CN1762586A - Cu-B catalyst for preparing tetrahydrofuran by hydrogenation of dimethyl maleate and its preparation process - Google Patents
Cu-B catalyst for preparing tetrahydrofuran by hydrogenation of dimethyl maleate and its preparation process Download PDFInfo
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- CN1762586A CN1762586A CN 200510029695 CN200510029695A CN1762586A CN 1762586 A CN1762586 A CN 1762586A CN 200510029695 CN200510029695 CN 200510029695 CN 200510029695 A CN200510029695 A CN 200510029695A CN 1762586 A CN1762586 A CN 1762586A
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Abstract
The new catalyst preparation method relates to selective hydrogenate dimethylmaleate to synthesize THF, which comprises: thermal treating carrier, dipping, chemical reducing, and obtaining the Cu-B catalyst. Wherein, the active constituent Cu exists as metal state, the carrier material is metal oxide. This method needs no adjuvant, and has high activity and selectivity.
Description
Technical field
The invention belongs to chemical technology field, is new catalyst that is used for preparing butylene oxide by hydrogenating dimethyl maleate 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.
Oxolane mainly is by 1 on the known technology, 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, and can produce in a step and obtain oxolane, thereby save 1, the intermediate steps of 4-butanediol, it is long to produce route, so production cost is higher.
Summary of the invention
The objective of the invention is to propose a kind of simple method for preparing of the new catalyst that is used for preparing butylene oxide by hydrogenating dimethyl maleate of a kind of high activity, high selectivity.
The present invention proposes a kind of Cu-B catalyst that is used for preparing butylene oxide by hydrogenating dimethyl maleate, this catalyst is by active component Cu, metal oxide carrier and B species composition, be that Cu-B loads on the metal oxide carrier, its each component proportion of composing is: the carrier quality is 1, Cu is 0.02～0.2, and the mol ratio of element B and Cu is 0.2～1.0.
The present invention proposes a kind of preparation method who is used for the Cu-B catalyst of preparing butylene oxide by hydrogenating dimethyl maleate, metal oxide carrier is after grinding, heat treatment through 200～1000 ℃, be immersed in the copper salt then, dipping finishes to heat up to dry and obtains catalyst precursor, and this presoma insulation back is by KBH
4Or NaBH
4Electronation washing solids again with methyl alcohol or ethanol washing, obtains the Cu-B catalyst of load to neutral.The metal oxide grind size generally at micron to millimeter level, visual response device size and deciding.Above steps all is prior aries, but with comprehensive content of the present invention, the relevant report of Shang Weijian realized of each step reaction.
The present invention's implementation condition preferably is as follows:
Among the present invention, carrier material is 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.
Among the present invention, carrier material is in the periodic table of elements the 3rd, the 4th, the metal oxide of period 5 or in the rare-earth oxide one or more.
Among the present invention, the carrier material metal oxide in the catalyst is one or more in magnesia, aluminium oxide, silica, zirconia, titanium oxide or the cerium oxide.
Among the present invention, metal oxide carrier is before use through Overheating Treatment, treatment temperature between 200～1000 ℃, processing time 3-6 hour.
Among the present invention, be immersed in CuCl through heat treated oxide carrier
2In the solution, CuCl
2Solution concentration is 0.1～0.5M.
Among the present invention, the insulation of the presoma of catalyst is to keep 10-12 hour down at 80～140 ℃, then reduction.
Among the present invention, reducing agent KBH
4Or NaBH
4The concentration of solution is 0.5～3M.
Among the present invention, the dipping temperature when presoma prepares is 30～80 ℃, and dip time is 3-6 hour.
Among the present invention, catalyst precursor dipping back bake out temperature is 80～140 ℃.
Better implement condition of the present invention is:
Among the present invention, CuCl
2Solution concentration is 0.1～0.3M.
Among the present invention, the catalyst precursor holding temperature is 90～110 ℃.
Among the present invention, reductant concentration is 1～3M.
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, 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 2～6MPa, preferred 4～6MPa, and reaction temperature is 150～320 ℃, preferred 180～300 ℃.Product after condensation with its composition of gas chromatographic analysis.
According to catalyst provided by the invention, active component Cu is evenly dispersed on the carrier material with crystalline form.Preparation method of the present invention is simple and easy, forms simply, need not to add auxiliary agent, and the catalyst that is used for preparing butylene oxide by hydrogenating dimethyl maleate has high activity, high selectivity.
The specific embodiment
Carrier A l
2O
3Through after the heat treatments at different, go up for another example and adopt chemical reduction method to prepare the Cu-B catalyst of load.The body phase composition and the specific surface of catalyst are listed in the table 1.
Further describe the application of the present invention in preparing butylene oxide by hydrogenating dimethyl maleate below by specific embodiment.
Embodiment 1:Cu-B/Al
2O
3(450 ℃) Preparation of catalysts and activity characterization
1g Al
2O
3(40-60 order) carrier impregnated in 10ml and is dissolved with 0.269g CuCl after 450 ℃ of heat treatment
22H
2In the solution of O, after keeping 6 hours 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 the deionized water washing afterwards, again with remaining water in the methyl alcohol displacement catalyst.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 2:Cu-B/Al
2O
3(1000 ℃) Preparation of catalysts and activity characterization
1g Al
2O
3(40-60 order) carrier impregnated in 10ml and is dissolved with 0.269g CuCl after 1000 ℃ of heat treatment
22H
2In the solution of O, after keeping 3 hours under 80 ℃, be warming up to 140 ℃ of evaporates to dryness, keep down spending the night at 140 ℃ again.After treating the catalyst cooling, drip the NaBH of 3.0mol/l
4Solution reduction, extremely neutral with the deionized water washing afterwards, exchange out water remaining in the catalyst with ethanol again.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 3: Cu-B/Al under the carrier treatment of different temperature
2O
3Activity of such catalysts result relatively
Table 4 has been listed four catalyst of treatment of different temperature 260 ℃ of following hydrogenation results, can find, along with carrier A l
2O
3The increase of heat treatment temperature, the hydrogenation activity of the Cu-B catalyst of its load and the selectivity of oxolane risen thereupon.
The Al of table 1 treatment of different temperature
2O
3The body phase composition and the specific area of loaded Cu-B catalyst
| Catalyst | Cu-B/Al 2O 3 (450℃) | Cu-B/Al 2O 3 (600℃) | Cu-B/Al 2O 3 (750℃) | Cu-B/Al 2O 3 (1000℃) |
| Body phase composition (mol ratio) | Cu 74B 26 | Cu 69B 31 | Cu 72B 28 | Cu 83B 17 |
| SBET(m 2/g) | 121 | 118 | 111 | 80 |
Table 2Cu-B/Al
2O
3The hydrogenation reaction result of (450 ℃) catalyst
| Reaction temperature (℃) | Yield (mol.%) | Conversion ratio (%) | Selectivity (mol.%) |
| 220 240 260 280 300 | 5.6 12.2 23.8 64.8 84.4 | 99.1 99.7 99.7 99.4 99.4 | 5.7 12.2 23.9 65.3 84.9 |
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/Al
2O
3The hydrogenation reaction result of (1000 ℃) catalyst
| Reaction temperature (℃) | Yield (mol.%) | Conversion ratio (%) | Selectivity (mol.%) |
| 220 240 260 280 300 | 14.2 28.9 58.8 88.9 95.6 | 100 99.9 99.8 100 100 | 14.2 28.9 58.8 88.9 95.6 |
Other reaction conditions are as follows: p=5MPa, H
2/ DMM (mol/mol)=120, DMM LSV=0.36ml (g
Cat.)
-1H
-1
The Al of table 4 treatment of different temperature
2O
3The hydrogenation reaction result of loaded Cu-B catalyst (T=260 ℃)
| Catalyst | Yield (mol.%) | Conversion ratio (%) | Selectivity (mol.%) |
| Cu-B/Al 2O 3(450℃) Cu-B/Al 2O 3(600℃) Cu-B/Al 2O 3(750℃) Cu-B/Al 2O 3(1000℃) | 23.8 33.3 46.4 58.8 | 99.7 100 99.1 99.8 | 23.9 33.3 46.8 58.8 |
Other reaction conditions: p=5MPa, H
2/ DMM (mol/mol)=120, DMM LSV=0.36ml (g
Cat.)
-1H
-1
Above-mentioned example is the part example of content embodiment of the present invention, because these those skilled in the art can directly obtain enforcement from content of the present invention, so content of the present invention is not limited to the foregoing description.
Claims (14)
1, a kind of Cu-B catalyst that is used for preparing butylene oxide by hydrogenating dimethyl maleate, it is characterized in that this catalyst is by active component Cu, metal oxide carrier and B species composition, be that Cu-B loads on the metal oxide carrier, its each component proportion of composing is: the carrier quality is 1, Cu is 0.02～0.2, and the mol ratio of element B and Cu is 0.2～1.0.
2, a kind of preparation method who is used for the Cu-B catalyst of preparing butylene oxide by hydrogenating dimethyl maleate, it is characterized in that metal oxide carrier is after grinding, heat treatment through 200～1000 ℃, be immersed in the copper salt then, dipping finishes to heat up to dry and obtains catalyst precursor, and this presoma insulation back is by KBH
4Or NaBH
4Electronation, washing solids again with methyl alcohol or ethanol washing, obtain the Cu-B catalyst of load to neutral.
3, Preparation of catalysts method according to claim 2 is characterized in that carrier material is 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.
4, Preparation of catalysts method according to claim 3 is characterized in that carrier material is in the periodic table of elements the 3rd, the 4th, the metal oxide of period 5 or in the rare-earth oxide one or more.
5, Preparation of catalysts method according to claim 4 is characterized in that carrier material metal oxide in the catalyst is one or more in magnesia, aluminium oxide, silica, zirconia, titanium oxide or the cerium oxide.
6, Preparation of catalysts method according to claim 2 is characterized in that metal oxide carrier before use through Overheating Treatment, treatment temperature between 200～1000 ℃, processing time 3-6 hour.
7, Preparation of catalysts method according to claim 2 is characterized in that being immersed in CuCl through heat treated oxide carrier
2In the solution, CuCl
2Solution concentration is 0.1～0.5M.
8, Preparation of catalysts method according to claim 2, the insulation that it is characterized in that the presoma of catalyst are to keep 10-12 hour down at 80～140 ℃, then reduction.
9, Preparation of catalysts method according to claim 2 is characterized in that reducing agent KBH
4Or NaBH
4The concentration of solution is 0.5～3M.
10, Preparation of catalysts method according to claim 2 is characterized in that the dipping temperature when presoma prepares is 30～80 ℃, and dip time is 3-6 hour.
11, Preparation of catalysts method according to claim 2 is characterized in that catalyst precursor dipping back bake out temperature is 80～140 ℃.
12, Preparation of catalysts method according to claim 7 is characterized in that CuCl
2Solution concentration is 0.1～0.3M.
13, Preparation of catalysts method according to claim 8 is characterized in that the catalyst precursor holding temperature is 90～110 ℃.
14, Preparation of catalysts method according to claim 9 is characterized in that reductant concentration is 1～3M.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100296957A CN100372606C (en) | 2005-09-15 | 2005-09-15 | Cu-B catalyst for preparing tetrahydrofuran by hydrogenation of dimethyl maleate and its preparation process |
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|---|---|---|---|
| CNB2005100296957A CN100372606C (en) | 2005-09-15 | 2005-09-15 | Cu-B catalyst for preparing tetrahydrofuran by hydrogenation of dimethyl maleate and its preparation process |
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|---|---|
| CN1762586A true CN1762586A (en) | 2006-04-26 |
| CN100372606C CN100372606C (en) | 2008-03-05 |
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Cited By (3)
| 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 |
| CN105032420A (en) * | 2015-07-14 | 2015-11-11 | 浙江工业大学 | Cu/SiO2 catalyst and method therefor for synthesizing tetrahydrofuran |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1099909C (en) * | 1999-08-31 | 2003-01-29 | 中国石油化工集团公司 | Process for preparing non-crystal Ni-B alloy catalyst |
| DE10351697A1 (en) * | 2003-11-05 | 2005-06-09 | Basf Ag | Process for the preparation of butanediol from γ-butyrolactone in the presence of water |
-
2005
- 2005-09-15 CN CNB2005100296957A patent/CN100372606C/en not_active Expired - Fee Related
Cited By (3)
| 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 |
| CN105032420A (en) * | 2015-07-14 | 2015-11-11 | 浙江工业大学 | Cu/SiO2 catalyst and method therefor for synthesizing tetrahydrofuran |
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