CN1493569A - Method of preparing gamma-butyrolactone and/or 1,4-butanediol using chromium less catalyst - Google Patents
Method of preparing gamma-butyrolactone and/or 1,4-butanediol using chromium less catalyst Download PDFInfo
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- CN1493569A CN1493569A CNA021463832A CN02146383A CN1493569A CN 1493569 A CN1493569 A CN 1493569A CN A021463832 A CNA021463832 A CN A021463832A CN 02146383 A CN02146383 A CN 02146383A CN 1493569 A CN1493569 A CN 1493569A
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Abstract
A process for preparing gamma-butyrolactone and/or 1,4-butanediol by use of Cr-free catalyst includes making the the dialkyl maleate and/or dialkyl succinate in contact with hydrocatalyst, reacting at 170-300 deg.c and 0.1-15 hr under 0.1-7 Mpa, and collecting products. Said hydrocatalyst is CuMnaAlbOc, where a=0.01-1.5, b=0.1-2 and c is number of necessary oxygen atoms. Its advantage is controllable ratio between both products.
Description
Technical field
The present invention relates to by gas phase catalytic hydrogenation prepared in reaction gamma-butyrolactone and/or 1 method of 4-butyleneglycol.
Technical background
Gamma-butyrolactone is the synthetic butyric acid compounds, polyvinyl pyrrolidone, vitamins B
1The intermediate of piracetam is the suitable solvent of acrylate and styrene polymer, is the useful component of coating washing composition and textile auxiliary agent.
Usually gamma-butyrolactone is with 1, and the 4-butyleneglycol is that raw material carries out dehydrogenation and makes, but 1,4-butyleneglycol in general price is still more expensive, along with C
4Oxidation prepares the development of cis-butenedioic anhydride technology, is that raw material hydrogenation preparing gamma-butyrolactone is rapidly developed with the cis-butenedioic anhydride.The company of changing into of Mitsubishi has developed the method for making gamma-butyrolactone from MALEIC ANHYDRIDE liquid-phase hydrogenatin, but this method needs react under high pressure 100atm condition, has increased the difficulty of manufacturing process, and what have also need adopt precious metals such as containing Pa, Rh, Ru.
About with the maleic acid alkyl ester being raw material prepares gamma-butyrolactone by vapour phase hydrogenation method.SU 1022969 has reported with CuO-Cr
2O
3-ZnO/Al
2O
3Being catalyzer, is 0.2-0.3h at 260 ℃-280 ℃, liquid hourly space velocity
-1Down, be gamma-butyrolactone with dibutyl maleinate hydrogenation, transformation efficiency 97mol%, the selectivity 85mol% of gamma-butyrolactone.CS 171623 has reported CuO-Cr
2O
3-ZnO/ silica gel is catalyzer, at 250-270 ℃, hydrogen/ester mol ratio is under 30: 1 the condition, dibutyl maleinate or succinate hydrogenation to be prepared gamma-butyrolactone, and the productive rate of gamma-butyrolactone is 70mol%.WO8607358 has reported with Cu-Cr-Ba or Mn catalyzer, at 170～260 ℃, and 11～30 crust, hydrogen/ester is under 50～1000: 1 (mol) condition, adopts two sections hydrogenation process, by C
4Carboxylicesters prepares the method for gamma-butyrolactone, and the selectivity of this method charging air speed and preparation gamma-butyrolactone is all not high.
Above-mentioned each prior art respectively has characteristics, but its weak point is: catalyzer contains strong toxicity, with serious pollution Cr component in the public technology that has, caused very big harm for producers and environment, pollute for eliminating Cr, the pollution that Cr caused must drop into substantial contribution producers are protected and administer, though so, still can not be solved, in addition, containing the Cr spent catalyst can't reclaim.Other technology need adopt high pressure or secondary hydrogenation technology, and facility investment is significantly increased, and simultaneously, activity of such catalysts is lower, and when temperature of reaction was 260 ℃-280 ℃, liquid hourly space velocity had only 0.2-0.3hr
-1
Summary of the invention
The purpose of this invention is to provide a kind of is raw material with maleic acid alkyl ester and/or succinic acid dialkyl ester, uses base metal not have the Cr catalyzer and carries out gas phase hydrogenation reaction and prepare gamma-butyrolactone and/or 1, the method for 4-butyleneglycol.
Preparation method provided by the invention comprises: maleic acid alkyl ester and/or succinic acid dialkyl ester are contacted with hydrogenation catalyst, are 150 ℃-300 ℃ in temperature of reaction, and pressure is 0.1-7.0MPa, and the air speed of ester is 0.1-15hr
-1, hydrogen/ester mol ratio is 5-250: reacts under 1 the condition, collects gamma-butyrolactone and/or 1, and the 4-butyleneglycol, said hydrogenation catalyst has following general formula: CuMn
aAl
bO
c, a=0.01-1.5 wherein, b=0.1-2, c are the oxygen atomicities that satisfies other element valence requirement.
Said temperature of reaction is 150 ℃-300 ℃, preferred 185 ℃-250 ℃; Said pressure is 0.1-7.0MPa, preferred 0.3-6.0MPa; The air speed of said ester is 0.1-15hr
-1, preferred 0.8-10hr
-1Said hydrogen/ester mol ratio is 5-250: 1, and preferred 20-200: 1.
Alkyl carbon number in said maleic acid alkyl ester and the succinic acid dialkyl ester is 1-4.
The composite oxides that the used catalyzer of the present invention is made up of Cu, Mn, Al, this catalyzer has following general formula: CuMn
aAl
bO
c, a=0.01-1.5 wherein, preferred 0.04-1.0, b=0.1-2, preferred 0.2-1.5.C is the oxygen atomicity that satisfies other element valence requirement.
The Preparation of catalysts method that the present invention is used: with Cu, Mn, the soluble salt of Al is dissolved in the deionized water, at 10～80 ℃, under preferred 20～50 ℃, with alkali precipitation to PH=4～11, preferred PH=5-8, aging 0～5 hour, preferred 0-3 filtered then, washing, collecting precipitation, in 70～200 ℃, preferred 70-150, dry 2～30 hours, again in 400～900 ℃, preferred 400-800 ℃, roasting 2～30 hours promptly gets the catalyzer that the present invention uses, and wherein soluble salt can be to contain Cu simultaneously, Mn, the solution of three kinds of metal-salts of Al, also can be only to contain the wherein solution of one or both metal-salts, if the latter can use alkali precipitation respectively with several solution that contain different metal salt earlier, again reacted solution is mixed the back and wear out.
The preferred nitrate separately of the soluble salt of described Cu, Mn, Al.
Described alkali can be volatile salt, bicarbonate of ammonia, ammoniacal liquor, yellow soda ash, sodium hydroxide and potassium hydroxide etc., preferred volatile salt, bicarbonate of ammonia, ammoniacal liquor.The concentration of alkali lye is 5-40wt%, preferred 10-35wt%.
Need give reduction before the used catalyzer of the present invention uses, reductive agent can adopt reducing gas such as hydrogen, carbon monoxide, and reduction is carried out under 0.1-2.0MPa, 150-300 ℃ condition, and the reducing gas flow is 50-500ml/min for every milliliter of catalyzer.
Catalyzer of the present invention in catalyzer manufacturing and use, makes operator's safety obtain guarantee owing to do not contain the very big chromium component of toxicity, and environment has obtained protection, and has saved the expense that is used for environmental protection in a large number.Catalyzer of the present invention is compared with existing chromium-containing catalyst, has higher activity.
Adopt volatile salt, bicarbonate of ammonia, ammoniacal liquor as precipitation agent in addition when Preparation of Catalyst, the consumption of washing water in the time of can significantly reducing Preparation of Catalyst reduces washing times, improves the production efficiency of catalyzer.
Method provided by the invention can be produced gamma-butyrolactone and 1 simultaneously, the 4-butyleneglycol, also can be according to the market requirement, in big scope to reaction product in gamma-butyrolactone and 1, the ratio of 4-butyleneglycol is regulated, and obtains the gamma-butyrolactone of high yield under near normal pressure, lower temperature of reaction and bigger liquid hourly space velocity.As: at 230 ± 1 ℃, LHSV=0.84hr
-1The time, transformation efficiency 100mol%, gamma-butyrolactone selectivity 94.9mol%.Also can under higher pressure, lower temperature of reaction and bigger liquid hourly space velocity, obtain 1 of high yield, the 4-butyleneglycol.As: at 189 ± 1 ℃, 5.8MPa, LHSV=3.7hr
-1The time, transformation efficiency 99.9mol%, 1,4-butyleneglycol selectivity 74mol%.
Embodiment
Embodiment 1～5 is a Preparation of catalysts.
Embodiment 1
With 52.2g Cu (NO
3)
2.3H
2O, 91g 50%Mn (NO)
2. the aqueous solution, 122gAl (NO
3)
3.9H
2O is dissolved in the 500ml deionized water, makes solution A.Na2CO3 (23mol) is made solution B.The 200ml deionized water of in the 1000ml beaker, packing into, under agitation add in the beaker simultaneously two kinds of solution of A.B, control A.B drips speed, makes PH remain at 5.5 ± 0.5, wears out 1 hour after the titration, filter then, through 6 washings, collecting precipitation was 120 ℃ of dryings 3 hours, 750 ℃ of roastings 2 hours promptly get catalyst A: CuMn
0.9Al
1.5O
4.2
Embodiment 2
With 35.5g Cu (NO
3)
2.3H
2O (Beijing Chemical Plant, chemical pure), 48.9g 50%Mn (NO)
2. the aqueous solution (Beijing Chemical Plant, chemical pure), 10.7g Al (NO
3)
3.9H
2O (Beijing Chemical Plant, chemical pure), is dissolved in the 500ml deionized water, under agitation dropping ammonia (23 heavy %, the Beijing Chemical Plant, chemical pure), being 6.5 ± 0.5 o'clock aging 1 hour to solution PH, filter then, wash one time collecting precipitation, 200 ℃ of dryings 2 hours, 500 ℃ of roastings 2 hours promptly get catalyst B: CuMn
0.46Al
0.2O
1.76
Embodiment 3
With 52.2g Cu (NO
3)
2.3H
2O, 5.6g 50%Mn (NO)
2. the aqueous solution, 74.9gAl (NO
3)
3.9H
2O is dissolved in the 500ml deionized water, makes solution A.With Na
2CO
3(23 heavy %) makes solution B.The 200ml deionized water of in the 1000ml beaker, packing into, under agitation add in the beaker simultaneously two kinds of solution of A.B, the molten speed of control A.B makes PH remain at 9 ± 0.5, wears out 1 hour after the titration, filter then, through 6 washings, collecting precipitation was 120 ℃ of dryings 2 hours, 600 ℃ of roastings 2 hours promptly get catalyzer C:CuMn
0.07Al
0.9O
2.42
Embodiment 4
With 35.5g Cu (NO
3)
2.3H
2O, 25.3g 50%Mn (NO)
2. the aqueous solution, 25gAl (NO
3)
3.9H
2O is dissolved in the 400ml deionized water, makes solution A.(12 heavy %) makes solution B with ammoniacal liquor.The 100ml deionized water of in the 1000ml beaker, packing into, under agitation add in the beaker simultaneously two kinds of solution of A.B, control A.B drips speed, makes PH remain at 7.1 ± 0.5, wears out 0.5 hour after the titration, filter then, washing once, collecting precipitation was 120 ℃ of dryings 2 hours, 700 ℃ of roastings 6 hours promptly get catalyzer D:CuMn
0.27Al
0.46O
1.96
Embodiment 5
With 35.5g Cu (NO
3)
2.3H
2O, 45.7g 50%Mn (NO)
2. aqueous solution 26.4g, Al (NO
3)
3.9H
2O is dissolved in the 500ml deionized water, makes solution A.(12 heavy %) makes solution B with ammoniacal liquor.The 900ml deionized water of in the 2000ml beaker, packing into, under agitation add in the beaker simultaneously two kinds of solution of A.B, control A.B drips speed, makes PH remain at 7.6 ± 0.5, wears out 1 hour after the titration, filter then, through once washing, collecting precipitation was 120 ℃ of dryings 12 hours, 750 ℃ of roastings 3 hours promptly get catalyzer E:CuMn
0.87Al
0.49O
2.61
The good use properties of embodiment 6～11 explanations catalyzer of the present invention.
Embodiment 6
Getting granularity and be 26-40 order catalyst A 3.2g packs in the tubular reactor that the stainless steel of internal diameter 8mm makes, under 200 ℃, 2.0Mpa condition, flow velocity with 300ml/min feeds hydrogen, reductase 12 0 hour, be raw material then with the dimethyl maleate, at 230 ± 1 ℃ of temperature of reaction, 0.3MPa, volume space velocity is 0.84h when hydrogen/ester=61: 1 (mol), the liquid of ester
-1Under the condition, reaction result sees Table 1.
Embodiment 7
To react after the method reduction of catalyst B by embodiment 5, different is 234 ± 1 ℃ of temperature of reaction, and the stock liquid hourly space velocity is 0.95hr
-1, pressure is 0.1Mpa, hydrogen/ester=20: 1 (mol).Reaction result sees Table 1.
Embodiment 8
Will catalyzer C react after the method reduction by embodiment 5, different is in temperature of reaction is 226 ± 1 ℃, and pressure is 0.1Mpa, and under hydrogen/ester=122: 1 (mol) condition, the stock liquid hourly space velocity is 0.84hr
-1, the reaction products therefrom is inferred through FID with the gas chromatograph of packed column PEG20000, the results are shown in Table 1.
Embodiment 9
Will catalyst B react after the method reduction by embodiment 5, different is in temperature of reaction is 189 ± 1 ℃, and pressure is 5.8 ± 0.2MPa, and under hydrogen/ester=200: 1 (mol) condition, the stock liquid hourly space velocity is 2.6hr
-1, the reaction products therefrom is inferred through FID with the gas chromatograph of packed column PEG20000, the results are shown in Table 1.
Embodiment 10
Will catalyzer D react after the method reduction by embodiment 5, different is in temperature of reaction is 189 ± 1 ℃, and pressure is 5.8 ± 0.2MPa, and under hydrogen/ester=140: 1 (mol) condition, the stock liquid hourly space velocity is 3.7hr
-1, the reaction products therefrom is inferred through FID with the gas chromatograph of packed column PEG20000, the results are shown in Table 1.
Embodiment 11
Will catalyzer E react after the method reduction by embodiment 5, different is in temperature of reaction is 189 ± 1 ℃, and pressure is 5.8 ± 0.2MPa, and under hydrogen/ester=100: 1 (mol) condition, the stock liquid hourly space velocity is 9.1hr
-1, the reaction products therefrom is inferred through FID with the gas chromatograph of packed column PEG20000, the results are shown in Table 1.
Comparative example 1
SU1022969 has reported with CuO-Cr
2O
3-ZnO/Al
2O
3Being catalyzer, is 0.2-0.3hr at 260 ℃-280 ℃, liquid hourly space velocity
-1Down, be gamma-butyrolactone with dibutyl maleinate hydrogenation, transformation efficiency 97mol%, the selectivity 85mol% of gamma-butyrolactone.
Table 1
| Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | ||
| The catalyzer numbering | ??A | ????B | ??C | ?B | ??D | ??E | |
| Temperature of reaction (℃) | ??230±1 | ????234±1 | ??226±1 | ?189±1 | ??189±1 | ??189±1 | |
| Reaction pressure (MPa) | ??0.3 | ????0.1 | ??0.1 | ?5.8± ??0.2 | ??5.8± ????0.2 | ??5.8± ????0.2 | |
| ????H 2/ ester (mol) | ??61 | ????20 | ??122 | ?200 | ??140 | ??100 | |
| Ester liquid hourly space velocity (hr -1) | ??0.84 | ????0.95 | ??0.84 | ?2.6 | ??3.7 | ??9.1 | |
| Ester conversion rate (mol%) | ??100 | ????100 | ??98.6 | ?99.9 | ??99.9 | ??100 | |
| Selectivity mol% | Tetrahydrofuran (THF) | ??2.0 | ????3.7 | ??1.5 | ?1.1 | ??1.9 | ??6.0 |
| Butanols | ??1.5 | ????2.7 | ??2.7 | ?0.6 | ??1.4 | ??4.4 | |
| Gamma-butyrolactone | ??94.9 | ????92.1 | ??94.5 | ?19 | ??22.5 | ??31.4 | |
| 1, the 4-butyleneglycol | ??1.5 | ????1.4 | ??1.2 | ?79.3 | ??74 | ??58.2 | |
Claims (10)
1. prepare gamma-butyrolactone and/or 1 with chromium-less catalyst, the method of 4-butyleneglycol, comprise: maleic acid alkyl ester and/or succinic acid dialkyl ester are contacted with hydrogenation catalyst, in temperature of reaction is 150 ℃-300 ℃, pressure is to react under the condition of 0.1-7.0MPa, collect gamma-butyrolactone and/or 1, the 4-butyleneglycol, said hydrogenation catalyst has following general formula: CuMn
aAl
bO
c, a=0.01-1.5 wherein, b=0.1-2, c are the oxygen atomicities that satisfies other element valence requirement.
2. according to the described preparation method of claim 1, it is characterized in that said temperature of reaction is 185 ℃-250 ℃, said pressure is 0.3-6.0MPa.
3. according to the described preparation method of claim 1, it is characterized in that the air speed of ester is 0.1-15hr
-1, hydrogen/ester mol ratio is 5-250: 1.
4. according to claim 1 or 3 described preparation methods, it is characterized in that the air speed of said ester is 0.8-10hr
-1Said hydrogen/ester mol ratio is 20-200: 1.
5. according to the described preparation method of claim 1, it is characterized in that the alkyl carbon number in said maleic acid alkyl ester and the succinic acid dialkyl ester is 1-4.
6. according to the described preparation method of claim 1, it is characterized in that, in the said catalyzer general formula, a=0.04-1.0, b=0.2-1.5.
7. according to the described preparation method of claim 1, it is characterized in that, said Preparation of catalysts method comprises: the soluble salt of Cu, Mn, Al is dissolved in the deionized water, 10～80 ℃ with alkali precipitation to PH=4～11, aging 0～5 hour, filter then, washing, collecting precipitation, in 70～200 ℃ of dryings 2～30 hours, again in 300～900 ℃ of roastings 2～30 hours.
8. according to the described preparation method of claim 7, it is characterized in that the soluble salt of said Cu, Mn, Al is selected from nitrate separately.
9. according to the described preparation method of claim 1, it is characterized in that said alkali is selected from volatile salt, bicarbonate of ammonia, ammoniacal liquor, yellow soda ash, sodium hydroxide and potassium hydroxide.
10. according to the described preparation method of claim 1, it is characterized in that said catalyzer need give reduction before using, reduction is carried out under 0.1-2.0MPa, 150-300 ℃ condition, and the reducing gas flow is 50-500ml/min for every milliliter of catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02146383 CN1216877C (en) | 2002-10-30 | 2002-10-30 | Method of preparing gamma-butyrolactone and/or 1,4-butanediol using chromium less catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02146383 CN1216877C (en) | 2002-10-30 | 2002-10-30 | Method of preparing gamma-butyrolactone and/or 1,4-butanediol using chromium less catalyst |
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| Publication Number | Publication Date |
|---|---|
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| CN1216877C CN1216877C (en) | 2005-08-31 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307042B (en) * | 2007-05-18 | 2011-04-20 | 中国石油化工股份有限公司 | Method for producing 1,4-butanediol and coproducing tetrahydrofuran, and gamma-butyrolactone |
| CN103100393A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN103566945A (en) * | 2012-07-23 | 2014-02-12 | 上海焦化有限公司 | Preparation method for producing efficient copper-manganese-aluminium catalyst for preparing 1, 4-butanediol |
| CN103641682A (en) * | 2013-11-06 | 2014-03-19 | 上海交通大学 | Method of preparing glycol by utilization of biomass derivative glycolide |
| CN103769157A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN103801321A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Catalyst for preparing 1,4-butanediol and preparation method |
| CN104399484A (en) * | 2014-10-20 | 2015-03-11 | 中科合成油淮南催化剂有限公司 | Catalyst for [gamma]-butyrolactone preparation through dimethyl maleate hydrogenation, and preparation method thereof |
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2002
- 2002-10-30 CN CN 02146383 patent/CN1216877C/en not_active Expired - Lifetime
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| CN101307042B (en) * | 2007-05-18 | 2011-04-20 | 中国石油化工股份有限公司 | Method for producing 1,4-butanediol and coproducing tetrahydrofuran, and gamma-butyrolactone |
| 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 |
| CN103100393A (en) * | 2011-11-09 | 2013-05-15 | 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 |
| CN103566945A (en) * | 2012-07-23 | 2014-02-12 | 上海焦化有限公司 | Preparation method for producing efficient copper-manganese-aluminium catalyst for preparing 1, 4-butanediol |
| 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 |
| CN103769157B (en) * | 2012-10-24 | 2015-07-22 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN103769157A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN103801321A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Catalyst for preparing 1,4-butanediol and preparation method |
| CN103801321B (en) * | 2012-11-07 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of catalyst for the preparation of BDO and preparation method |
| CN103641682B (en) * | 2013-11-06 | 2015-04-22 | 上海交通大学 | Method of preparing glycol by utilization of biomass derivative glycolide |
| CN103641682A (en) * | 2013-11-06 | 2014-03-19 | 上海交通大学 | Method of preparing glycol by utilization of biomass derivative glycolide |
| CN104399484A (en) * | 2014-10-20 | 2015-03-11 | 中科合成油淮南催化剂有限公司 | Catalyst for [gamma]-butyrolactone preparation through dimethyl maleate hydrogenation, and preparation method thereof |
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