CN103801321A - Catalyst for preparing 1,4-butanediol and preparation method - Google Patents
Catalyst for preparing 1,4-butanediol and preparation method Download PDFInfo
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- CN103801321A CN103801321A CN201210440185.9A CN201210440185A CN103801321A CN 103801321 A CN103801321 A CN 103801321A CN 201210440185 A CN201210440185 A CN 201210440185A CN 103801321 A CN103801321 A CN 103801321A
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Abstract
The invention discloses a catalyst for preparing 1,4-butanediol and a preparation method. The catalyst adopts zinc oxide as a carrier, adopts copper and nickel as active components, adopts M as an auxiliary agent, is a Cu-Ni-Zn-M-O catalyst, wherein M is manganese or magnesium. The catalyst comprises the following metal elements by weight: 30 wt%-60 wt% of copper elements, 2 wt%-10 wt% of nickel elements, 20 wt%-40 wt% of zinc elements, 2 wt%-10 wt% of M elements. The preparation method comprises the following steps: preparing a mixed solution of soluble salts of Cu, Ni, Zn, and M, stirring and mixing with a precipitating agent solution at 50-70 DEG C, controlling the pH value of 7-9, stirring for 1-3 hours, heating to 80-90 DEG C, aging for 2-10 hours, filtering to obtain a precipitate, and performing drying, roasting and molding to obtain the product. The catalyst of the invention has the advantages of high conversion rate, good product selectivity, long service life, low cost, and the like, and the preparation method is simple and easy to operate.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of catalyst for the preparation of BDO and preparation method.
Background technology
BDO (BDO) is a kind of important Organic Chemicals, mainly for the production of polybutylene terephthalate (PBT) (PBT), polyurethane (PU), gamma-butyrolacton (GBL) and oxolane (THF).In recent years, due to increasing rapidly of thermoplastic elastic fiber and elastomer demand, in great demand as the polytetramethylene ether diol (PTMEG) of monomer and PTMG (PTMG), makes also rapid growth of upstream raw material BDO demand.Therefore, the technology of Development and Production BDO has great importance.
The production line of BDO has following several: (1) Reppe method take acetylene and formaldehyde as raw material; (2) hydrogenation technique take cis-butenedioic anhydride as raw material; (3) the gas phase hydrogenation technique of maleate; (4) synthesis technique take propylene as raw material; (5) synthesis technique take butadiene as raw material.
CN1850328, CN101502803 disclose the catalyst of two kinds of one-part forms by maleate Hydrogenation BDO.But do not adopt pure dimethyl maleate raw material, but using the mixture of dimethyl maleate and methyl alcohol as raw material (methyl alcohol: dimethyl maleate=1:4).The in the situation that of same treatment amount, comparatively speaking, the productive rate of product is low, and the charging of device and separating energy consumption increase, and the energy consumption of whole device is increased greatly, and production cost raises.
CN1286142 discloses a kind of Cu-Zn-Mn-Al catalyst of succinic acid dialkyl ester Hydrogenation BDO, adopts one-part form reaction.But product BDO is high selectivity is 80.4%, await improving.
It is the method that raw material is prepared BDO co-producing tetrahydrofuran and gamma-butyrolacton that CN101891592, CN101307042 disclose by dialkyl maleate, all adopts two-part hydrogenation technique.Main feature, in synthetic reaction section, adopts two kinds of different catalyst, two kinds of catalyst layerings or point device filling.With one-part form reacting phase ratio, there is Catalyst Production and synthesis technique very complicated shortcoming.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of Catalysts and its preparation method for the preparation of BDO.Catalyst of the present invention has that conversion ratio is high, product selectivity good, the life-span is long, low cost and other advantages, and preparation method is simple, easy operating.
For the preparation of a catalyst for BDO, take zinc oxide as carrier, copper, nickel are active component, and M is auxiliary agent, Cu-Ni-Zn-M-O type catalyst, and wherein M is manganese or magnesium.In catalyst, the weight content of metallic element is: copper 30wt%～60wt%, and nickel element 2wt%～10wt%, zinc element is 20wt% ~ 40wt%, M element 2wt%～10wt%.
The preparation method of a kind of catalyst for the preparation of BDO of the present invention, comprises following content:
The soluble-salt of Cu, Ni, Zn and M is made into mixed solution, under 50～70 ℃ of stirrings, mix with precipitant solution, controlling pH value is 7～9, stirs 1～3 hour, is warming up to 80～90 ℃, aging 2～10 hours, filtration is precipitated thing, and sediment, through washing, is dried, roasting, moulding obtains product.
In the inventive method, soluble-salt mixed solution can directly mix with precipitant solution hybrid mode, also can adopt the mode that also drip adds.
Soluble-salt described in the present invention can be any in nitrate, acetate, sulfate and oxalates.
Precipitating reagent described in the inventive method can be one or more in sodium carbonate, NaOH, ammonium carbonate, carbonic hydroammonium and ammoniacal liquor.
In the inventive method, drying condition is: at 100～120 ℃, dry 8～16 hours, roasting condition is: roasting 6～10 hours at 700～1000 ℃.
Catalyst of the present invention can be applied to dimethyl maleate Hydrogenation and react for BDO.Catalyst of the present invention is applied to dimethyl maleate and prepares BDO reaction, and process conditions are preferably: reaction pressure is 3～6MPa, and reaction temperature is 180～240 ℃, and hydrogen ester mol ratio is 50:1～300:1, and the liquid hourly space velocity (LHSV) of ester is 0.2～2h
-1.Catalyst of the present invention needs reduction activation before use, the gas used that reduces be dilution after hydrogen (as H
2/ N
2, H
2/ Ar gaseous mixture), pressure is 0.1～2 MPa, temperature is 150～300 ℃.
Catalyst of the present invention is take the good copper of Hydrogenation, nickel as active component.In catalyst, add the second active component nickel, catalyst hydrogenation performance is improved, especially selective hydrogenation ability improves, and is conducive to the generation of object product BDO, improves the activity, selective of catalyst.High-temperature roasting at 700～1000 ℃, improves the acid resistance of catalyst, has extended the service life of catalyst.Preparing BDO when reaction for dimethyl maleate, the conversion ratio of ester approaches 100%, alcohol selectively on average more than 80%.Catalyst was through the life experiment of 1500 hours, and the activity and selectivity of catalyst remains unchanged substantially.
embodiment
Further describe technology contents of the present invention and effect below by specific embodiment, but therefore do not limit the present invention.
Catalyst provided by the invention can be used following method evaluation.
Catalyst powder after roasting is made material to 10～20 orders, investigates the activity of catalyst in micro fixed-bed reactor.Adopt reducing process in device, with H
2/ N
2gaseous mixture carries out activity rating after 180 ℃ of reduction.After reaction raw materials is mixed with hot hydrogen in required ratio, enter and answer device.After product condensation, use its composition of gas chromatographic analysis.
Embodiment 1
By 11gCu (NO
3)
23H
2o, 9.8gZn (NO
3)
26H
2o, 2gNi (NO
3)
26H
2o and 1.5g Mn (NO
3)
24H
2o is dissolved in 100mL water and is made into metal ion solution; 13.3gNa
2cO
3be dissolved in 120mL water and be precipitated agent solution.60 ℃ of water-baths drip two kinds of solution simultaneously under stirring, control pH value 7～9.Dropwise rear continuation and stir 2 hours, be warming up to 80 ℃ aging 2 hours.Then suction filtration, washing, 110 ℃ dry 10 hours, 900 ℃ of roastings 8 hours, obtain product A-1.In catalyst, each component element quality percentage composition is: Cu 40wt%, Ni 5.5wt%, Mn 4.5wt%, Zn 30wt%.
Comparative example 1
By 12gCu (NO
3)
23H
2o, 9.8gZn (NO
3)
26H
2o and 1.5g Mn (NO
3)
24H
2o is dissolved in 100mL water and is made into metal ion solution; 13.3gNa
2cO
3be dissolved in 120mL water and be precipitated agent solution.60 ℃ of water-baths drip two kinds of solution simultaneously under stirring, control pH value 7～9.Dropwise rear continuation and stir 2 hours, be warming up to 80 ℃ aging 2 hours.Then suction filtration, washing, 110 ℃ dry 10 hours, 900 ℃ of roastings 8 hours, obtain product D-1.In catalyst, each component element quality percentage composition is: Cu 45.5wt%, Mn 4.6wt%, Zn 30wt%.
Embodiment 2
By 10gCu (NO
3)
23H
2o, 9.8gZn (NO
3)
26H
2o, 2.5gNi (NO
3)
26H
2o and 2g Mn (NO
3)
24H
2o is dissolved in 100mL water and is made into metal ion solution; 13.3gNa
2cO
3be dissolved in 120mL water, be precipitated agent solution.60 ℃ of water-baths drip two kinds of solution simultaneously under stirring, control pH value 7～9.Dropwise rear continuation and stir 2 hours, be warming up to 80 ℃ aging 2 hours.Then suction filtration, washing, 110 ℃ dry 10 hours, 900 ℃ of roastings 8 hours, obtain product A-2.In catalyst, each component element quality percentage composition is: Cu 37wt%, Ni 6.9wt%, Mn 6.1wt%, Zn 30wt%.
Embodiment 3
By 12.5gCu (NO
3)
23H
2o, 10.2gZn (NO
3)
26H
2o, 1.5gNi (NO
3)
26H
2o and 1g Mn (NO
3)
24H
2o is dissolved in 100mL water and is made into metal ion solution; 13.3gNa
2cO
3be dissolved in 120mL water and be precipitated agent solution.60 ℃ of water-baths drip two kinds of solution simultaneously under stirring, control pH value 7～9.Dropwise rear continuation and stir 2 hours, be warming up to 80 ℃ aging 2 hours.Then suction filtration, washing, 110 ℃ dry 10 hours, 900 ℃ of roastings 8 hours, obtain product A-3.In catalyst, each component element quality percentage composition is: Cu 43wt%, Ni 3.9wt%, Mn 2.9wt%, Zn 30wt %.
Comparative example 2
By 12.5gCu (NO
3)
23H
2o, 10.2gZn (NO
3)
26H
2o, 1.5gNi (NO
3)
26H
2o and 1g Mn (NO
3)
24H
2o is dissolved in 100mL water and is made into metal ion solution; 13.3gNa
2cO
3be dissolved in 120mL water and be precipitated agent solution.60 ℃ of water-baths drip two kinds of solution simultaneously under stirring, control pH value 7～9.Dropwise rear continuation and stir 2 hours, be warming up to 80 ℃ aging 2 hours.Then suction filtration, washing, 110 ℃ dry 10 hours, 450 ℃ of roastings 8 hours, obtain product D-2.In catalyst, each component element quality percentage composition is: Cu 43wt%, Ni 3.9wt%, Mn 2.9wt%, Zn 30wt %.
Embodiment 4
By 12.5gCu (NO
3)
23H
2o, 10.2gZn (NO
3)
26H
2o, 1gNi (NO
3)
26H
2o and 2.5g Mn (NO
3)
24H
2o is dissolved in 100mL water and is made into metal ion solution, 13.3gNa
2cO
3be dissolved in 120mL water and be precipitated agent solution.60 ℃ of water-baths drip two kinds of solution simultaneously under stirring, control pH value 7～9.Dropwise rear continuation and stir 2 hours, be warming up to 80 ℃ aging 2 hours.Then suction filtration, washing, 110 ℃ dry 10 hours, 900 ℃ of roastings 8 hours, obtain product A-4.In catalyst, each component element quality percentage composition is: Cu 41wt%, Ni 2.5wt%, Mn 7wt%, Zn 28wt%.
Embodiment 5
By 20gCu (NO
3)
23H
2o, 10.2gZn (NO
3)
26H
2o, 2.0gNi (NO
3)
26H
2o and 2.5g Mg (NO
3)
26H
2o is dissolved in 100mL water and is made into metal ion solution, 13.3gNa
2cO
3be dissolved in 120mL water and be precipitated agent solution.60 ℃ of water-baths drip two kinds of solution simultaneously under stirring, control pH value 7～9.Dropwise rear continuation and stir 3 hours, be warming up to 80 ℃ aging 2 hours.Then suction filtration, washing, is dried 10 hours, 8 hours A-5 of 900 ℃ of roastings at 110 ℃.In catalyst, each component element quality percentage composition is: Cu 51wt%, Ni 3.9wt%, Mg 2.2wt%, Zn 22wt%.
Embodiment 6
By 10gCu (NO
3)
23H
2o, 10.2gZn (NO
3)
26H
2o, 3gNi (NO
3)
26H
2o and 3g Mn (NO
3)
2, be dissolved in 100mL water and be made into metal ion solution, 13.3gNa
2cO
3be dissolved in 120mL water, be precipitated agent solution.60 ℃ of water-baths drip two kinds of solution simultaneously under stirring, control pH value 7～9.Dropwise rear continuation and stir 2 hours, be warming up to 80 ℃ aging 2 hours.Then suction filtration, washing, 110 ℃ dry 10 hours, 900 ℃ of roastings 8 hours, obtain product A-6.In catalyst, each component element quality percentage composition is: Cu 34wt%, Ni 7.9wt%, Mn 8.6wt%, Zn 29wt%.
Embodiment 7
Take dimethyl maleate as raw material, in fixed bed reaction, carry out gas phase hydrogenation reaction, respectively catalyst A-1, A-2, A-3, A-4, A-5, A-6 and D-1 are evaluated, process conditions are: 200 ℃ of temperature, pressure 5.0MPa, hydrogen ester mol ratio is 200:1, and the volume space velocity of dimethyl maleate is 0.3h
-1.Evaluation result is in table 1.
Embodiment 8
Take dimethyl maleate as raw material, in fixed bed reaction, carry out gas phase hydrogenation reaction.Carry out 1500 hours life experiments with catalyst A-3, D-2, process conditions are: pressure 5.0MPa, and hydrogen ester mol ratio is 200:1, the volume space velocity of dimethyl maleate is 0.3h
-1.Appreciation condition the results are shown in Table 2.
Table 1 appreciation condition and result.
| Catalyst numbering | Ester conversion rate (%) | Alcohol selective (%) |
| A-1 | 100 | 84.8 |
| A-2 | 100 | 84.2 |
| A-3 | 100 | 85.3 |
| A-4 | 100 | 82.7 |
| A-5 | 100 | 86.9 |
| A-6 | >99 | 79.2 |
| D-1 | >99 | 78.6 |
Table 2 appreciation condition and result.
| The duration of runs (h) | Reaction temperature (℃) | Reaction pressure (MPa) | Liquid hourly space velocity (LHSV) (h -1） | Hydrogen ester mol ratio (mol/mol) | A-3 ester conversion rate (%) | A-3 alcohol selective (%) | D-2 ester conversion rate (%) | D-2 alcohol selective (%) |
| 100 | 200 | 5.0 | 0.3 | 200 | 100 | 85.3 | 100 | 85.3 |
| 450 | 200 | 5.0 | 0.3 | 200 | 100 | 85.3 | 100 | 83.7 |
| 600 | 200 | 5.0 | 0.3 | 200 | 100 | 85.0 | >99 | 82.9 |
| 800 | 210 | 5.0 | 0.3 | 200 | 100 | 85.6 | >99 | 83.2 |
| 1000 | 210 | 5.0 | 0.3 | 200 | 100 | 85.2 | 98 | 82.6 |
| 1150 | 210 | 5.0 | 0.3 | 200 | 100 | 85.0 | 97 | 81.5 |
| 1300 | 220 | 5.0 | 0.3 | 200 | 100 | 85.6 | 97 | 81.2 |
| 1500 | 220 | 5.0 | 0.3 | 200 | 100 | 85.2 | 95 | 79.4 |
| 1650 | 225 | 5.0 | 0.3 | 200 | >99 | 85.3 | 95 | 78.8 |
Find out from table 1 and table 2 data, the conversion ratio of this catalyst is high, and selective good high, stable performance compared with prior art has raising by a relatively large margin.
Claims (9)
1. for the preparation of a catalyst for BDO, it is characterized in that: take zinc oxide as carrier, copper, nickel are active component, and M is auxiliary agent, Cu-Ni-Zn-M-O type catalyst, wherein M is manganese or magnesium; In catalyst, the weight content of metallic element is: copper 30wt%～60wt%, and nickel element 2wt%～10wt%, zinc element is 20wt% ~ 40wt%, M element 2wt%～10wt%.
2. the preparation method of a catalyst claimed in claim 1, it is characterized in that comprising following content: the soluble-salt of Cu, Ni, Zn and M is made into mixed solution, under 50～70 ℃ of stirrings, mixes with precipitant solution, controlling pH value is 7～9, stir 1～3 hour, be warming up to 80～90 ℃, aging 2～10 hours, filter and be precipitated thing, sediment is through washing, dry, roasting, moulding obtains product.
3. preparation method according to claim 2, is characterized in that: the mode that soluble-salt mixed solution and precipitant solution hybrid mode adopt and drip adds.
4. preparation method according to claim 2, is characterized in that: described soluble-salt is any in nitrate, acetate, sulfate and oxalates.
5. preparation method according to claim 2, is characterized in that: described precipitating reagent is one or more in sodium carbonate, NaOH, ammonium carbonate, carbonic hydroammonium and ammoniacal liquor.
6. preparation method according to claim 2, is characterized in that: described drying condition is: at 100～120 ℃, dry 8～16 hours, roasting condition is: roasting 6～10 hours at 700～1000 ℃.
A catalyst claimed in claim 1 at dimethyl maleate Hydrogenation for the application in BDO reaction.
8. application according to claim 7, is characterized in that hydrogenation technique condition is: reaction pressure is 3～6MPa, and reaction temperature is 180～240 ℃, and hydrogen ester mol ratio is 50:1～300:1, and the liquid hourly space velocity (LHSV) of ester is 0.2～2h
-1.
9. according to the application described in claim 6 or 7, it is characterized in that catalyst needs reduction before use, the gas used that reduces is the hydrogen after dilution, and pressure is 0.1～2Mpa, and temperature is 150～300 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108114727A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its preparation method and application |
| CN111054324A (en) * | 2020-02-25 | 2020-04-24 | 贵州大学 | MnZnOx solid solution structure catalyst and preparation method thereof |
| CN114685242A (en) * | 2022-04-19 | 2022-07-01 | 天津大学 | Method for producing 1, 4-butanediol by one-step liquid phase hydrogenation of dimethyl maleate |
| CN115368208A (en) * | 2022-07-25 | 2022-11-22 | 朱义峰 | Coupled electrolytic hydrogen production-storage system and process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58193738A (en) * | 1982-05-06 | 1983-11-11 | Mitsubishi Heavy Ind Ltd | Catalyst for production of gas enriched with hydrogen |
| CN1138018A (en) * | 1995-06-14 | 1996-12-18 | 中国石油化工总公司 | Catalyst(A) for preparation of 1,4-butanediol by gas-phase hydrogenation |
| CN1493569A (en) * | 2002-10-30 | 2004-05-05 | 中国石油化工股份有限公司 | Method of preparing gamma-butyrolactone and/or 1,4-butanediol using chromium less catalyst |
-
2012
- 2012-11-07 CN CN201210440185.9A patent/CN103801321B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58193738A (en) * | 1982-05-06 | 1983-11-11 | Mitsubishi Heavy Ind Ltd | Catalyst for production of gas enriched with hydrogen |
| CN1138018A (en) * | 1995-06-14 | 1996-12-18 | 中国石油化工总公司 | Catalyst(A) for preparation of 1,4-butanediol by gas-phase hydrogenation |
| CN1493569A (en) * | 2002-10-30 | 2004-05-05 | 中国石油化工股份有限公司 | Method of preparing gamma-butyrolactone and/or 1,4-butanediol using chromium less catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 卢伟京等: "Pd（Ni）对铜基催化剂的调变及对顺酐选择性加氢产物的调控", 《催化学报》, vol. 23, no. 5, 30 September 2002 (2002-09-30) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108114727A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its preparation method and application |
| CN108114727B (en) * | 2016-11-28 | 2020-08-11 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
| CN111054324A (en) * | 2020-02-25 | 2020-04-24 | 贵州大学 | MnZnOx solid solution structure catalyst and preparation method thereof |
| CN114685242A (en) * | 2022-04-19 | 2022-07-01 | 天津大学 | Method for producing 1, 4-butanediol by one-step liquid phase hydrogenation of dimethyl maleate |
| 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 |
| CN115368208A (en) * | 2022-07-25 | 2022-11-22 | 朱义峰 | Coupled electrolytic hydrogen production-storage system and process |
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| CN103801321B (en) | 2016-01-20 |
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