CN103769110B - A kind of BDO dehydrogenation gamma-butyrolacton catalyst and its preparation method and application - Google Patents
A kind of BDO dehydrogenation gamma-butyrolacton catalyst and its preparation method and application Download PDFInfo
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Abstract
Open a kind of Isosorbide-5-Nitrae butanediol dehydrogenation gamma butyrolactone catalyst of the present invention and preparation method thereof.This catalyst is the composite oxides of Cu Zn Ti, and catalyst forms in terms of weight content: CuO 30%～55%, ZnO 30%～55%, TiO2 5%～15%；It is preferably CuO 40%～50%, ZnO 40%～50%, TiO2 8%～12%.A kind of Isosorbide-5-Nitrae butanediol dehydrogenation gamma butyrolactone catalyst, comprises the steps: the mixed solution containing Cu, Zn, Ti for (1) preparation and precipitant solution；(2) containing the mixed solution of Cu, Zn, Ti and precipitant solution and flow addition and carry out coprecipitation reaction, controlling precipitation temperature in precipitation process is 70 90 DEG C, and pH value is 7.5 9；(3) precipitation carries out aging after terminating, and control aging temperature is higher than precipitation temperature 20 50 DEG C, and aging pH value is higher than precipitation pH value 0.5 2, and ageing time is 5 20h；(4) material after aging prepares final catalyst after suction filtration, washing, drying, roasting, shaping.Not containing Cr in this catalyst, activity is high, and carbon accumulation resisting ability is strong, can long-time steady operation.
Description
Technical field
The present invention relates to a kind of BDO dehydrogenation gamma-butyrolacton catalyst and its preparation method and application.
Background technology
Gamma-butyrolacton (is called for short γ-BL or GBL), calls as GBL.Himself structure is a kind of containing 5-membered heterocycles
Compound, gamma-butyrolacton is a kind of colourless liquid, has the smell of similar acetone, has high boiling point and high solvability.
Its reactivity worth is good, and electrical conductivity is high, and good stability uses safety.As a kind of important organic solvent, gamma-butyrolacton is extensive
For many aspects such as petroleum industry, medicine, synthetic fibers, synthetic resin, agricultural chemicals.As a kind of important fine chemistry industry and having
Machine industrial chemicals, is mainly used in the products such as synthesis of pyrrolidine ketone, 1-METHYLPYRROLIDONE, vinyl pyrrolidone, and many
New purposes is constantly under development.The existing different processing technology routine of gamma-butyrolacton carries out industrial production, according to synthesis
Raw material is classified, and mainly has following three kinds of methods: furfural method, cis-butenedioic anhydride (MA) hydrogenation method and BDO (BDO) dehydriding.Furfural
Method process is complicated, relatively costly, loses the market competitiveness, and this method has been eliminated at present, and maleic anhydride hydrogenation method raw material is easy to get, and becomes
This is low, but in crude product, acidity is of a relatively high, and this brings certain impact to the separation of product and the quality of end-product.1,4-fourth
The accessory substance of glycol dehydriding is mainly oxolane (THF) and a small amount of butanol (BOL), and component is simple, and product is easily separated, closes
The gamma-butyrolacton quality better becoming, can meet the high request to gamma-butyrolacton quality as pharmaceutical raw material and battery electrolyte.
Based on BDO dehydrogenation gamma-butyrolacton used catalyst is with Cu-Cr series catalysts, such as United States Patent (USP)
5210229 employing Cu-Cr-Mn and/or Ba catalyst, add Alkali-Metal Na or K modified, although to reduce the acidity of catalyst,
Decrease dehydration, but reduce the activity of catalyst, need to improve reaction temperature and compensate (from 230 DEG C of raisings to 270
DEG C), as at 230 DEG C, H2/ alcohol (mole)=4:1, pressure 4kg/cm2(table), weight space velocity 3.0h-1When, BDO converts
Rate 91.39%, gamma-butyrolacton selectively 98.98%, oxolane selectively 0.14%, improve temperature to 270 DEG C, above three then
It is respectively 99.49%, 97.93% and 0.17%.61-246173(1986 as clear in Japan Patent), use Cu-Cr-Zn catalyst,
It forms Cu:Cr:Zn=35:68:38, and when reaction temperature 228 DEG C, in product, gamma-butyrolacton content is 98.2wt%.Japan is specially
Profit JP03,232,874 (1991), use Cu-Cr-Ba catalyst, wherein Cu:Cr:Ba=47:42:6, when 230 DEG C, Isosorbide-5-Nitrae-
Butanediol conversion ratio 96.1mol%, gamma-butyrolacton selectively 95.1 mol%.
Composite oxide catalysts without Cr is mainly Cu-Zn, Cu-Zn-Al and Cu-Mn etc..This type of catalyst is at tool
Production procedure adds different auxiliary agents to improve the reactivity worth of catalyst.Such as CN1111168, used catalyst by
Cu-Zn-Al oxide matrix and be sprayed on it Pd or Pt composition, reaction temperature 190-290 DEG C, reaction pressure normal pressure,
Use this catalyst under the conditions of hydrogen alcohol mol ratio 1-6, BDO conversion ratio up to 100%, gamma-butyrolacton selectivity up to
97%.CN1304795, uses Cu-Zn-Al catalyst, and auxiliary agent is at least one, in reaction temperature 200-260 in BaO, Pd two kinds
DEG C, reaction pressure is less than 0.05MPa, liquid hourly space velocity (LHSV) 0.1-1.2h-1, BDO conversion ratio is up to 100%, and gamma-butyrolacton selects
Selecting property is more than 96%.CN99113276.9 discloses the preparation method of a kind of Cu-contained catalyst, cupric oxide in the catalyst obtaining
10%～90%, the oxide of co-catalysis composition is 0%～50%, and aluminum oxide is 5%～40%, includes 0.1%～4. simultaneously
The alkali metal oxide of 0%, this catalyst may be used for hydrogenation or the dehydrogenation reaction of organic reaction, and the scope described in this patent is very
Extensively, when the catalyst that embodiment obtains is for preparing gamma-butyrolacton, using effect is unsatisfactory, is mainly manifested in catalyst
Carbon accumulation resisting ability difference, activity cannot keep.
In the prior art, for the reaction that gamma-butyrolacton is prepared in BDO dehydrogenation, Cu-Cr and Cu-Mn system
Catalyst reaction better performances, carbon accumulation resisting ability is relatively strong, but during the side reaction such as dehydration more, produce more tetrahydrochysene furan
Mutter and n-butanol.Other Cr has adverse influence to environmental and human health impacts.Cu/SiO prepared by infusion process2Catalyst price
Costly.And Cu-Zn and Cu-Zn-Al composite oxide catalysts for BDO dehydrogenation prepare gamma-butyrolacton when, though
Having preferable reactivity worth, conversion ratio and selectivity are all better than Cu-Cr and Cu-Mn series catalysts, but the anti-carbon deposit of catalyst
Ability is poor, it is impossible to long-term operation.Therefore Cu-Zn and Cu-Zn-Al series catalysts cannot substitute Cu-Cr series catalysts completely,
Poor mainly due to the former carbon accumulation resisting ability in course of reaction, it is impossible to the reactivity having kept for a long time.
Content of the invention
For the deficiencies in the prior art, the present invention provide a kind of BDO dehydrogenation gamma-butyrolacton catalyst and
Preparation method and application.Not containing Cr in this catalyst, activity is high, and carbon accumulation resisting ability is strong, can long-time steady operation.
A kind of BDO dehydrogenation gamma-butyrolacton catalyst, this catalyst is the composite oxides of Cu-Zn-Ti, urges
Agent forms in terms of weight content: CuO 30%～55%, ZnO 30%～55%, TiO2 5%～15%；Be preferably CuO 40%～
50%, ZnO 40%～50%, TiO2 8%～12%.
A kind of BDO dehydrogenation gamma-butyrolacton catalyst, comprises the steps:
(1) preparation contains mixed solution and the precipitant solution of Cu, Zn, Ti；
(2) containing the mixed solution of Cu, Zn, Ti and precipitant solution and flow addition and carry out coprecipitation reaction,
Controlling precipitation temperature in precipitation process is 70-90 DEG C, and pH value is 7.5-9；
(3) precipitation carries out aging after terminating, and control aging temperature is higher than precipitation temperature 20-50 DEG C, aging pH
Value is higher than precipitation pH value 0.5-2, and ageing time is 5-20h；
(4) material after aging prepares final catalyst after suction filtration, washing, drying, roasting, shaping.
In the inventive method step (1), Cu, Zn, Ti derive from any soluble-salt, such as nitrate, sulfate or chlorination
Salt；Preferably copper nitrate, zinc nitrate and titanium chloride.Precipitating reagent is various alkaline precipitating agents, such as NaOH, potassium hydroxide, carbonic acid
Sodium etc.；Preferably sodium carbonate.
In the inventive method step (2), controlling precipitation temperature in precipitation process is 75-85 DEG C, and pH value is 8.0-8.5.
In the inventive method step (3), control aging temperature is higher than precipitation temperature 25-40 DEG C, and aging pH value is higher than precipitation
PH value 0.8-1.5, ageing time is 8-15h, and pH is regulated by the amount being continuously added into precipitating reagent.
The application of a kind of BDO dehydrogenation gamma-butyrolacton catalyst, with BDO as raw material, in reaction pressure
Power (gauge pressure) 0～0.3MPa；Reaction temperature 220～270 DEG C, preferably 230～250 DEG C；Liquid feed volume air speed 1.0～
2.0h-1, preferably 1.2～1.5h-1；Charging H2/ 1,4-butanediol mol ratio 3:1～10:1 carries out dehydrogenation reaction and prepares γ-Ding Nei
Ester.
The present invention is found by research, uses the Cu-Zn-Ti composite oxide catalysts of suitable composition, not only can make
Catalyst has a preferable activity and selectivity, and the obvious Zeng Qiang of the carbon accumulation resisting ability of catalyst, result of the test surface, one
Under fixed reaction condition, the conversion ratio of BDO dehydrogenation up to more than 98%, the selectivity of gamma-butyrolacton up to 98% with
On, 500 hours coke contents of catalyst runs increase without obvious.Catalyst of the present invention is without adding alkaline assistant, and component is few, preparation
Method is simple.The inventive method is higher than precipitation temperature and pH value by control aging temperature and pH value in preparation process, can
Obtain more preferably technique effect.
Specific embodiments
Illustrate effect and the effect of the present invention below in conjunction with embodiment, but following example are not constituted to the present invention
Restriction.
Embodiment 1
By 136.7gCu (NO3)2·3H2O and 164.5gZn (NO3)2·6H2O is dissolved in 2L distilled water, adds
23.8gTiCl4Mix.106gNa2CO3It is configured to the aqueous solution of 1mol/L.The beaker of 5L adds a small amount of water, is placed in water
In bath, bath temperature controls at about 80 DEG C, under agitation by above two solution and flow in addition large beaker, completes altogether
Precipitation, in precipitation process, control ph is 8.0, and precipitation carries out aging after terminating, and control aging temperature is 105 DEG C, aging pH value
9.0, ageing time is 15h, and through suction filtration, the sediment of washing in 120 DEG C of dryings 12 hours after aging end, 450 DEG C of roastings 4 are little
When, obtain catalyst A, consist of: CuO the 45%th, ZnO45%, TiO210%.This catalyst fines is after compressing tablet, pulverizing, and sieve takes
The particle of 10-30 mesh.
Embodiment 2
By 91.2gCu (NO3)2·3H2O and 201.0gZn (NO3)2·6H2O is dissolved in 2L distilled water, adds
35.6gTiCl4Mix.Precipitation temperature is 75 DEG C, pH value 7.8；Aging temperature 115 DEG C, pH value is 9.3, ageing time
8h, makes catalyst B as described in Example 1, consists of CuO the 30%th, ZnO55%, TiO215%.This catalyst fines is through pressure
After piece, pulverizing, sieve takes the particle of 10-30 mesh.
Embodiment 3
By 167.1gCu (NO3)2·3H2O and 109.7gZn (NO3)2·6H2O is dissolved in 2L distilled water, adds
35.6gTiCl4Mix.Precipitation temperature is 83 DEG C, and pH value is 8.5；Aging temperature 113 DEG C, pH value is 9.3, ageing time
10h, makes catalyst C as described in Example 1, consists of CuO the 55%th, ZnO30%, TiO215%.This catalyst fines is through pressure
After piece, pulverizing, sieve takes the particle of 10-30 mesh.
Embodiment 4
By 151.9gCu (NO3)2·3H2O and 164.5gZn (NO3)2·6H2O is dissolved in 2L distilled water, adds
11.9gTiCl4Mix.Precipitation temperature is 88 DEG C, and pH value is 8.0；Aging temperature 116 DEG C, pH value is 9.2, ageing time
12h, makes catalyst D as described in Example 1, consists of CuO the 50%th, ZnO45%, TiO25%.This catalyst fines is through pressure
After piece, pulverizing, sieve takes the particle of 10-30 mesh.
Embodiment 5
A catalyst 20ml is diluted with 20ml quartz sand, is encased in fixed bed reactors, the high about 1.5m of reactor, interior
Footpath 18mm, built-in Thermal couple casing pipe, reactor has 4 sections of heating by electric cookers, and corresponding 4 thermocouple temperature controls, catalyst is contained in the 3rd section, instead
Its complementary space of device is answered all to be filled by quartz sand.
Reaction procatalyst need to use hydrogen reducing, and after reduction terminates, by cooking noodle, part reacts, temperature 240 DEG C；Often
Pressure；Volume space velocity 1.5h during feeding liquid-1；H2/ alcohol mol ratio 5:1, uses upper feeding mode, and raw material BDO is through gasifier
After preheating and gasifying, together enter reactor catalyst bed with hydrogen.1,4-butanediol conversion ratio 99.1%；Gamma-butyrolacton selects
Selecting property 99.0%.The 500 hours activity that operate are not decreased obviously.
Embodiment 6
Reaction unit is identical, and catalyst amount and reducing condition are same as in Example 5, selects B catalyst, by the part that cooks noodle
React, temperature 250 DEG C；0.3MPa；Charging liquid hourly space velocity (LHSV) 1.9h-1；H2/ alcohol mol ratio 3.5:1；1,4-butanediol conversion ratio
98.2%, gamma-butyrolacton selective 99.1%.The 500 hours activity that operate are not decreased obviously.
Embodiment 7
Reaction unit is identical, and catalyst amount and reducing condition are same as in Example 5, selects C catalyst, by the part that cooks noodle
React, temperature 230 DEG C；Normal pressure；Charging liquid hourly space velocity (LHSV) 1.0h-1；H2/ alcohol mol ratio 8:1；1,4-butanediol conversion ratio
99.0%, gamma-butyrolacton selective 98.8%.The 500 hours activity that operate are not decreased obviously.
Embodiment 8
Selecting D catalyst, other conditions are with embodiment 5, and reaction result is BDO conversion ratio 98.6%, γ-Ding Nei
Ester selective 99.0%.The 500 hours activity that operate are not decreased obviously.
Comparative example 1
Prepare catalyst E according to the method described in patent CN99113276.9, (consist of CuO45.0%；ZnO42.1%；
Al2O311.3%, K2O1.6%), test method and the condition according to embodiment 5, reaction result is BDO conversion ratio
99.1%, gamma-butyrolacton selective 98.5%, but after operating 120 hours, conversion ratio reduces to 94.4%, and the speed hereafter declining is more
Hurry up, operate 208 hours altogether, conversion ratio reduces to 76.6%.
Following table is the carbon deposition quantity (weight content) through certain time operating rear catalyst surface for the above each catalyst
| Catalyst | Operate 208 hours carbon deposition quantities, % | Operate 500 hours carbon deposition quantities, % |
| A(embodiment 5) | - | 2.2 |
| B(embodiment 6) | - | 2.0 |
| C(embodiment 7) | - | 1.9 |
| D(embodiment 8) | - | 2.6 |
| E(comparative example 1) | 13.8 |
Claims (8)
1. the preparation method of a BDO dehydrogenation gamma-butyrolacton catalyst, it is characterised in that: comprise the steps:
(1) preparation contains mixed solution and the precipitant solution of Cu, Zn, Ti；
(2) containing the mixed solution of Cu, Zn, Ti and precipitant solution and flow addition and carry out coprecipitation reaction, precipitation process controls
Precipitation temperature is 70-90 DEG C, and pH value is 7.5-9；
(3) precipitation carries out aging after terminating, and control aging temperature is higher than precipitation temperature 20-50 DEG C, and aging pH value is higher than precipitation pH
Value 0.5-2, ageing time is 5-20h；Material after aging prepares final catalysis after suction filtration, washing, drying, roasting, shaping
Agent；Final agent is the composite oxides of Cu-Zn-Ti, and catalyst forms in terms of weight content: CuO 30%～55%, ZnO 30%～
55%, TiO2 5%～15%.
2. method according to claim 1, it is characterised in that: catalyst forms in terms of weight content: CuO 40%～
50%, ZnO 40%～50%, TiO2 8%～12%.
3. method according to claim 1, it is characterised in that: in step (1), Cu, Zn, Ti derive from any soluble-salt,
Precipitating reagent is various alkaline precipitating agents.
4. method according to claim 3, it is characterised in that: Cu, Zn, Ti derive from copper nitrate, zinc nitrate and titanium chloride,
Precipitating reagent is sodium carbonate.
5. method according to claim 1, it is characterised in that: controlling precipitation temperature in step (2) in precipitation process is 75-
85 DEG C, pH value is 8.0-8.5.
6. according to the method described in claim 1, it is characterised in that: the aging temperature of control in step (3)
Degree is higher than precipitation temperature 25-40 DEG C, and aging pH value is higher than precipitation pH value 0.8-1.5, and ageing time is 8-15h.
7. the application of catalyst prepared by method described in claim 1, it is characterised in that: with BDO as raw material, instead
Pressure is answered to be calculated as 0～0.3MPa with gauge pressure；Reaction temperature 220～270 DEG C；Liquid feed volume air speed 1.0～2.0h-1； H2With
1,4-butanediol mol ratio 3:1～10:1 carries out dehydrogenation reaction and produces gamma-butyrolacton.
8. application according to claim 7, it is characterised in that: reaction temperature 230～250 DEG C；Liquid feed volume air speed
1.2～1.5h-1。
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| CN108855119A (en) * | 2017-05-11 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of production gamma-butyrolacton catalyst and preparation method |
| CN112371130A (en) * | 2020-11-11 | 2021-02-19 | 滨州裕能化工有限公司 | Dehydrogenation catalyst and preparation method thereof |
| CN112341339A (en) * | 2020-11-30 | 2021-02-09 | 江苏凯美普瑞工程技术有限公司 | Method and device for synthesizing 1, 4-butanediamine |
| CN115779957B (en) * | 2022-12-10 | 2024-03-19 | 南通格瑞凯泰工程技术有限公司 | Catalyst for preparing gamma-butyrolactone by low-pressure dehydrogenation of 1, 4-butanediol and application thereof |
| CN116173977B (en) * | 2023-03-30 | 2023-12-12 | 重庆中润新材料股份有限公司 | Dehydrogenation catalyst and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304795A (en) * | 2000-08-14 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing gamma-butyrolactone by dehydrogenation of 1,4-butanediol and its application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304795A (en) * | 2000-08-14 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing gamma-butyrolactone by dehydrogenation of 1,4-butanediol and its application |
Non-Patent Citations (1)
| Title |
|---|
| Cu-Zn-Ti催化剂上顺酐气相催化加氢制备γ-丁内酯;胡童杰等;《工业催化》;20060930;第14卷(第9期);第41页左栏，第42页的"1.1催化剂制备"，表1 * |
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