CN1087728C - Method for preparing butanediol from butydiol through two-step catalyzing hydrogenation - Google Patents
Method for preparing butanediol from butydiol through two-step catalyzing hydrogenation Download PDFInfo
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- CN1087728C CN1087728C CN97111848A CN97111848A CN1087728C CN 1087728 C CN1087728 C CN 1087728C CN 97111848 A CN97111848 A CN 97111848A CN 97111848 A CN97111848 A CN 97111848A CN 1087728 C CN1087728 C CN 1087728C
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- catalyst
- hydrogenation
- butynediol
- butanediol
- palladium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A 2-stage process is claimed for the catalytic hydrogenation of butynediol (BID) to butanediol (BAD). Stage 1 is carried out in a stirred reactor with a suspended, palladium-silver/aluminium oxide supported catalyst (A), giving complete conversion of (BID) into butenediol (BED) and 50-85% hydrogenation of (BED) to (BAD). Stage 2 is carried out in a solid-bed reactor with a supported nickel catalyst (B). A process for catalytic hydrogenation of butynediol into butanediol is provided to produce high purity butanediol with a high yield at a low production cost. The process for catalytic hydrogenation of butynediol into butanediol by a two-step method uses a suspension type palladium-carrier catalyst in an agitated reactor for the first step, and a nickel-carrier catalyst in a fixed bed reactor for the second step. The process is characterized in that the conversion of butynediol into butenediol is completed and the conversion of butenediol into butanediol is 50% to 85% in the first step, and the catalyst used in the first step is palladium-silver-aluminium oxide carrier catalyst.
Description
The present invention relates to the method for preparing butanediol from butydiol through two-step catalyzing hydrogenation, wherein, the first step is carried out in stirred reactor with suspension palladium-carried catalyst, and second step carried out in fixed-bed reactor with nickel-carried catalyst.
The industrial implementation of known butynediol hydrogenation preparing butyleneglycol has many methods, and these methods can be divided into so-called single stage method and two step method.
Know a kind of continuous high-pressure process with fixed bed catalytic reactor from DE-PS890944, butynediol is hydrogenated to butyleneglycol by a step in this method.Shortcoming of this step high-pressure process is that heat is led and loose badly, removes to dilute the butynediol aqueous solution and improves though this can return hydrogenation products by part.Moreover, also cause producing a large amount of byproducts, mainly contain butanols, acetal and high boiling point residue.Thereby, can only obtain comparatively impure product with this currently known methods, yield is also lower, is about 85%.
Know a kind of method of hydrotreating from DE-PS858094, this method is used the suspension nickel catalyzator under middle pressure, carry out in stirred reactor.Except the generation of byproduct, this currently known methods has only lower yield, is about 88%.The more known high-pressure process of loosing of leading of heat all is greatly improved during hydrogenation.
The shortcoming of known middle-pressure process with suspended catalyst is that this method must be carried out off and on, and the efficient of interrupter method is low.
For reducing the amount of byproduct as much as possible, hydrogenation material is made the step of two under differing temps hydrogenation be necessary, but the quality of the hydrogenation products that obtains like this is lower.The reason that by-products content is high always produces a large amount of aldehyde and acetal when remaining because of butynediol hydrogenation under the condition of currently known methods, and they only could partly be converted into butyleneglycol under the elevated pressures under comparatively high temps and particularly.
For avoiding described shortcoming, it is linked together to attempt the medium-pressure hydrocracking and the high pressure fixed bed hydrogenation that will be generally carry out in stirred reactor with Rayleigh nickel suspended catalyst.In this type of two one step process, butynediol is depressed in the first step and partly be hydrogenated to butyleneglycol in stirred reactor.And then as described in the US-PS3449445, use Ni-Cu-Mn-SiO in second step
2Catalyzer makes hydrogenation complete in the high pressure fixed-bed reactor, further like this aldehyde and the acetal that is generated of having removed.
Be about 90% though these class methods are brought up to yield, and significantly changed the quality of hydrogenation products simultaneously, it also has significant drawback, i.e. the first step hydrogenation and the above-mentioned the same batch operation that still needs.
Know a kind of method by DD-PS219184, the first step suspension nickel carried catalyst operate continuously in this method.The two-stage process of the operate continuously of Gou Chenging has shown obvious improvement thus.The main drawback of this method is the transformation efficiency of butynediol must be remained on 90%, and maximum is no more than in 98% this close limit.Outside this scope, the generation of byproduct will sharply increase.For avoiding it, must maintain this transformation efficiency scope.Butynediol also mustn't be hydrogenated to butyleneglycol, otherwise under the condition of this method, will generate acetal, and this has just hindered the hydrogenation of step of high pressure.
For keeping described butynediol transformation efficiency to require the complicated control of effort naturally, also must as far as possible accurately consider the fluctuation of some foreseeable hardly values such as catalyst deactivation and catalyst activity.
From reliability, must maintain above-mentioned butynediol transformation efficiency exactly, to stop a large amount of butylene glycol hydrogenation to producing in the first step.Because it is strong heat release that butynediol becomes the reaction of butyleneglycol, wherein the butylene glycol hydrogenation reaction is more faster than butynediol hydrogenation, so have such danger, promptly, destroyed the operation of the first step stirred reactor because the butylene glycol hydrogenation uncontrollably carries out.
In second step of this process, promptly the butylene glycol high-pressure hydrogenation is a butyleneglycol, because butylene glycol hydrogenation and remaining butynediol hydrogenation liberated heat, big problem also occurred aspect the heat dissipation capacity leading.
In a word, can confirm that the butyleneglycol yield of currently known methods and its product quality are not enhanced.
For avoiding these shortcomings, DD-PS265394 suggestion, the stirring reaction of the first step use operate continuously and the palladium carried catalyst of suspension, and second step use fixed-bed reactor and the nickel carried catalyst.This method is designed in this wise, and the butynediol transformation efficiency has reached 100% in the first step, and the butylene glycol transformation efficiency reaches＞95%.
This method by two step of butynediol hydrogenation preparing butyleneglycol also has following shortcoming.
Because dynamic (dynamical) unfavorable, unconverted material must have the long residence time in the first step hydrogenation butylene glycol transforms so that reach greatly, causes higher byproduct production rate thus again.
Used in addition Catalyst Production load is little, and promptly per hour every kg catalyst is 5 kilograms of butynediol, and the supply of a large amount of catalyzer causes the cost of this method to improve.In order to process the raw material of q.s, corresponding large-sized reactor must be arranged or this method is operated under quite high catalyst concn.It is disadvantageous using high concentration catalyst, because when catalyst separating or filtration, produced trouble thus.
This method also must add heating to the second step hydrogenation, but because the amount of hydrogenation very little in second step, deficiency is so that feed in raw material to maintain and transform fully under the required temperature.
The object of the present invention is to provide a kind of butynediol to be hydrogenated to improving one's methods of butyleneglycol, this method produces high yield and high purity with the little cost of safety and control techniques aspect.
Reach like this by this purpose of the present invention:
A) finish the conversion of butynediol in the first step basically, and butylene glycol is 50 to 85% at the transformation efficiency of the first step, preferred 70 to 80% to butylene glycol.
(b) used catalyzer is palladium-Yin-alumina base catalyst in the first step.
Thus, be partially converted to the butylene glycol afterreaction by the present invention and ended again, compare, avoided the reaction times of length in the first step with the method that the pursuit butylene glycol as far as possible all transforms.The second step fixed-bed reactor behind the first step hydrogenation, also stay abundant hydrogenation material by the inventive method, so can not need to carry out additional heating.
According to selected transforming degree, most of heat is emitted in the first step, so can avoid for second step overheated, this overheated meeting causes generating excessive by product.
Compare with the currently known methodss that mainly are the whole conversions of pursuit butylene glycol, butynediol all transforms and method that butylene glycol partly transforms, only require smaller control workload, this is because do not need exactly after butynediol transforms, and butylene glycol begins the moment of hydrogenation and goes stopped reaction.
As mentioning, the inventive method only need connect comparatively simple separating unit, and can obtain high butyleneglycol yield owing to greatly reduce the boil generation of component by product of height in the hydrogenation step back.
Obtained optionally to improve by remove to revise palladium with silver.Preferably adopt θ-aluminum oxide as carrier, it produces when calcination aluminium hydroxide, so be low acidity because the hydroxyl that contains of this θ-aluminum oxide is few.This θ-alumina pore texture ratio broad can stop carbon laydown in addition, has improved selectivity so again.
By an embodiment of the inventive method, the catalytic amount that it is characterized in that importing the first step is between 0.1 and 1 weight %, preferably between 0.2 and 0.5 weight %.
By the required catalyzer of the inventive method is fewer.Another advantage with little amount of catalyst is that good filterability is arranged.
Used catalyzer preferably has the nickel carried catalyst of a little copper (about 1 to 3%) in second step.The adding of copper has improved selectivity of catalyst and activity.
By also further suggestion of method of the present invention, the first step working pressure is 5 to 50 crust, preferred 20 to 30 crust, and temperature is 50 to 100 ℃, preferred 60 to 80 ℃; The second step working pressure is 10 to 50 crust, preferred 20 to 40 crust, and temperature is 100 to 150 ℃, preferred 125 to 140 ℃.
The present invention and other embodiments of the present invention can be described in detail by following two embodiment, and BID, BED and BAD are respectively the abbreviation of butynediol, butylene glycol and butyleneglycol here.
Embodiment 1 (lab setup)
The first step hydrogenation:
4mol/l BID feeds intake
Palladium/silver-colored carried catalyst (0.24%Pd, 0.21%Ag,
100ppm Na is loaded in Al
2O
3On, bulk density is 1110
Grams per liter) screening (%) is as follows:
＜20μm 7.0
20-40μm 12.1
40-63μm 40.3
63-80μm 25.9
80-100μm 14.6
＞100μm 0.1
Catalyst concn C
Kat=2g/l
T＝60℃
The P=21 crust
1 liter of liquid of agitated autoclave
Transformation efficiency: U
BID≈ 100%, U
BED≈ 75%
Than catalyst loading ≈ 20g BID/g catalyzer hour
The second step hydrogenation
The product of the first step that feeds intake hydrogenation
Nickel/copper-carried catalyst
56.1％Ni；14.0％NiO；1.9％Cu，
Surplus is diatomite
The 5-3mm sheet
Bulk density 1110g/l
Side pressure strength 136N
T＝120℃
The P=21 crust
LHSV:0.5-1 hour
-1
Trickle bed: 20ml catalyzer
Yield: A
BAD≈ 93-95mol% embodiment 2 (demonstration plant's device) the first step hydrogenation:
Feed intake: ≈ 4mol/l BID synthetic product
Palladium/silver catalyst (going into embodiment 1)
Catalyst concn C
Kat=4g/l
T＝65℃
The P=20 crust
Agitated autoclave: 37 liters of liquid
Transformation efficiency: U
BID≈ 100% the second steps hydrogenation:
Feed intake: the first step hydrogenation products
Nickel/copper catalyst (as embodiment 1)
T＝130℃
The P=21 crust
LHSV:0.3-0.5 hour
-1
Trickle bed: 1.75 and 2.3 liters of catalyzer
Yield: A
BAD≈ 94～95mol%
Claims (10)
1, the method for preparing butanediol from butydiol through two-step catalyzing hydrogenation, wherein, the first step is carried out in a stirred reactor with suspension palladium-carried catalyst, and second step carried out in fixed-bed reactor with nickel-carried catalyst, it is characterized by:
A) butynediol all is converted into butylene glycol basically in the first step, and the transforming degree of butylene glycol in the first step is 50 to 85%, and
B) used catalyzer is palladium-Yin-aluminum oxide-carried catalyst in the first step.
2, by the method for claim 1, it is characterized in that the transforming degree of butylene glycol in the first step is 70 to 80%.
By the method for claim 1 or 2, it is characterized in that 3, used catalyzer is that copper content is nickel-carried catalyst of 1-3 weight % in second step.
By the method for claim 1 or 2, it is characterized in that 4, the catalytic amount of the input the first step is between 0.1 and 1 weight %.
By the method for claim 1 or 2, it is characterized in that 5, the catalytic amount of the input the first step is between 0.2 and 0.5 weight %.
By the method for claim 1 or 2, it is characterized in that 6, the first step working pressure is 5 to 50 crust, temperature is 50 to 100 ℃; The second step working pressure is 10 to 50 crust, and temperature is 100 to 150 ℃.
By the method for claim 6, it is characterized in that 7, the first step working pressure is 20 to 30 crust.
8, by the method for claim 6, it is characterized in that the temperature of the first step is 60 to 80 ℃.
By the method for claim 6, it is characterized in that 9, the second step working pressure is 20 to 40 crust.
By the method for claim 6, it is characterized in that 10, the temperature in second step is 125 to 140 ℃.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1996125189 DE19625189C1 (en) | 1996-06-24 | 1996-06-24 | Two-stage catalytic hydrogenation of butyne-diol to butane-diol |
| DE19625189.3 | 1996-06-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1172792A CN1172792A (en) | 1998-02-11 |
| CN1087728C true CN1087728C (en) | 2002-07-17 |
Family
ID=7797821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97111848A Expired - Fee Related CN1087728C (en) | 1996-06-24 | 1997-06-24 | Method for preparing butanediol from butydiol through two-step catalyzing hydrogenation |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100368733B1 (en) |
| CN (1) | CN1087728C (en) |
| DE (1) | DE19625189C1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005042184A1 (en) | 2005-09-06 | 2007-03-08 | Basf Ag | Process for the separation of polymeric by-products from 1,4-butynediol |
| DE102005049568A1 (en) * | 2005-10-17 | 2007-04-19 | Basf Ag | Process for continuous hydrogenation or hydrogenating amination |
| CN102408307B (en) * | 2010-09-21 | 2014-02-05 | 中国石油化工股份有限公司 | Method for preparing butanediol by carrying out two-stage catalytic hydrogenation on butynediol |
| CN103418409B (en) * | 2013-07-20 | 2015-07-29 | 大连理工大学 | A kind of metal silicide catalyst of selec-tive hydrogenation Isosorbide-5-Nitrae-butynediols and application |
| CN104326871A (en) * | 2014-10-11 | 2015-02-04 | 江苏常州酞青新材料科技有限公司 | Preparation method for butanediol |
| CN110483242B (en) * | 2019-09-11 | 2022-07-22 | 岭南师范学院 | Method for synthesizing 1, 4-butanediol by hydrogenation of 1, 4-butynediol |
| CN114105730B (en) * | 2020-08-31 | 2024-06-11 | 中国石油化工股份有限公司 | Method and system for preparing 1, 4-butanediol and co-producing 1, 4-butenediol by hydrogenating 1, 4-butynediol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD248113A1 (en) * | 1986-04-16 | 1987-07-29 | Leuna Werke Veb | PROCESS FOR PREPARING BUTANDIOL-1,4 |
| DD265394A1 (en) * | 1986-04-16 | 1989-03-01 | Leuna Werke Veb | PROCESS FOR PREPARING BUTANDIOL-1,4 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD219184A1 (en) * | 1983-10-10 | 1985-02-27 | Buna Chem Werke Veb | METHOD FOR THE CATALYTIC HYDROGENATION OF BUT-2-IN1,4-DIOL |
-
1996
- 1996-06-24 DE DE1996125189 patent/DE19625189C1/en not_active Expired - Lifetime
-
1997
- 1997-02-28 KR KR1019970007156A patent/KR100368733B1/en not_active IP Right Cessation
- 1997-06-24 CN CN97111848A patent/CN1087728C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD248113A1 (en) * | 1986-04-16 | 1987-07-29 | Leuna Werke Veb | PROCESS FOR PREPARING BUTANDIOL-1,4 |
| DD265394A1 (en) * | 1986-04-16 | 1989-03-01 | Leuna Werke Veb | PROCESS FOR PREPARING BUTANDIOL-1,4 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100368733B1 (en) | 2003-06-12 |
| DE19625189C1 (en) | 1997-10-23 |
| CN1172792A (en) | 1998-02-11 |
| KR980001994A (en) | 1998-03-30 |
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Free format text: CORRECT: APPLICANT; FROM: LINDE AG.; YUKONG LIMITED; SOUTHERN CHEMICAL STOCK CO., LTD. TO: SK CO.,LTD. |
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Address after: Seoul Applicant after: SK Co. Address before: Wiesbaden, Federal Republic of Germany Applicant before: Linde AG Applicant before: Yukong Ltd. Applicant before: Sued Chemie AG |
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Owner name: SK RESOURCE CO., LTD. Free format text: FORMER OWNER: SK CO.,LTD. Effective date: 20080111 |
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Granted publication date: 20020717 |