CN1256970A - Processf or preparing copper-containing catalyst - Google Patents
Processf or preparing copper-containing catalyst Download PDFInfo
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- CN1256970A CN1256970A CN 98121080 CN98121080A CN1256970A CN 1256970 A CN1256970 A CN 1256970A CN 98121080 CN98121080 CN 98121080 CN 98121080 A CN98121080 A CN 98121080A CN 1256970 A CN1256970 A CN 1256970A
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Abstract
The present invention discloses a preparation method of copper-containing catalyst. It is characterized by adopting organic acid or its ammonium salt as precipitant, and using coprecipitation method to prepare copper-containing catalyst. Its specific surface is larger and pore volume is high, and its cost also is reduced.
Description
The present invention relates to the method that a kind of coprecipitation prepares Cu-contained catalyst.Especially coprecipitation prepares the method for copper-zine oxide or copper-zinc oxide-aluminium oxide catalyst.
Cu-contained catalyst is widely used in the industrial process as copper-zinc oxide, copper-zinc oxide-aluminium oxide catalyst, and they are the catalyst that generally adopt in the processes such as low-temperature conversion, synthesizing methanol and hydrogenation dehydrogenation.
The preparation Cu-contained catalyst adopts coprecipitation usually, promptly in water-soluble mantoquita, zinc salt and aluminium mixed salt solution, add alkaline coprecipitator, as sodium carbonate, sodium acid carbonate and ammonium carbonate salts, copper, zinc and the aluminium form with insoluble subcarbonate is precipitated out, forms catalyst through filtration, washing, drying, roasting, moulding then.EP125,698 disclose the preparation method of the synthetic Cu-contained catalyst of a kind of methyl alcohol, this catalyst copper/zinc atom ratio is 2.8～3.8 (corresponding to the cupric oxide of 26.9～36.5 parts zinc oxide/100 part), the umber of aluminium oxide is 8～12, in this catalyst preparation process, copper and zinc are by adding the sodium carbonate precipitating reagent in metal salt solution, being incorporated in the catalyst in the co-precipitation mode.Aluminium oxide joins in the catalyst with the aluminum hydroxide sol form.US4,876,402 disclose a kind of is that coprecipitator prepares the method for aldehyde gas phase hydrogenation with copper/Zinc oxide catalytic with sodium carbonate, in order to improve activity of such catalysts and selectivity, has added potassium and nickel again in addition in catalyst, in this Preparation of catalysts process in order to reach the trace sodium salt of removing on the coprecipitate, sodium content on the assurance catalyst is less than 0.1%, and sediment will carry out four making beating, washing and filter, because former document US 3,303,001; US4,048,196; US4,393,251 point out emphatically, and the sodium on the catalyst is undesirable.In a word, Cu-contained catalyst all was to adopt alkaline matter in the document in the past, particularly sodium carbonate is that coprecipitator comes co-precipitation, and this method precipitates under alkali condition, and zinc compound generates precipitation prior to copper compound, thereby easily form uneven coprecipitate, but in order to obtain best catalytic activity and stability, the crystal grain of copper oxide equably separates, thereby in order to improve catalytic performance, the gained catalyst needs further modification, as add improver again in catalyst; Employing sodium carbonate is that another shortcoming of coprecipitator is owing to need wash sodium salt, coprecipitate must pull an oar repeatedly washing, filter, consumes a large amount of water purification, and produces a large amount of waste water and need processing, contaminated environment has increased the complexity of Preparation of Catalyst and the cost of catalyst; This method gained catalyst specific surface is not high enough in addition, pore volume is less, the heap is lower, and it is not ideal enough to show activity and selectivity on catalytic performance, and stability is good inadequately.
The objective of the invention is to find a kind ofly can solve environmental issue in the prior art, catalyst performance is good, and the Preparation of Catalyst good reproducibility, the preparation method of raw material and lower-cost Cu-contained catalyst.
Preparation of catalysts method provided by the present invention is:
The co-precipitation work salting liquid of soluble metallic salt is mixed with a kind of organic acid or its ammonium salt aqueous solution coprecipitator, co-precipitation goes out a kind of mixture of insoluble metallic salt, obtain filter cake through aging, filtration, drying, roasting form the catalyst mix oxide again, and last compression moulding is catalyst.Catalyst can be sheet, column, bar shaped, sphere or other suitable shape.
Described soluble metallic salt can be mantoquita, zinc salt and aluminium salt, also can be mantoquita and zinc salt.They can be in chlorate, sulfate, nitrate and the acetate one or more; The organic acid coprecipitator is one or more in ethanedioic acid, malonic acid, succinic acid, glutaric acid and the ammonium salt thereof.Preferred malonic acid, ethanedioic acid and ammonium salt thereof.
The coprecipitation process of slaine:
With the slaine is that raw material is mixed with certain density co-precipitation work salting liquid, and solution concentration is 0.10M～0.80M, is preferably 0.30M～0.50M; With organic acid or ammonium is that raw material is mixed with certain density coprecipitator solution, and the concentration of solution is 0.1～0.8M, is preferably 0.3～0.5M, and its pH value is 3.0～7.0, is preferably 4.0～6.0; The precipitating reagent consumption is preferably 10～15% (by weight percentage) for surpassing stoichiometric 5～20% (by weight percentage) of the complete precipitation reaction of metal ion in the work salting liquid; Co-precipitation temperature is 15～70 ℃, is preferably 25～45 ℃.Under insulation and stirring condition, they are mixed, obtain the coprecipitate that suspends, step such as wear out, filter, dry and obtain the coprecipitate filter cake through being incubated again.
Above-mentioned co-precipitation mode can be that the work salting liquid is joined in the precipitant solution, or precipitant solution is joined in the work salting liquid, also can be after they are heated respectively, joins in the stillpot simultaneously.
Above-mentioned coprecipitation process can be the work salting liquid to be joined respectively in two parallel gravity tanks simultaneously with precipitant solution be heated to 15～70 ℃, is preferably 25～45 ℃, joins simultaneously in the low level stillpot respectively under insulation and stirring condition.
The concrete preparation process of catalyst:
Above-mentioned coprecipitate filter cake is dry earlier, roasting again, the oxide mixture that obtains and a certain amount of pressing aid agent compression moulding promptly obtain catalyst.Baking temperature is 80～150 ℃, is preferably 100～120 ℃, and the time is 6～20 hours, is preferably 8～10 hours; Sintering temperature is 300～500 ℃, is preferably 340～370 ℃, and the time is 2～8 hours, is preferably 4～5 hours; The pressing aid agent is 2.0～5.0% with the ratio of butt weight, and the pressing aid agent can be graphite, stearic acid etc.
Above-mentioned oxide through step gained such as super-dry, roastings also can be mixed together evenly with pressing aid agent and adhesive, is pressed into catalyst.Adhesive can be zeolite, carborundum, silica, silica-alumina, silicate, aluminate and borate or the like
Catalyst of the present invention is the same with general Cu-contained catalyst, before use must be through reduction.Reducing medium can be pure hydrogen or contain hydrogen and nitrogen gas.Be warmed up to uniform temperature under reducing medium, constant temperature reduction is some to be cooled to after long-time to advance raw material under the reaction temperature and begin reaction.For avoiding occurring bigger temperature rise in the reduction process, even temperature runaway burns out catalyst, influence the catalytic performance of catalyst, reducing medium is preferably the nitrogen that contains 5% (volume) hydrogen, and programming rate should be strict controlled in the beds temperature rise and be lower than 20 ℃, reduction temperature is 200～250 ℃, is preferably 210～230 ℃.
Method for preparing catalyst of the present invention is suitable for various copper/zinc oxide/alumina Preparation of catalysts, as CO, CO
2And H
2Gaseous mixture synthesizing methanol catalyst system therefor; Low temperature conversion catalyst; Be particularly suitable for the preparation of the used copper/Zinc oxide catalytic of dehydrogenation of the gas phase hydrogenation and the alcohol of aldehyde, ketone.
Compared with prior art, method for preparing catalyst of the present invention is not owing to relate to the sodium problem of washing, not only simplified preparation flow, environmental issues such as useless and wastewater treatment have been eliminated because of the wave of washing the water purification that sodium causes, particularly since in the middle of this method insoluble salt coprecipitate structure single, thereby Preparation of Catalyst good reproducibility; And because in this coprecipitation process, copper and zinc precipitate simultaneously, generate the crystalline deposit thing of uniform ultrafine particle, gained catalyst specific surface, pore volume, aperture are bigger, heap is than higher, compare with the catalyst of conventional sodium carbonate method preparation, catalyst of the present invention has activity, selectivity is higher and stable better advantage, and catalyst raw material and preparation cost are reduced.
Further specify this patent below by embodiment.
Comparative example 1
This example is with US5, and 302,569 method prepares CuO/ZnO/Al
2O
3Catalyst.
435.6 gram copper nitrates, 261.5 gram zinc nitrates and 89.5 gram aluminum nitrates are dissolved in 1800 ml deionized water and form mixing salt solution, be heated to 80 ℃; 375.0 gram sodium carbonate are dissolved in 3000 ml deionized water, are heated to 80 ℃.
In stillpot, add 800 ml deionized water, be heated to 80 ℃, under stirring condition, in 20 minutes with above-mentioned two kinds of solution respectively but flow in the stillpot simultaneously, two bursts of logistics will match to guarantee that the solution pH value in the stillpot is 7.5～7.8, and temperature constant is 80 ℃.
After precipitation was finished, suspension continued to stir 2 minutes, filters, then with 12 liters of deionized waters 60～65 ℃ of down washings 2 hours, filter the back filter cake in 110 ℃ dry 8 hours down, 400 ℃ of following roastings 4 hours, add an amount of graphite then and mix back compression moulding, promptly get CuO/ZnO/Al
2O
3Catalyst.
The BET specific area of above-mentioned catalyst is 120.1m
2/ g, pore volume are 0.45ml/g, and average pore radius is 150 * 10
-10M.
Example 1
This example prepares CuO/ZnO/Al with reference to catalyst metals proportioning in the comparative example 1
2O
3Catalyst.
435.6 gram copper nitrates, 261.5 gram zinc nitrates and 89.5 gram aluminum nitrates are mixed with 2000 milliliters of mixing salt solutions, 416.0 gram malonic acid are mixed with 2000 milliliters of precipitant solution, both are placed in the parallel gravity tank respectively, be heated to 25 ℃ simultaneously.
Under water bath heat preservation and strong mixing, with both in 20 minutes respectively but be added to simultaneously in the low level stillpot, weak then the stirring aging 5 minutes down, filter, filter cake is following dry 8 hours at 110 ℃, 360 ℃ of following roastings 4 hours, add an amount of graphite then and mix back compression moulding, promptly get Cu/ZnO/Al
2O
3Catalyst.
The BET specific area of this catalyst is 136.2m
2/ g, pore volume 0.58ml/g, average pore radius is 171 * 10
-10M.
Comparative example 2
This example is with US4, and 876,402 method prepares the CuO/ZnO catalyst.
The solution of 41.7 gram copper (adding with the copper nitrate form) and 85.8 gram zinc (form with zinc nitrate adds) is heated to 43 ℃ for 1600 milliliters, spray into be in the mechanical agitation and constant temperature in 60 ℃ 1300 milliliter 15.7% sodium carbonate liquor, the pH value about 7.9～8.5 that precipitation mixture is last.At post precipitation basic copper carbonate zinc is filtered, then with 37.8～48.8 ℃ deionized water making beating washing, so filter, making beating washing 4 times,, make the sodium content on the mixed oxide after the roasting reduce to 0.10～0.15% to remove the sodium salt on the filter cake.Filter cake 110 ℃ dry 8 hours down, 400 ℃ of following roastings 4 hours, add an amount of graphite and mix back compression moulding and promptly get catalyst.
The BET specific area of this catalyst is 36.5m
2/ g, pore volume are 0.16ml/g, and average pore diameter is 175 * 10
-10M.
Example 2
This example prepares the CuO/ZnO catalyst with the metal proportioning of comparative example 2.
96.5 gram copper nitrates and 235.0 gram zinc nitrates are mixed with 2000 milliliters of mixing salt solutions, 170.0 gram oxalic acid are mixed with 3000 milliliters of precipitant solution, and its pH value is adjusted to 5.0, join respectively then in two parallel gravity tanks and be heated to 45 ℃, under water bath heat preservation and strong mixing, in 20 minutes respectively but be added to simultaneously in the low level stillpot, weak then the stirring aging 0.5 hour down, filter, dry, obtain filter cake and descended dry 8 hours, 360 ℃ of following roastings 4 hours at 110 ℃, mixed oxide that obtains and suitable amount of graphite mix back compression moulding, promptly get catalyst.
The BET specific area of this catalyst is 41.4m
2/ g, pore volume are 0.20ml/g, and average pore diameter is 191 * 10
-10M.
Example 3
This example is with reference to the metal proportioning (Cu/Zn:1: 1) preparation catalyst of the Japanese dayglow commodity CuO/ZnO N211 of company catalyst.
151.8 gram copper nitrates and 182.7 gram zinc nitrates are mixed with 1000 milliliters of mixing salt solutions, place the low level stillpot, 172.0 gram ammonium oxalate are mixed with 1500 milliliters of precipitant solution, its pH value is 7.0, place gravity tank, both are heated to 60 ℃ simultaneously, in 15 minutes ammonium oxalate solution are joined in the mixed salt solution under strong mixing, according to the step and the moulding of condition drying and roasting of example 4, get catalyst then.
The BET specific area of this catalyst is 29.1m
2/ g, pore volume are 0.16ml/g, and average pore diameter is 222 * 10
-10M; And the BET specific area of dayglow catalyst is 22.5m
2/ g, pore volume are 0.11ml/g, and average pore diameter is 201 * 10
-10M.
4 examples of example have compared the hydrogenation of n-butyraldehyde catalytic performance of comparative example 2 with example 2.
Estimate on the micro fixed-bed reactor device, catalyst amount is 4 milliliters, and granularity is 0.45～0.90mm.Earlier logical hydrogen (gas agent volume ratio is 500: 1), Hydrogen Vapor Pressure is 0.40MPa, is warming up to 220 ℃ by room temperature in 4 hours, and the constant temperature reduction is 1 hour then, is cooled to 150 ℃ of laggard butyraldehyde, and the butyraldehyde air speed is 0.5h
-1, hydrogen and butyraldehyde volume ratio are 6000: 1.Employing is carrier gas with the helium, is fixer with poly-ethanol nonyl phenylate, be fixing phase with the female Sha Bai W of network (Chromosorb W), is the gas chromatographic analysis of assessor with the conductance cell, with the relative amount of each component in the area normalization method calculating product.The results are shown in table 1.
Table 1: butyraldehyde hydrogenation catalyst performance comparison
Example comparative example 2 examples 2
Conversion ratio, % (weight) 99.2 99.7
The butanols selectivity, % 98.8 99.5
Example 5
This example has compared the sec-butyl alcohol dehydrogenizing performance of example 3 and commodity Cu/ZnO catalyst (Japanese dayglow company produces, and the trade mark is N211) to be estimated on the small fixed reactor assembly, and catalyst amount is 20 milliliters, and granularity is 0.45～1.8mm.Be warming up to 150 ℃ by room temperature in 3 hours, and advanced sec-butyl alcohol, air speed is 2.0h
-1, pressure is 0.20MPa, constant temperature reduction 8 hours continues to be warming up to 260 ℃ with the programming rate of 50 ℃/h then, stablizes post-sampling analysis in 8 hours.Employing is carrier gas with hydrogen, is fixing phase with high molecular polymer porous microsphere GDX-103, and conductance cell is the gas chromatographic analysis of assessor, calculates each components contents in the product with area normalization method.The results are shown in table 2.
Table 2: sec-butyl alcohol catalytic dehydrogenation catalytic performance contrast
Embodiment commercial catalyst N211 embodiment 3
Conversion ratio, % (weight) 75.2 80.1
The MEK selectivity, % 96.1 98.0
Claims (15)
1. the preparation method of a Cu-contained catalyst adopts coprecipitation to prepare catalyst, it is characterized in that method used precipitating reagent in shallow lake, common shallow lake is organic acid or its ammonium salt solution.
2. according to the preparation method of the described Cu-contained catalyst of claim 1, it is characterized in that described catalyst comprises cupric oxide and zinc oxide.
3. according to the preparation method of the described Cu-contained catalyst of claim 1, it is characterized in that described catalyst comprises cupric oxide, zinc oxide and aluminium oxide.
4. according to the preparation method of the described Cu-contained catalyst of claim 1, it is characterized in that described organic acid or its ammonium salt are malonic acid or its ammonium salt.
5. according to the preparation method of the described Cu-contained catalyst of claim 1, it is characterized in that described organic acid or its ammonium salt are ethanedioic acid or its ammonium salt.
6. according to the preparation method of the described Cu-contained catalyst of claim 1, it is characterized in that described organic acid or its ammonium salt are succinic acid or its ammonium salt.
7. according to the preparation method of the described Cu-contained catalyst of claim 1, the concentration that it is characterized in that the used work salting liquid of described coprecipitation process is 0.10～0.80M.
8. according to the preparation method of the described Cu-contained catalyst of claim 1, the concentration that it is characterized in that the used precipitant solution of described coprecipitation process is 0.10～0.80M, and the pH value is 3.0～7.0.
9. according to the preparation method of the described Cu-contained catalyst of claim 1, the temperature that it is characterized in that described coprecipitation process co-precipitation is 15 ℃～70 ℃.
10. according to the preparation method of the described Cu-contained catalyst of claim 1, it is characterized in that in the described coprecipitation process precipitating reagent consumption by weight percentage, metal ion is precipitated out 5%～20% of required chemical reaction metering fully in the work salting liquid in order to surpass.
11. according to the preparation method of the described Cu-contained catalyst of claim 1, the work concentration of salt solution that it is characterized in that described coprecipitation process is 0.3M～0.5M.
12. according to the preparation method of the described Cu-contained catalyst of claim 1, it is characterized in that shallow lake, described shallow lake agent solution concentration is 0.3M～0.5M, the pH value is 4.0～6.0.
13. according to the preparation method of the described Cu-contained catalyst of claim 1, the temperature that it is characterized in that described co-precipitation is 25 ℃～45 ℃.
14. preparation method according to the described Cu-contained catalyst of claim 1, it is characterized in that in the described coprecipitation process precipitating reagent consumption by weight percentage, metal ion is precipitated out 10%～15% of required chemical reaction metering fully in the work salting liquid in order to surpass.
15. preparation method according to the described Cu-contained catalyst of claim 1, it is characterized in that in the described coprecipitation process, the work salting liquid joins respectively in two parallel head tanks with precipitant solution and heats, and joins simultaneously in the low level stillpot respectively under insulation and stirring condition.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98121080A CN1101274C (en) | 1998-11-16 | 1998-11-16 | Processf or preparing copper-containing catalyst |
| JP32029999A JP4295406B2 (en) | 1998-11-16 | 1999-11-10 | Copper-containing catalyst and method for producing the same |
| EP99121980A EP1000658B1 (en) | 1998-11-16 | 1999-11-10 | A copper-containing catalyst, a process for the preparation and use thereof |
| DE69933184T DE69933184T2 (en) | 1998-11-16 | 1999-11-10 | Copper-containing catalyst, its method of preparation and its use |
| US09/439,928 US6689713B1 (en) | 1998-11-16 | 1999-11-12 | Copper-containing catalyst and a process for the preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98121080A CN1101274C (en) | 1998-11-16 | 1998-11-16 | Processf or preparing copper-containing catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1256970A true CN1256970A (en) | 2000-06-21 |
| CN1101274C CN1101274C (en) | 2003-02-12 |
Family
ID=5226992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98121080A Expired - Lifetime CN1101274C (en) | 1998-11-16 | 1998-11-16 | Processf or preparing copper-containing catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1101274C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376822B (en) * | 2007-08-27 | 2012-08-29 | 中国石油化工股份有限公司 | Gasoline sweetening catalyst, preparation and use thereof |
| CN102039134B (en) * | 2009-10-21 | 2013-07-24 | 中国石油化工股份有限公司 | Light oil hydrogenation sweetening catalyst and preparation method and application thereof |
| CN103372443A (en) * | 2012-04-13 | 2013-10-30 | 中国石油化工股份有限公司 | Preparation method of copper-based catalyst |
| CN104560251A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Cleaning agent and use thereof |
| CN105289642A (en) * | 2015-10-30 | 2016-02-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing copper-manganese composite oxide of porous structure |
| CN109420502A (en) * | 2017-08-23 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of preparation method of heat-resisting copper-zinc-based catalyst |
| CN111204709A (en) * | 2020-01-10 | 2020-05-29 | 湘潭大学 | Water-gas shift reaction method and catalyst thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5053380A (en) * | 1989-12-21 | 1991-10-01 | Union Carbide Chemicals And Plastics Technology Corporation | Cu-al catalyst for hydrogenation |
| DE4127318A1 (en) * | 1991-08-17 | 1993-02-18 | Hoechst Ag | CATALYSTS CONTAINING COPPER ZINC OXIDE ALUMINUM |
-
1998
- 1998-11-16 CN CN98121080A patent/CN1101274C/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376822B (en) * | 2007-08-27 | 2012-08-29 | 中国石油化工股份有限公司 | Gasoline sweetening catalyst, preparation and use thereof |
| CN102039134B (en) * | 2009-10-21 | 2013-07-24 | 中国石油化工股份有限公司 | Light oil hydrogenation sweetening catalyst and preparation method and application thereof |
| CN103372443A (en) * | 2012-04-13 | 2013-10-30 | 中国石油化工股份有限公司 | Preparation method of copper-based catalyst |
| CN103372443B (en) * | 2012-04-13 | 2015-07-22 | 中国石油化工股份有限公司 | Preparation method of copper-based catalyst |
| CN104560251A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Cleaning agent and use thereof |
| CN104560251B (en) * | 2013-10-28 | 2017-04-19 | 中国石油化工股份有限公司 | Cleaning agent and use thereof |
| CN105289642A (en) * | 2015-10-30 | 2016-02-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing copper-manganese composite oxide of porous structure |
| CN109420502A (en) * | 2017-08-23 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of preparation method of heat-resisting copper-zinc-based catalyst |
| CN111204709A (en) * | 2020-01-10 | 2020-05-29 | 湘潭大学 | Water-gas shift reaction method and catalyst thereof |
| CN111204709B (en) * | 2020-01-10 | 2024-07-09 | 湘潭大学 | Water vapor shift reaction method and catalyst thereof |
Also Published As
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|---|---|
| CN1101274C (en) | 2003-02-12 |
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