CN1236668A - Non-crystal Cu/SiO2 catalyst and its preparing process and usage - Google Patents
Non-crystal Cu/SiO2 catalyst and its preparing process and usage Download PDFInfo
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- CN1236668A CN1236668A CN98108655A CN98108655A CN1236668A CN 1236668 A CN1236668 A CN 1236668A CN 98108655 A CN98108655 A CN 98108655A CN 98108655 A CN98108655 A CN 98108655A CN 1236668 A CN1236668 A CN 1236668A
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- sio
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- kbh
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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
- 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
Abstract
A non-crystal Cu/SiO2 catalyst contains Cu (1-39 wt.%), B (0.001-0.1 wt.%) and SiO2 (60-90 wt.%), and is prepared from ultrafine SiO2 as carrier, CaSO4 and KBH4 as precursor, complexing agent and anti-corrosive scale inhibitor by deposition method. Said catalyst can be used to prepare methanol from methyl formate as raw material through hydrogenolysis, and features superfine particle effect and higher low-temp catalytic activity.
Description
The invention belongs to a kind of catalyst and method for making thereof and purposes, relate in particular to a kind of non-crystal Cu/SiO 2 catalyst and method for making thereof and purposes.
The amorphous alloy catalyst that past is studied is basically all with the quenching method preparation, and its specific area is very little, thereby is difficult to embody catalytic performance preferably.Chemist was developed the electronation sedimentation and was prepared bigger serface, highly active amorphous state cobalt-based alloy and nickel-base alloy catalyst afterwards, made the research of amorphous alloy catalyst material bring up to a more level of Gao Gengxin.Adopting the sodium borohydride solution amorphous superfine particle Ni-B alloy that reaction makes as reducing agent and nickel salt solution as people such as Li Tongxin is catalyst, and studied the catalytic performance that is used for benzene hydrogenation, find to prepare the Ni-B alloy of different compositions and different dispersities by control reaction condition (as reaction density and rate of addition etc.), and specific area and the catalyst of benzene hydrogenation had certain difference, and active temperature is lower.The amorphous alloy that experiment showed, the preparation of electronation sedimentation has very little particle diameter, even reaches nanoscale, belongs to ultrafine particle.Its main feature is surface atom ratio big (generally being not less than 5%), the big (10-70m of specific area
2/ g) can be high with the surface.The surface state of atom level changes the surface electronic state.So amorphous superfine particle alloy integrates the characteristic of amorphous state and ultrafine particle,, have many unique functions as catalysis material.At present, the report of Co and Ni and other amorphous metal attitude alloy is more, and amorphous state Cu/SiO
2Catalyst is not found by retrieval as yet.
Goal of the invention of the present invention provides a kind of non-crystal Cu/SiO 2 catalyst and method for making and purposes.
Catalyst of the present invention is formed (percentage by weight):
Cu???????1-39％?????B??0.001-0.1％
SiO
2???60-90％
Aforesaid SiO
2Be that specific area is 900-1200m
2/ g, apparent bulk density are 0.04-0.05g/cm
2Ultra-fine SiO
2
Preparation of catalysts method of the present invention comprises the steps:
(1) predecessor of catalyst composition is CuSO
4And KBH
4, take by weighing various compositions by above-mentioned composition content, CuSO
4Be made into the aqueous solution that concentration is 0.5-1.0mol/l, KBH
4Be made into the aqueous solution that concentration is 0.5-1.0mol/;
(2) at ultra-fine SiO
2Add deionized water in the carrier and constantly stir formation SiO
2Suspension adds the CuSO for preparing again
4The aqueous solution, and the adding complexing agent makes the Cu in the solution
2+Complexing fully adds different propene phosphoric acid acrylic copolymer corrosion inhibiting and descaling agent, and the content that makes antisludging agent in the solution is 10-50PPm, fully stirs 12 hours, with the KBH for preparing
4The aqueous solution dropwise adds, and the generation black precipitate is swift in response;
(3) the isolated sediment of washing is to neutral, and with acetone washing 3-5 time, air dry obtains amorphous Cu/SiO again
2Catalyst.
Aforesaid ultra-fine SiO
2The preparation method be to be catalyst with acetic acid, adopt sol-gel process that ethyl orthosilicate (TEOS) hydrolysis is obtained silicon dioxide gel, make ultra-fine SiO through supercritical drying
2Concrete preparation method sees Catalysis Today 30 (196) 171-175.
The purposes of catalyst of the present invention be with the methyl formate be raw material 80 ℃ of reaction temperatures, 1.0MPa reaction pressure, air speed are to carry out hydrogenolysis under the condition of 3600ml/l.g.catal flow rate of liquid to make methyl alcohol.
The present invention compared with prior art has following advantage:
(1) specific area of catalyst is big, the duct prosperity.
(2) catalyst that makes has the ultrafine particle effect.
(3) has advantages of high catalytic activity.
Embodiment 1
(1) prepares ultra-fine SiO
2: at first press H
2The O/TEOS mol ratio is 4: 1 a ratio, ethyl orthosilicate is made into the aqueous solution, be 0.1: 1 ratio with acetic acid/TEOS mol ratio again, acetic acid is added in the aqueous solution of ethyl orthosilicate, the concentration that adds an amount of ethanol modulation TEOS at last is 1.0mol/l, stir and be hydrolyzed in 2 hours, in autoclave, carry out supercritical drying then and obtain ultra-fine SiO
2
(2) precursor C uSO
4Be made into the aqueous solution of 0.5mol/l concentration, KBH
4Be made into the aqueous solution of 0.5mol/l concentration;
(3) take by weighing 5.90g SiO
2Carrier and add deionized water after constantly stir and form suspension, add CUSO again
4Aqueous solution 50ml, citric acid complexing agent 10g and different propene phosphoric acid acrylic copolymer corrosion inhibiting and descaling agent, making the concentration that contains antisludging agent in the solution is 10ppm, fully stirs 12 hours, with KBH
4Aqueous solution 75ml dropwise adds, and the generation black precipitate that is swift in response washes with water to neutrality precipitating and isolating, and with acetone washing 3 times, air dry is consisted of (percentage by weight) Cu 5.79%, B0.07%, SiO again
2Amorphous Cu/SiO of 94.12%
2Catalyst.
Embodiment 2
(1) prepares ultra-fine SiO
2(with embodiment 1):
(2) precursor C uSO
4Be made into the aqueous solution of 0.5mol/l concentration, KBH
4Be made into the aqueous solution of 0.5mol/l concentration;
(3) take by weighing 5.0g SiO
2Carrier and add deionized water after constantly stir and form suspension, add CuSO again
4Aqueous solution 75ml, oxalic acid 30g and different propene phosphoric acid acrylic copolymer corrosion inhibiting and descaling agent, making the concentration that contains antisludging agent in the solution is 10ppm, fully stirs 12 hours, with KBH
4Aqueous solution 100ml dropwise adds, and the generation black precipitate that is swift in response washes with water to neutrality precipitating and isolating, and with acetone washing 3 times, air dry is consisted of (percentage by weight) Cu 13.98% again, and B 0.06%, SiO
2Amorphous Cu/SiO of 85.95%
2Catalyst.
Embodiment 3
(1) prepares ultra-fine SiO
2(with embodiment 1);
(2) precursor C uSO
4Be made into the aqueous solution of 0.5mol/l concentration, KBH
4Be made into the aqueous solution of 0.5mol/l concentration;
(3) take by weighing 5.0g SiO
2Carrier and add deionized water after constantly stir and form suspension, add CuSO again
4Aqueous solution 100ml, citric acid 20g and different propene phosphoric acid acrylic copolymer corrosion inhibiting and descaling agent, making the concentration that contains antisludging agent in the solution is 60ppm, fully stirs 12 hours, with KBH
4Aqueous solution 130ml dropwise adds, and the generation black precipitate that is swift in response washes with water to neutrality precipitating and isolating, and with acetone washing 3 times, air dry is consisted of (percentage by weight) Cu 19.78%, B0.08%, SiO again
2Amorphous Cu/SiO of 80.13%
2Catalyst.
Embodiment 4
(1) prepares ultra-fine SiO
2(with embodiment 1);
(2) precursor C uSO
4Be made into the aqueous solution of 1.0mol/l concentration, KBH
4Be made into the aqueous solution of 0.5mol/l concentration;
(3) take by weighing 3.0g SiO
2Carrier and add deionized water after constantly stir and form suspension, add CuSO again
4Aqueous solution 100ml, malic acid 20g and different propene phosphoric acid acrylic copolymer corrosion inhibiting and descaling agent, making the concentration that contains antisludging agent in the solution is 30ppm, fully stirs 12 hours, with KBH
4Aqueous solution 150ml dropwise adds, and the generation black precipitate that is swift in response washes with water to neutrality precipitating and isolating, and with acetone washing 3 times, air dry is consisted of (percentage by weight) Cu 26.75%, B0.06%, SiO again
2Amorphous Cu/SiO of 73.25%
2Catalyst.
Embodiment 5
(1) prepares ultra-fine SiO
2(with embodiment 1);
(2) precursor C uSO
4Be made into the aqueous solution of 0.5mol/l concentration, KBH
4Be made into the aqueous solution of 0.5mol/l concentration;
(3) take by weighing 2.5g SiO
2Carrier and add deionized water after constantly stir and form suspension, add CuSO again
4Aqueous solution 100ml, citric acid 10g and different propene phosphoric acid acrylic copolymer corrosion inhibiting and descaling agent, making the concentration that contains antisludging agent in the solution is 30ppm, fully stirs 12 hours, with KBH
4Aqueous solution 100ml dropwise adds, and the generation black precipitate that is swift in response washes with water to neutrality precipitating and isolating, and with acetone washing 3 times, air dry is consisted of (percentage by weight) Cu 37.96%, B0.09%, SiO again
2Amorphous Cu/SiO of 61.94%
2Catalyst.
Embodiment 6
Carried non-crystal Cu/SiO
2Catalyst is 80 ℃ in reaction temperature, and Hz/ methyl formate mol ratio is 4.5 in the unstripped gas, catalyst amount 1.0g, and pressure 1.0MPa, weight space velocity are under the condition of 3600 (ml/h.gcat), the reaction result of hydrogenolysis of methyl formate system methyl alcohol sees Table 1.
Table 1 carried non-crystal Cu/SiO
2Catalyst methyl esters hydrogenolysis result
| Catalyst | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Copper content (wt%) | ?????5.79 | ????14.66 | ????19.78 | ????28.70 | ????37.86 |
| Methyl formate conversion ratio % | ????29.87 | ????31.86 | ????38.61 | ????25.46 | ????24.29 |
| Methyl alcohol selectivity (%) | ????97.63 | ????96.86 | ????95.74 | ????98.97 | ????99.89 |
Claims (4)
1. non-crystal Cu/SiO 2 catalyst is characterized in that catalyst forms (percentage by weight) and be:
Cu???????1-39％????B??0.001-0.1％
SiO
2????60-90％
2. a kind of non-crystal Cu/SiO 2 catalyst according to claim 1 is characterized in that described SiO
2Be that specific area is 900-1200m
2/ g, apparent bulk density are 0.04-0.05g/cm
2
3. the preparation method of a non-crystal Cu/SiO 2 catalyst is characterized in that comprising the steps:
(1) predecessor of catalyst composition is CuSO
4And KBH
4, take by weighing various compositions by above-mentioned composition content, CuSO
4Be made into the aqueous solution that concentration is 0.5-1.0mol/l, KBH
4Be made into the aqueous solution that concentration is 0.5-1.0mol/;
(2) at ultra-fine SiO
2Add deionized water in the carrier and constantly stir formation SiO
2Suspension adds the CuSO for preparing again
4The aqueous solution, and the adding complexing agent makes the Cu in the solution
2+Fully complexing, adding different propene phosphoric acid acrylic copolymer corrosion inhibiting and descaling agent, to make the content of antisludging agent in the solution be 10-50PPm, fully stirred 12 hours, with the KBH for preparing
4The aqueous solution dropwise adds, and the generation black precipitate is swift in response;
(3) isolated sediment is washed to neutrality, and with acetone washing 3-5 time, air dry obtains amorphous Cu/SiO again
2Catalyst.
4. the purposes of a non-crystal Cu/SiO 2 catalyst, it is characterized in that be with the methyl formate be raw material 80 ℃ of reaction temperatures, 1.0MPa reaction pressure, air speed are to carry out hydrogenolysis under the condition of 3600ml/l.g.catal flow rate of liquid to make methyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98108655A CN1089033C (en) | 1998-05-22 | 1998-05-22 | Non-crystal Cu/SiO2 catalyst and its preparing process and usage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98108655A CN1089033C (en) | 1998-05-22 | 1998-05-22 | Non-crystal Cu/SiO2 catalyst and its preparing process and usage |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1236668A true CN1236668A (en) | 1999-12-01 |
| CN1089033C CN1089033C (en) | 2002-08-14 |
Family
ID=5219727
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98108655A Expired - Fee Related CN1089033C (en) | 1998-05-22 | 1998-05-22 | Non-crystal Cu/SiO2 catalyst and its preparing process and usage |
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|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102423710A (en) * | 2010-12-13 | 2012-04-25 | 西南化工研究设计院 | Catalyst used in preparation of ethanol through hydrogenation of acetate and preparation method thereof |
| CN102872869A (en) * | 2012-09-11 | 2013-01-16 | 常州大学 | Methanol dehydrogenation catalyst used in process of preparing methyl formate and preparation and application of catalyst |
| CN114029095A (en) * | 2021-12-16 | 2022-02-11 | 常州大学 | Cu/SiO for preparing cyclohexanone by efficiently catalyzing anaerobic dehydrogenation of cyclohexanol2Preparation method and application of catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5952255A (en) * | 1982-09-20 | 1984-03-26 | Ricoh Co Ltd | Dry tyre developing toner |
| US5340437A (en) * | 1993-10-08 | 1994-08-23 | Memc Electronic Materials, Inc. | Process and apparatus for etching semiconductor wafers |
-
1998
- 1998-05-22 CN CN98108655A patent/CN1089033C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102423710A (en) * | 2010-12-13 | 2012-04-25 | 西南化工研究设计院 | Catalyst used in preparation of ethanol through hydrogenation of acetate and preparation method thereof |
| CN102423710B (en) * | 2010-12-13 | 2013-03-13 | 西南化工研究设计院 | Catalyst used in preparation of ethanol through hydrogenation of acetate and preparation method thereof |
| CN102872869A (en) * | 2012-09-11 | 2013-01-16 | 常州大学 | Methanol dehydrogenation catalyst used in process of preparing methyl formate and preparation and application of catalyst |
| CN114029095A (en) * | 2021-12-16 | 2022-02-11 | 常州大学 | Cu/SiO for preparing cyclohexanone by efficiently catalyzing anaerobic dehydrogenation of cyclohexanol2Preparation method and application of catalyst |
| CN114029095B (en) * | 2021-12-16 | 2023-08-22 | 常州大学 | Cu/SiO for preparing cyclohexanone by efficiently catalyzing cyclohexanol to perform anaerobic dehydrogenation 2 Preparation method and application of catalyst |
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| Publication number | Publication date |
|---|---|
| CN1089033C (en) | 2002-08-14 |
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