CN1743068A - Copper-boron catalyst for preparing butylene oxide by hydrogenating dimethyl maleate and preparing method - Google Patents
Copper-boron catalyst for preparing butylene oxide by hydrogenating dimethyl maleate and preparing method Download PDFInfo
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- CN1743068A CN1743068A CN 200510028244 CN200510028244A CN1743068A CN 1743068 A CN1743068 A CN 1743068A CN 200510028244 CN200510028244 CN 200510028244 CN 200510028244 A CN200510028244 A CN 200510028244A CN 1743068 A CN1743068 A CN 1743068A
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Abstract
The catalyst is Cu-B catalyst which is obtained by adopting chemical reduction method and utilizing reductant KBH4 or NaBH4 to make reduction, and loading on metal oxide. Said invention utilizes addition of adjuvant to optimize catalytic effect of catalyst, the active component Cu of said catalyst mainly is existed as metal state, its carrier material is some metal compounds, and the adjuvant is Cr, Mo, Fe and Co, etc.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of new catalyst that is used for dimethyl maleate hydrogenation system oxolane and preparation method thereof.
Background technology
Oxolane is the important chemical product, 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.
At present, oxolane mainly is by 1, and the dehydration of 4-butanediol 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.BASF adopts butane oxidation to maleic anhydride at the device of oxolane of building and PolyTHF recently, can produce in a step and obtain oxolane, thereby save 1, the intermediate steps of 4-butanediol.
The present invention is raw material with the dimethyl maleate, and through the Cu-B of load catalyst to catalyzing hydrogenating, the ester group hydrogenation products is mainly gamma-butyrolacton and oxolane.By the modulation reaction condition, can obtain oxolane by highly selective.
Summary of the invention
The objective of the invention is to propose a kind of new catalyst that dimethyl maleate is selected the hydrogenation preparing oxolane that is used for of good reaction selectivity, and proposed this Preparation of catalysts method.
The catalyst that is used for dimethyl maleate selection hydrogenation preparing oxolane provided by the invention is a kind of support type Cu-B catalyst, and wherein, oxide carried active Cu component is modified through auxiliary agent M, then by KBH
4Or NaBH
4Reduction obtains.This loaded catalyst is made up of active component Cu, auxiliary agent M and oxide carrier, if with the oxide carrier quality as 1, then Cu is 0.02～0.2, the mol ratio of auxiliary agent M and Cu is 0～0.8, preferred 0.1-0.5, the mol ratio of element B and Cu is 0.2～2.
Metal promoter M of the present invention can be one or more in IB family, IIB family, group vib, the group VIII metallic element in the periodic table of elements, in preferred IIB family, group vib, the group VIII one or more, metal promoter commonly used are one or more among Cr, Mo, W, Fe, the Co; The predecessor of described M ion is that M is cationic salt, preferably its chloride or nitrate.
The carrier material of catalyst of the present invention can be the metal oxide of the periodic table of elements the the 3rd, the 4th, the 5th, period 6 or in the rare-earth oxide one or more, in the metal oxide of preferred the 3rd, the 4th, period 5 one or more, more preferably one or more in magnesia, aluminium oxide, silica, zirconia, the titanium oxide.
According to catalyst provided by the invention, active component Cu is evenly dispersed on the carrier material with crystalline form.
The catalyst that the present invention proposes can adopt the chemical reduction method preparation, and concrete steps are as follows: carrier grinds to form 40～60 purpose particles, at CuCl
2And flooded 3-10 hour in the mixed solution of auxiliary agent M, dipping temperature is 30-80 ℃, CuCl
2Solution concentration is 0.1～0.5M, preferred 0.1～0.3M.The evaporate to dryness that heats up then obtains catalyst precursor; Under 80～140 ℃, preferred 90～110 ℃ of maintenances (were generally 10-18 hour) more than 10 hours with catalyst precursor; Drip KBH then
4Or NaBH
4Solution reduction, the concentration of reducing agent are 0.5～3M, preferred 1～3M.Wash solids then to neutral, with methyl alcohol or ethanol washing, can obtain catalyst of the present invention again.
Activity of such catalysts provided by the invention can be tested with the following method:
In miniature flowing bed reactor, investigate catalyst activity.Catalyst is packed into methyl alcohol in the reaction tube, after the sealing, dries up the methyl alcohol of carrying secretly in the catalyst with hydrogen stream.The raw material dimethyl maleate is dissolved in methyl alcohol (v/v=1/4) as reactant liquor, squeezes in the reaction tube through constant-flux pump.The temperature reaction of pressurizeing then.Reaction pressure is 2～8MPa, preferred 4～6MPa, and reaction temperature is 150～320 ℃, preferred 180～300 ℃.Product is formed with its product of gas chromatographic analysis after condensation.
The specific embodiment
Further describe the present invention below by specific embodiment.
Embodiment 1:Cu-B/ZrO
2Catalyst
1g ZrO
2(40-60 order) carrier impregnation is dissolved with 0.269g CuCl in 10ml
22H
2In the solution of O, after keeping 8h under 30 ℃, the intensification evaporate to dryness kept 10 hours down at 100 ℃ again.After treating the catalyst cooling, drip the KBH of 1.5mol/l
4Solution reduction, extremely neutral with deionized water, methanol wash afterwards.Catalyst is transferred in the reaction tube in the lump with methanol solution, is forced into 5MPa after airtight, with H
2Purge after several minutes, the heat temperature raising sample introduction carries out active testing.Select hydrogenation to the results are shown in table 1.
Embodiment 2:Cu-Cr (5%)-B/ZrO
2Catalyst
1g ZrO
2(40-60 order) carrier impregnation is dissolved with 0.269g CuCl in 10ml
22H
2O and 0.021g CrCl
36H
2In the solution of O, after keeping 8h under 40 ℃, the intensification evaporate to dryness keeps down spending the night at 140 ℃ again.After treating the catalyst cooling, drip the KBH of 1.5mol/l
4Solution reduction, extremely neutral with deionized water, methanol wash afterwards.Catalyst is transferred in the reaction tube in the lump with methanol solution, is forced into 5MPa after airtight, with H
2Purge after several minutes, the heat temperature raising sample introduction carries out active testing.Select hydrogenation to the results are shown in table 2.
Embodiment 3:Cu-B/TiO
2Catalyst
1g TiO
2(40-60 order) carrier impregnation is dissolved with 0.269g CuCl in 10ml
22H
2In the solution of O, after keeping 6h under 50 ℃, the intensification evaporate to dryness kept 12 hours down at 80 ℃ again.After treating the catalyst cooling, drip the KBH of 1.5mol/l
4Solution reduction, extremely neutral with deionized water, methanol wash afterwards.Catalyst is transferred in the reaction tube in the lump with methanol solution, is forced into 5MPa after airtight, with H
2Purge after several minutes, the heat temperature raising sample introduction carries out active testing.Select hydrogenation to the results are shown in table 3.
Embodiment 4:Cu-Cr (5%)-B/TiO
2Catalyst
1g TiO
2(40-60 order) carrier impregnation is dissolved with 0.269g CuCl in 10ml
22H
2O and 0.021g CrCl
36H
2In the solution of O, after keeping 10h under 30 ℃, be warming up to 80 ℃ of evaporates to dryness, keep down spending the night at 120 ℃ again.After treating the catalyst cooling, drip the KBH of 1.5mol/l
4Solution reduction, extremely neutral with deionized water, methanol wash afterwards.Catalyst is transferred in the reaction tube in the lump with methanol solution, is forced into 5MPa after airtight, with H
2Purge after several minutes, the heat temperature raising sample introduction carries out active testing.Select hydrogenation to the results are shown in table 4.
Embodiment 5:Cu-B/Al
2O
3Catalyst
1g Al
2O
3(40-60 order) carrier impregnation is dissolved with 0.269g CuCl in 10ml
22H
2In the solution of O, after keeping 3h under 70 ℃, the intensification evaporate to dryness keeps down spending the night at 100 ℃ again.After treating the catalyst cooling, drip the KBH of 1.5mol/l
4Solution reduction, extremely neutral with deionized water, methanol wash afterwards.Catalyst is transferred in the reaction tube in the lump with methanol solution, is forced into 5MPa after airtight, with H
2Purge after several minutes, the heat temperature raising sample introduction carries out active testing.Select hydrogenation to the results are shown in table 5.
Embodiment 6:Cu-Cr (5%)-B/Al
2O
3Catalyst
1g Al
2O
3(40-60 order) carrier impregnation is dissolved with 0.269g CuCl in 10ml
22H
2O and 0.021g CrCl
36H
2In the solution of O, after keeping 6h under 30 ℃, be warming up to 80 ℃ of evaporates to dryness, keep down spending the night at 100 ℃ again.After treating the catalyst cooling, drip the KBH of 1.5mol/l
4Solution reduction, extremely neutral with deionized water, methanol wash afterwards.Catalyst is transferred in the reaction tube in the lump with methanol solution, is forced into 5MPa after airtight, with H
2Purge after several minutes, the heat temperature raising sample introduction carries out active testing.Select hydrogenation to the results are shown in table 6.
Embodiment 7:Cu-Cr (30%)-B/Al
2O
3Catalyst
1g Al
2O
3(40-60 order) carrier impregnation is dissolved with 0.269g CuCl in 10ml
22H
2O and 0.126g CrCl
36H
2In the solution of O, after keeping 10h under 30 ℃, be warming up to 70 ℃ of evaporates to dryness, keep down spending the night at 100 ℃ again.After treating the catalyst cooling subsequently, drip the KBH of 1.5mol/l
4Solution reduction, extremely neutral with deionized water, methanol wash afterwards.Catalyst is transferred in the reaction tube in the lump with methanol solution, is forced into 5MPa after airtight, with H
2Purge after several minutes, the heat temperature raising sample introduction carries out active testing.Select hydrogenation to the results are shown in table 7.
Table 1Cu-B/ZrO
2The hydrogenation reaction result of catalyst
| Reaction temperature (℃) | Yield (mol.%) | Conversion ratio (%) | Selectivity (mol.%) |
| 220 240 260 280 300 | 1.5 10.9 34.4 72.0 81.7 | 100 100 100 100 100 | 1.5 10.9 34.4 72.0 81.7 |
Other reaction conditions are as follows: p=5MPa, H
2/ DMM (mol/mol)=120, DMM LSV=0.36ml (g
Cat.)
-1H
-1
Table 2Cu-Cr (5%)-B/ZrO
2The hydrogenation reaction result of catalyst
| Reaction temperature (℃) | Yield (mol.%) | Conversion ratio (%) | Selectivity (mol.%) |
| 220 240 260 280 300 | 9.9 20.4 44.6 83.9 78.6 | 100 100 100 100 100 | 9.9 20.4 44.6 83.9 78.6 |
Other reaction conditions are as follows: p=5MPa, H
2/ DMM (mol/mol)=120, DMM LSV=0.36ml (g
Cat.)
-1H
-1
Table 3Cu-B/TiO
2The hydrogenation reaction result of catalyst
| Reaction temperature (℃) | Yield (mol.%) | Conversion ratio (%) | Selectivity (mol.%) |
| 220 240 260 280 300 | 9.9 21.2 44.9 74.2 73.5 | 100 100 100 99.2 99.8 | 9.9 21.2 44.9 74.6 73.6 |
Other reaction conditions are as follows: p=5MPa, H
2/ DMM (mol/mol)=120, DMM LSV=0.36ml (g
Cat.)
-1H
-1
Table 4Cu-Cr (5%)-B/TiO
2The hydrogenation reaction result of catalyst
| Reaction temperature (℃) | Yield (mol.%) | Conversion ratio (%) | Selectivity (mol.%) |
| 220 240 260 280 300 | 11.5 20.5 42.6 71.0 82.1 | 100 100 100 99.7 99.8 | 11.5 20.5 42.6 71.2 82.2 |
Other reaction conditions are as follows: p=5MPa, H
2/ DMM (mol/mol)=120, DMM LSV=0.36ml (g
Cat.)
-1H
-1
Table 5Cu-B/Al
2O
3The hydrogenation reaction result of catalyst
| Reaction temperature (℃) | Yield (mol.%) | Conversion ratio (%) | Selectivity (mol.%) |
| 220 240 260 280 300 | 3.1 10.1 40.4 67.9 76.5 | 99.2 98.1 99.3 99.8 99.4 | 3.1 10.3 40.4 68.0 77.0 |
Other reaction conditions are as follows: p=5MPa, H
2/ DMM (mol/mol)=120, DMM LSV=0.36ml (g
Cat.)
-1H
-1
Table 6Cu-Cr (5%)-B/Al
2O
3The hydrogenation reaction result of catalyst
| Reaction temperature (℃) | Yield (mol.%) | Conversion ratio (%) | Selectivity (mol.%) |
| 220 240 260 280 300 | 8.2 16.6 41.7 72.9 94.9 | 99.7 96.6 98.4 99.4 99.7 | 8.2 17.2 42.3 73.3 95.2 |
Other reaction conditions are as follows: p=5MPa, H
2/ DMM (mol/mol)=120, DMM LSV=0.36ml (g
Cat.)
-1H
-1
Table 7Cu/Cr (30%)/B-Al
2O
3The hydrogenation reaction result of catalyst
| Reaction temperature (℃) | Yield (mol.%) | Conversion ratio (%) | Selectivity (mol.%) |
| 220 240 260 280 300 | 10.6 25.4 71.0 93.8 94.5 | 100 99.9 98.9 99.7 100 | 10.6 25.4 71.8 94.0 94.5 |
Other reaction conditions are as follows: p=5MPa, H
2/ DMM (mol/mol)=120, DMM LSV=0.36ml (g
Cat.)
-1H
-1
Claims (4)
1. the catalyst that preparing butylene oxide by hydrogenating dimethyl maleate is used is to be active component with Cu, by auxiliary agent M modification, by KBH
4Or NaBH
4The Cu-B loaded catalyst that reduction obtains, it is characterized in that each component ratio is as follows: with the carrier quality as 1, then Cu is 0.02～0.2, the mol ratio of auxiliary agent M and Cu is 0～0.8, the mol ratio of element B and Cu is 0.2～2, wherein, carrier material be in the periodic table of elements the the 3rd, the 4th, the 5th, in the metal oxide of period 6 or the rare-earth oxide one or more; Auxiliary agent M is one or more in IB family, IIB family, group vib, the group VIII metallic element in the periodic table of elements; Cu is evenly dispersed on the carrier material with crystalline form.
2. catalyst according to claim 1 is characterized in that described carrier material is one or more in magnesia, aluminium oxide, silica, zirconia, titanium oxide, the cerium oxide.
3. catalyst according to claim 1 is characterized in that described auxiliary agent M is selected from one or more among Cr, Mo, W, Fe, the Co.
4. a Preparation of catalysts method as claimed in claim 1 is characterized in that adopting chemical reduction method, and concrete steps are: with carrier at CuCl
2And flooded 3-10 hour in the mixed solution of auxiliary agent, dipping temperature is 30-80 ℃, CuCl
2Solution concentration is 0.1～0.5M; The evaporate to dryness that heats up then obtains catalyst precursor, keeps more than 10 hours down at 80～140 ℃ again; Use KBH
4Or NaBH
4Solution reduction, reducing agent KBH
4Or NaBH
4The concentration of solution is 0.5～3M; The washing solids is to neutral, again with methyl alcohol or ethanol washing.
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|---|---|---|---|
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|---|---|---|---|
| CN 200510028244 CN1743068A (en) | 2005-07-28 | 2005-07-28 | Copper-boron catalyst for preparing butylene oxide by hydrogenating dimethyl maleate and preparing method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400162C (en) * | 2006-10-19 | 2008-07-09 | 复旦大学 | Method for preparing catalyst for preparing 1,4-cis-butanediol by dimethyl maleate hydrogenation |
| CN101891714A (en) * | 2010-08-12 | 2010-11-24 | 湖南长岭石化科技开发有限公司 | Method for producing tetrahydrofuran |
| CN111569876A (en) * | 2020-04-29 | 2020-08-25 | 厦门大学 | Hydrogenation catalyst, preparation method and application thereof |
| US11390959B2 (en) * | 2018-04-24 | 2022-07-19 | Total Se | Boron-doped copper catalysts for efficient conversion of CO2 to multi-carbon hydrocarbons and associated methods |
-
2005
- 2005-07-28 CN CN 200510028244 patent/CN1743068A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400162C (en) * | 2006-10-19 | 2008-07-09 | 复旦大学 | Method for preparing catalyst for preparing 1,4-cis-butanediol by dimethyl maleate hydrogenation |
| CN101891714A (en) * | 2010-08-12 | 2010-11-24 | 湖南长岭石化科技开发有限公司 | Method for producing tetrahydrofuran |
| US11390959B2 (en) * | 2018-04-24 | 2022-07-19 | Total Se | Boron-doped copper catalysts for efficient conversion of CO2 to multi-carbon hydrocarbons and associated methods |
| CN111569876A (en) * | 2020-04-29 | 2020-08-25 | 厦门大学 | Hydrogenation catalyst, preparation method and application thereof |
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