CN100400162C - Method for preparing catalyst for preparing 1,4-cis-butanediol by dimethyl maleate hydrogenation - Google Patents
Method for preparing catalyst for preparing 1,4-cis-butanediol by dimethyl maleate hydrogenation Download PDFInfo
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- CN100400162C CN100400162C CNB2006101172956A CN200610117295A CN100400162C CN 100400162 C CN100400162 C CN 100400162C CN B2006101172956 A CNB2006101172956 A CN B2006101172956A CN 200610117295 A CN200610117295 A CN 200610117295A CN 100400162 C CN100400162 C CN 100400162C
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- butanediol
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- copper
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Abstract
The present invention belongs to the field of chemical engineering technology. It relates to a new catalyst for preparing 1,4-butanediol by utilizing hydrogenation of dimethyl maleate. Said invention uses mesopore molecular sieve MCM-41 as carrier and impregnates it with Cu salt solution to prepare catalyst precursor, then the precursor is calcined so as to obtain the invented Cu/MCM41 catalyst. Said catalyst has higher activity and higher 1,4-butanediol selectivity.
Description
Technical field
The invention belongs to chemical technology field, is to be used for dimethyl maleate hydrogenation preparing 1, the Preparation of catalysts method of 4-butanediol.
Background technology
1, the 4-butanediol is the important rapidly basic organic synthesis raw material of development in recent years.Because carbochain is longer, be that synthetic polyester of raw material or polyurethane ratio are that the synthetic polymer of raw material has balanced physical property by ethylene glycol or propane diols with it.1, the purposes of 4-butanediol is very extensive, and it mainly contains 3 product chains: 1, produce oxolane (being called for short THF), oxolane is produced polytetramethylene ether diol (being called for short PTMEG) through ring-opening polymerisation, medicine intermediate or directly be used as solvent; 2, produce gamma-butyrolacton (being called for short GBL). gamma-butyrolacton further generates 2-Pyrrolidone, vinyl pyrrolidone and PVP with acetylene reaction again; 3, produce the PBT resin that is used for household electrical appliances, color TV trade.Above-mentioned 3 big class purposes make 1, and the consumption figure of 4-butanediol heightens, and become important basic organic chemical industry's product.Particularly in China, in recent years to 1,4-butanediol in great demand annually needs a large amount of imports to satisfy downstream industry production.
Industrialized at present 1, the 4-butanediol is produced route and is mainly contained following 5 kinds: 1, be the Reppe method of raw material with acetylene and formaldehyde; 2, with the cis-butenedioic anhydride be the hydrogenation technique of raw material; 3, the gas phase hydrogenation technology of maleate; 4, with third rare be the synthesis technique of raw material; 5, with the butadiene be the synthesis technique of raw material, at present most widely used is Reppe method technology.But the gas phase hydrogenation technology of maleate is because the boiling point of its raw material is relatively low, and can more and more come into one's own with ripe relatively fixed-bed reactor.But the present used catalyst based (Cu/ZnO/Al of Cu
2O
3Or Cu/ZnO etc.) in since activity component metal copper more easily reunite, so catalyst activity descends easily.
Summary of the invention
The objective of the invention is to obtain a kind of active high, effective dimethyl maleate hydrogenation preparing 1, Preparation of catalysts method of 4-butanediol of being used for.
The dimethyl maleate that is used for provided by the invention is selected hydrogenation system 1, and the catalyst of 4-butanediol is a kind of novel mesoporous molecular sieve carried copper-based catalysts.It is characterized in that utilizing regular duct of mesopore molecular sieve and big specific area to disperse the copper activity position.Concrete preparation process is: in the time of the preparation of a.MCM-41: 0-50 ℃, 1-6g softex kw (CTAB) is dissolved in the 40-300ml distilled water, after stirring 1-10h, add 5-40ml 25-28% concentrated ammonia liquor, add the positive tetraethyl orthosilicate of 3-60ml (TEOS) behind the 0-5h, filter behind the 0-4h, with distilled water washing 5 times, the oven dry of spending the night under 90 ℃, roasting 5h obtains carrier MCM-41 under 550 ℃ of air atmosphere.The preparation of b.Cu/MCM-41: mesopore molecular sieve MCM-41 is added in the aqueous solution of mantoquita, the concentration of copper salt solution is 0.3-3.0mol/L, adding MCM-41 in the 100ml copper salt solution is 1-10g, 20-100 ℃ of following evaporate to dryness then, under 100-120 ℃, spend the night, then 300-600 ℃ following roasting 4-8 hour, the gained catalyst gets final product after the compressing tablet granulation, catalyst is used for needing reduction activation before the reaction.
Mesopore molecular sieve MCM-41 can make by oneself by art methods but prepare the laboratory on a small quantity from commercially available acquisition.Need reduction activation before the catalyst reaction, this is the technology general knowledge that these those skilled in the art all know.
Copper ion solution in the Cu/MCM-41 catalyst that is made by above-mentioned steps provided by the invention can be its nitrate, acetate, oxalates or other the soluble-salt aqueous solution, but can not contain Cl, S ion.
The Cu/MCM-41 carried catalyst that is made by above-mentioned steps provided by the invention is made up of active ingredient copper and support oxide, and each components contents is in the catalyst: copper 5～80wt%, silica 20～95wt%.
The aperture of mesopore molecular sieve MCM-41 is between the 2-10nm.
Activity of such catalysts provided by the invention can be tested with the following method:
In miniature flowing bed reactor, investigate catalyst activity.Catalyst powder granulation to 40 after the roasting～60 orders is in the little anti-device reaction tube (internal diameter is 11mm) of packing into, with the H of dilution
2The gas reduction activation.The raw material dimethyl maleate is dissolved in methyl alcohol (v/v=1/4) as reactant liquor, squeezes in the reaction tube temperature reaction of pressurizeing then through constant-flux pump.Reaction pressure is 2～6MPa, preferred 4～6MPa, and reaction temperature is 160～260 ℃, preferred 180～240 ℃.Product after condensation with its composition of gas chromatographic analysis.Experimental result shows, when the Cu/MCM-41 catalyst is used for this reaction product have higher 1,4-butanediol selectivity
Method for preparing catalyst of the present invention is simple, and technology realizes convenient, and catalyst has higher activity and higher 1,4-butanediol selectivity.
The specific embodiment
Catalyst precursor is by sol-gel and immersion process for preparing, with the H of dilution
2Be used for dimethyl maleate hydrogenation reaction selectivity preparation 1 after the gas reduction activation, the 4-butanediol.
Further describe the present invention in dimethyl maleate hydrogenation system 1 below by specific embodiment, the application in the 4-butanediol.
Embodiment 1:Cu/MCM-41-1 catalyst
Under the room temperature, 5.528g CTAB is dissolved in the 440ml water, and stirring 4h continues adding 31ml ammoniacal liquor then, continues to stir 5h, adds 26ml TEOS then, filters behind the stirring 3h, and with distilled water washing 3 times, 90 ℃ of dryings, 550 ℃ of roasting 5h get the MCM-41 carrier.
10.0g Cu (NO
3)
23H
2O is dissolved in 50ml H
2O is made into metal ion solution, under agitation adds the MCM-41 of 4g aperture 10nm, 60 ℃ of evaporates to dryness, and 120 ℃ are dried by the fire 12h down, and 10K/min is warming up to 450 ℃ of roasting 4h in the Muffle furnace.
With catalyst powder granulation to 40～60 orders, with H
2/ N
2Carry out active testing after the gaseous mixture reduction.Select hydrogenation to the results are shown in table 1.
Embodiment 2:Cu/MCM-41-2 catalyst
5.0g Cu (NO
3)
23H
2O is dissolved in 50ml H
2O is made into metal ion solution, under agitation adds the commercially available aperture 3nmMCM-41 of 4.5g, 60 ℃ of evaporates to dryness, and 120 ℃ are dried by the fire 12h down, and 10K/min is warming up to 450 ℃ of roasting 4h in the Muffle furnace.
With catalyst powder granulation to 40～60 orders, with H
2Carry out active testing after the reduction of/Ar gaseous mixture.Select hydrogenation to the results are shown in table 2.
Embodiment 3:Cu/MCM-41-3 catalyst
7.5g Cu (NO
3)
23H
2O is dissolved in 105ml H
2O is made into metal ion solution, under agitation adds the MCM-41 of 4.0g embodiment 1,90 ℃ of evaporates to dryness, and 120 ℃ are dried by the fire 12h down, and 10K/min is warming up to 550 ℃ of roasting 4h in the Muffle furnace.
With catalyst powder granulation to 40～60 orders, with H
2Carry out active testing after the reduction of/Ar gaseous mixture.Select hydrogenation to the results are shown in table 3
Embodiment 4:Cu/MCM-41-4 catalyst
2.8g Cu (C
2O
4) H
2O is dissolved in 40ml H
2O is made into metal ion solution, under agitation adds the MCM-41 of 3.5g embodiment 1,80 ℃ of evaporates to dryness, and 120 ℃ are dried by the fire 12h down, and 10K/min is warming up to 350 ℃ of roasting 4h in the Muffle furnace.
With catalyst powder granulation to 40～60 orders, with H
2Carry out active testing after the reduction of/Ar gaseous mixture.Select hydrogenation to the results are shown in table 4
Embodiment 5:Cu/MCM-41-5 catalyst
6.5g Cu (Ac)
23H
2O is dissolved in 68ml H
2O is made into metal ion solution, under agitation adds the MCM-41 of 4g embodiment 2,70 ℃ of evaporates to dryness, and 100 ℃ are dried by the fire 12h down, and 10K/min is warming up to 550 ℃ of roasting 4h in the Muffle furnace.
With catalyst powder granulation to 40～60 orders, with H
2Carry out active testing after the reduction of/Ar gaseous mixture.Select hydrogenation to the results are shown in table 5
The hydrogenation reaction result of table 1Cu/MCM-41-1 catalyst
Other reaction condition is as follows: p=6MPa, H
2/ DMM (mol/mol)=120, DMM LSV=0.12ml (g
Cat.)
-1H
-1
The hydrogenation reaction result of table 2Cu/MCM-41-2 catalyst
Other reaction conditions are as follows: p=5MPa, H
2/ DMM (mol/mol)=200, DMM LSV=1.08ml (g
Cat.)
-1H
-1
The hydrogenation reaction result of table 3Cu/MCM-41-3 catalyst
Other reaction conditions are as follows: p=2MPa, H
2/ DMM (mol/mol)=80, DMM LSV=0.36ml (g
Cat.)
-1H
-1
The hydrogenation reaction result of table 4Cu/MCM-41-4 catalyst
Other reaction conditions are as follows: p=6MPa, H
2/ DMM (mol/mol)=200, DMM LSV=0.24ml (g
Cat.)
-1H
-1
The hydrogenation reaction result of table 5Cu/MCM-41-5 catalyst
Other reaction conditions are as follows: p=5MPa, H
2/ DMM (mol/mol)=200, DMM LSV=0.18ml (g
Cat.)
-1H
-1
Claims (3)
1. one kind is used for dimethyl maleate hydrogenation preparing 1, the Preparation of catalysts method of 4-butanediol, it is characterized in that mesopore molecular sieve MCM-41 is added in the aqueous solution of mantoquita, the concentration of the copper salt solution of copper nitrate, Schweinfurt green or cupric oxalate is 0.3-3.0mol/L, adding MCM-41 in the 100ml copper salt solution is 1-10g, 20-100 ℃ of following evaporate to dryness then, under 100-120 ℃, spend the night, then 300-600 ℃ following roasting 4-8 hour, the gained catalyst gets final product after the compressing tablet granulation, and catalyst is used for needing reduction activation before the reaction.
2. preparation method according to claim 1 is characterized in that the mass content of copper, silicon in the prepared catalyst is: copper 5～80wt%, silica 20～95wt%.
3. preparation method according to claim 1, the aperture that it is characterized in that MCM-41 is between 2-10nm.
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| CNB2006101172956A CN100400162C (en) | 2006-10-19 | 2006-10-19 | Method for preparing catalyst for preparing 1,4-cis-butanediol by dimethyl maleate hydrogenation |
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| CN101531568B (en) * | 2009-04-13 | 2011-12-07 | 烟台万华聚氨酯股份有限公司 | Method for synthesizing 1,6-hexamethylene glycol by using dimethyl adipate gas phase and hydrogen |
| TWI564072B (en) | 2011-11-09 | 2017-01-01 | China Petrochemical Technology Co Ltd | Hydrogenation catalyst and preparation method thereof |
| CN106345512B (en) * | 2016-08-03 | 2019-03-05 | 江苏大学 | A kind of bianry alloy catalyst and its preparation method and application |
| CN107473954A (en) * | 2017-08-29 | 2017-12-15 | 南京雪郎化工科技有限公司 | A kind of greenization production method of succinic acid |
Citations (4)
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| US5387753A (en) * | 1993-12-02 | 1995-02-07 | Eastman Chemical Company | Process for the preparation of alcohols and diols |
| US6239292B1 (en) * | 1997-11-13 | 2001-05-29 | Basf Aktiengesellschaft | Process for preparing gamma-butyrolactone, butane-1,4-diol and tetrahydrofuran |
| CN1743068A (en) * | 2005-07-28 | 2006-03-08 | 复旦大学 | Copper-boron catalyst for preparing butylene oxide by hydrogenating dimethyl maleate and preparing method |
| CN1762586A (en) * | 2005-09-15 | 2006-04-26 | 复旦大学 | Cu-B catalyst for preparing tetrahydrofuran by hydrogenation of dimethyl maleate and its preparation process |
-
2006
- 2006-10-19 CN CNB2006101172956A patent/CN100400162C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5387753A (en) * | 1993-12-02 | 1995-02-07 | Eastman Chemical Company | Process for the preparation of alcohols and diols |
| US6239292B1 (en) * | 1997-11-13 | 2001-05-29 | Basf Aktiengesellschaft | Process for preparing gamma-butyrolactone, butane-1,4-diol and tetrahydrofuran |
| CN1743068A (en) * | 2005-07-28 | 2006-03-08 | 复旦大学 | Copper-boron catalyst for preparing butylene oxide by hydrogenating dimethyl maleate and preparing method |
| CN1762586A (en) * | 2005-09-15 | 2006-04-26 | 复旦大学 | Cu-B catalyst for preparing tetrahydrofuran by hydrogenation of dimethyl maleate and its preparation process |
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