CN100408176C - Preparing method of Cu-base solid catalyst - Google Patents
Preparing method of Cu-base solid catalyst Download PDFInfo
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- CN100408176C CN100408176C CNB2006100127991A CN200610012799A CN100408176C CN 100408176 C CN100408176 C CN 100408176C CN B2006100127991 A CNB2006100127991 A CN B2006100127991A CN 200610012799 A CN200610012799 A CN 200610012799A CN 100408176 C CN100408176 C CN 100408176C
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Abstract
The present invention discloses a preparing method of a Cu-base solid catalyst, which is characterized in that solid super acid and a Cu-base compound carry out a solid phase reaction to prepare a Cu-based solid phase catalyst, wherein the solid super acid and the Cu-base compound are mixed and ground according to the mass ratio of 1:1 to 12:1, the mixed powder is heated for 2 to 8h at the temperature of 300 DEGC to 800 DEGC in a tubular heater, and the solid phase catalyst of the Cu-based compound is prepared; absolute methanol, the catalyst, O2 and CO are added into continuous high-pressure reaction vessels, and dimethyl carbonate is synthesized at the temperature of 120 DEG C to 150 DEG C and under the pressure of 3.0 to 5.0 MPas; the selectivity of a target product is from 90.00% to 99.97%, and the space time yield of DMC reaches 0.5 to 3.5g. g<-1>. h<-1>. The present invention has the advantages of simple preparation process, high catalyst activity, high catalyst selectivity, high catalyst stability, reactor corrosiveness great reduction and good industrial application prospects.
Description
Technical field
The present invention relates to the catalyst based preparation method of a kind of Cu, a kind of specifically solid super-strong acid and copper-containing compound of adopting promptly is a kind of preparation method of Cu base solid catalyst by a kind of Cu Quito item Preparation of catalysts method that solid phase reaction prepares.
Background technology
Dimethyl carbonate is a kind of important green Organic Chemicals, is widely used in the synthetic of high performance resin, medicine, pesticide intermediate.The preparation method of dimethyl carbonate has phosgenation, ester-interchange method and oxidative carbonylation of methanol method (comprising vapor phase method and liquid phase method).Phosgenation production is because the raw material phosgene has severe toxicity, and it is superseded that environmental pollution seriously has been tending towards, and the clean synthesis technique of relevant DMC has caused extensive concern both domestic and external in recent years, and has done a large amount of correlative studys.Wherein methanol solution phase oxidation carbonylation method has raw material and is easy to get, and technology is simple, low cost and other advantages.Italy Enichem company is catalyst with the stannous chloride, and the synthetic dimethyl carbonate of methanol solution phase oxidation carbonylation has been realized industrialization.Stannous chloride is corrosive to reaction unit, must add anti-corrosion materials such as glass lining at reactor wall, but this obstacle (Ind.Chim.21 (1), 1985) that has become device to maximize.
(US 4625044 in U.S. Dow chemical industrial company, 1986, US 5004827,1991, US 51625631998)) with activated carbon loaded metal Cu, chloride catalysts such as Pd are used for the synthetic DMC research of methanol solution phase oxidation carbonylation method, and activity and selectivity are not high, and because the loss life-span of Cl weak point in the course of reaction, and HCl gas attack equipment.
Poplar equality (CN 1376665A, 2002) the polymer P VP CuCl of solubility
2Carried out the test of the synthetic DMC of oxidative carbonylation, by the effect of ligand, can reduce corrosion greatly, and improve the selectivity of conversion of methanol and DMC simultaneously reactor, but Cl after all
-Also be present in the reaction system, corrosivity is not thoroughly stopped, and has the losing issue of Cl.Fact proved with CuCl
2Though, have the inactivation and the equipment corrosion problem that cause catalyst owing to the loss of Cl ion for the loaded catalyst of active constituent can improve catalytic performance by adding auxiliary agent.
With CuCl is major catalyst, magnesium chloride, calcium chloride etc. though improved the dissolubility of stannous chloride in reactant liquor, have improved catalyst activity for the composite catalyst of auxiliary agent preparation, but the etching problem to equipment does not still solve (CN 1197792A, 1998).
Heterocyclic compound and macromolecule with nitrogen atom are part, make catalyst with the complex compound that stannous chloride forms, and implement the reaction of methanol solution phase oxidation carbonization Synthesis of dimethyl carbonate.This complex catalyst can improve the selectivity of conversion of methanol and dimethyl carbonate, greatly reduces the corrosivity (CN1333086A, 2002) to reactor simultaneously.
As seen, in the methanol oxidation carbonylation, Cl in the catalyst
-Existence be particular importance for activity of such catalysts and stability.As everyone knows, CuCl is an oxidative carbonylation catalyst preferably, if select a kind of solid acid with suitable acid strength, to replace the Cl among the CuCl
-Just there has not been the losing issue of Cl ion in ion and form stable solid matter when using as catalyst, thereby avoids causing the etching problem of catalysqt deactivation and equipment because the Cl ion runs off.And molecular sieve and solid super-strong acid are exactly to meet this material with acid strength.At home and many in the world researchers molecular sieve has been done a large amount of research as the carrier of CuCl by the catalyst of solid phase reaction preparation.
People such as Lamberti (J.Phy.Chem.B, 1997,101) research thinks that the solid ion exchange at high temperature takes place for CuCl and HY, the mixture of HZSM-5 molecular sieve, and copper is with Cu
+Absolute predominance is present in the molecular sieve, has replaced the H of former Bronsted acid
+, Cl deviates from the HCl form, and following reaction takes place:
CuCl+H
+Ze → Cu
+Ze
-+ HCl ↑ (Ze
-: the framework of molecular sieve anion)
People such as Li Zhong (Appl.Catal.A, 2001.209,205) have done research with CuCl by the catalyst that solid phase reaction makes to mesoporous material MCM-41 and molecular sieve (HY, ZSM-5, DASY), find Cu among the CuCl
+With the H in the molecular sieve
+Ion exchanges, thereby makes Cu
+Load on the molecular sieve, and Cl
-Then with molecular sieve on H
+Ions binding generates HCl and removes.Not only Cl content is few for this catalyst, and equipment corrosion is low, and the synthetic dimethyl carbonate of methanol oxidation carbonylation is had catalytic activity preferably.
Based on above analysis, the present invention is that raw material is prepared a kind of Cu base solid catalyst by solid phase reaction with solid super-strong acid and copper compound, this catalyst has catalytic activity preferably to the methanol oxidation carbonylation, and corrosivity is lower, does not see the report of the inventive method at home and abroad.
Summary of the invention
The present invention solid super-strong acid and copper based compound, make the Cu base solid catalyst by solid phase reaction, implement the reaction of the synthetic dimethyl carbonate of methanol oxidation carbonylation, low and with the space-time yield that solves methyl alcohol selectivity low and dimethyl carbonate to the corrosion problems of reactor assembly, its objective is the preparation method that a kind of Cu base solid catalyst is provided.
The method that the present invention prepares the Cu base solid catalyst comprises following process:
(1) the Cu base solid catalyst that adopts solid super-strong acid and copper based compound to make by solid phase reaction;
(2) adopting the carrier of solid super-strong acid is ZrO
2, TiO
2, ZrO
2-TiO
2, Al
2O
3, SiO
2Or its mixed oxide, the acidic materials of load are H
3PO
4, (NH
4)
3PO
4, (NH
4)
2HPO
4, (NH
4) H
2PO
4, H
3PO
3, H
2SO
4, H
2SO
3Or (NH
4)
2S
2O
8, the load capacity of acidic materials is the 1%-20% of carrier quality.
(3) copper compound of Cai Yonging is CuCl, CuCl
2, CuBr, CuBr
2Or Cu (NO
3)
2
(4) be 1 with solid super-strong acid and copper based compound in mass ratio: 1-12: 1 ratio mixed grinding, heat 2-8h down in 300 ℃-800 ℃ and make copper based compound solid-phase catalyst in tubular heater.
The present invention adopts solid super-strong acid and copper-containing compound to prepare catalyst by solid phase reaction, and its special advantage is that the carrier of solid super-strong acid used in the catalyst is ZrO
2, TiO
2, Al
2O
3, SiO
2Or its mixed oxide, the acidic materials of load are H
3PO
4, (NH
4)
3PO
4, (NH
4)
2HPO
4, H
3PO
3, (NH
4) H
2PO
4, H
2SO
4, H
2SO
3, (NH
4)
2S
2O
8Or its mixture, the load capacity of acidic materials is the 1%-20% of carrier quality, copper compound is CuCl, CuCl
2, CuBr, CuBr
2Or Cu (NO
3)
2The space-time yield of the catalyst based not only methyl alcohol of this Cu and the selectivity of dimethyl carbonate are higher, and greatly reduce the corrosivity of reactor assembly.
The inventive method prepares the Cu base solid catalyst and draws the following fact through test: (1) catalyst Cl ion under higher roast temperature removes from catalyst system gradually, and the stability of catalyst increases gradually, and corrosivity reduces; (2) the roast temperature of catalyst is more suitable in 400 ℃ of-700 ℃ of intervals; When (3) the Cu base solid catalyst was applied to the reaction of methanol solution phase oxidation carbonization Synthesis of dimethyl carbonate, at 100 ℃-160 ℃ Range of measuring temp internal object product selectivity 90.00%-99.97%, the space-time yield of DMC reached 0.5-3.5gg
-1H
-1
Specifically execute routine mode
Come the present invention is further described below by the mode of specifically executing
Embodiment 1
(1) with 15.69g ZrOCl
28H
2O is dissolved in the 487ml distilled water, and stirring drips 0.5mol/L ammoniacal liquor down, stops to drip the down aging 6h of normal temperature behind the continuation stirring 60min when pH=8.Filtration washing is precipitated to AgNO then
3Solution detects less than Cl
-After the existence, with sediment dry 10h under 100 ℃.
(2) below crushed after being dried to 110 order, add 5% H of its quality
3PO
4(0.1mol/L) H
3PO
4Solution), adsorb 24h, remove by filter excessive acid solution, dry 24h under 120 ℃ can make 6.8g H in 500 ℃ of roasting 3h then in tubular heater
3PO
4/ ZrO
2Solid super-strong acid.
(3) with 3g H
3PO
4/ ZrO
2Solid super-strong acid and 1.5g CuCl (mass ratio 2: 1) mixed grinding heats 4h down in 550 ℃ and makes H under nitrogen protection
3PO
4/ ZrO
2-CuCl catalyst 4.2g.
(4) take by weighing 3g H
3PO
4/ ZrO
2-CuCl catalyst adds in the 250ml autoclave, adds the 100ml absolute methanol again, with mist (O
2: 8%, the CO:92%) air in the metathesis reactor at room temperature uses this gas punching press to 3.0MPa then.120 ℃ of reactions 2 hours.The cooling back is with gas chromatographic analysis.The selectivity 99.97% of dimethyl carbonate, the space-time yield of catalyst are 1.78gg
-1H
-1
Embodiment 2
(1) with 6gZrO
2(commercially available) is crushed to below 110 orders, adds 5% H of its quality
3PO
4(0.1mol/L H
3PO
4Solution), adsorb 24h, remove by filter excessive acid solution, dry 24h under 120 ℃ can make 5.6g H in 500 ℃ of roasting 3h then in tubular heater
3PO
4/ ZrO
2Solid super-strong acid.
(2) with 3g H
3PO
4/ ZrO
2Solid super-strong acid and 1.0g CuBr (mass ratio 3: 1) mixed grinding heats 4h down in 350 ℃ and makes H under nitrogen protection
3PO
4/ ZrO
2-CuBr catalyst 3.8g.
(3) take by weighing 3g H
3PO
4/ ZrO
2-CuBr catalyst adds in the 250ml autoclave, adds the 100ml absolute methanol again, with mist (O
2: 8%, the CO:92%) air in the metathesis reactor at room temperature uses this gas punching press to 3.0MPa then.120 ℃ of reactions 2 hours.The cooling back is with gas chromatographic analysis.The selectivity 98.56% of dimethyl carbonate, the space-time yield of catalyst are 2.45gg
-1H
-1.
Embodiment 3
(1) under the room temperature with 15ml Ti (OCH
9) splash in the 70ml absolute ethyl alcohol, with obtaining homogeneous transparent solution behind the constant temperature blender with magnetic force stirring 30min, pour separatory funnel into.In the beaker of 250ml, pour the 50ml absolute ethyl alcohol into, glacial acetic acid, each 10ml of distilled water, magnetic stirrer, open the separatory funnel valve then, butyl titanate one ethanolic solution that the prepares speed with 3ml/min is added drop-wise in the beaker solution that is just stirring, obtain transparent colloidal sol after, continue to stir 10min, at room temperature left standstill 2 days, and formed gel.
(2) below crushed after being dried to 110 order, add 15% H of its quality
2SO
4(0.5mol/L H
2SO
4Solution), adsorb 24h, remove by filter excessive acid solution, dry 24h under 120 ℃ can make 6.8g SO in 800 ℃ of roasting 3h then in tubular heater
4 2-/ TiO
2Solid super-strong acid.
(3) with 3g SO
4 2-/ TiO
2Solid super-strong acid and 0.3g CuCl
2(mass ratio 10: 1) mixed grinding heats 4h down in 550 ℃ and makes SO under nitrogen protection
4 2-/ TiO
2-CuCl
2Catalyst 3.2g.
(4) take by weighing 3g SO
4 2-/ TiO
2-CuCl
2Catalyst adds in the 250ml autoclave, adds the 100ml absolute methanol again, with mist (O
2: 8%, the CO:92%) air in the metathesis reactor at room temperature uses this gas punching press to 3.0MPa then.120 ℃ of reactions 2 hours.The cooling back is with gas chromatographic analysis.Dimethyl carbonate selectivity 90.00%, the space-time yield 1.0gg of catalyst
-1H
-1
Embodiment 4
(1) with 6g TiO
2(commercially available) is crushed to below 110 orders, adds 10% H of its quality
2SO
4(0.5mol/L H
2SO
4Solution), adsorb 24h, remove by filter excessive acid solution, dry 24h under 120 ℃ can make 6.2g SO in 500 ℃ of roasting 3h then in tubular heater
4 2-/ TiO
2Solid super-strong acid.
(2) with 3g SO
4 2-/ TiO
2Solid super-strong acid and 0.15g Cu (NO
3)
2(mass ratio 20: 1) mixed grinding heats 4h down in 350 ℃ and makes SO under nitrogen protection
4 2-/ TiO
2-Cu (NO
3)
2Catalyst 3.1g.
(3) take by weighing 3g SO
4 2-/ TiO
2-Cu (NO
3)
2Catalyst adds in the 250ml autoclave, adds the 100ml absolute methanol again, with mist (O
2: 8%, the CO:92%) air in the metathesis reactor at room temperature uses this gas punching press to 3.0MPa then.120 ℃ of reactions 2 hours.The cooling back is with gas chromatographic analysis.Dimethyl carbonate selectivity 95.2%, the space-time yield 0.5gg of catalyst
-1H
-1
Embodiment 5
(1) under the room temperature with 15ml Ti (OCH
9) splash in the 70ml absolute ethyl alcohol, with obtaining homogeneous transparent solution behind the constant temperature blender with magnetic force stirring 30min, pour separatory funnel into.In the beaker of 250ml, pour the 50ml absolute ethyl alcohol into, glacial acetic acid, each 10ml of distilled water, magnetic stirrer joins 2g ZrO2 pressed powder in the clear solution, opens the separatory funnel valve then butyl titanate one ethanolic solution that the prepares speed with 3ml/min is added drop-wise in the beaker solution that is just stirring, after obtaining transparent colloidal sol, continue to stir 10min, at room temperature left standstill 2 days, form gel.
(2) below crushed after being dried to 110 order, add 10% (NH of its quality
4)
2S
2O
8(0.75mol/L (NH
4)
2S
2O
8Solution), adsorb 24h, remove by filter excessive acid solution, dry 24h under 120 ℃ can make 6.8g S in 500 ℃ of roasting 3h then in tubular heater
2O
8 2-/ ZrO
2-TiO
2Solid super-strong acid.
(3) with 3g S
2O
8 2-/ ZrO
2-TiO
2Solid super-strong acid and 1g CuCl
2(mass ratio 3: 1) mixed grinding heats 4h down in 650 ℃ and makes S under nitrogen protection
2O
8 2-/ ZrO
2-TiO
2-CuCl
2Catalyst 3.4g.
(4) take by weighing 3g S
2O
8 2-/ ZrO
2-TiO
2-CuCl
2Catalyst add in the 250ml autoclave, add the 100ml absolute methanol again, with mist (O
2: 8%, the CO:92%) air in the metathesis reactor at room temperature uses this gas punching press to 3.0MPa then.120 ℃ of reactions 2 hours.The cooling back is with gas chromatographic analysis.Dimethyl carbonate selectivity 99.50%, the space-time yield 1.43gg of catalyst
-1H
-1
Embodiment 6
(1) with 6g Al
2O
3(commercially available) is crushed to below 110 orders, adds 10% H of its quality
2SO
4(0.5mol/L H
2SO
4Solution), adsorb 24h, remove by filter excessive acid solution, dry 24h under 120 ℃ can make 6.2g SO in 500 ℃ of roasting 3h then in tubular heater
4 2-/ Al
2O
3Solid super-strong acid.
(2) with 3g SO
4 2-/ Al
2O
3Solid super-strong acid and 1.5g CuCl (mass ratio 2: 1) mixed grinding heats 6h down in 800 ℃ and makes SO under nitrogen protection
4 2-/ Al
2O
3-CuCl catalyst 4.2g.
(3) take by weighing 3g SO
4 2-/ Al
2O
3-CuCl catalyst adds in the 250ml autoclave, adds the 100ml absolute methanol again, with mist (O
2: 8%, the CO:92%) air in the metathesis reactor at room temperature uses this gas punching press to 3.0MPa then.120 ℃ of reactions 2 hours.The cooling back is with gas chromatographic analysis.Dimethyl carbonate selectivity 96.80%, the space-time yield 2.25gg of catalyst
-1H
-1
Embodiment 7
(1) with 6g SiO
2(commercially available) is crushed to below 110 orders, adds 10% (NH of its quality
4)
3PO
4(0.5mol/L (NH
4)
3PO
4Solution), adsorb 24h, remove by filter excessive acid solution, dry 24h under 120 ℃ can make 6.2g PO in 500 ℃ of roasting 3h then in tubular heater
4 3-/ SiO
2Solid super-strong acid.
(2) with 4g PO
4 3-/ SiO
2Solid super-strong acid and 1.0g CuBr
2(mass ratio 4: 1) mixed grinding heats 8h down in 450 ℃ and makes PO under nitrogen protection
4 3-/ SiO
2-CuBr
2Catalyst 4.8g.
(3) take by weighing 3g PO
4 3-/ SiO
2-CuBr
2Catalyst add in the 250ml autoclave, add the 100ml absolute methanol again, with mist (O
2: 8%, the CO:92%) air in the metathesis reactor at room temperature uses this gas punching press to 3.0MPa then.120 ℃ of reactions 2 hours.The cooling back is with gas chromatographic analysis.Dimethyl carbonate selectivity 95.50%, the space-time yield 3.15gg of catalyst
-1H
-1
Claims (2)
1. the preparation method of a Cu base solid catalyst, it is characterized in that this method is that solid super-strong acid and copper based compound are 1 in mass ratio: 1-12: 1 ratio mixed grinding, in tubular heater, heat 2-8h down and carry out solid phase reaction in 300 ℃-800 ℃, make the Cu base solid catalyst, the carrier of described solid super-strong acid is ZrO
2, TiO
2, Al
2O
3, SiO
2Or its mixed oxide, the acidic materials of load are H
3PO
4, (NH
4)
3PO
4, (NH
4)
2HPO
4, (NH
4) H
2PO
4, H
3PO
3, H
2SO
4, H
2SO
3Or (NH
4)
2S
2O
8, the load capacity of acidic materials is the 1%-20% of carrier quality.
2. according to the preparation method of the described a kind of Cu base solid catalyst of claim 1, it is characterized in that described copper based compound is CuCl, CuCl
2, CuBr, CuBr
2Or Cu (NO
3)
2
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| CN108889303B (en) * | 2018-07-20 | 2021-02-12 | 太原理工大学 | Supported high-dispersion copper-based catalyst for preparing methanol from carbon dioxide, preparation method and application thereof |
| CN112246240B (en) * | 2020-10-15 | 2023-06-16 | 江苏金聚合金材料有限公司 | Preparation and application of dimethyl carbonate catalyst |
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| US6172272B1 (en) * | 1998-08-21 | 2001-01-09 | The University Of Utah | Process for conversion of lignin to reformulated, partially oxygenated gasoline |
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2006
- 2006-06-06 CN CNB2006100127991A patent/CN100408176C/en not_active Expired - Fee Related
Patent Citations (5)
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| US4935212A (en) * | 1988-12-13 | 1990-06-19 | Man Technologie Gmbh | Method of decomposing organic halogen compounds in gaseous phase |
| US5679867A (en) * | 1996-03-01 | 1997-10-21 | Hoechst Celanese Corporation | Carbonylation via solid acid catalysis |
| US6172272B1 (en) * | 1998-08-21 | 2001-01-09 | The University Of Utah | Process for conversion of lignin to reformulated, partially oxygenated gasoline |
| CN1343194A (en) * | 1999-03-10 | 2002-04-03 | 巴斯福股份公司 | Catalytic gas phase oxidation of propene into acrylic acid |
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Assignee: Guangdong Nanfang Soda ASH Industrial Co.,Ltd. Assignor: Taiyuan University of Technology Contract fulfillment period: 2008.11.1 to 2013.11.1 contract change Contract record no.: 2009440001732 Denomination of invention: Preparing method of Cu-base solid catalyst Granted publication date: 20080806 License type: Exclusive license Record date: 20091026 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.11.1 TO 2013.11.1; CHANGE OF CONTRACT Name of requester: GUANGDONG SOUTHERN ALKALI CO., LTD. Effective date: 20091026 |
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Granted publication date: 20080806 Termination date: 20130606 |