CN102133544B - 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
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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 of making 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 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 the activity that improves catalyst, selective and stable 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 uneconomical to adopt reguline metal silver to do on the 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 catalytic performance and the economy of catalyst.Alkali and alkaline earth metal ions is the auxiliary agent of commonly using.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, initial activity and selectively 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 large defective of one.How keeping in 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.It is the carrier loaded silver of Alpha-alumina that industrial silver catalyst adopts chief component.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 processed, 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, be coated with the unformed silica that is covered with 0.03-20wt% on surface, carrier duct, the silicon oxide surface modified support that afterwards drying and 700-1500 ℃ high-temperature roasting obtains, it is said behind this carrier loaded active component silver and the auxiliary agent, in inert atmosphere and 400-950 ℃ of lower heat treatment, the gained catalyst has higher selective, active and lasting service life again.
US Patent No. 5733840 has been reported a kind of by dipping method, is coated with the titanium oxide that is covered with 0.05-10wt% on surface, alumina support duct, the titania surface modified support that afterwards drying and 400-700 ℃ high-temperature roasting 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 and adopted the method that deposits other compounds at alumina carrier surface can improve the performance of silver catalyst, but how further to have improved the activity, selective and stable of rhenium-containing silver catalyst, is a major issue of numerous researchers' 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 thus a kind of surface deposition that alkali earth metal fluoride is arranged, and carried silver catalyst prepared therefrom.The silver catalyst of preparation has excellent catalytic activity and stability thus.
Detailed description of the invention
One aspect of the present invention provides the alumina support of a kind of gas-solid phase catalytic oxidation ethylene production 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 the 0.05-2.0 % by 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.
The chief component of alumina support of the present invention is Alpha-alumina, has not to be 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 the 0.05-2.0 % by weight, preferred 0.1-1.0 % by weight.
Alumina support of the present invention can be the common form in this area, for example annular, spherical, cylindricality or porous column shape, 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: first with the moulding prefabricated one-tenth semi-finished product of industrial hydrated alumina alpha-alumina supports, process through the aqueous solution pre-preg of the 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 again 0.2-3wt% hydrofluoric acid solution impregnation process, after the leaching again in 100-800 ℃ of lower 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 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 lower 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 District of Zhejiang Province 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 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) lower dry at 60-200 ℃;
(d) make it to be converted into Alpha-alumina 1200-1600 ℃ of lower roasting.
In prefabricated carrier preparation method of the present invention, used α-gibbsite can be burnt till through prebake all or part of replacement of powder of Alpha-alumina, transition aluminas, and the weight ratio of itself and a false water aluminium oxide still is 1: 1～4: 1.
In prefabricated carrier preparation method of the present invention, but the adding of after-flame carbonaceous material is in order to make macropore, thereby makes carrier have suitable 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 % by weight of raw alumina gross weight, preferred 0.01-20 % by weight, more preferably 0.1-10 % by weight.
In prefabricated carrier preparation 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 % by weight of raw alumina gross weight, preferred 0.1-2.5 % by weight.
In prefabricated carrier preparation 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 the transformation of crystal of accelerated oxidation aluminium, and reduces the following pore of 0.1 μ m.The addition of described fluoride is the 0-3 % by weight of raw alumina gross weight, preferred 0.1-2 % by weight, more preferably 0.3-1.8 % by weight.
In prefabricated carrier preparation 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 becomes the paste of extrusion molding.Used bonding agent comprises acid, such as nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid etc., and preferred nitric acid or acetic acid.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 substantially whole at 1200-1600 ℃ of lower roasting 2-8 hour, for example was converted into α-Al more than 90%
2O
3Obtain thus prefabricated semi-finished product alpha-alumina supports.
Then use prefabricated semi-finished product alpha-alumina supports to be raw material, 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 under 100-900 ℃ of temperature and roasting 5-600 minute; (iii) employing is 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 the alumina support of the present invention of preparation 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 carrier preparation.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 afterwards leaching is removed redundant solution and realized through heat treatment.Used silver compound can use the precursor compound of the silver such as silver nitrate, silver oxalate, but preferred silver oxalate.For guaranteeing all even abundant loads of silver, carrier preferably vacuumizes in advance, dipping, after the leaching in 200-500 ℃ moving air or the 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 other auxiliary agents such as the collaborative auxiliary agent sulphur compound of rhenium compound and rhenium and group vib metallic compound (such as the compound of chromium, molybdenum), 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 % by 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 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) 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 ammonium oxalate or the oxalic acid aqueous solution reaction of silver nitrate, separate out the silver oxalate precipitation, after the filtration, with the deionized water washing, until without 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, then impregnated carrier.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 % by 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 packing volume 1ml (12-18 order), inert filler is arranged at the bottom, makes beds be positioned at the flat-temperature zone of heating jacket.
The catalytic activity that the present invention adopts and standard evaluation condition following (reaction condition of reality sees that embodiment illustrates) optionally:
Reacting gas forms (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 form.Measurement result carries out calculating as follows after volume contraction is proofreaied and correct selective (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, then add the rare nitric acid 132.0g of 17 % by weight, 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 % by weight calcium acetate aqueous solution, to soak 30 minutes, solution is removed in afterwards leaching, in 500 ℃ moving airs stream dry 10 minutes, again in Muffle furnace further 700 ℃ of lower roastings 180 minutes.The gained carrier is with 190g 0.8 % by 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 lower roastings in Muffle furnace.The carrier calcium content is 0.25 % by 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 % by weight calcium acetate aqueous solution, soaked 30 minutes, solution is removed in afterwards leaching, in 500 ℃ moving airs stream dry 10 minutes, again in Muffle furnace further 800 ℃ of lower roastings 3 hours.The gained carrier is with 90g 0.8 % by 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 lower 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, then add the rare nitric acid 147.0g of 17 % by weight, 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 % by weight calcium acetate aqueous solution, to flood 30 minutes, solution is removed in afterwards leaching, in 500 ℃ moving airs stream dry 10 minutes, again in Muffle furnace further 700 ℃ of lower roastings 180 minutes.The gained carrier is with 180g 1.2 % by 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 lower 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.
The preparation of catalyst
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 at 0-15 ℃, silver oxalate is all dissolved.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, unnecessary solution is removed in leaching, then heats 5 minutes cooling 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 respectively the container of vacuum-pumping, be evacuated to below the 10mmHg, put into respectively above argentiferous maceration extract 35g, the submergence carrier kept 30 minutes, and unnecessary solution is removed in leaching, then in 280 ℃ air stream, heated 5 minutes, cool off, prepare the silver catalyst of embodiment 1 and 2, silver content is respectively 17.0%wt and 17.1wt% after measured.
Be under the reaction condition of 2.5% (mole) at reactor outlet ethylene oxide concentration as mentioned before, will implement agent 1 and 2 and the catalyst of comparative example 1 comparative evaluation simultaneously, acquired results sees the following form 1.
Table 1
| Sample | Evaluation time (my god) | Air speed (h -1) | Reaction temperature (℃) | Selectively (%) |
| 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 |
Upper table 1 shows, compares with the catalyst of comparative example 1, and embodiment 1 and 2 catalyst have higher catalytic activity, and approaching is selective, and activity is especially outstanding, and shows excellent stability in reaching 30 days evaluation procedure.As seen, the catalyst that is made by the present invention has more excellent, comprehensive 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 at 0-15 ℃, silver oxalate is all dissolved.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, unnecessary solution is removed in leaching, then heats 5 minutes cooling 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 unnecessary solution is removed in leaching, then in 280 ℃ air stream, heated 5 minutes, 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) at foregoing gas composition and reactor outlet ethylene oxide concentration with the silver catalyst of Comparative Examples 2 and embodiment 3, the results are shown in following table 2.
Table 2
| Sample | Evaluation time (my god) | Air speed (h -1) | Reaction temperature (℃) | Selectively (%) |
| 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 (19)
1. an ethylene epoxidizing is produced the alumina support that oxirane is used silver catalyst, its skeleton principal crystalline phase is Alpha-alumina, and deposit the alkali earth metal fluoride of counting the 0.05-2 % by weight with alkaline-earth metal on its surface, duct, its specific area that has is not higher than 2.0m
2/ g, and always pore volume is 0.3-0.7ml/g,
Wherein said alumina support is prepared by a method comprising 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 prefabricated semi-finished product alpha-alumina supports 5-60 minute, leaching;
(ii) dry under 100-900 ℃ of temperature and roasting 5-600 minute;
(iii) employing is 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 ℃.
2. according to claim 1 alumina support, wherein said duct deposits the alkali earth metal fluoride of counting the 0.1-1.0 % by weight with alkaline-earth metal on the surface.
3. according to claim 1 alumina support, its total pore volume that has is 0.4-0.7ml/g.
4. according to claim 1 alumina support, its specific area that has is 0.5-2.0m
2/ g.
5. according to claim 4 alumina support, its total pore volume that has is 0.4-0.7ml/g.
6. each alumina support according to claim 1-5, wherein said alkali earth metal fluoride are the fluoride of strontium, calcium, magnesium or barium.
7. a method for preparing according to claim 1 each alumina support in-6 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 prefabricated semi-finished product alpha-alumina supports 5-60 minute, leaching;
(ii) dry under 100-900 ℃ of temperature and roasting 5-600 minute;
(iii) employing is 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 ℃.
8. according to claim 7 method, wherein said alkali earth metal fluoride is the fluoride of strontium, calcium, magnesium or barium.
9. according to claim 7 or 8 method, wherein said prefabricated semi-finished product alpha-alumina supports is 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 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) lower dry at 60-200 ℃;
(d) make it to be converted into Alpha-alumina 1200-1600 ℃ of lower roasting.
10. according to claim 9 method, the wherein said carbonaceous material that burnouts is petroleum coke, graphite or vaseline.
11. method according to claim 9, wherein said alkali salt are magnesium salts or barium salt.
12. method according to claim 9, wherein said fluoride are aluminum fluoride or ammonium fluoride.
13. method according to claim 9, wherein said bonding agent are nitric acid or acetic acid.
14. method according to claim 9, wherein said α-gibbsite is all or part of to be burnt till Alpha-alumina or transition aluminas through prebake powder replaces, and the weight ratio of itself and a false water aluminium oxide is 1: 1～4: 1.
15. an ethene catalytic gas phase oxidation is produced the vinyl epoxide argentum catalyst of oxirane, each described alumina support in comprising according to claim 1-6 deposits 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.
16. silver catalyst according to claim 15, wherein said alkali metal is selected from one or more among Li, Na, K, Rb, the Cs.
17. silver catalyst according to claim 15, wherein said alkaline-earth metal is selected from one or more among Ca, Sr, the Ba.
18. silver catalyst according to claim 15, wherein the collaborative auxiliary agent of rhenium is sulphur compound and/or VIB subgroup metallic compound.
19. each described silver catalyst is used in ethylene oxide production according to claim 15-18.
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| 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 |
| US8987482B2 (en) | 2011-10-28 | 2015-03-24 | Basf Se | Process for producing a supported silver catalyst |
| 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 |
| 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 |
| 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 |
| 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 |
| CN103816940B (en) * | 2012-11-19 | 2019-03-26 | 中国石油化工股份有限公司 | A kind of alumina support and preparation method thereof |
| TW201442779A (en) * | 2013-02-07 | 2014-11-16 | Scient Design Co | Modified carrier for silver based ethylene oxide catalyst |
| EP3341123B1 (en) | 2015-08-28 | 2019-10-30 | Lyondell Chemical Technology, L.P. | Epoxidation catalysts |
| 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 |
| 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 |
| 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 |
| KR20240065284A (en) | 2021-09-23 | 2024-05-14 | 다우 글로벌 테크놀로지스 엘엘씨 | Methods for Reducing Age-Related Deactivation of Highly Selective 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 |
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