CN101502803B - Catalyst for preparing 1,4-butanediol or tetrahydrofuran from selective hydrogenation of dimethyl maleate and preparation method thereof - Google Patents
Catalyst for preparing 1,4-butanediol or tetrahydrofuran from selective hydrogenation of dimethyl maleate and preparation method thereof Download PDFInfo
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- CN101502803B CN101502803B CN 200910047800 CN200910047800A CN101502803B CN 101502803 B CN101502803 B CN 101502803B CN 200910047800 CN200910047800 CN 200910047800 CN 200910047800 A CN200910047800 A CN 200910047800A CN 101502803 B CN101502803 B CN 101502803B
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- butanediol
- dimethyl maleate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 20
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title abstract description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title abstract 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 238000001556 precipitation Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 6
- 230000004913 activation Effects 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 22
- 239000011701 zinc Substances 0.000 claims description 19
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 5
- 238000003483 aging Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 2
- 239000012018 catalyst precursor Substances 0.000 abstract 1
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 229920002334 Spandex Polymers 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000004759 spandex Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- -1 polytetramethylene Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- 229910009367 Zn M Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of chemical technology, and in particular relates to a catalyst for preparing 1, 4-butanediol or tetrahydrofuran by selective hydrogenation of dimethyl maleate and a preparation method thereof. The catalyst consists of Cu, Zn, Al, M and O, and the mol content of each metal element is as follows: 30 to 60 percent of Cu, 10 to 50 percent of Zn, 5 to 20 percent of Al and 0 to 10 percent of M, wherein M is any one of Mn, Mg and Cr. The preparation method for the catalyst comprises precipitation, ageing, washing, drying and baking of a catalyst precursor, and reduction activation before use. The catalyst is applied to the hydrogenation reaction of the dimethyl maleate, and the yield of the 1, 4-butanediol at a reaction temperature of 180 DEG C is 73.6 percent; and the yield of the tetrahydrofuran is 96 percent at a reaction temperature of 220 DEG C. Product composition of the catalyst can be well adjusted by changing the reaction condition to adapt to different market demands, and the catalyst has extremely high industrial application value.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of dimethyl maleate that is used for and select hydrogenation preparing 1, the Catalysts and its preparation method of 4-butanediol or oxolane.
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 classes are used to 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.
Oxolane then is the fine solvent of natural resin and synthetic resin, can be used for producing polyurethane, elastomer, artificial rubber, copolyesters etc.Oxolane is main to be the production that is used for PTMEG (PolyTHF dihydroxylic alcohols), and the latter is a base stock of producing resiliency spandex, and spandex is mainly used in senior gym suit, the contour stretch knit product of swimsuit produced.Because spandex has good performance, in a lot of fabrics, add 3～5% spandex and can improve it greatly and wear performance.Oxolane mainly is by 1 on the known technology, and 4-butanediol dehydration (CN 1675190A) obtains, and perhaps makes gamma-butyrolacton, 1 simultaneously by maleic acid (or its ester) hydrogenation, behind 4-butanediol and the oxolane, carries out product again and separates.
On the hydrogenation catalyst of maleic acid list or dibasic acid esters, has good selectivity at a certain product often, to 1, the selectivity of 4-butanediol reaches 80%, but lower to the selectivity of oxolane such as a kind of Cu-Mn-Al-Ni-M-O (M is La or Ce) catalyst (CN 1356168A).And activated carbon supported Pd catalyst (CN 1485322A) is used for hydrogenation of maleic acid, and the selectivity of oxolane is reached 72.8%, and to 1, the selectivity of 4-butanediol is almost nil; S.P.M ü ller (J.Catal.2003,218,419) has reported that the Cu/ZnO catalyst of a kind of extrusion preparation is used for the dimethyl maleate hydrogenation, can reach 98% to the selectivity of oxolane.Though these catalyst selectivity is higher, little to the adjustable range that hydrogenation products is formed, be not enough to tackle that the variation of the market demand causes 1, the fluctuation of 4-butanediol or oxolane product price.
Summary of the invention
The objective of the invention is to propose a kind of dimethyl maleate that is used for and select hydrogenation preparing 1, the Catalysts and its preparation method of 4-butanediol or oxolane.
The dimethyl maleate that is used for that the present invention proposes is selected hydrogenation preparing 1, the catalyst of 4-butanediol or oxolane, this catalyst is a Cu-Zn-Al-M-O type catalyst, the molar content of each metallic element is: copper 30～60%, zinc 10～50%, aluminium 5～20%, M 0～10%, M be among Mn, Mg or the Cr any.
The dimethyl maleate that is used for that the present invention proposes is selected hydrogenation preparing 1, the Preparation of catalysts method of 4-butanediol or oxolane, and concrete steps are as follows:
(1) under 50～90 ℃, the mixed solution of Cu, Zn, M soluble-salt and precipitating reagent and drip are added co-precipitation, control Cu, Zn, M metal ion total concentration are 0.5～1.2M, are preferably 0.8～1.2M; Precipitating reagent concentration is 0.5～1.6M, and concrete concentration is decided according to concentration of metal ions, and keeping precipitation system pH value is 6.8-7.2, drips and finishes, and constant temperature stirred 50-70 minute, and washing obtains the Cu-Zn-M-O precipitation;
(2) add aluminium hydroxide and deionized water mixing in the sediment of step (1) gained, the precipitation temperature that is warming up to Cu, Zn, M stirs 25-35min; The addition of aluminium hydroxide is 5～20% of Cu, Zn, M soluble-salt and an aluminium hydroxide total mole number, and the addition of deionized water is to dissolve 80～120% of Cu, Zn, M soluble-salt and the required water cumulative volume of precipitating reagent in the step (1);
(3) product that step (2) the is obtained oven dry of under 100～120 ℃, spending the night, at 350～550 ℃ of following roasting 4-8 hours, the gained catalyst got final product after the compressing tablet granulation, and catalyst is used for needing reduction activation before the reaction.
Among the present invention, described catalyst needs reduction activation before reaction, with the H after the dilution
2Gas is (as H
2/ N
2, H
2/ Ar gaseous mixture) temperature programmed reduction.
Among the present invention, described Cu, Zn, M soluble-salt can be in its nitrate, acetate or the oxalates etc. any, but can not contain Cl, S ion; Precipitating reagent can be in NaOH, sodium carbonate, ammoniacal liquor or the oxalic acid etc. any.
Provided by the invention have a catalyst that Cu-Zn-Al-M-O forms by what above-mentioned steps made, form by active ingredient copper species, zinc oxide, aluminium oxide and a spot of other metal oxides, the molar content of each metal component is in the catalyst: copper 30～60%, zinc 10～50%, aluminium 5～20%, M (M be among Mn, Mg or the Cr etc. any) 0～10%.
Have in the catalyst that Cu-Zn-Al-M-O forms according to provided by the invention, the active ingredient copper species disperse, modify by the metal oxide in the catalyst.This catalyst is used for the dimethyl maleate hydrogenation reaction, the highly selective preparation 1 respectively, and 4-butanediol or oxolane promptly prepare 1 of high selectivity under lower reaction temperature, the 4-butanediol, highly selective obtains oxolane under higher reaction temperature.
Activity of such catalysts provided by the invention can be estimated with the following method:
Evaluation of catalyst activity in miniature flowing bed reactor.With the catalyst powder granulation to 40 after the roasting～60 orders, 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 170～260 ℃, preferred 175～240 ℃.Product is collected after condensation with its composition of gas chromatographic analysis.This catalyst is used for the dimethyl maleate hydrogenation reaction, and under 180 ℃ of reaction temperatures 1, the yield of 4-butanediol reaches 73.6%; Under 220 ℃ of reaction temperatures, the yield of oxolane reaches 96%.
Preparation of catalysts method provided by the invention comprises that earlier precipitation obtains Cu-Zn-M and forms, and the two-step method production process of mixing with aluminium hydroxide again can solve well like this that the precipitation presoma is difficult to filtration or the presoma component is mixed uneven problem.With the dimethyl maleate is raw material, the catalyst with Cu-Zn-Al-M-O composition that the method that proposes with us prepares carries out catalytic hydrogenation, can prepare 1 respectively by highly selective by changing reaction condition, 4-butanediol or oxolane, so greatly strengthen the elasticity of dimethyl maleate hydrogenation reaction route reply turn of the market, have better industrial application prospect.
The specific embodiment
Further describe the present invention in dimethyl maleate hydrogenation system 1 below by specific embodiment, the application in 4-butanediol or the oxolane.
Embodiment 1
10.0g Cu (NO
3)
23H
2O, 9.8g Zn (NO
3)
26H
2O is dissolved in 75ml H
2O is made into metal ion solution, 8.7gNa
2CO
3Be dissolved in 82ml H
2O obtains precipitant solution.60 ℃ of water-baths are stirred and are dripped metal ion solution and precipitant solution co-precipitation down simultaneously.Drip and finish ageing 1 hour.Foreign ion is removed in washing precipitation, adds 1.68gAl (OH) then
3The mixture that obtains like this adds the 150ml deionized water, is warming up to 60 ℃ and stirs 30min.The filter cake that suction filtration the is obtained oven dry of spending the night under 120 ℃, 10K/min is warming up to 450 ℃ of roastings 4 hours in the Muffle furnace, obtains catalyst A.
Embodiment 2
10.0g Cu (NO
3)
23H
2O, 9.8g Zn (NO
3)
26H
2O and 0.15g Mn (NO
3)
2Be dissolved in 75ml H
2O is made into metal ion solution, 8.7g Na
2CO
3Be dissolved in 82ml H
2O obtains precipitant solution.60 ℃ of water-baths are stirred and are dripped metal ion solution and precipitant solution co-precipitation down simultaneously.Drip and finish ageing 1 hour.Foreign ion is removed in washing precipitation, adds 1.68gAl (OH) then
3The mixture that obtains like this adds the 150ml deionized water, is warming up to 60 ℃ and stirs 30min.The filter cake that suction filtration the is obtained oven dry of spending the night under 120 ℃, 10K/min is warming up to 450 ℃ of roastings 4 hours in the Muffle furnace, obtains Mn content and be 1% catalyst B.Change the Mn (NO that adds
3)
2Consumption, adopt identical condition to prepare Mn content and be respectively 2% and 5% catalyst C and D.
Embodiment 3
10.0g Cu (NO
3)
23H
2O, 9.8g Zn (NO
3)
26H
2O and 0.21g Mg (NO
3)
26H
2O is dissolved in 75ml H
2O is made into metal ion solution, 8.7g Na
2CO
3Be dissolved in 82ml H
2O obtains precipitant solution.60 ℃ of water-baths are stirred and are dripped metal ion solution and precipitating reagent co-precipitation down simultaneously.Drip and finish ageing 1 hour.Foreign ion is removed in washing precipitation, adds 1.68g Al (OH) then
3The mixture that obtains like this adds the 150ml deionized water, is warming up to 60 ℃ and stirs 30min.The filter cake that suction filtration the is obtained oven dry of spending the night under 120 ℃, 10K/min is warming up to 450 ℃ of roastings 4 hours in the Muffle furnace, obtains Mg content and be 1% catalyst E.Change the Mg (NO that adds
3)
2Consumption, adopt identical condition to prepare Mg content and be respectively 2% and 5% catalyst F and G.
Embodiment 4
10.0g Cu (NO
3)
23H
2O, 9.8g Zn (NO
3)
26H
2O and 0.33g Cr (NO
3)
39H
2O is dissolved in 75ml H
2O is made into metal ion solution, 8.7g Na
2CO
3Be dissolved in 82ml H
2O obtains precipitant solution.60 ℃ of water-baths are stirred and are dripped metal ion solution and precipitating reagent co-precipitation down simultaneously.Drip and finish ageing 1h.Foreign ion is removed in washing precipitation, adds 1.68gAl (OH) then
3The mixture that obtains like this adds the 150ml deionized water, is warming up to 60 ℃ and stirs 30min.The filter cake that suction filtration is obtained is at 120 ℃ of baking 12h down, and 10K/min is warming up to 450 ℃ of roasting 4h in the Muffle furnace, obtains Cr content and be 1% catalyst H.Change the Cr (NO that adds
3)
3Consumption, adopt identical condition to prepare Cr content and be respectively 2% and 5% catalyst I and J.
Table Cu-Zn-Al-Mn-O catalyst is used for the active result of dimethyl maleate hydrogenation reaction
Continuous table
Other reaction conditions are as follows: H
2/ DMM (mol/mol)=200, DMM LSV=0.18ml (g
Cat.)
-1H
-1(DMM-dimethyl maleate, DMS-dimethyl succinate, BDO-1,4-butanediol, GBL-gamma-butyrolacton, THF-oxolane).
Claims (2)
1. one kind is used for dimethyl maleate selection hydrogenation preparing 1, the Preparation of catalysts method of 4-butanediol or oxolane, this catalyst is a Cu-Zn-Al-M-O type catalyst, the molar content of each metallic element is: copper 30～60%, zinc 10～50%, aluminium 5～20%, M 0～10%, M be among Mn, Mg or the Cr any; It is characterized in that concrete steps are as follows:
(1) under 50～90 ℃, the mixed solution of Cu, Zn, M soluble-salt and precipitating reagent and drip are added co-precipitation, control Cu, Zn, M metal ion total concentration are 0.5～1.2M, precipitating reagent concentration is 0.5～1.6M, keeping precipitation system pH value is 6.8-7.2, drips and finishes, and constant temperature stirred 50-70 minute, washing obtains the Cu-Zn-M-O precipitation;
(2) in the sediment of step (1) gained, add aluminium hydroxide and deionized water, mix, the addition that is warming up to the precipitation temperature stirring 25-35min aluminium hydroxide of Cu, Zn, M is 5～20% of Cu, Zn, M soluble-salt and an aluminium hydroxide total mole number, and the addition of deionized water is to dissolve 80～120% of Cu, Zn, M soluble-salt and the required water cumulative volume of precipitating reagent in the step (1);
(3) product that step (2) the is obtained oven dry of under 100～120 ℃, spending the night, at 350～550 ℃ of following roasting 4-8 hours, the gained catalyst got final product after the compressing tablet granulation, and catalyst is used for needing reduction activation before the reaction.
2. the dimethyl maleate that is used for according to claim 1 is selected hydrogenation preparing 1, the Preparation of catalysts method of 4-butanediol or oxolane, it is characterized in that described Cu, Zn, M soluble-salt in its nitrate, acetate or the oxalates any, precipitating reagent be in NaOH, sodium carbonate, ammoniacal liquor or the oxalic acid any.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910047800 CN101502803B (en) | 2009-03-19 | 2009-03-19 | Catalyst for preparing 1,4-butanediol or tetrahydrofuran from selective hydrogenation of dimethyl maleate and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910047800 CN101502803B (en) | 2009-03-19 | 2009-03-19 | Catalyst for preparing 1,4-butanediol or tetrahydrofuran from selective hydrogenation of dimethyl maleate and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101502803A CN101502803A (en) | 2009-08-12 |
| CN101502803B true CN101502803B (en) | 2011-11-02 |
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| CN103100393B (en) * | 2011-11-09 | 2014-12-31 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| US9168509B2 (en) * | 2011-11-09 | 2015-10-27 | China Petroleum & Chemical Corp. | Hydrogenation catalysts and the preparation processes thereof |
| CN103566945B (en) * | 2012-07-23 | 2015-10-28 | 上海华谊能源化工有限公司 | A kind of preparation method producing the high-efficiency copper manganese Al catalysts of BDO |
| CN103769111B (en) * | 2012-10-24 | 2016-04-13 | 中国石油化工股份有限公司 | A kind of preparation method of hydrogenation catalyst |
| CN103551154B (en) * | 2013-10-31 | 2015-02-18 | 西北化工研究院 | Preparation methods and catalysis method of dimethyl maleate hydrogenation catalyst |
| CN105435798B (en) * | 2014-08-27 | 2018-10-23 | 中国石油化工股份有限公司 | Carboxylate hydrogenation copper base catalyst |
| CN109201056B (en) * | 2017-06-30 | 2021-07-09 | 中国石油化工股份有限公司 | Catalyst for preparing 1, 4-butanediol from dimethyl maleate |
| CN110773174B (en) * | 2019-09-24 | 2020-11-10 | 浙江大学 | Catalyst for preparing gamma-butyrolactone through dehydrogenation of 1, 4-butanediol and preparation method thereof |
| CN113731442B (en) * | 2021-08-20 | 2024-02-02 | 河南省生物基材料产业研究院有限公司 | Catalyst for dimethyl maleate hydrogenation reaction and preparation method and application thereof |
| CN113649021B (en) * | 2021-09-09 | 2023-12-01 | 濮阳圣恺环保新材料科技股份有限公司 | Preparation method of copper hydrogenation catalyst |
| CN113600186A (en) * | 2021-09-09 | 2021-11-05 | 濮阳圣恺环保新材料科技股份有限公司 | Preparation method of copper-based hydrogenation catalyst with high mechanical strength |
| CN114685242B (en) * | 2022-04-19 | 2023-08-22 | 天津大学 | Method for producing 1, 4-butanediol by one-step liquid-phase hydrogenation of dimethyl maleate |
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| US7037877B1 (en) * | 1999-02-12 | 2006-05-02 | Council Of Scientific And Industrial Research | Process for the preparation of copper chromite catalyst |
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| CN1034541A (en) * | 1987-12-23 | 1989-08-09 | 标准石油公司 | The vapor-phase hydrogenation maleic anhydride prepares tetrahydrofuran (THF) and r-J lactone |
| US7037877B1 (en) * | 1999-02-12 | 2006-05-02 | Council Of Scientific And Industrial Research | Process for the preparation of copper chromite catalyst |
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