CN102133544A - Alkaline-earth metal fluoride modified alumina supporter, preparation method thereof, and silver catalyst made from alumina supporter and application of silver catalyst in ethylene epoxide (EO) production - Google Patents
Alkaline-earth metal fluoride modified alumina supporter, preparation method thereof, and silver catalyst made from alumina supporter and application of silver catalyst in ethylene epoxide (EO) production Download PDFInfo
- Publication number
- CN102133544A CN102133544A CN2010101008799A CN201010100879A CN102133544A CN 102133544 A CN102133544 A CN 102133544A CN 2010101008799 A CN2010101008799 A CN 2010101008799A CN 201010100879 A CN201010100879 A CN 201010100879A CN 102133544 A CN102133544 A CN 102133544A
- Authority
- CN
- China
- Prior art keywords
- alumina
- fluoride
- earth metal
- silver catalyst
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to an alumina supporter which has the surface modified through alkaline-earth metal fluoride and is used for producing ethylene epoxide through epoxidation reaction of ethylene by gas-solid catalyst, a preparation method of the alumina supporter, a silver catalyst made from the alumina supporter and application of the silver catalyst in ethylene epoxide (EO) production. The silver catalyst produced by adopting the invention contains effective amount of silver for catalysis, optional alkali metal or a mixture thereof, optional alkaline-earth metal or a mixture thereof, a rhenium auxiliary agent and an Alpha-alumina supporter with the surface thereof modified through alkaline-earth metal fluoride. The supporter and the obtained silver catalyst have higher activity and long-term stability when being used for preparing ethylene epoxide through epoxidation reaction of ethylene.
Description
Technical field
The present invention relates to a kind of gas and solid phase catalyzing epoxidation of ethylene and produce oxirane with the alumina support of silver catalyst, its preparation method, by its silver catalyst made and the application in ethylene oxide production thereof.
Technical background
It is an important catalytic reaction process that the direct oxidation reaction on argent of ethene and oxygen generates oxirane.Used silver catalyst can be an elemental metals silver, also can be carried silver catalyst.At present, the silver catalyst of industrial use is the alumina load silver catalyst.Be effective rate of utilization and raising activity of such catalysts, selectivity and the stability that further improves argent, improve the economy of producing, each research and development company is constantly carrying out unremitting exploration at aspects such as carrier, adjuvant system, preparation technology and reaction process conditions.
It is industrial uneconomical to adopt reguline metal silver to make catalyst, and catalytic performance is not good yet in addition, so also be added with other auxiliary agent under the more susceptible condition to improve the catalytic performance and the economy of catalyst.Alkali metal and alkaline-earth metal are the auxiliary agents of using always.US4039561 has reported a kind of Alpha-alumina carried silver catalyst, and outside the desilver, it contains alkali metal K and Cs, Tl and is selected from least a of IVA family metallic element, this catalyst selectivity only about 78%.US4207210 (Shell Oil Company, 1980) has reported one or more the Alpha-alumina carried silver catalyst among a kind of alkali metal containing K, Rb, the Cs, wherein alkali metal promoter can be in advance or simultaneously and silver flood together.The high selectivity about 80% of gained catalyst.The silver catalyst of US4305844 (Huels Chemische Werke AG, 1981) report contains 0.01-0.25% barium and alkali metal promoter, and initial activity and selectivity are also all very low.
Patent US4761394 (Shell Oil Company, 1988) has reported a kind of carrier loaded silver catalyst of porous heat-resistant that contains alkali metal and rhenium auxiliary agent, and catalyst selectivity is obviously improved.Patent US4766105 (Shell Oil Company, 1988) has further reported a kind of carrier loaded silver catalyst of porous heat-resistant that contains the collaborative auxiliary agent of alkali metal, rhenium auxiliary agent and rhenium, and catalyst selectivity is further improved.It should be noted that these rhenium-containing catalysts when initial selectivity improves, active and stability obviously reduces, and is the big defective of one.How keeping under the high optionally situation, further improving the initial activity of rhenium-containing silver catalyst and stability and be one of problem that the present invention puts forth effort to solve.
Carrier is the important component part of loaded catalyst.Industrial silver catalyst adopts the carrier loaded silver that mainly consists of Alpha-alumina.Suitable carrier not only should have higher intensity, and suitable specific surface and pore structure also should be able to be provided.By Manufactured carrier is handled, can be to the carrier surface modification, improve the dispersion situation of catalytic active component silver, the Acidity of Aikalinity of change carrier surface, the suction of modulation metal silver surface electronics situation and reaction species, desorption situation, thereby the catalytic performance of raising silver catalyst.The more existing research work reports of this respect.
Chinese patent CN1044416 has reported a kind of method by dipping, the unformed silica of 0.03-20wt% on the surface-coated of carrier duct, the silicon oxide surface modified support that drying and 700-1500 ℃ high-temperature roasting afterwards obtains, it is said behind this carrier loaded active component silver and the auxiliary agent, in inert atmosphere and 400-950 ℃ of following heat treatment, the gained catalyst has higher selectivity, activity and lasting service life again.
U.S. Pat 5733840 has been reported a kind of by dipping method, the titanium oxide of 0.05-10wt% on the surface-coated of alumina support duct, the titania surface modified support that drying and 400-700 ℃ high-temperature roasting afterwards obtains.It is said that the catalyst of making behind this carrier loaded active component silver and the auxiliary agent has higher activity and selectivity.
Having known that employing can improve the performance of silver catalyst in the method that alumina carrier surface deposits other compounds, but how further to have improved activity, selectivity and the stability of rhenium-containing silver catalyst, is a major issue of numerous researcher's thinkings.
Above-mentioned patent adopts carries out surface modification treatment in the method for alumina carrier surface deposition oxide to carrier, to improve the catalytic performance of catalyst.The present invention does not adopt oxide, then adopts alkali earth metal fluoride that alumina support is carried out surface modification treatment, and another kind of thinking is provided.
The general introduction of invention
The object of the invention is to provide the more excellent alumina support of a kind of performance and produces the silver catalyst of oxirane and their preparation method by the ethylene epoxidizing that is used for that it is made.
The present invention adopts alkali earth metal fluoride that alumina support is carried out surface modification treatment, and the ethylene epoxidizing production oxirane silver catalyst carrier that provides a kind of surface deposition that alkali earth metal fluoride is arranged thus, and carried silver catalyst prepared therefrom.Zhi Bei silver catalyst has excellent catalytic activity and stability thus.
Detailed description of the invention
One aspect of the present invention provides a kind of gas and solid phase catalyzing ethylene oxide to produce the alumina support of oxirane with silver catalyst, the skeleton principal crystalline phase of this carrier is the alkali earth metal fluoride that Alpha-alumina and its duct surface deposition have 0.05-2.0 weight %, in alkaline-earth metal.
In alumina support of the present invention, operable alkali earth metal fluoride is the fluoride of magnesium, calcium, strontium or barium, the fluoride of preferred calcium.
Alumina support of the present invention mainly consist of Alpha-alumina, have and be not higher than 2.0m
2The specific area of/g is preferably 0.5-2.0m
2/ g; The total pore volume of carrier is 0.3-0.7ml/g, preferred 0.4-0.7ml/g; The quality percentage composition of the alkaline-earth metal in the carrier is 0.05-2.0 weight %, preferred 0.1-1.0 weight %.
Alumina support of the present invention can be the common form in this area, for example annular, spherical, cylindricality or porous cylindricality, and preferred external diameter is 7-9mm, hole diameter is that the cellular or external diameter of the seven apertures in the human head of 1-2mm is that 7-9mm, internal diameter are the circular particle of single hole of 2-5mm.
Carrier of the present invention prepares as follows: earlier with the moulding prefabricated one-tenth semi-finished product of industrial hydrated alumina alpha-alumina supports, handle through the aqueous solution pre-preg of soluble-salts such as the acetate of 0.2-4.0wt% alkaline-earth metal, nitrate again, afterwards through 100-900 ℃ of drying and roasting, use 0.2-3wt% hydrofluoric acid solution impregnation process again, after the leaching again in 100-800 ℃ of following roasting, thereby alkali earth metal fluoride on the surface deposition of carrier duct is made the carrier finished product.
Prefabricated semi-finished product alpha-alumina supports can adopt an industrial α-gibbsite and a false water aluminium oxide to make.For further reduction sintering temperature, increase carrier mechanical strength also can be added with alkali salt and fluoride carrier auxiliary agent, behind mixed-forming, become the semi-finished product carrier 1200-1600 ℃ of following roasting.Can use the gibbsite of producing from Bayer process as industrial α-gibbsite.Can use the false water aluminium oxide of WHA404 type of Wenzhou, Zhejiang aluminium manufacturer production as a false water aluminium oxide.
Particularly, prefabricated semi-finished product alpha-alumina supports can be prepared by a method comprising the following steps:
(a) the burnouted carbonaceous material of mixed industrial α-gibbsite, a false water aluminium oxide, 0-30%, the alkali salt of 0-2.5%, fluoride, bonding agent and the water of 0-3%, described percentage number average is based on the gross weight of raw alumina, wherein the weight ratio of a α-gibbsite and a false water aluminium oxide is 1: 1～4: 1, and the total amount of binding agent and water is the 15-30% of alumina raw material gross weight;
(b) extrusion modling;
(c) dry down at 60-200 ℃;
(d) make it to be converted into Alpha-alumina 1200-1600 ℃ of following roasting.
In prefabricated preparing carriers method of the present invention, used α-gibbsite can be burnt till all or part of replacement of powder of Alpha-alumina, transition aluminas through prebake, and the weight ratio of itself and a false water aluminium oxide still is 1: 1～4: 1.
In prefabricated preparing carriers method of the present invention, 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, rosin, the vaseline etc., preferred petroleum coke, graphite or vaseline.Carbonaceous material is oxidation in roasting process, generates gas and overflows, and forms macropore in carrier.The addition of described carbonaceous material is the 0-30 weight % of raw alumina gross weight, preferred 0.01-20 weight %, more preferably 0.1-10 weight %.
In prefabricated preparing carriers method of the present invention, described alkali salt is magnesium or barium salt, preferred inorganic salts, the more preferably nitrate of magnesium or barium, sulfate or chloride.The addition of described alkali salt is the 0-2.5 weight % of raw alumina gross weight, preferred 0.1-2.5 weight %.
In prefabricated preparing carriers method of the present invention, described fluoride comprises hydrogen fluoride, ammonium fluoride, aluminum fluoride, magnesium fluoride, ice crystal etc. or its mixture, preferred fluorinated aluminium or ammonium fluoride.The effect of described fluoride is that the crystal formation of accelerated oxidation aluminium transforms, and reduces the following pore of 0.1 μ m.The addition of described fluoride is the 0-3 weight % of raw alumina gross weight, preferred 0.1-2 weight %, more preferably 0.3-1.8 weight %.
In prefabricated preparing carriers method of the present invention, add bonding agent, the vacation one water aluminium oxide in it and the mixture generates aluminium colloidal sol, each component is bonded together, but become the paste of extrusion molding.Used bonding agent comprises acid, as nitric acid, formic acid, acetate, propionic acid and hydrochloric acid etc., and preferred nitric acid or acetate.Perhaps a false water aluminium oxide and acid can be replaced with aluminium colloidal sol.When using acid as bonding agent, aqueous solution of nitric acid most preferably, wherein the weight ratio of nitric acid and water is 1: 1.25-10.
Can be dried to moisture below 10% after the extrusion molding of gained paste.Baking temperature is 60-200 ℃, and be controlled at 1-24 hour according to moisture drying time.
Dried paste made aluminium oxide whole substantially at 1200-1600 ℃ of following roasting 2-8 hour, for example was converted into α-Al more than 90%
2O
3Obtain prefabricated semi-finished product alpha-alumina supports thus.
Use prefabricated semi-finished product alpha-alumina supports to be raw material then, prepare alumina support of the present invention by the method that comprises the following steps: (i) adopt the 0.2-4wt% aqueous solution of the soluble-salt that is equivalent to prefabricated semi-finished product alpha-alumina supports quality 1-3 alkaline-earth metal doubly to flood leaching prefabricated the about 5-60 of semi-finished product alpha-alumina supports minute; (ii) dry and roasting 5-600 minute under 100-900 ℃ of temperature; (iii) adopt and be equivalent to prefabricated semi-finished product alpha-alumina supports quality 1-3 0.2-3wt% hydrofluoric acid aqueous solution impregnated carrier doubly 5-120 minute, leaching; (iv) descend dry and roasting 5-600 minute at 100-800 ℃.
The specific surface of Zhi Bei alumina support of the present invention is not higher than 2.0m thus
2/ g, preferred 0.5-2.0m
2/ g; Total pore volume is 0.3-0.7ml/g, preferred 0.4-0.7ml/g; And its duct surface deposition has 0.05-2.0 quality %, and the alkali earth metal fluoride of preferred 0.1-1.0 quality % is in alkaline-earth metal.
Silver catalyst of the present invention adopts above-mentioned preparing carriers.Silver catalyst of the present invention can prepare in the usual way, for example by preparing with the above-mentioned alumina support of the solution impregnation of a kind of Ag-containing compound and organic amine.
The interpolation of active component silver can be adopted carrier is immersed in the silver-colored amine complex solution that contains ethylenediamine and monoethanolamine by traditional infusion process, and leaching is afterwards removed redundant solution and realized through heat treatment.Used silver compound can use the precursor compound of silver such as silver nitrate, silver oxalate, but preferred silver oxalate.For guaranteeing all even abundant load of silver, carrier preferably vacuumizes in advance, dipping, after the leaching in 200-500 ℃ moving air or air-flows such as inert gas such as nitrogen, argon gas fast activating more than 2 minutes.For guaranteeing that catalyst has higher activity, activation temperature should not be higher than 500 ℃.In order further to improve the performance of catalyst, silver catalyst of the present invention also can add compound or its mixture of alkali metal lithium, sodium, potassium, rubidium, caesium in the preparation simultaneously, the compound of alkaline earth metals calcium, strontium, barium or its mixture, and the collaborative auxiliary agent sulphur compound of rhenium compound and rhenium and group vib metallic compound (as the compound of chromium, molybdenum) wait other auxiliary agent, these catalyst promoters 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.
Silver catalyst of the present invention contains 1-45 weight % silver, 0-1000ppmw alkali metal (in metal) and 0-3000ppmw alkaline-earth metal (in metal) and 10-2000ppmw rhenium (in metal).
Particularly, the preparation method of silver catalyst of the present invention comprises the steps:
1) with the silver compound, organic amine that contain q.s and the optional alkali metal/base earth metal promoter and the above-mentioned alumina support of solution impregnation of rhenium auxiliary agent and/or its collaborative auxiliary agent;
2) the leaching maceration extract and
3) in air or inert gas to step 2) the gained carrier activates, and makes described silver catalyst.
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.Then with the gained dipping solution vacuum less than the condition of 10mmHg under dipping above-mentioned alumina support 10-60 minute, drain, in air or inert gas, in 200-500 ℃ temperature range, kept 2 minutes～120 minutes, preferred 2 minutes～60 minutes, to activate.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 1～45% weight in the finally prepd catalyst, preferred 5～40% weight, and more preferably 8-35 weight % is in total catalyst weight.
Various silver catalyst of the present invention is estimated initial catalytic perfomance and stability with laboratory microreactor (hereinafter to be referred as " little anti-").The reactor that the micro anti-evaluation device uses is the stainless steel reaction pipe of internal diameter 4mm, and reaction tube places heating jacket.Catalyst admission space 1ml (12-18 order), inert filler is arranged at the bottom, makes beds be positioned at the flat-temperature zone of heating jacket.
Catalytic activity that the present invention adopts and standard evaluation condition following (reaction condition of reality sees that embodiment illustrates) optionally:
Reacting gas is formed (mol%):
Ethene (C
2H
4) 30.0 ± 1.2
Oxygen (O
2) 7.3 ± 0.3
Carbon dioxide (CO
2)＜1.3
Put steady gas (N
2) surplus
Inhibitor 1,2-dichloroethanes 0.6-1.1ppmv
Reaction pressure 1.8MPa
Air speed 5000-7000h
-1
The concentration 2.5% of EO in the reactor outlet tail gas
When under certain operation air speed condition, when stable reaction is got off, and after reaching above-mentioned reaction condition, METHOD FOR CONTINUOUS DETERMINATION reactor inlet and exit gas are formed.Measurement result carries out calculating as follows after volume contraction is proofreaied and correct selectivity (S):
Wherein Δ EO is that reactor entry and exit ethylene oxide concentration is poor, gets the experimental result of the average of ten groups of above experimental datas as the same day.
Embodiment
The present invention adopts the following examples to be described further, but scope of the present invention is not limited to the situation of following embodiment.
The preparation of carrier
Comparison vehicle A
Place blender to mix in 372.0g industry α-gibbsite, the false water aluminium oxide of 110.0g, 8.0g ammonium fluoride, 1.0g barium sulfate and 10.0g vaseline, add the rare nitric acid 132.0g of 17 weight % then, but fully be kneaded into the paste of extrusion modling, (this cylinder has seven parallel ducts vertically to be squeezed into the honeycomb coaly seven apertures in the human head cylinder of external diameter 8.3mm, high 8.0mm again, center-hole diameter 1.7mm centers on the aperture that centre bore is evenly distributed with six 1.5mm diameters all around).The carrier base of forming is warmed up to 1300-1350 ℃ again in the 40h in the high temperature jar kiln more than oven dry 3h about 80-100 ℃, and constant temperature 6h, obtains comparison vehicle A.The carrier A specific area is 1.34m
2/ g, pore volume are 0.53ml/g.
The embodiment carrier B
Get above-mentioned gained carrier A 100g and place plastic cup, to wherein injecting the 190g 0.5 weight % calcium acetate aqueous solution, to soak 30 minutes, solution is removed in leaching afterwards, in 500 ℃ moving airs stream dry 10 minutes, again in Muffle furnace further 700 ℃ of following roastings 180 minutes.The gained carrier is with 190g 0.8 weight % hydrofluoric acid aqueous solution dipping 30 minutes, and after redundant solution was removed in leaching, 300 ℃ of dryings were 10 minutes in moving air, and further obtain carrier B in 180 minutes 500 ℃ of following roastings in Muffle furnace.The carrier calcium content is 0.25 weight % by analysis, and specific area is 1.38m
2/ g, pore volume are 0.52ml/g.
The embodiment support C
Get comparison vehicle A 50g, to wherein injecting the 90g 0.5 weight % calcium acetate aqueous solution, soaked 30 minutes, solution is removed in leaching afterwards, in 500 ℃ moving airs stream dry 10 minutes, again in Muffle furnace further 800 ℃ of following roastings 3 hours.The gained carrier is with 90g 0.8 weight % hydrofluoric acid aqueous solution dipping 30 minutes, and after redundant solution was removed in leaching, 400 ℃ of dryings were 20 minutes in moving air, and further obtain support C in 120 minutes 600 ℃ of following roastings in Muffle furnace.The carrier calcium content is 0.25% by analysis, and specific area is 1.37m
2/ g, pore volume are 0.52ml/g.
Comparison vehicle D and embodiment carrier E
Place blender to mix in 420.0g industry α-gibbsite, the false water aluminium oxide of 180.0g, 8.2g ammonium fluoride, 40.0g petroleum coke and 13.0g barium sulfate, add the rare nitric acid 147.0g of 17 weight % then, but fully be kneaded into the paste of extrusion modling, (this cylinder has seven parallel ducts vertically to be squeezed into the honeycomb coaly seven apertures in the human head cylinder of external diameter 8.3mm, high 8.0mm again, center-hole diameter 1.7mm centers on the aperture that centre bore is evenly distributed with six 1.5mm diameters all around).The carrier base substrate of forming is warming up to 1450-1500 ℃ again in the 40h in the High Temperature Gas kiln more than oven dry 3h about 80-100 ℃, and constant temperature 3h, obtains comparison vehicle D.Carrier D specific area is 1.27m
2/ g, pore volume are 0.66ml/g.
Get above-mentioned gained carrier D 100g and place plastic cup, to wherein injecting the 180g 0.4 weight % calcium acetate aqueous solution, to flood 30 minutes, solution is removed in leaching afterwards, in 500 ℃ moving airs stream dry 10 minutes, again in Muffle furnace further 700 ℃ of following roastings 180 minutes.The gained carrier is with 180g 1.2 weight % hydrofluoric acid aqueous solutions dipping 30 minutes, and after redundant solution was removed in leaching, 300 ℃ of dryings were 10 minutes in moving air, and further obtain carrier E in 120 minutes 600 ℃ of following roastings in Muffle furnace.The carrier calcium content is 0.3% by analysis, and specific area is 1.32m
2/ g, pore volume are 0.63ml/g.
Preparation of catalysts
Comparative example 1
In the glass flask that band stirs, add 35.4g ethylenediamine, 13.0g monoethanolamine, 54.0g deionized water.When stirring the silver oxalate 76.6g of silver content 62.6% is slowly added in the mixed liquor, keep solution temperature, silver oxalate is all dissolved at 0-15 ℃.Add 0.220g cesium sulfate, 0.243g strontium acetate, 0.116g ammonium perrhenate, 0.015g ammonium molybdate ((NH
4)
6Mo
7O
244H
2O), 0.0288g potassium hydroxide, 0.0475g lithium sulfate and deionized water, make the solution gross mass reach 200g, gained solution mixes stand-by.
Get comparison vehicle A 30g, place the container of vacuum-pumping, be evacuated to below the 10mmHg, put into above argentiferous maceration extract 60g, the submergence carrier, kept 30 minutes, excessive solution is removed in leaching, heats cooling 5 minutes then in 280 ℃ air stream, prepare the silver catalyst of comparative example 1, silver content is 17.3wt% after measured.
Embodiment 1 and 2
Adopt identical maceration extract in the above-mentioned comparative example 1, get each 20g of embodiment carrier B and C, place the container of vacuum-pumping respectively, be evacuated to below the 10mmHg, put into above argentiferous maceration extract 35g respectively, the submergence carrier kept 30 minutes, and excessive solution is removed in leaching, in 280 ℃ air stream, heated 5 minutes then, cool off, prepare the silver catalyst of embodiment 1 and 2, silver content is respectively 17.0%wt and 17.1wt% after measured.
At reactor outlet ethylene oxide concentration as mentioned before is under the reaction condition of 2.5% (mole), will implement agent 1 and 2 and the catalyst of comparative example 1 comparative evaluation simultaneously, and gained the results are shown in following table 1.
Table 1
| Sample | Evaluation time (my god) | Air speed (h -1) | Reaction temperature (℃) | Selectivity (%) |
| Embodiment 1 | ?3 | ?5000 | ?223.0 | ?83.5 |
| Embodiment 2 | ?3 | ?5000 | ?224.0 | ?83.6 |
| Comparative example 1 | ?3 | ?5000 | ?231.6 | ?83.4 |
| Embodiment 1 | ?10 | ?5000 | ?225.7 | ?84.0 |
| Embodiment 2 | ?10 | ?5000 | ?226.5 | ?83.9 |
| Comparative example 1 | ?10 | ?5000 | ?233.6 | ?83.9 |
| Embodiment 1 | ?30 | ?5000 | ?226.4 | ?84.5 |
| Comparative example 1 | ?30 | ?5000 | ?236.1 | ?84.3 |
Last table 1 shows, compares with the catalyst of comparative example 1, and embodiment 1 and 2 catalyst have higher catalytic activity, and approaching selectivity, activity are especially outstanding, and shows excellent stability in reaching 30 days evaluation procedure.As seen, the catalyst that is made by the present invention has excellent, comprehensive more catalytic performance on the whole.
Comparative example 2
In the glass flask that band stirs, add 34.4g ethylenediamine, 11.3g monoethanolamine, 54.0g deionized water.When stirring the silver oxalate 76.0g of silver content 62.6% is slowly added in the mixed liquor, keep solution temperature, silver oxalate is all dissolved at 0-15 ℃.Add 0.211g cesium sulfate, 0.240g strontium acetate, 0.122g ammonium perrhenate, 0.017g ammonium molybdate, 0.0474g lithium sulfate and deionized water, make the solution gross mass reach 200g, gained solution mixes stand-by.
Get comparison vehicle D 30g, place the container of vacuum-pumping, be evacuated to below the 10mmHg, put into above argentiferous maceration extract 60g, the submergence carrier, kept 30 minutes, excessive solution is removed in leaching, heats cooling 5 minutes then in 280 ℃ air stream, prepare the silver catalyst of comparative example 2, silver content is 18.8wt% after measured.
Embodiment 3
Adopt identical maceration extract in the above-mentioned comparative example 2, get embodiment carrier E 30g, place the container of vacuum-pumping, be evacuated to below the 10mmHg, put into the Ag-containing solution 60g described in the comparative example 2, the submergence carrier kept 30 minutes, and excessive solution is removed in leaching, in 280 ℃ air stream, heated 5 minutes then, cool off, prepare the silver catalyst of embodiment 3, silver content is 18.2wt% after measured.
Be comparative evaluation under the reaction condition of 2.5% (mole) with the silver catalyst of Comparative Examples 2 and embodiment 3, the results are shown in following table 2 at foregoing gas composition and reactor outlet ethylene oxide concentration.
Table 2
| Sample | Evaluation time (my god) | Air speed (h -1) | Reaction temperature (℃) | Selectivity (%) |
| Embodiment 3 | ?4 | ?7000 | ?234.1 | ?84.0 |
| Comparative example 2 | ?4 | ?7000 | ?239.0 | ?83.7 |
| Embodiment 3 | ?56 | ?7000 | ?238.2 | ?86.4 |
| Comparative example 2 | ?56 | ?7000 | ?245.2 | ?86.2 |
Claims (16)
1. an ethylene epoxidizing is produced the alumina support of oxirane with silver catalyst, and its skeleton principal crystalline phase is an Alpha-alumina, and deposits 0.05-2 weight % on its surface, duct, the alkali earth metal fluoride (in alkaline-earth metal) of preferred 0.1-1.0 weight %.
2. according to the alumina support of claim 1, the specific area that has is not higher than 2.0m
2/ g, preferred 0.5-2.0m
2/ g, and always pore volume is 0.3-0.7ml/g, preferred 0.4-0.7ml/g.
3. according to the alumina support of claim 1 or 2, wherein said alkali earth metal fluoride is the fluoride of strontium, calcium, magnesium or barium, the fluoride of preferred calcium.
4. a method for preparing according to each alumina support among the claim 1-3 comprises the steps:
(i) adopt the 0.2-4wt% aqueous solution of the soluble-salt that is equivalent to prefabricated semi-finished product alpha-alumina supports quality 1-3 alkaline-earth metal doubly to flood leaching prefabricated the about 5-60 of semi-finished product alpha-alumina supports minute;
(ii) dry and roasting 5-600 minute under 100-900 ℃ of temperature;
(iii) adopt and be equivalent to prefabricated semi-finished product alpha-alumina supports quality 1-3 0.2-3wt% hydrofluoric acid aqueous solution impregnated carrier doubly 5-120 minute, leaching;
(iv) descend dry and roasting 5-600 minute at 100-800 ℃.
5. according to the method for claim 4, wherein said alkali earth metal fluoride is the fluoride of strontium, calcium, magnesium or barium, the fluoride of preferred calcium.
6. according to the method for claim 4 or 5, wherein prefabricated semi-finished product alpha-alumina supports is prepared by a method comprising the following steps described in the claim 4:
(a) the burnouted carbonaceous material of mixed industrial α-gibbsite, a false water aluminium oxide, 0-30%, the alkali salt of 0-2.5%, fluoride, bonding agent and the water of 0-3%, described percentage number average is based on the gross weight of raw alumina, wherein the weight ratio of a α-gibbsite and a false water aluminium oxide is 1: 1～4: 1, and the total amount of binding agent and water is the 15-30% of alumina raw material gross weight;
(b) extrusion modling;
(c) dry down at 60-200 ℃;
(d) make it to be converted into Alpha-alumina 1200-1600 ℃ of following roasting.
7. according to the method for claim 6, but wherein said after-flame carbonaceous material is petroleum coke, graphite or vaseline.
8. according to the method for claim 6, wherein said alkali salt is magnesium salts or barium salt.
9. according to the method for claim 6, wherein said fluoride is aluminum fluoride or ammonium fluoride.
10. according to the method for claim 6, wherein said bonding agent is nitric acid or acetate.
11. according to the method for claim 6, the powder that wherein said α-gibbsite is all or part of can be burnt till Alpha-alumina or transition aluminas through prebake replaces, the weight ratio of itself and a false water aluminium oxide is 1: 1～4: 1.
12. an ethene catalytic gas phase oxidation is produced the vinyl epoxide argentum catalyst of oxirane, comprise according to each described porous carrier among the claim 1-11, deposit the silver of catalytically effective amount, optional alkali metal promoter, optional base earth metal promoter and rhenium compound and collaborative auxiliary agent thereof on it.
13. according to the silver catalyst of claim 12, wherein said alkali metal is selected from one or more among Li, Na, K, Rb, the Cs.
14. according to the silver catalyst of claim 12, wherein said alkaline-earth metal is selected from one or more among Ca, Sr, the Ba.
15. according to the silver catalyst of claim 12, the collaborative auxiliary agent of wherein said rhenium is sulphur compound and/or VIB subgroup metallic compound.
16. in ethylene oxide production, use according to each described silver catalyst among the claim 12-15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101008799A CN102133544B (en) | 2010-01-25 | 2010-01-25 | Alkaline-earth metal fluoride modified alumina supporter, preparation method thereof, and silver catalyst made from alumina supporter and application of silver catalyst in ethylene epoxide (EO) production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101008799A CN102133544B (en) | 2010-01-25 | 2010-01-25 | Alkaline-earth metal fluoride modified alumina supporter, preparation method thereof, and silver catalyst made from alumina supporter and application of silver catalyst in ethylene epoxide (EO) production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102133544A true CN102133544A (en) | 2011-07-27 |
| CN102133544B CN102133544B (en) | 2013-04-24 |
Family
ID=44293549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101008799A Active CN102133544B (en) | 2010-01-25 | 2010-01-25 | Alkaline-earth metal fluoride modified alumina supporter, preparation method thereof, and silver catalyst made from alumina supporter and application of silver catalyst in ethylene epoxide (EO) production |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102133544B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102950029A (en) * | 2011-08-19 | 2013-03-06 | 中国石油化工股份有限公司 | Modified alumina carrier, its preparation method, silver catalyst prepared from it, and its application in production of ethylene oxide |
| WO2013061294A1 (en) * | 2011-10-28 | 2013-05-02 | Basf Se | Process for producing supported silver catalyst |
| CN103357442A (en) * | 2012-03-28 | 2013-10-23 | 中国石油化工股份有限公司 | Carrier of silver catalyst for olefin epoxidation as well as preparation method and application thereof |
| CN103357436A (en) * | 2012-03-28 | 2013-10-23 | 中国石油化工股份有限公司 | Alkali treatment modification method of alumina carrier as well as preparation method and application of silver catalyst supported by alumina carrier |
| CN103357441A (en) * | 2012-03-28 | 2013-10-23 | 中国石油化工股份有限公司 | Silver catalyst carrier and preparation method thereof as well as catalyst prepared by silver catalyst carrier and application thereof |
| CN103372466A (en) * | 2012-04-25 | 2013-10-30 | 中国石油化工股份有限公司 | Preparation method of silver catalyst carrier for production of ethylene oxide and application thereof |
| CN103769233A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst carrier and preparation method as well as catalyst prepared by carrier and application of catalyst |
| CN103816940A (en) * | 2012-11-19 | 2014-05-28 | 中国石油化工股份有限公司 | Aluminum oxide carrier and preparation method thereof |
| US20140221196A1 (en) * | 2013-02-07 | 2014-08-07 | Scientific Design Company, Inc. | Modified carrier for silver based ethylene oxide catalyst |
| US8987482B2 (en) | 2011-10-28 | 2015-03-24 | Basf Se | Process for producing a supported silver catalyst |
| CN103721755B (en) * | 2012-10-12 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of surface modifying method of silver catalyst porous alpha-alumina supports |
| CN106492798A (en) * | 2016-11-02 | 2017-03-15 | 漯河职业技术学院 | Catalyst of Direct Epoxidation production expoxy propane and preparation method thereof |
| CN106732509A (en) * | 2016-12-31 | 2017-05-31 | 天津碧水源膜材料有限公司 | The preparation method of modified aluminium oxide supports, catalytic ozone oxidation catalyst and its application |
| CN106955744A (en) * | 2016-01-08 | 2017-07-18 | 中国石油化工股份有限公司 | The alpha-alumina supports of alkene epoxidation silver catalyst and its preparation and application |
| CN107960063A (en) * | 2015-08-28 | 2018-04-24 | 利安德化学技术有限公司 | Epoxidation technique and its catalyst used |
| WO2023049057A1 (en) | 2021-09-23 | 2023-03-30 | Dow Global Technologies Llc | Process for reducing the aging-related deactivation of high selectivity ethylene oxide catalysts |
| CN115999528A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | Anthraquinone degradation product regeneration method, regenerated catalyst and preparation thereof |
| WO2024076943A1 (en) | 2022-10-04 | 2024-04-11 | Dow Global Technologies Llc | Process for reducing the overchloriding of high selectivity ethylene oxide catalysts during restarts |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1232349C (en) * | 2002-12-31 | 2005-12-21 | 中国石油化工股份有限公司北京燕山分公司研究院 | Carrier for producing silver catalyst for epoxy ethane production, its preparing method and use |
-
2010
- 2010-01-25 CN CN2010101008799A patent/CN102133544B/en active Active
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102950029A (en) * | 2011-08-19 | 2013-03-06 | 中国石油化工股份有限公司 | Modified alumina carrier, its preparation method, silver catalyst prepared from it, and its application in production of ethylene oxide |
| CN102950029B (en) * | 2011-08-19 | 2016-03-30 | 中国石油化工股份有限公司 | Modified aluminium oxide supports, its preparation method, the silver catalyst be made up of it and the application in ethylene oxide production thereof |
| WO2013061294A1 (en) * | 2011-10-28 | 2013-05-02 | Basf Se | Process for producing supported silver catalyst |
| US9199223B2 (en) | 2011-10-28 | 2015-12-01 | Basf Se | Process for producing a supported silver catalyst |
| US8987482B2 (en) | 2011-10-28 | 2015-03-24 | Basf Se | Process for producing a supported silver catalyst |
| CN103357436B (en) * | 2012-03-28 | 2016-02-24 | 中国石油化工股份有限公司 | The preparations and applicatio of the silver catalyst of alumina support alkali treatment modifying, its load |
| CN103357441A (en) * | 2012-03-28 | 2013-10-23 | 中国石油化工股份有限公司 | Silver catalyst carrier and preparation method thereof as well as catalyst prepared by silver catalyst carrier and application thereof |
| CN103357436A (en) * | 2012-03-28 | 2013-10-23 | 中国石油化工股份有限公司 | Alkali treatment modification method of alumina carrier as well as preparation method and application of silver catalyst supported by alumina carrier |
| CN103357441B (en) * | 2012-03-28 | 2016-03-30 | 中国石油化工股份有限公司 | Silver catalyst carrier, its preparation method, the catalyst be made up of it and application |
| CN103357442B (en) * | 2012-03-28 | 2016-03-30 | 中国石油化工股份有限公司 | The carrier of alkene epoxidation silver catalyst, its preparation method and application thereof |
| CN103357442A (en) * | 2012-03-28 | 2013-10-23 | 中国石油化工股份有限公司 | Carrier of silver catalyst for olefin epoxidation as well as preparation method and application thereof |
| CN103372466A (en) * | 2012-04-25 | 2013-10-30 | 中国石油化工股份有限公司 | Preparation method of silver catalyst carrier for production of ethylene oxide and application thereof |
| CN103372466B (en) * | 2012-04-25 | 2015-06-17 | 中国石油化工股份有限公司 | Preparation method of silver catalyst carrier for production of ethylene oxide and application thereof |
| CN103721755B (en) * | 2012-10-12 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of surface modifying method of silver catalyst porous alpha-alumina supports |
| CN103769233A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst carrier and preparation method as well as catalyst prepared by carrier and application of catalyst |
| CN103769233B (en) * | 2012-10-25 | 2016-03-30 | 中国石油化工股份有限公司 | Catalyst carrier and preparation method and the catalyst prepared by this carrier and application thereof |
| CN103816940A (en) * | 2012-11-19 | 2014-05-28 | 中国石油化工股份有限公司 | Aluminum oxide carrier and preparation method thereof |
| US9321035B2 (en) * | 2013-02-07 | 2016-04-26 | Scientific Design Company, Inc. | Modified carrier for silver based ethylene oxide catalyst |
| US20140221196A1 (en) * | 2013-02-07 | 2014-08-07 | Scientific Design Company, Inc. | Modified carrier for silver based ethylene oxide catalyst |
| CN107960063A (en) * | 2015-08-28 | 2018-04-24 | 利安德化学技术有限公司 | Epoxidation technique and its catalyst used |
| US11980872B2 (en) | 2015-08-28 | 2024-05-14 | Lyondell Chemical Technology, L.P. | Epoxidation processes and catalysts for use therein |
| CN106955744B (en) * | 2016-01-08 | 2019-09-27 | 中国石油化工股份有限公司 | The alpha-alumina supports and its preparation and application of alkene epoxidation silver catalyst |
| CN106955744A (en) * | 2016-01-08 | 2017-07-18 | 中国石油化工股份有限公司 | The alpha-alumina supports of alkene epoxidation silver catalyst and its preparation and application |
| CN106492798A (en) * | 2016-11-02 | 2017-03-15 | 漯河职业技术学院 | Catalyst of Direct Epoxidation production expoxy propane and preparation method thereof |
| CN106492798B (en) * | 2016-11-02 | 2018-12-11 | 漯河职业技术学院 | The catalyst and preparation method thereof of Direct Epoxidation production propylene oxide |
| CN106732509A (en) * | 2016-12-31 | 2017-05-31 | 天津碧水源膜材料有限公司 | The preparation method of modified aluminium oxide supports, catalytic ozone oxidation catalyst and its application |
| CN106732509B (en) * | 2016-12-31 | 2019-08-06 | 天津碧水源膜材料有限公司 | Preparation method, catalytic ozone oxidation catalyst and its application of modified aluminium oxide supports |
| WO2023049057A1 (en) | 2021-09-23 | 2023-03-30 | Dow Global Technologies Llc | Process for reducing the aging-related deactivation of high selectivity ethylene oxide catalysts |
| CN115999528A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | Anthraquinone degradation product regeneration method, regenerated catalyst and preparation thereof |
| WO2024076943A1 (en) | 2022-10-04 | 2024-04-11 | Dow Global Technologies Llc | Process for reducing the overchloriding of high selectivity ethylene oxide catalysts during restarts |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102133544B (en) | 2013-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102133544B (en) | Alkaline-earth metal fluoride modified alumina supporter, preparation method thereof, and silver catalyst made from alumina supporter and application of silver catalyst in ethylene epoxide (EO) production | |
| CN101850243B (en) | Carrier of silver catalyst for producing ethylene oxide, preparation method thereof, silver catalyst prepared by using same and application thereof in producing ethylene oxide | |
| CN102397795A (en) | Silver catalyst carrier for ethylene oxide production, preparation method, silver catalyst prepared by silver catalyst carrier, and application thereof | |
| TWI529002B (en) | An alumina support, a preparation method for the same, and a silver catalyst prepared from the same, and use thereof | |
| KR20080096678A (en) | A carrier for olefin oxidation catalyst, preparation method and application thereof | |
| CN102441435B (en) | Method for preparing alumina carrier for silver catalyst, carrier prepared by using method and application thereof | |
| CN103372466B (en) | Preparation method of silver catalyst carrier for production of ethylene oxide and application thereof | |
| CN106311353B (en) | A kind of alpha-alumina supports, corresponding silver catalyst and application | |
| CN102145285A (en) | Carrier of silver catalyst for producing epoxy ethane, preparation method and application of carrier of silver catalyst | |
| CN102950029B (en) | Modified aluminium oxide supports, its preparation method, the silver catalyst be made up of it and the application in ethylene oxide production thereof | |
| CN108855237A (en) | Porous alumina carrier and preparation method thereof and silver catalyst and application | |
| CN104707664A (en) | Preparation method of alpha-alumina carrier for silver catalyst | |
| CN104707592A (en) | Preparation method of alpha-alumina carrier for silver catalyst | |
| CN105618047A (en) | Method for preparation of silver catalyst for epoxidation and application thereof | |
| CN105080618B (en) | A kind of preparation method of alpha-aluminium oxide carrier for silver catalyst | |
| CN108855115A (en) | A kind of coated catalysts and preparation method and application | |
| CN1310703C (en) | Ethylene oxide catalyst carrier preparation | |
| CN103831106B (en) | A kind of preparation method and application of silver catalyst | |
| CN111054350B (en) | Cu-ZnO/attapulgite clay composite catalyst and preparation method and application thereof | |
| CN111437816B (en) | Supported silver catalyst and preparation method and application thereof | |
| CN104549545B (en) | For silver catalyst alpha-aluminium oxide carrier and preparation method thereof of alkene epoxidation | |
| CN112121780B (en) | Alpha-alumina carrier, preparation method thereof, silver catalyst and application | |
| CN100393412C (en) | Ethylene oxide catalyst | |
| CN103357442B (en) | The carrier of alkene epoxidation silver catalyst, its preparation method and application thereof | |
| CN111905733B (en) | Method for activating silver catalyst and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |