixture of material powder, adhesive, gas pore-forming agent to be made, and wherein contains Si composition and Na composition as impurity.Si content is with SiO
2The scaled value meter is generally 0.5～7.0 % by weight, is preferably 1.8～7.0 % by weight; Na content is with Na
2O scaled value meter is generally 0.05～0.50 % by weight, is preferably 0.16～0.45 % by weight.Above-mentioned Si composition and the content range of Na composition are to consider and definite value from the angle that improves catalyst selectivity.
In the 1st invention, use ratio that the large and Si composition of surface area and Na become to divide at the carrier of certain limit, that is, specific area is 0.6～3.0m
2The weight ratio of the content of/g, Si and Na is with SiO
2/ Na
2The O scaled value is counted 2～50 carrier.When the carrier of such condition is satisfied in use, can improve the promoting catalysis of Re, obtain the selective catalyst that significantly improves.
Particularly from keeping the viewpoint consideration of the catalyst lifes such as catalyst selectivity, the specific area of carrier is preferably 0.8～2.0m
2/ g, more preferably 1.2～1.6m
2/ g; Particularly consider the weight ratio (SiO of the content of Si and Na from the viewpoint that improves catalyst selectivity
2/ Na
2The O scaled value) is preferably 6～27.And described specific area is the value that adopts the B.E.T. method to measure.
About catalyst carrier with porous refractory Alpha-alumina particularly, the commercialization of goods of the various grades that specific area, impurity content are different.Therefore, in the 1st invention, can from commercially available porous refractory, select to satisfy the goods of above-mentioned character, used as carrier.In addition, the content of the Si composition in the carrier and Na composition can clean to regulate to carrier by the aqueous acid with debita spissitudo.
Silver content accounts for 5～40 % by weight of total catalyst weight usually, considers from the viewpoint of the effect of improving catalyst life, is preferably 15～30 % by weight.The same with existing known catalyst, Cs content is generally 10～10000ppm with respect to total catalyst weight, is preferably 50～5000ppm.
Cs content depends on Re content described later, must be 0.3～19 scope in the Cs/Re mol ratio.The Cs/Re mol ratio is preferably 1.7～4.5, and more preferably 2.2～4.5.The Cs/Re mol ratio is less than 0.3 or greater than 19 o'clock, and the effect of improving catalyst selectivity is all insufficient.
In addition, Re content depends on the specific area of employed carrier, with respect to every 1m of carrier
2The described specific area of/g (specific area of the carrier before being embedded in the catalyst), described Re content is 170～600ppm, is preferably 200～500ppm, more preferably 250～450ppm.Re content is less than 170ppm/ (m
2/ g) or surpass 600ppm/ (m
2/ g) time, the effect of improving catalyst selectivity is insufficient.
In the 1st invention, can be as required on above-mentioned carrier carrying alkali metal as pre-treatment.Consider that from the viewpoint of further raising catalyst performance this support pretreatment is recommendable.Here, the pre-treatment alkali-metal load that refers to carry out before load silver compound is processed.As the alkali metal that in pre-treatment, uses, usually use Li and/or Cs, preferably use Li and Cs.And the Cs in above-mentioned " Cs/Re mol ratio " refers to be carried on the Cs content on the catalyst in post processing (processing of loaded Ag, Re and Cs).Be carried on the surface that Cs on the catalyst is considered to be present in Re Ag in the post processing.
The consumption of Li and Cs with pre-treatment after Li or Cs content meter in the carrier be generally 100～1000ppm.Li content is preferably 400～1000ppm, and more preferably 550～1000ppm is particularly preferably 585～1000ppm.Cs content is preferably 100～500ppm.When the Li in the carrier and Cs content during less than 100ppm, the effect of improving catalyst life is insufficient; And when it surpassed 1000ppm, effect can not improve again, thereby and uneconomical.And Cs used herein directly is carried on the carrier, and it is different from Cs in the above-mentioned post processing in this.Because as previously mentioned, the Cs in the post processing is considered to be attached on the Ag with Re.
In the oxirane catalyst for producing of the 1st invention, consider that from the viewpoint of the effect of improving catalyst life the Li/Re mol ratio is generally 6～63, is preferably 25～63, more preferably 35～63, be particularly preferably 37～63; The Li/Ag weight ratio is generally 0.0007～0.0073, is preferably 0.0029～0.0073, and more preferably 0.0040～0.0073, be particularly preferably 0.0043～0.0073.
The load of the alkali metal in the aforementioned pre-treatment (Li and Cs) can use the water-soluble alkali compound to carry out according to known method in the past.As above-mentioned alkali metal compound, such as listing nitrate, hydroxide, halide, carbonate, bicarbonate, oxalates, carboxylate etc., particularly preferably carbonate.They can use with the form of the aqueous solution of debita spissitudo according to content.
In aforementioned post processing, it is easy using the following catalyst that makes to contain immersion liquid: the water miscible Re compound of dissolving and water miscible Cs compound in argent-amine complex solution, and dissolve again as required water miscible Li compound.
Ag compound as being used for argent-amine complex solution can list silver oxide, silver nitrate, silver carbonate, silver acetate, silver oxalate etc.; As amine, can list the monoamines such as ammonia, pyridine, butylamine; The hydramine such as monoethanolamine; Ethylenediamine, 1, the polyamines such as 3-propane diamine.As water miscible Re compound, can list rhenium halide, hydroxyl rhenium halide, rhenate, cross rhenate etc.As water miscible Cs compound, can list with pre-treatment in identical compound, but preferably nitrate or hydroxide.Catalyst contains the concentration of above-mentioned each composition in the immersion liquid, can suitably determine according to the content of each composition.
As the impregnation method in the pre-treatment step, can list the method for carrier impregnation in solution, perhaps to the method for carrier spray solution.Process as drying, can list following method etc.: impregnation after processing separates carrier and residual solution, then drying under reduced pressure or carry out drying by heat treated.As heat treated, can list the method for non-active gas such as utilizing air, nitrogen or overheated steam.Heating-up temperature is generally 100～300 ℃, is preferably 130～270 ℃.
As the impregnation method in the post-processing step, can list method same as described above.Heat treated after the impregnation should be measured Ag and implement in necessary temp and time that carrier is separated out.Preferred select following condition, described condition so that silver with as far as possible evenly and the form of subparticle be present on the carrier.Heat treated can use air non-active gas such as (or) nitrogen or the overheated steam of heating to carry out.Heating-up temperature is generally 130～300 ℃, is generally 5～30 minutes heat time heating time.
Adopt catalyst manufacture method of the present invention can easily obtain the high catalyst of Ag load factor, for example the Ag load factor is the catalyst of 15～30 % by weight (take catalyst as benchmark), wherein the catalyst manufacture method of the present invention load operation that is following method: Ag divides more than 2 times and carries out, and the Cs of at least a portion amount that contains in the catalyst and Re are loads when the last load operation of Ag.Consider that from the viewpoint of catalytic performance the Cs of preferred amount over half and Re are loads when the last load operation of Ag.The amount of the Cs of load and Re more than 3/4 of amount of Cs and Re more preferably during the last load operation of Ag is preferably amount whole of Cs and Re.In addition, also be the same for Cs with Re composition in addition.The manufacture method of catalyst according to the invention, Cs, Re etc. when the last load operation of Ag with the Ag load, and adopt behind the last load operation of Ag, when carrying out independently mutually the method for load of Cs, Re etc. with this operation, the performance reduction of catalyst.
Use the oxirane manufacture method of the oxirane catalyst for producing of the 1st invention, can carry out according to known condition.Reaction pressure is generally 0～3.5MPaG; Reaction temperature is generally 180～350 ℃, is preferably 200～300 ℃.Composition as reactor feed gas, the mist of normal operation ethene 1～40 capacity % and molecular oxygen 1～20 capacity %, in addition, generally can there be the diluent of certain proportion (for example 1～70 capacity %), non-active gas such as methane, nitrogen.As the gas that contains molecular oxygen, usually use air or tonnage oxygen.In addition, for example adding in the reactor feed gas, the halogenated hydrocarbon about 0.1～50ppm can prevent from like this forming in the catalyst focus, and can significantly improve catalyst performance, particularly selective as the reaction adjusting agent.
The catalyst of the＜the 2 invention 〉
The oxirane catalyst for producing of the 2nd invention is used for making oxirane by ethene, and it comprises silver (Ag), caesium (Cs), rhenium (Re) and carrier at least; Wherein, as required, carrying alkali metal and then loads on Ag, Cs and Re on this carrier as pre-treatment on carrier, thereby obtains this catalyst, as described carrier, use be that specific area is 0.6～3.0m
2/ g and have the carrier of the following Kα of pKa5.0 is with respect to every 1m of carrier
2The described specific area of/g, the content of described Re (take carrier as benchmark) is 170～600ppm, and the mol ratio of described Cs/Re is 0.3～19.That is, the 2nd invention defines Kα, replaces the SiO that in the 1st invention carrier is done
2/ Na
2The restriction of O ratio, in this, they are different from the 1st invention.And, with restriction SiO
2/ Na
2The situation of O ratio is identical, by the above-mentioned promoting catalysis that can improve equally Re to the restriction of Kα.
The suitable Kα that limits in the 2nd invention refers to: the intensity that pKa5.0 is following, and have chromogenic reaction take methyl red as indicator.In addition, the intensity of Kα is when pKa3.2 is following, if cause the amount of weak chromogenic reaction degree, then can not affect the selective of catalyst, if but this amount increases to the degree that causes strong chromogenic reaction, then can make the elective reduction of catalyst, therefore also not preferred.The following Kα of pKa3.2 refers to have the chromogenic reaction take methyl yellow as indicator.In addition, the above ionization constant of base of not preferred pKa7.3, this refers to can present chromogenic reaction with bromthymol blue.
(Chang Yizhu " acid base catalysator " is 161 pages under field section great three and the bamboo for clear and on April 26th, 41, the distribution of industry books Co., Ltd. for Acidity of Aikalinity that can be by easily judging carrier surface based on the chromogenic reaction of indicator method; Clear and on May 1st, 61, the distribution of talk society, catalysis association compiles that " 170 pages of catalyst experiment handbook are not rolled up in the catalysis lecture; Clear and on June 25th, 59, the distribution of the kind Co., Ltd. of ball, " a chemical brief guide basis piece of writing " the 3rd edition, II-342 page or leaf are compiled by Japanization association).
In addition, the value of Kα can be obtained by following method: with alkali such as n-butylamines the sample by above-mentioned indicator colour developing is carried out titration.Usually, judge that by range estimation the terminal point of indicator chromogenic reaction and alkalimetric titration reaction is feasible.
The catalyst of the＜the 3 invention 〉
The oxirane catalyst for producing of the 3rd invention comprises silver (Ag), lithium (Li), caesium (Cs), rhenium (Re) and carrier at least.In this, its catalyst with the optimal way of the 1st invention is identical.
The 3rd the invention in, use be that specific area is 0.6～3.0m
2The carrier of/g.Identical with the carrier of use in the 1st invention in this.Ratio (the SiO that Si composition in the carrier that limits in the 1st invention and Na become to divide
2/ Na
2O) be optimum condition, but not necessary condition.Other condition about carrier is identical with the 1st invention.
In the 3rd invention, the Li content of catalyst is 400～1000ppm with respect to vehicle weight.This Li content is the value of putting down in writing as preferable range in the 1st invention.The Cs that limits in the 1st invention and content and the Cs/Re mol ratio of Re are optimum conditions, but not necessary condition.About other condition of catalyst component, identical with the 1st invention.In addition, the manufacture method of the catalyst of the 3rd invention is also identical with the 1st invention with using method.
Embodiment
Below, illustrate in greater detail the present invention by embodiment, but the present invention is only otherwise break away from its main points, then is not subjected to the restriction of these embodiment.And, below the assay method of the physical property used in each example as described below.In addition, " embodiment " represents that with mark " A " in " comparative example " these examples are relevant with aforementioned the 1st invention; And mark " B " expression is relevant with aforementioned the 3rd invention.
(1) specific area:
Adopt the B.E.T. method to measure.Being adsorbed under the 77K of nitrogen carried out, and adopts BET1 point method to calculate specific area.
(2) Si in the carrier and Na content:
Sample is pulverized, then that it is compressing, utilize fluorescent x-ary analysis to measure.
(3) CS, the Re in pre-treatment carrier and the catalyst and Li content:
Extract mentioned component with nitric acid, adopt aas determination Cs and Li, adopt the ICP luminescence method to measure Re.
(4) the Ag content in the catalyst:
Extract Ag with nitric acid, adopt potential difference titration to measure.
(5) acid of carrier, basicity:
The acid of following mensuration carrier, basicity.That is, carrier in 120 ℃ times dry 3 hours, after the cooling, is added into it in dry toluene.To wherein adding the several indicator (0.001 % by weight) that are dissolved in the toluene, fully then vibration leaves standstill again.Then, investigate for each indicator whether chromogenic reaction is arranged.
Embodiment 1A:
(1) mensuration of the acid of carrier, basicity:
To alpha-alumina supports (surface area 1.0m
2/ g, water absorption rate 35.7 % by weight, SiO
23.0 % by weight, Na
2O 0.35 % by weight, SiO
2/ Na
2The O weight ratio is 9, is shaped as the ring-type of 8mm φ * 8mm) carry out the mensuration of acid-base value.
Use pKa is that red chromogenic reaction does not appear in the methyl yellow below 3.2, and use pKa is that the methyl red below 5.0 then demonstrates red chromogenic reaction.In addition, using pKa is the chromogenic reaction that blueness does not appear in bromthymol blue 7.3 or more.As known from the above, above-mentioned carrier has the Kα of 3.2＜pKa≤5.0, does not have the ionization constant of base of pKa 〉=7.3.
(2) pre-treatment of carrier:
The above-mentioned alpha-alumina supports of 100g is immersed in is dissolved with 0.156g cesium carbonate (Cs
2CO
3) and 1.69g lithium carbonate (Li
2CO
3) the 200mL aqueous solution in, remove remaining liquid, then it heat 15 minutes in 150 ℃ overheated steam, flow velocity is 2m/ second, contains the carrier that is soaked with Li and Cs composition thereby prepare.Li content in the carrier is 500ppm, and Cs content is 230ppm.The physical property of employed carrier has been shown in the table 1.
(3) preparation of argent-amine complex solution:
With 322g silver nitrate (AgNO
3) be dissolved in the 1.4L water, with 192g potassium oxalate monohydrate (K
2C
2O
4H
2O) be dissolved in the 1.6L water, they are heated to 60 ℃ in hot bath, and in this process with they slow mixing, obtain white precipitate silver oxalate (Ag
2C
2O
4).By the filtered and recycled sediment, with the distilled water washing, obtain aqueous oxalic acid silver (water content 23.3 % by weight).The aqueous oxalic acid silver that 375g is obtained so slowly adds in the following solution and makes it dissolving, preparation argent-amine complex solution, and described solution is by 103g ethylenediamine, 28.1g 1, and 3-propane diamine and 133g water consist of.
(4) preparation of Ag catalyst:
In the argent-amine complex solution of the above-mentioned acquisition of 12.7g, add 0.6mL cesium nitrate (CsNO
3) concentration is the aqueous solution, the 0.6mL ammonium perrhenate (NH of 5.54 % by weight
4ReO
4) concentration is the aqueous solution, the 2.1mL water of 3.05 % by weight, obtained impregnation solution.For the impregnation solution of such acquisition, in rotary evaporator, under reduced pressure, be heated to 40 ℃, it is contained be immersed in 30g and contain in the alpha-alumina supports that is soaked with Li and Cs.Then this impregnation carrier was heated 15 minutes in 200 ℃ overheated steam, flow velocity is 2m/ second, thereby obtains catalyst.The content of Ag, Cs, Re, Li in this catalyst (take carrier as benchmark) is respectively 13.6 % by weight (being shown 12.0 % by weight take catalyst as master meter), 980ppm, 420ppm, 500ppm.
(5) oxidation reaction of ethene
The Ag catalyst of above-mentioned preparation is pulverized 6～10 orders, wherein 3mL is filled in the SUS reaction tube processed of internal diameter 7.5mm, with GHSV4300 hour
-1, pressure 0.7MPaG condition by reaction gas (ethene 30%, oxygen 8.5%, vinyl chloride 1.5ppm, carbon dioxide 6.0%, surplus are nitrogen), react.The conditioned reaction temperature is so that the oxirane output (STY) of unit catalyst volume, unit interval is 0.25kg-EO/hL-cat.Increase with evaluation time, selectively raising first of oxirane reduced again.Table 3 and table 4 show catalyst component and catalytic performance.And, to selectively representing take ethene as benchmark of oxirane.In addition, the Cs* of " Cs*/Re " in table 3 and the table 4/the be illustrated in Cs content of catalyst institute load in the post processing.In addition, " degradation speed " of catalyst performance expression is with respect to the selective decline of accumulation ring oxidative ethane (EO) 1000kg-EO/L-cat, and unit is " %/EO1000 ".
Embodiment 2A～12A and comparative example 1A～11A
Mode by embodiment 1A is carried out pre-treatment, and different is: use the carrier with physical property shown in table 1 and the table 2, and change the amount of lithium carbonate and cesium carbonate so that during pre-treatment the content of Li and Cs shown in table 3 and table 4.Then, " the argent-amine complex solution " that preparation is identical with composition among the embodiment 1A, but when " preparation of Ag catalyst " of embodiment 1A, the concentration of change cesium nitrate and ammonium perrhenate makes Cs and the catalyst of Re content shown in table 3 and table 4.And the Ag content in any catalyst (take carrier as benchmark) is 13.6 % by weight.Then, use various catalyst and embodiment 1A similarly to carry out ethylene oxidation reactions.Table 3 and table 4 show catalyst component and catalyst performance.
By above-mentioned table 1～table 4 as can be known:
(1) in the catalyst that comprises Ag, Cs, Re and carrier, in satisfying the embodiment 1A～12A of following condition, high selectivity is 84.7～86.5%, and wherein, described condition is: the SiO of the carrier of use
2/ Na
2The O weight ratio was 2～50 (or having the following Kα of pKa5.0); With respect to every 1m
2/ g carrier specific area, the content of Re (take carrier as benchmark) is 170～600ppm; The Cs*/Re mol ratio is 0.3～19.
(2) particularly at the SiO of the carrier that uses
2/ Na
2The O weight ratio is 6～27, the Cs*/Re mol ratio is that high selectivity is up to 85.7～86.5% among embodiment 1A～8A of 2.2～4.5, and above-mentioned scope is preferred as can be known.
(3) compare the SiO of carrier with the situation of embodiment 1A～12A
2/ Na
2Among the comparative example 1A～3A of O weight ratio outside 2～50 scope, high selectivity is low, is 80.8～83.4%, and hence one can see that: in order to improve the selective of catalyst, the SiO of carrier
2/ Na
2The O weight ratio must be in above-mentioned scope.And, the SiO of carrier
2/ Na
2When the O weight ratio was in or be not in 2～50 scope, it was 3.1% that selective difference is come the words of comparison with maximum, and this is very large.
(4) compare with the situation of embodiment 1A～12A, with respect to every 1m
2At the comparative example 4A of 170～600ppm scope, its high selectivity is not low, is 81.9% for the Re content of/g carrier specific area (take carrier as benchmark).Hence one can see that: in order to improve the selective of catalyst, Re content must be in above-mentioned scope.
(5) comparative example 5A～11A shows: for the catalyst that does not contain Re, and the SiO of carrier
2/ Na
2The O weight ratio selectively there is no effect to catalyst.That is, at the SiO of carrier
2/ Na
2The O weight ratio (is SiO in 2～50 scope
2/ Na
2The O weight ratio is 11) comparative example 5A and 6A in, Cs content has been carried out the result after the optimization be: high selectivity is 81.9%.Relative therewith, at the SiO of carrier
2/ Na
2The O weight ratio is among 0.6 the comparative example 7A and 8A, and Cs content has been carried out the result after the optimization be: high selectivity is 80.8%, and at the SiO of carrier
2/ Na
2The O weight ratio is among comparative example 9A～11A of 68, and Cs content has been carried out the result after the optimization be: high selectivity is 81.6%; The SiO of carrier
2/ Na
2The O weight ratio not the catalyst in 2～50 scope selectively be 80.8～81.6%.That is, the SiO of carrier
2/ Na
2When the O weight ratio was in or be not in 2～50 scope, it was 0.3% that selective difference is come the words of comparison with maximum, and this value is very little, and only for to contain 1/10 of Re catalyst, it there is no effect as can be known.
Embodiment 1B:
(1) pre-treatment of carrier
Undertaken by similarly operating with embodiment 1A, different is: use surface area 1.4m2/g, water absorption rate 41.6 % by weight, SiO
22.8 % by weight, Na
2O 0.25 % by weight, SiO
2/ Na
2The O weight ratio is 11, be shaped as the ring-type alpha-alumina supports of 8mm φ * 8mm, and changes the amount of lithium carbonate and cesium carbonate, so that the content of Li and Cs is as shown in table 6 during pre-treatment, contains the carrier that is soaked with Li and Cs composition thereby prepared.Li content in the carrier is 600ppm, and Cs content is 340ppm.The physical property of employed carrier has been shown in the table 5.
(2) preparation of argent-amine complex solution:
Carry out preparation argent-amine complex solution by the operation identical with embodiment 1A.
(3) preparation of Ag catalyst:
Undertaken by the operation identical with embodiment 1A, obtain catalyst.The content of Ag, Cs, Re, Li in this catalyst (take carrier as benchmark) is respectively 13.6 % by weight (being 12.0 % by weight when representing take catalyst as benchmark), 1090ppm, 420ppm, 600ppm.
(4) oxidation reaction of ethene:
React by the operation identical with embodiment 1A.Table 6 shows catalyst component and catalyst performance.Implication every in the table 6 is identical with table 3 and table 4.
Embodiment 2B～6B and comparative example 1B～8B:
At first, as embodiment 1B, obtain Li/Cs content carrier as shown in table 6, different is: use the carrier with characteristic shown in the table 5 in " pre-treatment of carrier " of embodiment 1B, and change the amount of lithium carbonate and cesium carbonate, so that the content of Li and Cs is as shown in table 6 during pre-treatment.Then, " the argent-amine complex solution " that preparation is identical with composition among the embodiment 1B, but in embodiment 1B described " preparation of Ag catalyst " step, change the concentration of cesium nitrate and ammonium perrhenate, make Cs and Re content catalyst as shown in table 6.At this moment, the example for further load Li in the post processing in " preparation of Ag catalyst " step, adds a certain amount of lithium nitrate (LiNO
3).And the Ag content in any catalyst (take carrier as benchmark) is 13.6 % by weight.Then, use various catalyst and embodiment 1B similarly to carry out ethylene oxidation reactions.Catalyst component and catalyst performance have been shown in the table 6.
Embodiment 7B:
At first, as embodiment 1B, obtain Li/Cs content carrier as shown in table 6, different is: use the alpha-alumina supports (water absorption rate 34.6 % by weight) with characteristic shown in the table 5 in " pre-treatment of carrier " of embodiment 1B, and change the amount of lithium carbonate and cesium carbonate, so that the content of Li and Cs is as shown in table 6 during pre-treatment.Then, " the argent-amine complex solution " that preparation is identical with composition among the embodiment 1B divides the load operation that carries out Ag 2 times by following main points.
(the 1st Ag load operation)
In the argent-amine complex solution of the above-mentioned acquisition of 12.7g, add 1.3mL water, obtain impregnation solution.For the impregnation solution of such acquisition, in rotary evaporator, under reduced pressure, be heated to 40 ℃, it is contained be immersed in 30g and contain in the alpha-alumina supports that is soaked with Li and Cs.Then this impregnation carrier was heated 15 minutes in 200 ℃ overheated steam, flow velocity is 2m/ second.
(the 2nd Ag load operation)
In the argent-amine complex solution of the above-mentioned acquisition of 12.7g, add 0.5mL cesium nitrate (CsNO
3) concentration is the aqueous solution, the 0.5mL ammonium perrhenate (NH of 9.97 % by weight
4ReO
4) concentration is the aqueous solution, the 0.2mL lithium nitrate (LiNO of 5.75 % by weight
3) concentration is the aqueous solution and the 0.2mL water of 10.1 % by weight, obtains impregnation solution.For the impregnation solution of such acquisition, in rotary evaporator, under reduced pressure, be heated to 40 ℃, it is contained be immersed in the above-mentioned carrier of having finished the 1st Ag load operation.Then this impregnation carrier was heated 15 minutes in 200 ℃ overheated steam, flow velocity is 2m/ second, thereby obtains catalyst.The content of Ag, Cs, Re, Li in this catalyst (take carrier as benchmark) is respectively 26.2 % by weight (being 20.8 % by weight when representing take catalyst as benchmark), 1500ppm, 530ppm, 660ppm.Use this catalyst and embodiment 1B similarly to carry out ethylene oxidation reactions.Catalyst component and catalyst performance have been shown in the table 6.
[table 5]
By above-mentioned table 5 and table 6 as can be known:
(1) in the carrier that comprises Ag, Li, Cs, Re, in Li content (take carrier as benchmark) was aggregated in embodiment 1B～6B in 400～1000ppm scope, high selectivity was 85.3～86.2%, degradation speed is 4.8～24.0.Relative therewith, at Li content not among the comparative example 1B and 2B in above-mentioned scope, high selectivity is 83.4～84.0%, degradation speed is 33.0～80.0, has selectively descended 2.1%, degradation speed reaches 6.9 times.That is, hence one can see that: Li content is limited in the above-mentioned scope, and can the rugged catalyst life-span.
(2) particularly in Li content (take carrier as benchmark) is aggregated in embodiment 1B～4B in 550～1000ppm scope, high selectivity is 85.3～86.2%, degradation speed is 4.8～9.1.Relative therewith, at Li content not among the comparative example 5B and 6B in above-mentioned scope, high selectivity is 85.5～86.1%, degradation speed is 11.0～24.0, and degradation speed reaches 2.3 times.That is, hence one can see that: Li content is limited in the above-mentioned scope, and can the rugged catalyst life-span.
(3) in addition, for embodiment 1B～5B and comparative example 3B～6B or embodiment 6B and comparative example 7B, 8B, as shown in table 5, the carrier that uses in catalyst is identical, and Li content adds up to all in the scope of 400～1000ppm, and its difference is whether contain Re.The former selectively is respectively 85.3～86.2% and 81.3～81.7%, and the latter selectively is respectively 86.1% and 81.6%, contains as can be known the selective height of Re catalyst.That is, hence one can see that: when the use specific area is 0.6～3.0m
2When the carrier of/g and lithium content were 400～1000ppm with respect to total catalyst weight, the interpolation of Re selectively was effective for what improve catalyst.
(4) thus carry out the Ag load operation at minutes 2 times and improved among the embodiment 7B of Ag load factor, catalyst degradation speed is 2.5, catalytic life is significantly improved.
Claims (17)
1. oxirane catalyst for producing, this catalyst are used for making oxirane by ethene, and it comprises silver (Ag), caesium (Cs), rhenium (Re) and carrier at least; Wherein,
As required, carrying alkali metal and then loads on Ag, Cs and Re on this carrier as pre-treatment on carrier, thereby obtains this catalyst,
As described carrier, use be that specific area is 0.6～3.0m
2The weight ratio of the content of/g and silicon (Si) and sodium (Na) is with SiO
2/ Na
2The O scaled value is counted 6～27 carrier,
Every 1m with respect to carrier
2The described specific area of/g, the content of described Re is 170～600ppm, and this content is take carrier as benchmark, and the mol ratio of described Cs/Re is 2.2～4.5, Cs in the mol ratio of described Cs/Re refers to post processing, is the Cs content that is carried in the processing of loaded Ag, Cs and Re on the catalyst.
2. the catalyst of claim 1, wherein, the principal component of carrier is Alpha-alumina.
3. the catalyst of claim 1, wherein, the Si content in the carrier is with SiO
2Scaled value is counted 0.5～7.0 % by weight.
4. the catalyst of claim 2, wherein, the Si content in the carrier is with SiO
2Scaled value is counted 0.5～7.0 % by weight.
5. the catalyst of claim 1, wherein, the Na content in the carrier is with Na
2The O scaled value is counted 0.05～0.50 % by weight.
6. the catalyst of claim 2, wherein, the Na content in the carrier is with Na
2The O scaled value is counted 0.05～0.50 % by weight.
7. the catalyst of claim 3, wherein, the Na content in the carrier is with Na
2The O scaled value is counted 0.05～0.50 % by weight.
8. the catalyst of claim 4, wherein, the Na content in the carrier is with Na
2The O scaled value is counted 0.05～0.50 % by weight.
9. each catalyst in the claim 1～8, wherein, the alkali metal that is used for support pretreatment is lithium, the Li content after the pre-treatment in the carrier is 100～1000ppm.
10. each catalyst in the claim 1～8, wherein, the alkali metal that is used for support pretreatment is caesium (Cs), the Cs content after the pre-treatment in the carrier is 100～1000ppm.
11. the catalyst of claim 9, wherein, the alkali metal that is used for support pretreatment also comprises caesium (Cs), and the Cs content after the pre-treatment in the carrier is 100～1000ppm.
12. each catalyst in the claim 1～8, wherein, silver content accounts for 5～40 % by weight of total catalyst weight.
13. the catalyst of claim 9, wherein, silver content accounts for 5～40 % by weight of total catalyst weight.
14. the catalyst of claim 10, wherein, silver content accounts for 5～40 % by weight of total catalyst weight.
15. the catalyst of claim 11, wherein, silver content accounts for 5～40 % by weight of total catalyst weight.
16. the manufacture method of a catalyst, the method is the manufacture method that comprises at least each described catalyst in the claim 1～15 of silver (Ag), caesium (Cs), rhenium (Re) and carrier, wherein, the load operation of described Ag divides more than 2 times and carries out, and the Cs of at least a portion amount that contains in the catalyst and Re are loads when the last load operation of Ag.
17. the manufacture method of an oxirane, wherein, in claim 1～15 each described catalyst in the presence of, ethene is carried out oxidation.
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| JP107330/2006 | 2006-04-10 | ||
| PCT/JP2007/000352 WO2007116585A1 (en) | 2006-04-10 | 2007-03-30 | Catalyst for ethylene oxide production, method for producing the same, and method for producing ethylene oxide |
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| US11400437B2 (en) * | 2016-08-08 | 2022-08-02 | Basf Se | Catalyst for the oxidation of ethylene to ethylene oxide |
| TWI808125B (en) * | 2018-02-07 | 2023-07-11 | 德商巴斯夫歐洲公司 | Catalyst effective in the oxidative conversion of ethylene to ethylene oxide |
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| JP4206404B2 (en) * | 1995-09-25 | 2009-01-14 | 三菱化学株式会社 | Catalyst for ethylene oxide production |
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| CN1060839A (en) * | 1989-10-18 | 1992-05-06 | 联合碳化化学品及塑料有限公司 | The alkylene oxide catalyst that contains high silver content |
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