CN100441300C - Method of preparing loading type silver catalyst by micro-reduction - Google Patents
Method of preparing loading type silver catalyst by micro-reduction Download PDFInfo
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- CN100441300C CN100441300C CNB2006101354297A CN200610135429A CN100441300C CN 100441300 C CN100441300 C CN 100441300C CN B2006101354297 A CNB2006101354297 A CN B2006101354297A CN 200610135429 A CN200610135429 A CN 200610135429A CN 100441300 C CN100441300 C CN 100441300C
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- reduction
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- 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
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Abstract
A process for preparing the carried Ag catalyst by microbe reducing, which can be used to prepare epoxy ethan from ethene by oxidizing, includes such steps as separating Bacillus licheniformis from the soil and water in gold mine, culturing, enlarge culture, grinding to obtain microbial powder, calcining carrier, cooling, vacuumizing, immersing it in the liquid prepared from AgNO3 and CsNO3, drying to obtain the precursor, mixing it with the suspension prepared from said bacterial powder, and vacuum drying. Said catalyst is composed of Ag, Cs and carrier proportionally.
Description
Technical field
The present invention relates to a kind of silver catalyst, especially relate to a kind of loading type silver catalyst that is used for ethene oxidation production oxirane and preparation method thereof.
Background technology
The ethene oxidation mainly generates oxirane under the silver catalyst effect, side reaction takes place simultaneously generate carbon dioxide and water.Activity, selectivity and stability are the main performance index of silver catalyst.The performance of catalyst often with carrier on the size and the distribution situation thereof of the silver particles of disperseing closely related.(petrochemical industry .1995,24 (11): 821) report, when the silver-colored particle diameter in the prepared silver catalyst for ethylene oxide of SD company was 10～15nm, the oxirane selectivity was up to 83.5% for Mao Dongsen etc.This is because silver-colored particulate has the caused surface and interface effect of nano material characteristic, critical dimension effect, quantum size effect and quantum tunneling effect etc. equally.So in preparation silver catalyst process, control the size and the distribution situation of silver-colored particle effectively,, particularly improve selection of catalysts and will produce great influence, thereby reduce production costs to reducing silver-colored load capacity.
The preparation method of silver catalyst generally adopts infusion process in the prior art, is about in the solution of carrier immersion silver salt, organic amine and various auxiliary agent composition, makes dipping carrier activation afterwards by adding thermal reduction then.Adopt the method for preparing loading type silver catalyst, owing to high temperature reduction and decomposition, often easily cause migration, the recrystallization of carrier surface silver particles, cause silver-colored particulate average diameter big, its result will inevitably have influence on the decentralization of silver on catalyst carrier, thereby influences the performance of catalyst.In order to reduce the negative effect of these phenomenons as far as possible, the catalysis worker of various countries has carried out many effort from different aspects, and (US 5374748,1995 as SD company; US 5444034,1995) the multistage activation method of preparation high selectivity and stable silver catalyst has been proposed, be carrier behind the silver salt dipping, the branch level Four activates in the inert atmosphere of oxygen content in being lower than air, makes carrier combine in comparatively gentle mode with silver salt; (EP 716884 for the patented method of Mitsubishi Chemical Ind, 1996) be that maceration extract with components such as argentiferous, caesiums was earlier the ultrasonic wave processing 10min of 20kHz with frequency before impregnated carrier, with such solution impregnating carrier of handling, each component is more evenly distributed, thereby improves activity of such catalysts and stability.
The technology that above-mentioned patent documentation is mentioned can be improved distribution of particle sizes to a certain extent, reduce the sintering tendency, but owing in the metallic particles forming process, still adopt high-temperature technology, may cause metal dispersity not ideal enough or be difficult to controlledly effectively, influence taping the latent power of the possible best efficiency of catalyst.There is report to utilize the method for micro-reduction silver ion can be reduced to silver-colored simple substance under normal temperature condition, Pseudomonas stutzeri (Pseudomonas Stutzeri) AG259 contained AgNO as Klaus T
3The LB agar medium in cultivate, find this bacterium the cell periplasmic space deposit a large amount of silver nano-grains (TrendsBiotechnol, 2001,19:15); (Crystal Growth ﹠amp such as Nair; Design, 2002,2 (4): 293) find that lactic acid bacteria (Lactobacillus sp.) also can reduce silver ion and form simple substance silver crystal; (Colloids and Surfaces 2003:313) adds AgNO with fungi verticillium sp (Verticillium sp.) to Mukherjee P. etc.
3In the solution, the result reduces the simple substance silver particle that obtains a large amount of 25 ± 12nm sizes in born of the same parents; (Current Science, 2003,85 (2): such as Ahmad 162) with sickle mycete (Fusarium oxysporum) reduction AgNO
3, the result forms the silver-colored particle of multiple shapes such as the sphere of 5～50nm or triangle in solution.Liu Yueying etc. (Chinese patent ZL02102604.1) isolate bacillus licheniformis Bacillus licheniformis R08 from goldfield soil and pit water, and adopt this bacterial strain to reclaim palladium effectively from low concentration palladium ion solution.
Summary of the invention
Purpose of the present invention aim to provide a kind of utilize microorganism under normal temperature condition with Ag
+Be reduced to Ag
0Nano particle prepares the method for high degree of dispersion loading type silver catalyst then, and this catalyst is applied to the ethene oxidation and produces in the process of oxirane, has higher initial performance.
The composition of the said loading type silver catalyst of the present invention (pressing mass ratio) is for silver 1%～22%, and is preferred 5%～18%, caesium 100～1000ppm, and preferred 200～700ppm, surplus is a carrier.The preparation method is as follows:
1) from goldfield soil and pit water, isolates bacillus licheniformis (Bacillus licheniformis) R08, with the medium culture of dusty yeast or beef extract, soy peptone, agar preparation, will to grind to form attritive powder standby through enlarging bacterium mud after cultivating;
2) with α-Al
2O
3Carrier is put into the container that can vacuumize at 500～600 ℃ of following roasting 2～4h after the cooling, be evacuated to more than the 10mmHg;
3) press catalyst and form proportioning preparation AgNO
3And CsNO
3The maceration extract of forming adopts the iso volumetric impregnation method that maceration extract is loaded on the carrier then, and 60～80 ℃ of vacuum drying 1～2h make catalyst precursor;
4) the bacterium powder that contains R08 that step 1 is obtained is mixed with the microbial bacteria suspension, under 20～80 ℃, best 20～30 ℃, mixed microorganism bacteria suspension and catalyst precursor, the ratio of dry bacterium powder addition and Ag is (0.2～0.4): 1, and the control pH of mixed is 2～6, best 4～6, make its 18～24h that interacts, last 60～80 ℃ of following vacuum drying 1～2h promptly make loading type silver catalyst.
The performance evaluation of catalyst is carried out in homemade micro anti-evaluation device, and is active in optionally condition determination is as follows:
Reacting gas consists of ethene 11.36%, carbon dioxide 4.87%, oxygen 7.64%, nitrogen 76.13% (V/V%).Reaction pressure 2.1MPa, air speed 7000/h, reactor outlet EO concentration 1.38%, the loadings 1mL of catalyst.Evaluation result shows that the selectivity of ethene oxidation can reach 87.0% under 250 ℃ of conditions, and the EO exit concentration is 1.38%, has better choice than the catalyst that makes according to the conventional chemical infusion process under the condition on year-on-year basis.
The present invention utilizes microbial cells " grappling ", the reduction silver particles at alumina carrier surface uniform load nanoscale, Ag
+Reduction degree reaches more than 90%, and silver-colored mean particle dia is 20～40nm.Thereby make the high degree of dispersion loading type silver catalyst, prepared silver catalyst is applicable in the reaction of ethene oxidation production oxirane.
The specific embodiment
The invention will be further described below by embodiment.
Embodiment 1
The preparation method of bacterium powder: isolate bacillus licheniformis Bacillus licheniformis (strain R08) from gold mine waste, culture medium is dusty yeast (or beef extract) 5g, soy peptone 10g, agar 15～20g, Millipore ultra-pure water 1000mL, pH7.2～7.4,30 ℃ cultivation 24h.Culture after enlarging cultivation is at 3500～4000r.min
-1Centrifugal 15min under the condition, bacterium mud is dried to constant weight under 60 ℃ with after the ultra-pure water washing 3 times, and it is standby to grind to form attritive powder after the cooling.
With 40～60 order specific surfaces is 0.99m
2α-Al of/g
2O
3Carrier is at 500 ℃ of following roasting 4h, and weighing 2g puts into the container that can vacuumize after cooling, vacuumizes 0.5h under 80 ℃.Get 3.58g AgNO
3Be dissolved in the ultra-pure water, be settled to 10mL, obtain AgNO
3Solution.Get 0.2g CsNO
3Be dissolved in the ultra-pure water, be settled to 100mL, obtain the CsNO of 2mg/mL
3Solution.Pipette the AgNO that 2.4mL has prepared respectively
3CsNO with 0.5mL 2mg/mL
3Solution loads on the carrier according to the ratio of iso volumetric impregnation, and 60 ℃ of following vacuum drying 1h make silver catalyst precursor A g
+/ α-Al
2O
3
The bacteria suspension and the catalyst precursor immixture 24h that will contain 0.1g R08 dry bacterium powder, 30 ℃ of reaction temperatures, pH is 6; The elimination supernatant cleans respectively once with ultra-pure water and absolute ethyl alcohol, the Ag/ α-Al of gained
2O
3At 80 ℃ of following vacuum drying 2h, make loading type silver catalyst.The silver mean particle dia is 20～40nm.
Activation condition: CO
2With air Mixture (1: 4, V/V%) in the atmosphere, be warming up to 400 ℃ gradually, and under this temperature, keep 1h from room temperature, reduce to room temperature.Use the microreactor evaluating apparatus to measure activity of such catalysts and selectivity, the results are shown in Table 1.
Comparative example 1
According to conventional chemical immersion process for preparing catalyst, the method for preparing catalyst precursor is not introduced the bacterium powder and direct activation with embodiment 1 in down-stream, and activation condition is also with embodiment 1.Activity of such catalysts and selectivity see Table 1.
Table 1
Embodiment 2～6: prepare catalyst precursor according to the method identical with embodiment 1, change change pH values then, all the other are with embodiment 1, and different pH values are R08 dry bacterium powder reduction Ag down
+Prepared activity of such catalysts and selectivity the results are shown in Table 2.
Table 2
Embodiment 7～11: prepare catalyst precursor according to the method identical with embodiment 1, change reduction temperature then, all the other are with embodiment 1, R08 dry bacterium powder reduction Ag under the different temperatures
+Prepared activity of such catalysts and selectivity the results are shown in Table 3.
Table 3
Claims (5)
1. the method for preparing loading type silver catalyst by micro-reduction, it is characterized in that said loading type silver catalyst by mass ratio consist of silver 1%～22%, caesium 100～1000ppm, surplus is a carrier; Said Preparation of catalysts method is as follows:
1) from goldfield soil and pit water, isolate bacillus licheniformis Bacillus licheniformis R08, with the medium culture of dusty yeast or beef extract, soy peptone, agar preparation, will be standby through the bacterium mud grind into powder that enlarges after cultivating;
2) carrier is evacuated to vacuum greater than 10mmHg at 500～600 ℃ of following roasting 2～4h after the cooling;
3) press catalyst and form proportioning preparation AgNO
3And CsNO
3The maceration extract of forming adopts the iso volumetric impregnation method that maceration extract is loaded on the carrier then, and 60～80 ℃ of vacuum drying 1～2h make catalyst precursor;
4) the bacterium powder that contains bacillus licheniformis Bacillus licheniformis R08 that step 1 is obtained is mixed with the microbial bacteria suspension, under 20～80 ℃, mixed microorganism bacteria suspension and catalyst precursor, the ratio of Ag and dry bacterium powder addition is 1: 0.2～0.4, the control pH of mixed is 2～6, make its 18～24h that interacts, last 60～80 ℃ of following vacuum drying 1～2h promptly make loading type silver catalyst.
2. the method for preparing loading type silver catalyst by micro-reduction as claimed in claim 1 is characterized in that said carrier is α-Al
2O
3
3. the method for preparing loading type silver catalyst by micro-reduction as claimed in claim 1, it is characterized in that silver catalyst by mass ratio consist of silver 5%～18%, caesium 200～700ppm, surplus is a carrier.
4. the method for preparing loading type silver catalyst by micro-reduction as claimed in claim 1 is characterized in that in step 4) in 20～30 ℃ of following mixed microorganism bacteria suspensions and catalyst precursor.
5. the method for preparing loading type silver catalyst by micro-reduction as claimed in claim 1 is characterized in that the control pH of mixed is 4～6 in step 4).
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| CNB2006101354297A CN100441300C (en) | 2006-12-31 | 2006-12-31 | Method of preparing loading type silver catalyst by micro-reduction |
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| CN100441300C true CN100441300C (en) | 2008-12-10 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102836748A (en) * | 2012-09-17 | 2012-12-26 | 湖北省环境科学研究院 | Method for preparing ozone oxidation catalyst by utilizing waste beer yeast |
| CN111229216B (en) * | 2018-11-29 | 2022-08-05 | 万华化学集团股份有限公司 | Eggshell type silver catalyst and preparation method and application thereof |
| CN114426527B (en) * | 2020-10-15 | 2023-11-10 | 中国石油化工股份有限公司 | Silver catalyst carrier for ethylene oxide, preparation method and silver catalyst and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5374748A (en) * | 1993-03-01 | 1994-12-20 | Scientific Design Company, Inc. | Process for preparing silver catalyst for ethylene epoxidation |
| CN1388256A (en) * | 2002-01-16 | 2003-01-01 | 厦门大学 | Method of recovering Pd from low-concentration waste Pd ion liquid with becteria thallus |
| CN1792433A (en) * | 2005-11-21 | 2006-06-28 | 厦门大学 | Microorganism reduced noble metal (S) modified TiO2 catalyst and its prepn. method |
-
2006
- 2006-12-31 CN CNB2006101354297A patent/CN100441300C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5374748A (en) * | 1993-03-01 | 1994-12-20 | Scientific Design Company, Inc. | Process for preparing silver catalyst for ethylene epoxidation |
| CN1388256A (en) * | 2002-01-16 | 2003-01-01 | 厦门大学 | Method of recovering Pd from low-concentration waste Pd ion liquid with becteria thallus |
| CN1792433A (en) * | 2005-11-21 | 2006-06-28 | 厦门大学 | Microorganism reduced noble metal (S) modified TiO2 catalyst and its prepn. method |
Non-Patent Citations (6)
| Title |
|---|
| Biosorption and bioreduction of diamine silver complexby corynebacterium. Haoran Zhang etc.Journal of Chemical Technology and Biotechnology,No.80. 2005 |
| Biosorption and bioreduction of diamine silver complexby corynebacterium. Haoran Zhang etc.Journal of Chemical Technology and Biotechnology,No.80. 2005 * |
| 地衣芽孢杆菌R08吸附和还原钯(Pd2+)的研究. 林钟玉等.科学通报，第47卷第5期. 2002 |
| 地衣芽孢杆菌R08吸附和还原钯(Pd2+)的研究. 林钟玉等.科学通报，第47卷第5期. 2002 * |
| 纳米级银颗粒的制备方法. 张昊然等.贵金属，第26卷第2期. 2005 |
| 纳米级银颗粒的制备方法. 张昊然等.贵金属，第26卷第2期. 2005 * |
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