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Silver catalyst for epoxyethane production, its preparation method and application
CN1426836A
China
- Other languages
Chinese - Inventor
张志祥 金积铨 高政 陈建设 蒋文贞 何学勤 蒋军 崔宝林 - Current Assignee
- Beijing Research Institute of Beijing Yanshan Petrochemical Corp
Worldwide applications
2001
CN
Application CN01144552A events
2001-12-20
2003-07-02
2004-10-20
Application granted
2004-10-20
2021-12-20
Anticipated expiration
Status
Expired - Lifetime
Description
translated from
Technical field
The present invention relates to a kind of silver catalyst and preparation method thereof, more particularly the present invention relates to a kind of silver catalyst of producing by the ethene oxidation in oxirane and preparation method thereof that is used for, also relate to this catalyst and produce purposes in the oxirane in the ethene oxidation.
Background technology
The ethene oxidation mainly generates oxirane under the silver catalyst effect, side reaction takes place simultaneously generate carbon dioxide and water, and wherein activity, selectivity and stability are the main performance index of silver catalyst.So-called activity is meant reaction temperature required when process for ethylene oxide production reaches certain reaction load.Reaction temperature is low more, and activity of such catalysts is high more.So-called selectivity is meant that conversion of ethylene in the reaction becomes the ratio of the overall reaction molal quantity of the molal quantity of oxirane and ethene.So-called stability then is expressed as active and fall off rate optionally, and the fall off rate stability of small catalyst more is good more.The silver catalyst that uses high activity, high selectivity and have good stability in the process of ethene oxidation production oxirane can be increased economic efficiency greatly, and the silver catalyst of therefore making high activity, high selectivity and good stability is the main direction of silver catalyst research.The performance of silver catalyst has the important relationship except that composition and the preparation method with catalyst, and also the performance and the preparation method of the carrier that uses with catalyst have important relationship.
In the prior art preparation method of silver catalyst comprise the preparation and administration to active component of porous carrier (as aluminium oxide) and auxiliary agent to as described in this two processes on the carrier.
Know,, must provide high silver granuel specific surface for improving catalyst activity.Thereby require carrier that enough big specific surface is arranged.But specific surface is crossed conference and is caused withdrawing from the reaction heat difficulty, and the aggravation side reaction descends selectivity.For improving catalyst selectivity, the desirable pore structure that adapts with the surface just must be arranged, cause the good heat transfer mass transfer condition, reduce the generation of side reaction.Because reaction is to carry out, therefore seek pore structure has become development high selectivity silver catalyst with the carrier of specific surface collocation the best key subjects under near the condition of DIFFUSION CONTROLLED.
Japanese patent application JP4363139, European patent application EP 0255975 and EP0299569 use SnSO
4Improve alumina support Deng as additive, described selection of catalysts of these patents and activity are still on the low side, are about 80% as selectivity among the JP4363139, and reaction temperature is 228-233 ℃; The selectivity of EP0255975 is about 79.6-82.5%, and reaction temperature is 230 ℃; The selectivity of EP0299569 is less than 82%, and reaction temperature is up to 242 ℃.So, use the cost of these Catalyst Production oxirane still higher.In addition, the experimental result of JP4363139 shows: compare with not additivated catalyst, the adding of Sn salt has only improved 0.8% with selection of catalysts, but has but significantly reduced the activity of silver catalyst, makes reaction temperature improve 7 ℃.
Therefore, in the preparation process of silver catalyst, for α-Al
2O
3Carrier for key component, suitable specific surface and pore structure need, and will reaction heat be spread out for epoxidation of ethylene provides enough spaces on the one hand, also help the timely desorption of product oxirane on the other hand, avoid deep oxidation to generate the accessory substance carbon dioxide.It is 0.2-2m that the gibbsite that China authorization patent CN1009437B (China Petrochemical Corporation etc., 1988) has disclosed the ratio appropriate mix is mixed with out specific surface
2The alumina support of/g, the about 0.5mg/g of pore volume, wherein the hole greater than 30 μ m accounts for more than 25%, is used for the selectivity that epoxidation of ethylene can reach 83-84%.
In addition, the method that active component silver and various auxiliary agents are applied on the carrier mainly is an infusion process, promptly alumina support is dipped in the solution that silver salt, organic amine and various auxiliary agent make, and removes to add thermal reduction behind the solution and make the soaked carrier activation.Alkali metal is the most frequently used auxiliary agent, uses the patent of base earth metal promoter few.JP55049147 (Mitsui Toatsu Chem.Inc., 1980) makes its regeneration with the fatty alcohol solution dipping dead catalyst of caesium and calcium; Silver catalyst baric 0.01-0.25% and alkali metal promoter that US4305844 (corresponding to EP0017725, Huels Chemische Werke AG, 1981) makes, initial activity and selectivity are all very low; US4350616 (The Dow Chemical Company, 1982) has also used caesium and barium in the silver catalyst manufacture process, but the activity of the silver catalyst of making and selectivity are all very low, and selectivity is up to 84.0%; The epimere that US4376718 (Huels Chemische Werke AG, 1983) has described at reactor has added the auxiliary agent bed, and auxiliary agent is selected from the compound of potassium, rubidium, caesium, barium, has improved the stability of beds; The carrier specific surface that the silver catalyst preparation method that US4400308 (EC ErdoelchemieGmbh, 1983) discloses is used is 0.4-0.5m
2/ g, the particle diameter of load silver are 0.3-0.4 μ m, use the alkali metal caesium of 0.001-0.03% and the alkaline-earth metal barium of 0.05-0.5%, and the silver catalyst selectivity of making is the highest only to reach 81.5%; SU1685510 (Chlorine Ind.Res.Des.Int., 1991) uses specific surface less than 1m
2The alumina support of/g, amido complex compound, alkali metal salt, alkaline earth metal compound with silver salt are handled carrier, handle with alkali metal salt and surfactant again after the drying, the alkali salt that patent is used is calcium nitrate and barium nitrate, add the DeGrain that alkaline-earth metal is obtained, space-time yield during less than 180gEO/1/h selectivity be up to 78.2%; DD289413A and DD288067 (Veb Leuna-Werke AG, 1991) have disclosed with organic acid silver, excessive lactic acid, alkaline-earth metal and alkali-metal acid solution and have been coated onto specific surface less than 0.3m
2The method for preparing silver catalyst on the/g carrier, the alkaline-earth metal that uses is barium, and catalyst selectivity is made moderate progress, but high selectivity only is 77%; US4812437 (corresponding to EP0247414, MitsubishiPetrochemical Co., 1989) is with silver and be selected from least a of sodium, potassium, rubidium, caesium, is deposited on to contain Al
6Si
2O
13Carrier on, sodium content has also used barium salt up to 0.08-1.2% on the carrier in catalyst preparation process, the selectivity of the silver catalyst of making is up to 81.2%; The first depositing silver of DE3310752 (corresponding to US4760042) and US4841080 (ScientificDesign Co., 1988,1989) is at specific surface 0.3-0.8m
2On the carrier of/g, deposit alkali metal 50-300ppm after the activation again, patent claims that catalyst also comprises base earth metal promoter, preferred barium, and the selectivity of the silver catalyst that this patent is made only reaches 79.7%; WO9613493 is (corresponding to EP789693, Shell Int.Research, 1996) when preparation rhenium-containing silver catalyst, deposit alkaline-earth metal earlier before depositing silver, alkali metal promoter, rhenium auxiliary agent and the assistance agent thereof, preferred barium and/or magnesium, the initial activity that only deposits the catalyst that alkaline-earth metal and silver and alkali metal promoter make in the patent is higher, but selectivity only reaches 81.5%, and this patent is improved the initial activity of rhenium-containing silver catalyst by the pre-deposition alkaline-earth metal.
Although above-mentioned patent documentation has improved alumina support itself respectively and has used base earth metal promoter, especially barium, but the effect that obtains is still not obvious, so this area still needs a kind of silver catalyst that comprehensively is improved and preparation method thereof on activity, selectivity and stability.
Summary of the invention
Situation in view of above-mentioned prior art, the present inventor has carried out research extensively and profoundly in the silver catalyst field, found that on specific porous alumina carrier the solution that dipping is mixed with by silver compound, organic amine and specific auxiliary agent, through air or oxygen content less than 21% nitrogen oxygen atmosphere in after the heat treatment prepared silver catalyst in ethylene oxidation reactions activity, selectivity and activity and optionally stability all be improved.The present invention uses specific surface at 0.5-2.0m
2Between/the g, α-Al with appropriate bore structure
2O
3Carrier, be immersed in the mixed solution of silver salt, organic amine, alkali metal promoter and base earth metal promoter composition, make silver catalyst after the drying activation, has higher initial performance and stability, especially the adding of alkaline-earth metal strontium can make the first selectivity of catalyst reach 85.3%, and the stability of this catalyst sample obviously improves especially.
Therefore, the purpose of this invention is to provide a kind of novel silver catalyst, it demonstrates good, stable activity and selectivity in the process of ethene oxidation production oxirane.
Another object of the present invention provides a kind of preparation method of above-mentioned silver catalyst.
A further object of the present invention provides the application of above-mentioned silver catalyst in ethene oxidation production oxirane.
These and other purposes of the present invention, feature and advantage will become more clear after reading this specification in conjunction with the accompanying drawings.
The accompanying drawing summary
Fig. 1 produces the curve map that concerns between the oxirane total amount of reaction temperature in the process of oxirane and selectivity and generation for the catalyst sample of the explanation embodiment of the invention in the ethene oxidation.
Detailed Description Of The Invention
One aspect of the present invention provides a kind of novel silver catalyst, and described catalyst is prepared by a method comprising the following steps: the solution impregnation porous alpha-alumina supports of 1) using the silver compound, organic amine, alkali metal promoter and the base earth metal promoter that contain q.s; 2) elimination maceration extract, dry impregnated carrier; With 3) in containing oxygen gas mixture to step 2) the gained carrier activates, and makes described silver catalyst.
The present invention relates to the application of above-mentioned novel silver catalyst in ethene oxidation production oxirane on the other hand.
Porous α-the Al that is used for silver catalyst of the present invention
2O
3Carrier preferably contains α-Al
2O
3Porous α more than 90%-Al
2O
3Carrier, its preparation method is as follows: i) preparation has the mixture of following composition: a) based on the mixture total weight amount be 50 orders-150 order, the three water α-Al of 10-44% weight
2O
3B) based on the mixture total weight amount be 150 orders-250 order, the three water α-Al of 10-44% weight
2O
3C) based on the mixture total weight amount be 250 orders-500 order, the three water α-Al of 10-44% weight
2O
3D) be that the granularity of 5-39% weight is greater than the false water α-Al of 200 purposes based on the mixture total weight amount
2O
3E) but be the after-flame carbonaceous material of 5-30% weight based on the mixture total weight amount; F) based on the mixture total weight amount be the flux of 0.01-2.0% weight; G) based on the mixture total weight amount be the fluoride-mineralization agent of 0.01-2.0% weight; H) based on the mixture total weight amount be the binding agent of 25-59% weight; And g) water of surplus; Ii) with i) in the mixture that obtains mediate evenly and extrusion molding; The iii) dry product that obtains in ii), at high temperature roasting becomes α-Al then
2O
3
The adding of flux is in order to make carrier have good intensity under low sintering temperature.The example of flux comprises magnesium compound, for example the mixture of one or more in magnesia, magnesium sulfate, magnesium nitrate and the magnesium carbonate.
But the adding of after-flame carbonaceous material is in order to make macropore, thereby makes carrier have proper pore structure and specific surface.Described carbonaceous material comprises a kind of or its mixture in petroleum coke, carbon dust, graphite, polyethylene, polypropylene, the rosin etc.Carbonaceous material is oxidation in roasting process, generates gas and overflows, and forms macropore in carrier.Granularity according to carbonaceous material of the present invention is 20～300 orders, and preferred size is 20-50 order and 40-300 purpose mixture, and the ratio (based on weight) of the two consumption is 0.05-5.0: 1, and preferred 0.1-3.0: 1.The addition of described carbonaceous material is 5～30% weight of mixture total weight amount, preferred 20～30% weight, and adding too much can make the intensity of carrier obviously descend.
The fluoride-mineralization agent that the present invention selects for use comprises one or more the mixture in hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride, the ice crystal etc., and the crystal formation that its role is to accelerated oxidation aluminium transforms, and eliminates the following pore of 5 μ m.
By adding binding agent, the vacation one water α-Al in it and the mixture
2O
3Generation aluminium colloidal sol bonds together each component, but becomes the paste of extrusion molding.Used binding agent comprises acid, as nitric acid, formic acid, acetate, propionic acid and hydrochloric acid etc., and aluminium colloidal sol.When using acid as binding agent, aqueous solution of nitric acid preferably, wherein the weight ratio of nitric acid and water is 1: 1.25～10.
The compound that can also add other additives such as zirconium and/or tin in the preparation process of carrier is as the acetate of zirconium or tin, sulfate, oxide etc., to improve the performance of gained carrier.
Be dried to moisturely below 10% after the extrusion molding of gained paste, support shapes can be annular, spherical, cylindricality or porous cylindricality.Baking temperature is 80～120 ℃, and be controlled at 1 hour～24 hour according to moisture drying time.
Dried paste makes aluminium oxide all be converted into α-Al 1250～1550 ℃ of following roastings 2～6 hours
2O
3Roasting can make carrier that enough intensity and good surface properties are arranged in the said temperature scope, can influence activity of such catalysts and the selectivity of making if sintering temperature is too high, and the too low then support strength of sintering temperature is relatively poor.The crushing strength of this carrier is 40N/ grain～90N/ grain, preferred 45N/ grain～70N/ grain; Specific surface is 0.5～2.0m
2/ g, preferred 0.8～1.4m
2/ g; Water absorption rate is not less than 60%, preferably is not less than 70%; Pore volume is 0.5-0.8ml/g, preferred 0.5-0.7ml/g; The aperture accounts for 99% of total pore volume greater than the hole of 0.5 μ m, and the aperture accounts for the 10-40% of total pore volume greater than the hole of 60 μ m.
Silver catalyst of the present invention is by preparing with the above-mentioned alumina support of the solution impregnation of a kind of Ag-containing compound, organic amine, alkali metal promoter and base earth metal promoter.
In the preparation of silver catalyst of the present invention, at first make the aqueous solution and the ammonium oxalate or the oxalic acid aqueous solution reaction of silver nitrate, separate out the silver oxalate precipitation, after the filtration, spend deionised water, until no nitrate ion, then silver oxalate is dissolved in organic amine such as pyridine, butylamine, ethylenediamine, 1, in the aqueous solution of 3-propane diamine, monoethanolamine or its mixture, add auxiliary agent, be made into dipping solution.Flood above-mentioned alumina support with the gained dipping solution then, drain, in being not more than 21% nitrogen oxygen atmosphere, air stream or oxygen content in 200～700 ℃, preferred 200-500 ℃ temperature range, kept 1 minute～120 minutes, and preferred 1 minute～60 minutes, to carry out thermal decomposition.Also available silver oxide replaces silver nitrate, and silver oxalate also can not analysed filter, direct and organic amine complexing, impregnated carrier then.The amount of the silver compound that uses in the dipping process of the present invention should be enough to make argentiferous 1-30% weight in the finally prepd catalyst, and preferred 5～25% weight are in total catalyst weight.
Alkali metal promoter among the present invention can be compound or its any two kinds combination of lithium, sodium, potassium, rubidium or caesium, and alkali-metal content is 5～2000ppm in the final catalyst, preferred 10～1200ppm.Alkali metal promoter can be before dipping silver, simultaneously or be applied to afterwards on the carrier, also can after silver compound is reduced, be immersed on the carrier.
Base earth metal promoter among the present invention can be the compound of magnesium, calcium, strontium or barium, as oxide, oxalates, sulfate, acetate or nitrate, or its mixture, the content of alkaline-earth metal is 5～2000ppm in the final catalyst, preferred 10～1200ppm.Base earth metal promoter can be before dipping silver, simultaneously or be applied to afterwards on the carrier, also can after silver compound is reduced, be immersed on the carrier.
The mensuration of catalyst performance
Various silver catalyst of the present invention is tested its initial performance and stability with laboratory reaction device (following letter " little anti-") evaluating apparatus.The micro anti-evaluation device use reactor be the stainless steel tube of internal diameter 4mm, reactor places heating jacket.The admission space of catalyst is 1ml, and inert filler is arranged at the bottom, makes beds be positioned at the flat-temperature zone of heating jacket.Initial activity, optionally measure
The activity that the present invention uses and optionally condition determination is as follows:
Reacting gas is formed (mol%)
Ethene (C
2H
4) 28 ± 1
Oxygen (O
2) 7.4 ± 0.2
Carbon dioxide (CO
2)＜8
Cause steady gas (N
2) surplus
Inhibitor dichloroethanes 0.1ppm-2.0ppm
Reaction pressure 2.1MPa
Air speed 7000/h
Reactor goes out EO concentration 1.35%
Space-time yield 185gEO/mlCat./h
Stable back METHOD FOR CONTINUOUS DETERMINATION reactor is gone into, the exit gas composition when reaction reaches.Measurement result carries out calculating as follows after volume contraction is proofreaied and correct selectivity:
Wherein Δ EO works off one's feeling vent one's spleen poorly with the inlet gas ethylene oxide concentration, and the average of getting 10 groups of above test datas is as result of the test.2. the mensuration of catalyst stability
The mensuration of catalyst stability adopts contrast intensification's test (referring to " petrochemical technology " 1998, V5 (1), p17) method is under the condition of above-mentioned gas composition, reaction pressure and air speed, control reactor outlet ethylene oxide concentration is 2.4%, this moment, space-time yield was 330gEO/mlCat./h., carried out long run test.Assaying reaction temperature and selectivity when the every accumulative total of amount of ethylene oxide that per volume of catalyst (every milliliter) is produced reaches 500g are according to the stability curve of result of the test drafting catalyst.
The present invention compares with prior art following advantage: silver catalyst uses special porous alumina carrier made in accordance with the present invention, add base earth metal promoter, do not contain the transition metal auxiliary agent, have higher activity, selectivity and good stable, be specially adapted to the reaction that oxirane is produced in the ethene oxidation.
Embodiment
The present invention is described further below in conjunction with embodiment, but scope of the present invention is not limited to these embodiment.
The preparation of carrier:
With 30-150 order, 150-250 order and 250-500 purpose three water α-Al
2O
3Each 104g, the false water α-Al of 200 purposes
2O
3104g, petroleum coke 81g, NH
4F7g and Mg (NO
3)
2Mix 8.5g put into blender, change in the kneader, add 0.18 liter in rare nitric acid (nitric acid: water=1: 3, weight ratio), but be kneaded into the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours down at 80～120 ℃, and free water content is reduced to below 10%.
Above-mentioned five hole columns are put into top-hat kiln, and through being elevated between 1350 ℃～1550 ℃ from room temperature about 30 hours, constant temperature 2 hours obtains white α-Al
2O
3Support samples.
After measured, the gained carrier has following performance:
Mean intensity (N/ grain) 63
Specific surface (m
2/ g) 1.01
Water absorption rate (%) 80
＞60 μ m holes (%) 25
Pore volume (ml/g) 0.56
Preparation of catalysts: Comparative example
Getting the 700g silver nitrate is dissolved in the 750ml deionized water.Get in the deionized water that the 325g ammonium oxalate is dissolved in 250ml50 ℃.Under vigorous stirring, mix two kinds of solution, generate white silver oxalate precipitation.Aging more than 30 minutes, filter, spend deionised water and be precipitated to no nitrate ion.Filter cake argentiferous about 60%, moisture about 15%.
In the glass container that band stirs, add the 300g ethylenediamine, 110g hydramine, 375g deionized water.Stir following silver oxalate paste that makes and slowly add in the mixed liquor, temperature remains on below 40 ℃, and silver oxalate is all dissolved, and the addition of silver oxalate makes the maceration extract argentiferous 22% (weight) that makes.Add the 2.2g cesium sulfate, add deionized water again and make the solution gross mass reach 2000g, make solution for later use.
Get the support samples that 100g prepares above and put into the container that can vacuumize.Be evacuated to more than the 10mmHg, put into above maceration extract, the submergence carrier kept 30 minutes.Excessive solution is gone in leaching.Soaked carrier heated 5 minutes in 500 ℃ air stream, and silver catalyst for ethylene oxide is promptly made in cooling.
Embodiment 1-14
Repeat the program identical with comparative example, different is magnesium acetate, calcium acetate, barium acetate or the strontium acetate that adds amount as shown in table 1 below in addition.
Silver and auxiliary agent content to the catalyst made are analyzed, and the results are shown in following table 2, and wherein content is in metal.
Use the microreactor evaluating apparatus to measure the activity and the selectivity of catalyst sample under aforementioned process conditions, result of the test is listed in the table below 2.The addition of base earth metal promoter in the table 1 embodiment 1-14 catalyst sample preparation process
| Embodiment number | The alkaline-earth metal kind | Addition (g) |
| Embodiment 1 | Magnesium acetate | ?????5.9 |
| Embodiment 2 | Magnesium acetate | ?????9.4 |
| Embodiment 3 | Calcium acetate | ?????2.4 |
| Embodiment 4 | Calcium acetate | ?????4.0 |
| Embodiment 5 | Calcium acetate | ?????6.9 |
| Embodiment 6 | Calcium acetate | ?????7.9 |
| Embodiment 7 | Barium acetate | ?????1.2 |
| Embodiment 8 | Barium acetate | ?????1.9 |
| Embodiment 9 | Barium acetate | ?????2.8 |
| Embodiment 10 | Barium acetate | ?????3.6 |
| Embodiment 11 | Strontium acetate | ?????1.2 |
| Embodiment 12 | Strontium acetate | ?????2.4 |
| Embodiment 13 | Strontium acetate | ?????3.5 |
| Embodiment 14 | Strontium acetate | ?????4.9 |
The result of the test of table 2 embodiment 1-14 catalyst sample
Embodiment 15-18
| Embodiment number | Silver content (%) | The content of alkali metal caesium (ppm) | Alkaline-earth metal | Reaction temperature (℃) | EO (％) | Selectivity (%) | |
| Kind | Content (ppm) | ||||||
| Comparative example | ?17.2 | ????669 | ?222 | ?1.36 | ?82.1 | ||
| Embodiment 1 | ?17.2 | ????668 | ?Mg | ????412 | ?224 | ?1.38 | ?82.4 |
| Embodiment 2 | ?17.2 | ????669 | ?Mg | ????670 | ?220 | ?1.33 | ?80.3 |
| Embodiment 3 | ?17.1 | ????669 | ?Ca | ????262 | ?225 | ?1.37 | ?82.9 |
| Embodiment 4 | ?17.2 | ????665 | ?Ca | ????423 | ?226 | ?1.36 | ?83.5 |
| Embodiment 5 | ?17.1 | ????674 | ?Ca | ????648 | ?223 | ?1.33 | ?83.1 |
| Embodiment 6 | ?17.2 | ????670 | ?Ca | ????851 | ?222 | ?1.34 | ?82.3 |
| Embodiment 7 | ?17.2 | ????668 | ?Ba | ????252 | ?225 | ?1.38 | ?83.9 |
| Embodiment 8 | ?17.2 | ????666 | ?Ba | ????406 | ?224 | ?1.30 | ?83.2 |
| Embodiment 9 | ?17.3 | ????662 | ?Ba | ????591 | ?226 | ?1.38 | ?83.0 |
| Embodiment 10 | ?17.2 | ????665 | ?Ba | ????833 | ?226 | ?1.38 | ?82.7 |
| Embodiment 11 | ?17.2 | ????667 | ?Sr | ????202 | ?223 | ?1.38 | ?84.1 |
| Embodiment 12 | ?17.3 | ????672 | ?Sr | ????410 | ?220 | ?1.37 | ?85.3 |
| Embodiment 13 | ?17.2 | ????675 | ?Sr | ????583 | ?225 | ?1.39 | ?84.7 |
| Embodiment 14 | ?17.2 | ????673 | ?Sr | ????820 | ?222 | ?1.33 | ?84.5 |
Repeat the program identical with comparative example, different is the addition of change cesium sulfate as shown in table 3 below and adds barium acetate or strontium acetate.
Silver and auxiliary agent content to the catalyst made are analyzed, and the results are shown in following table 4, and wherein content is in metal.
Use the microreactor evaluating apparatus to measure the activity and the selectivity of catalyst sample under aforementioned process conditions, result of the test is listed in the table below 4.
The addition of base earth metal promoter in the table 3 embodiment 15-18 catalyst sample preparation process
| Embodiment number | Cesium sulfate addition (g) | The alkaline-earth metal kind | Addition (g) |
| Embodiment 15 | ?????1.8 | Barium acetate | ????1.2 |
| Embodiment 16 | ?????2.7 | Barium acetate | ????1.2 |
| Embodiment 17 | ?????1.8 | Strontium acetate | ????2.4 |
| Embodiment 18 | ?????2.7 | Strontium acetate | ????2.4 |
The result of the test of table 4 embodiment 15-18 catalyst sample
| Embodiment number | Silver content (%) | The content of alkali metal caesium (ppm) | Alkaline-earth metal | Reaction temperature (℃) | EO (％) | Selectivity (%) | |
| Kind | Content (ppm) | ||||||
| Embodiment 15 | ?17.1 | ????531 | ????Ba | ????241 | ?215 | ?1.37 | ?82.8 |
| Embodiment 7 | ?17.2 | ????668 | ????Ba | ????252 | ?225 | ?1.39 | ?83.9 |
| Embodiment 16 | ?17.0 | ????865 | ????Ba | ????255 | ?229 | ?1.37 | ?83.3 |
| Embodiment 17 | ?16.8 | ????526 | ????Sr | ????426 | ?218 | ?1.38 | ?84.0 |
| Embodiment 12 | ?17.3 | ????672 | ????Sr | ????439 | ?221 | ?1.37 | ?85.3 |
| Embodiment 18 | ?17.2 | ????877 | ????Sr | ????415 | ?225 | ?1.38 | ?84.8 |
Choose the catalyst sample of embodiment 7,12,15, adopt aforesaid its stability of contrast intensification's determination of test method, result of the test is plotted in Fig. 1.
Claims (29)
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Claims (29)
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1. produce the used silver catalyst of oxirane by the ethene oxidation for one kind, by the method preparation that may further comprise the steps: 1) with the solution impregnation porous alpha-alumina supports of the silver compound, organic amine, alkali metal promoter and the base earth metal promoter that contain q.s; 2) elimination maceration extract, dry impregnated carrier; With 3) in containing oxygen gas mixture to step 2) the gained carrier activates, and makes described silver catalyst.
2. silver catalyst as claimed in claim 1, wherein the porous alpha-alumina supports is prepared by the method that comprises the steps: i) preparation has the following mixture of forming:
A) based on the mixture total weight amount be 50 orders-150 order, the three water α-Al of 10-44% weight
2O
3
B) based on the mixture total weight amount be 150 orders-250 order, the three water α-Al of 10-44% weight
2O
3
C) based on the mixture total weight amount be 250 orders-500 order, the three water α-Al of 10-44% weight
2O
3
D) be that the granularity of 5-39% weight is greater than the false water α-Al of 200 purposes based on the mixture total weight amount
2O
3
E) but be the after-flame carbonaceous material of 5-30% weight based on the mixture total weight amount;
F) based on the mixture total weight amount be the flux of 0.01-2.0% weight;
G) based on the mixture total weight amount be the fluoride-mineralization agent of 0.01-2.0% weight;
H) based on the mixture total weight amount be the binding agent of 25-59% weight; And
G) water of surplus; Ii) with i) in the mixture that obtains mediate evenly and extrusion molding; The iii) dry product that obtains in ii), at high temperature roasting becomes α-Al then
2O
3
3. silver catalyst as claimed in claim 2, wherein said flux are the magnesium compounds that is selected from magnesia, magnesium sulfate, magnesium nitrate and magnesium carbonate, or its mixture.
4. silver catalyst as claimed in claim 2, wherein said carbonaceous material are petroleum coke, carbon dust, graphite, rosin, polyethylene, polypropylene or its mixture, and its consumption is 20～30% of a described mixture total weight amount.
5. silver catalyst as claimed in claim 2, wherein said fluoride-mineralization agent are one or more the mixture in hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride, the ice crystal.
6. silver catalyst as claimed in claim 2, wherein said binding agent are acid or aluminium colloidal sol.
7. silver catalyst as claimed in claim 6, wherein said acid are aqueous solution of nitric acid, and wherein the weight ratio of nitric acid and water is 1: 1.25～10.
8. silver catalyst as claimed in claim 2, wherein said porous alumina carrier forms through high-temperature roasting, and sintering temperature is 1250 ℃～1550 ℃.
9. silver catalyst as claimed in claim 1, wherein said porous alumina carrier has following feature: specific surface is 0.5m
2/ g～2.0m
2/ g, pore volume are 0.5～0.8ml/g, water absorption rate 〉=60%, and crushing strength is 40N/ grain～80N/ grain.
10. silver catalyst as claimed in claim 9, wherein said porous alumina carrier has following feature: specific surface is 0.8m
2/ g～1.4m
2/ g, pore volume are 0.5～0.7ml/g, water absorption rate 〉=70%, and crushing strength is 45N/ grain～70N/ grain.
11. silver catalyst as claimed in claim 1, wherein silver compound is silver oxide, silver nitrate or silver oxalate.
12. silver catalyst as claimed in claim 1, wherein should to make the content of silver in described silver catalyst be 1%～30% to the addition of silver compound, based on the gross weight of described silver catalyst.
13. silver catalyst as claimed in claim 12, wherein the content of silver in described silver catalyst is 5%～25%, based on the gross weight of described silver catalyst.
14. silver catalyst as claimed in claim 1, wherein said alkali metal promoter are compound or its any two kinds combination of lithium, sodium, potassium, rubidium or caesium.
15. silver catalyst as claimed in claim 14, wherein said alkali metal are caesium.
16. it is 5ppm～2000ppm that silver catalyst as claimed in claim 14, wherein said alkali-metal addition should make the content of described alkali metal in described silver catalyst, based on the gross weight of described silver catalyst.
17. it is 10ppm～1200ppm that silver catalyst as claimed in claim 16, wherein said alkali-metal addition should make the content of described alkali metal in described silver catalyst, based on the gross weight of described silver catalyst.
18. silver catalyst as claimed in claim 1, wherein said base earth metal promoter are oxide, oxalates, sulfate, acetate or the nitrate of magnesium, calcium, strontium or barium, or its mixture.
19. silver catalyst as claimed in claim 18, wherein said alkaline-earth metal are calcium.
20. silver catalyst as claimed in claim 18, wherein said alkaline-earth metal are barium.
21. silver catalyst as claimed in claim 18, wherein said alkaline-earth metal are strontium.
22. it is 5ppm～2000ppm that silver catalyst as claimed in claim 18, the addition of wherein said alkaline-earth metal should make the content of described alkaline-earth metal in described silver catalyst, based on the gross weight of described silver catalyst.
23. it is 10ppm～1200ppm that silver catalyst as claimed in claim 18, the addition of wherein said alkaline-earth metal should make the content of described alkaline-earth metal in described silver catalyst, based on the gross weight of described silver catalyst.
24. silver catalyst as claimed in claim 1, wherein said auxiliary agent before dipping silver, simultaneously or be applied on the carrier afterwards, or after silver compound is reduced, be immersed on the carrier.
25. silver catalyst as claimed in claim 2 wherein also adds the compound of zirconium and/or tin in the preparation process of described carrier.
26. silver catalyst as claimed in claim 1, wherein said activation process are to carry out in air or oxygen content are not more than 21% nitrogen oxygen atmosphere.
27. silver catalyst as claimed in claim 1, the temperature of wherein said activation process are controlled between 200 ℃～700 ℃, preferred 200 ℃～500 ℃.
28. silver catalyst as claimed in claim 1, the time of wherein said activation process is 1 minute～120 minutes, preferred 1 minute～60 minutes.
29. a method of producing oxirane by the ethene oxidation is wherein used as each described silver catalyst in the claim 1～28.