CN1286142A - Catalyst for preparing 1,4-butanediol by gas-phase hydrogenation of dialkyl maleate and/or dialkyl succinate - Google Patents
Catalyst for preparing 1,4-butanediol by gas-phase hydrogenation of dialkyl maleate and/or dialkyl succinate Download PDFInfo
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- CN1286142A CN1286142A CN99113206A CN99113206A CN1286142A CN 1286142 A CN1286142 A CN 1286142A CN 99113206 A CN99113206 A CN 99113206A CN 99113206 A CN99113206 A CN 99113206A CN 1286142 A CN1286142 A CN 1286142A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
A catalyst for preparing 1,4-butanediol by gas-phase hydrogenation of dialkyl maleate and/or dialkyl succinate features its chemical formula: CuZnaMnbAlcOx, where a=0.1-10, b=0.05-5 and C=0.05-5. Its advantages are no Cr element which can pollute environment, and excellent catalytic activity and selectivity.
Description
The invention relates to maleic acid alkyl ester and/or succinic acid dialkyl ester gas phase hydrogenation system 1, the catalyzer of 4-butyleneglycol, more particularly, be maleic acid alkyl ester and/or succinic acid dialkyl ester gas phase hydrogenation system 1 about containing Cu, Zn, Mn, Al, the catalyzer of 4-butyleneglycol (BDO).1,4-BDO is a kind of important basic Organic Chemicals, be mainly used in and produce polybutylene terephthalate (PBT), urethane, gamma-butyrolactone (GBL) and tetrahydrofuran (THF) (THF), alkynes aldehyde method is still so far produces 1 in the world, the main method of 4-BDO, but because as the increase of the normal butane residual content of gasoline blend composition, thereby stimulated people to make the exploration of the new purposes of high added value petrochemicals by it, the development for preparing the MALEIC ANHYDRIDE technology along with n butane oxidation, adopting the base metal mixed oxide is catalyzer, make 1 from the maleate gas phase hydrogenation, the technology of 4-BDO develops rapidly.
(EPO143634, WO88/00937 WO86/03189) disclose with containing the Cu-Cr catalyzer at 150～240 ℃, 25～75bar, H Davy Mckee
2/ ester ratio is 150～800: 1 (mol), and raw material liq volume charging air speed (LHSV) is 0.1～0.6hr
-1, adopt gas phase hydrogenation to make 1,4-BDO, and the method for coproduction GBL and THF by diethyl maleate and/or diethyl succinate.It is a kind of 1 that CN1116616A discloses, and the preparation method of 4-butyleneglycol is to be raw material with maleic acid alkyl ester and/or succinic acid dialkyl ester, is Cu at general formula
aZnCr
bM
cO
x(M is a kind of element that is selected from the IV B family, particularly Zr element) catalyzer carry out gas-phase catalytic hydrogenation prepared in reaction 1,4-BDO under existing.CN1138018A adopts CuCr
aZn
cO
x, CN1137944A CuCr
aMn
bBa
cM
dO
x(M=Al or Ti), CN1182639A CuCr
aZn
bTi
cO
x, CN1154872A CuZn
aCr
bM
cRe
dO
x(M=Mn or Zr) hydrogenation MALEIC ANHYDRIDE and/or its ester system 1,4-BDO.Above catalyzer all adopts chromium-containing oxide type catalyzer, though they have advantages of high catalytic activity and good selectivity, but the manufacturing of this class catalyzer and recovery all can have serious pollution to environment, the catalyzer that contains chromium must adopt appropriate method to handle, and particularly sexavalent chrome is difficult for being removed.USP5008235 (1991) discloses use Cu-Al-X (X=Mg, Zn, TiZr, Sn, Ni, Co or their mixture) result of hydrogenation diethyl maleate under the different reductive conditions, the Cu-Zn-Al catalyzer generates 1, the best result of 4-BDO selectivity is that catalyzer consists of Cu: Zn: Al=27: 12: 68 (wt%), at the reduction temperature-rise period is 0.1 ℃/min, 220 ℃ of reaction conditionss, 450psig, GHSV=15000/hr, during LHSV=0.6/hr, product consists of EtOH: THF: BuOH: GBL: 1,4-BDO: DES=51.9: 36: 0.4: 20.7: 15.3: 6.3 (wt%), activity of such catalysts and 1,4-BDO selectivity are all not really high.
The object of the present invention is to provide a kind of maleic acid alkyl ester and/or succinic acid dialkyl ester gas phase hydrogenation system 1 of being used for, the catalyzer of 4-butyleneglycol, this catalyzer does not contain the Cr element that environment is produced pollution, and has excellent catalytic activity, selectivity.
Specifically, catalyzer of the present invention has following composition: CuZn
aMn
bAl
cO
x, a=0.1～10 wherein, b=0.05～5, c=0.05～5 are represented the atomicity of Zn, Mn, Al respectively, are for satisfying the needed oxygen atomicity of other element valence requirement.
Catalyzer of the present invention makes with coprecipitation method, the precursor that is about to Cu, Zn, Mn and Al is scattered in the deionized water in required ratio, be heated to 50 ℃ from room temperature, stir down with alkali precipitation to pH=3.0～8.0, filter washing then, collecting precipitation, at 100～120 ℃ of drying 2～8hr,, get catalyzer again at 250～550 ℃ of following roasting 2～24hr.
The precursor of the Cu that uses among the present invention, Zn, Mn and Al can be their soluble salt, for example nitrate, vitriol or hydrochloride etc., and wherein preferred their nitrate, the precursor of described Mn also can be used MnO
2Or MnCO
3
The alkali that adopts among the present invention can be alkali metal hydroxide, alkaline carbonate or both mixtures, also can be ammoniacal liquor, wherein preferred alkali metal carbonate.
Catalyzer of the present invention needs to carry out in reactor or outside the reactor catalyzer being carried out prereduction before use, and reductive agent can be H
2, reducing gas such as CO, also can be with inert gas dilution reducing gas.Reduction can be undertaken by known method, for example under 0.1～4.0MPa pressure, every liter of catalyzer is reduced 12～36 hours at 250 ℃ with 5000～10000 liters/hour flow velocity feeding reducing gas.
The reaction raw materials that is suitable for catalyzer of the present invention can be a maleic acid alkyl ester, also can be succinic acid dialkyl ester, or both mixtures.
Catalyzer of the present invention is used for maleic acid alkyl ester and/or succinic acid dialkyl ester gas phase hydrogenation system 1, and during the 4-butyleneglycol, suitable temperature is 180～280 ℃, and reaction pressure is 3.0～10.0MPa, H
2/ ester ratio is 80～400: 1 (mol), the liquid air speed LHSV=0.1～2.0hr of ester
-1
Catalyzer provided by the invention has excellent catalytic activity, selectivity, and continuous operation is after 1500 hours, and at hydrogen pressure 6.0MPa, during 227 ℃ of top temperatures, transformation efficiency is still up to 99%, 1,4-butyleneglycol selectivity 65.5%.
Following example is used to illustrate in greater detail the present invention, but the present invention is not limited to this.
Example 1～12
Preparation of catalysts and pre-treatment: with 75.0g Cu (NO
3)
23H
2O (chemical pure, Beijing Chemical Plant), 89.3g Zn (NO
3)
26H
2O, 9.6g Mn (NO
3)
26H
2O, 12.5g Al (NO
3)
39H
2O joins in the 3L deionized water, is heated to 50 ℃ under stirring then, keeps dissolving to add 1M Na for 50 ℃
2CO
3Solution to pH=7～8, continue to stir 1 hour, agingly filter, wash to mother liquor neutrality more than 4 hours, 100～120 ℃ of dry 4hr, 350 ℃ of roasting 4hr, the mixed oxide of catalyst solid Cu, Zn, Mn, Al.
(this catalyst solid of 1.0～2.0mm) internal diameter of packing into is φ 12mm, and length overall is the stainless steel tubular type reactor middle part of 370mm, the porcelain ring of respectively packing into up and down to get 17ml (23.5g) granularity and be 10～18 orders.Use earlier the nitrogen purging reactive system, normal pressure feeds 10: 90 (vol) H of general hydrogen (producing 504 reductor deoxidations through the Dalian Chemistry and Physics Institute) down
2: N
2Gas mixture, be warming up to 120 ℃ with the heat-up rate of 50 ℃/hr, be warming up to 150 ℃ with 30 ℃/hr then, be warming up to 190 ℃ with 20 ℃/hr, be warming up to 208 ℃ with 8 ℃/br, at 208 ℃ of constant temperature reduction 8hr, again with the H of 50: 50 (vol)
2: N
2Gas mixture reduction 1hr all is general hydrogen reduction 2hr.Use the H of 10: 90 (vol) instead
2: N
2Gas mixture, in 1hr, reactor is warming up to 250 ℃, uses general hydrogen reduction 1hr instead behind the reduction 1hr, be cooled to 220 ℃, hydrogen pressure is risen to 4.0MPa, reductase 12 4hr is warming up to 230 ℃, 4.0MPa pressure, reduction 1hr, temperature of reactor is transferred to temperature of reaction (said temperature of reaction is the top temperature point), press the listed condition of table 1, H
2: the general hydrogen of deoxidation of ester=100: 1 (mol) and dibutyl maleate (the laboratory self-control contains dibutylester 97wt%) feed in the reactor and react, and reaction product is analyzed with 102 gas chromatographs that analytical instrument factory in Shanghai produces.
Example 13
Preparation of catalysts and pre-treatment: with 260g Cu (NO
3)
23H
2O (chemical pure, Beijing Chemical Plant), 298g Zn (NO
3)
26H
2O, 32g Mn (NO
3)
26H
2O, 60g Al (NO
3)
39H
2O joins in the 10L deionized water, is heated to 50 ℃ under stirring then, keeps solution to add 1M Na for 50 ℃
2CO
3Solution to pH=7～8, continue to stir 1 hour, agingly filter, wash to mother liquor neutrality more than 4 hours, 100～120 ℃ of dry 4hr, 350 ℃ of roasting 4hr, the mixed oxide of catalyst solid Cu, Zn, Mn, Al.
This catalyst solid of getting the 80ml granularity and being φ 5mm * 3mm internal diameter of packing into is φ 25mm, and length overall is the stainless steel tubular type reactor middle part of 370mm, and the porcelain ring of respectively packing into up and down adopts the described method of reducing of precedent to catalyst pretreatment.
Temperature of reactor is transferred to temperature of reaction, press the listed condition of table 2, general hydrogen of deoxidation and dibutyl maleate (the laboratory self-control contains dibutylester 96.2wt%) are fed in the reactor and reacts, and reaction product is analyzed with 102 gas chromatographs that analytical instrument factory in Shanghai produces.
The reaction conditions of table 1 example 1～12 and test-results
The condition of the longevity test of table 2. example 13 and result
Claims (8)
1. one kind is used for maleic acid alkyl ester and/or succinic acid dialkyl ester gas phase hydrogenation system 1, and the catalyzer of 4-butyleneglycol is characterized in that: CuZn
aMn
bAl
cO
x, a=0.1～10 wherein, b=0.05, c=0.05～5 are represented the atomicity of Zn, Mn, Al respectively, are for satisfying the needed oxygen atomicity of other element valence requirement.
2. a described maleic acid alkyl ester and/or succinic acid dialkyl ester gas phase hydrogenation system 1 of being used for of claim 1, the Preparation of catalysts method of 4-butyleneglycol, it is characterized in that: the precursor of Cu, Zn, Mn and Al is scattered in the deionized water in required ratio, is heated to 50 ℃, stir with alkali precipitation to pH=3.0～8.0 from room temperature, filter then, washing, collecting precipitation is at 100～120 ℃ of drying 2～8hr, at 250～550 ℃ of following roasting 2～24hr, get catalyzer again.
3. according to the described Preparation of catalysts method of claim 2, it is characterized in that: the precursor of Cu, Zn, Mn and Al is the soluble salt of each element.
4. according to the described Preparation of catalysts method of claim 3, it is characterized in that: the precursor of Cu, Zn, Mn and Al is the nitrate of each element.
5. according to the described Preparation of catalysts method of claim 2, it is characterized in that: the precursor of Mn is MnO
2
6. according to the described Preparation of catalysts method of claim 2, it is characterized in that: the precursor of Mn is MnCO
3
7. according to the described Preparation of catalysts method of claim 2, it is characterized in that: said alkali is ammoniacal liquor alkali metal hydroxide and/or alkaline carbonate.
8. the described catalyzer of claim 1 is used for maleic acid alkyl ester and/or succinic acid dialkyl ester gas phase hydrogenation system 1, the 4-butyleneglycol, and suitable temperature is 180～280 ℃, reaction pressure is 3.0～10.0MPa, H
2/ ester ratio is 80～400: 1 (mol), the liquid air speed LHSV=0.1～2.0hr of ester
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113206A CN1117622C (en) | 1999-08-27 | 1999-08-27 | Catalyst for preparing 1,4-butanediol by gas-phase hydrogenation of dialkyl maleate and/or dialkyl succinate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113206A CN1117622C (en) | 1999-08-27 | 1999-08-27 | Catalyst for preparing 1,4-butanediol by gas-phase hydrogenation of dialkyl maleate and/or dialkyl succinate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1286142A true CN1286142A (en) | 2001-03-07 |
| CN1117622C CN1117622C (en) | 2003-08-13 |
Family
ID=5276420
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99113206A Expired - Fee Related CN1117622C (en) | 1999-08-27 | 1999-08-27 | Catalyst for preparing 1,4-butanediol by gas-phase hydrogenation of dialkyl maleate and/or dialkyl succinate |
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|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102302937A (en) * | 2011-07-06 | 2012-01-04 | 上海焦化有限公司 | Catalyst for preparing neopentyl glycol by hydrogenation of hydroxypivalaldehyde and preparation method thereof |
| CN102784651A (en) * | 2012-08-24 | 2012-11-21 | 北京旭阳化工技术研究院有限公司 | High selectivity hydrogenation catalyst for preparing 1,4-butanediol by hydrogenation of dimethyl succinate as well as preparation method and application of high selectivity hydrogenation catalyst |
| US9168509B2 (en) | 2011-11-09 | 2015-10-27 | China Petroleum & Chemical Corp. | Hydrogenation catalysts and the preparation processes thereof |
| CN106607044A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst and method for preparing 1, 6-hexanediol by hydrogenation of dialkyl 1, 6-adipate |
-
1999
- 1999-08-27 CN CN99113206A patent/CN1117622C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102302937A (en) * | 2011-07-06 | 2012-01-04 | 上海焦化有限公司 | Catalyst for preparing neopentyl glycol by hydrogenation of hydroxypivalaldehyde and preparation method thereof |
| US9168509B2 (en) | 2011-11-09 | 2015-10-27 | China Petroleum & Chemical Corp. | Hydrogenation catalysts and the preparation processes thereof |
| CN102784651A (en) * | 2012-08-24 | 2012-11-21 | 北京旭阳化工技术研究院有限公司 | High selectivity hydrogenation catalyst for preparing 1,4-butanediol by hydrogenation of dimethyl succinate as well as preparation method and application of high selectivity hydrogenation catalyst |
| CN106607044A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst and method for preparing 1, 6-hexanediol by hydrogenation of dialkyl 1, 6-adipate |
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| Publication number | Publication date |
|---|---|
| CN1117622C (en) | 2003-08-13 |
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