CN105622336A - Method for preparing 1,4-butynediol - Google Patents
Method for preparing 1,4-butynediol Download PDFInfo
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- CN105622336A CN105622336A CN201610114205.1A CN201610114205A CN105622336A CN 105622336 A CN105622336 A CN 105622336A CN 201610114205 A CN201610114205 A CN 201610114205A CN 105622336 A CN105622336 A CN 105622336A
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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
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
Abstract
The invention discloses a method for preparing 1,4-butynediol. The method comprises the steps that firstly, a copper catalyst is activated to obtain a copper acetylide/bismuth catalyst, acetylene and formaldehyde are subjected to a reaction under the effect of the copper acetylide/bismuth catalyst to obtain a 1,4-butynediol and copper acetylide/bismuth catalyst mixed solution, and in a reaction kettle, the mixed solution is filtered through a metal film filter to obtain a 1,4-butynediol clear solution which is fed outside the reaction kettle to be subjected to follow-up technological treatment to obtain a finished product. In the reaction process, copper acetylide/bismuth catalyst turbid liquid is extracted periodically, then, an equimolar copper acetylide/bismuth catalyst or a copper catalyst is supplemented, a clear solution obtained after the extracted copper acetylide/bismuth catalyst turbid liquid is filtered is subjected to the follow-up technological treatment to obtain a finished product finally, and copper acetylide/bismuth catalyst cakes are subjected to a regeneration procedure to be recycled; the 1,4-butynediol clear solution is adopted for performing back flushing on the metal film filter periodically. Due to periodic extraction and supplementing of the catalyst, production losses caused by frequent stopping are avoided, and the product yield and output are improved.
Description
Technical field
The present invention relates to a kind of method preparing organic compound, particularly a kind of method preparing 1,4-butynediol, belongs to Organic chemical products production technical field.
Background technology
1,4-butynediol (C4H6O2), white oblique square crystal, water soluble, acid, ethanol and acetone, be insoluble to benzene, ether, and eye mucous membranes, skin and the upper respiratory tract are had hormesis. Can be used for preparing a series of important Organic chemical products such as butylene glycol, butyleneglycol, propyl carbinol, dihydrofuran, tetrahydrofuran (THF), also can be used as brightening agent. Industrially, the main production process of 1,4-butynediol is Reppe method: namely acetylene is under the effect of copper catalyst and a molecule formaldehyde addition, generates propiolic alcohol, the latter again with a formaldehyde molecule addition, generate 1,4-butynediol. In reaction process, catalyzer adopts copper as main active component, and using bismuth as promotor and copper catalyst, main component is CuO-Bi2O3, (Cu content about 20%, Bi content about 2��3%). Before reaction, in reactor, add copper catalyst (CuO-Bi2O3), and 25��35% formaldehyde solutions, it is 60��100 DEG C in temperature, leads to the acetylene gas into 0.10��0.15MPa and activate, after 8��12h, make active ingredient copper be converted into acetylene copper, obtain acetylene copper/bismuth catalyst. And then add formaldehyde solution and acetylene continuously, control reacting kettle inner pressure is 0.05��0.15MPa, temperature is 80��100 DEG C, formaldehyde and acetylene is made to carry out being obtained by reacting 1 under the effect of acetylene copper/bismuth catalyst, 4-butynediol crude product, reaction feed liquid again the deep bed filter in reactor filter, filtrate 1,4-butynediol crude product obtains finished product through concentrated refining. This preparation method, in reaction process, along with the increase in reaction times, the activity of catalyzer acetylene copper/bismuth can reduce, and the receipts rate of 1,4-butynediol also can reduce, General reactions is after 3��6 months, and the activity of catalyzer acetylene copper/bismuth can thoroughly be lost, the catalyzer now needing to stop and more renewing. In whole reaction process, owing to catalyst activity is more and more lower, causing acetylene and formaldehyde reaction process unstable, reaction safety is poor, and receipts rate is more and more lower. Wherein deep bed filter is owing to its intensity is low and resistance to crocking is poor, within general 3 months, also needs to stop and changes. Therefore traditional 1,4-butynediol production technique is interval, changes a filter bag and catalyzer every 3 months needs, in the process changing filter bag and catalyzer, material can be caused to leak, affect continuous production, causing production cost to increase, output reduces, and affects the economic benefit of enterprise.
Summary of the invention
It is an object of the invention to provide a kind of method preparing 1,4-butynediol, to solve the problem that in 1,4-butynediol production process, catalyzer and filter bag are frequently changed, it is achieved produce continuous and steady operation.
It is such that the present invention solves the technical scheme that its technical problem takes. Prepare a method for 1,4-butynediol, comprise the following steps:
(1) catalyzer activates first
Adopt built-in metal film filter reactor, drive first, with mass ratio 1:(8��12 in reactor) ratio add copper catalyst CuO-Bi2O3With the formaldehyde solution of massfraction 25%��35%, it is 60��100 DEG C in temperature, leads to the acetylene gas into 0.10��0.15MPa and activate, after 8��12h, make active ingredient copper be converted into acetylene copper, obtain acetylene copper/bismuth catalyst;
(2) successive reaction
Control reacting kettle inner pressure is 0.05��0.15MPa, temperature is 80��100 DEG C, lead to continuously into acetylene gas in reactor, acetylene air speed is 4��5min-1, add the formaldehyde solution of massfraction 25%��35% continuously, acetylene and formaldehyde are obtained by reacting 1 under the effect of acetylene copper/bismuth catalyst, the mixing solutions of 4-butynediol and acetylene copper/bismuth catalyst, time initial, 1, the receipts rate of 4-butynediol is greater than 91%, when 1, when the receipts rate of 4-butynediol is reduced to 70%��80%, the activity decrease of acetylene copper/bismuth catalyst is obvious, now extraction part acetylene copper/bismuth catalyst suspension liquid, then the acetylene copper/bismuth catalyst added in reactor etc. mole or copper catalyst,
The mode adding catalyzer has two kinds:
A, outside reactor, configure a little catalyst activation tank, in catalyst activation tank, first prepare acetylene copper/bismuth catalyst, from catalyst activation tank, add the acetylene copper/bismuth catalyst needed in reactor;
B, directly to adding in reactor and the copper catalyst CuO-Bi of extraction catalyzer etc. mole2O3, limit coronite is added;
(3) continuous filtration
In reactor, the mixing solutions of the 1,4-butynediol that step (2) obtains and acetylene copper/bismuth catalyst filters through metal membrane filter device, and filtrate 1,4-butynediol enters subsequent technique and finally obtains finished product outside sending reactor; Acetylene copper/bismuth catalyst is trapped in reactor by metallic membrane, continues reaction; In filtration procedure, adopt the clear liquid of 1,4-butynediol to recoil a metallic membrane every 50��300S, remove the cake layer of metallic film surface, to ensure the continuity of separation.
(4) process of extraction acetylene copper/bismuth catalyst suspension liquid
Outside reactor, the acetylene copper/bismuth catalyst suspension liquid of extraction after filtering clear liquid enter subsequent technique and finally obtain finished product, acetylene copper/bismuth catalyst cake reuse after step for regeneration;
In the present invention, in reactor, in metal membrane filter device, the filtering accuracy of metallic membrane is 0.5��30 ��m.
The useful effect that the present invention obtains is as follows:
(1) in reaction process of the present invention, catalyzer regularly quantitative extraction with add, it is ensured that the continuous and steady operation of reaction process, it is to increase 1,4-butynediol receipts rate;
(2) compared with traditional technology, in the present invention, in reactor, adopting metal membrane filter device to replace deep bed filter, its physical strength and antifouling property are better than deep bed filter, within general 2��3 years, stop regeneration once, can continue to use;
(3) while ensure that the long-term safety steady running that 1,4-butynediol is produced, the loss that causes of stopping is avoided, it is to increase product yield.
Accompanying drawing explanation
Fig. 1, Fig. 2 are the process flow diagram of catalyzer two kinds of different additional ways of the present invention.
Embodiment
Following examples are for illustration of the present invention.
Embodiment 1
The preparation method of 1,4-butynediol, process flow sheet is as shown in Figure 1. Preparation method's step is as follows:
(1) catalyzer activates first
Adopt the reactor of built-in metal film filter, drive first, in reactor, add 6t copper catalyst (CuO-Bi2O3, Cu content about 20%, Bi content about 3%) and 27t formaldehyde solution (massfraction 28%), it is 80 DEG C in temperature, leads to the acetylene gas into 0.13MPa and activate, after 9h, make active ingredient copper be converted into acetylene copper, obtain acetylene copper/bismuth catalyst;
(2) successive reaction
Control reacting kettle inner pressure 0.08MPa, temperature is 90 DEG C, lead to continuously into acetylene gas in reactor, acetylene air speed is 4min-1, add formaldehyde solution (massfraction 28%) continuously, in reaction medium, acetylene copper/bismuth catalyst content is 10%, acetylene and formaldehyde are obtained by reacting 1 under the effect of acetylene copper/bismuth catalyst, the mixing solutions of 4-butynediol and acetylene copper/bismuth catalyst, now 1, the receipts rate of 4-butynediol is greater than 91%, when 1, when the receipts rate of 4-butynediol is reduced to 73%, the activity decrease of acetylene copper/bismuth catalyst is obvious, now extraction part acetylene copper/bismuth catalyst suspension liquid, then the acetylene copper/bismuth catalyst added in reactor etc. mole,
Wherein, in reactor, catalyzer is added in the following ways:
Outside reactor, configure a little catalyst activation tank, first in catalyst activation tank, prepare acetylene copper/bismuth catalyst, from catalyst activation tank, add the acetylene copper/bismuth catalyst of requirement in reactor;
(3) continuous filtration
In reactor, the mixing solutions of the 1,4-butynediol that step (2) obtains and acetylene copper/bismuth catalyst filters through metal membrane filter device, and filtrate 1,4-butynediol enters subsequent technique and finally obtains finished product outside sending reactor; Acetylene copper/bismuth catalyst is trapped in reactor by metallic membrane, continues reaction; In filtration procedure, adopt the clear liquid of 1,4-butynediol to recoil a metallic membrane every 80S, remove the cake layer of metallic film surface, to ensure the continuity of separation;
(4), after the acetylene copper/bismuth catalyst solution of extraction filters, clear liquid is sent into subsequent technique and is finally obtained finished product, acetylene copper/bismuth catalyst cake reuse after step for regeneration.
In reactor used, in metal membrane filter device, the filtering accuracy of metallic membrane is 5 ��m.
Embodiment 2
The preparation method of 1,4-butynediol, process flow sheet is as shown in Figure 2. Preparation process is as follows:
(1) catalyzer activates first
Adopt the reactor of built-in metal film filter, drive first, in reactor, add 12t copper catalyst (CuO-Bi2O3, Cu content about 20%, Bi content about 2.5%) and 50t formaldehyde solution (massfraction 33%), it is 70 DEG C in temperature, leads to the acetylene gas into 0.15MPa and activate, after 10h, make active ingredient copper be converted into acetylene copper, obtain acetylene copper/bismuth catalyst;
(2) successive reaction
Control reacting kettle inner pressure is 0.10MPa, temperature is 85 DEG C, lead to continuously into acetylene gas in reactor, acetylene air speed is 4.5min-1, adding formaldehyde solution (massfraction 33%) continuously, in reaction medium, acetylene copper/bismuth catalyst content is 9%, acetylene and formaldehyde are obtained by reacting 1,4-butynediol and the mixing solutions of acetylene copper/bismuth catalyst under the effect of acetylene copper/bismuth catalyst; Now the receipts rate of 1,4-butynediol is greater than 91%, and when the receipts rate of 1,4-butynediol is reduced to 76%, the activity decrease of acetylene copper/bismuth catalyst is obvious, now extraction partially catalyzed agent suspension liquid, the copper catalyst CuO-Bi then added in reactor etc. mole2O3;
Wherein, adding catalyzer mode in reactor is:
Directly to adding in reactor and the copper catalyst CuO-Bi of extraction acetylene copper/bismuth catalyst etc. mole2O3, limit coronite is added;
(3) continuous filtration
In reactor, the mixing solutions of the 1,4-butynediol that step (2) obtains and acetylene copper/bismuth catalyst filters through metal membrane filter device, and filtrate 1,4-butynediol enters subsequent technique and finally obtains finished product outside sending reactor; Acetylene copper/bismuth catalyst is trapped in reactor by metallic membrane, continues reaction; In filtration procedure, adopt the clear liquid of 1,4-butynediol to recoil a metallic membrane every 200S, remove the cake layer of metallic film surface, to ensure the continuity of separation;
(4) process of extraction acetylene copper/bismuth catalyst suspension liquid
Outside reactor, the acetylene copper/bismuth catalyst suspension liquid of extraction after filtering clear liquid enter subsequent technique and finally obtain finished product, acetylene copper/bismuth catalyst cake reuse after step for regeneration.
In reactor used, in metal membrane filter device, the filtering accuracy of metallic membrane is 1 ��m.
Claims (3)
1. prepare the method for 1,4-butynediol for one kind, it is characterised in that comprise the following steps:
(1) catalyzer activates first
Adopt built-in metal film filter reactor, drive first, with mass ratio 1:(8��12 in reactor) ratio add copper catalyst CuO-Bi2O3With the formaldehyde solution of massfraction 25%��35%, it is 60��100 DEG C in temperature, leads to the acetylene gas into 0.10��0.15MPa and activate, after 8��12h, make active ingredient copper be converted into acetylene copper, obtain acetylene copper/bismuth catalyst;
(2) successive reaction
Control reacting kettle inner pressure is 0.05��0.15MPa, temperature is 80��100 DEG C, lead to continuously into acetylene gas in reactor, acetylene air speed is 4��5min-1, add the formaldehyde solution of massfraction 25%��35% continuously, acetylene and formaldehyde are obtained by reacting 1 under the effect of acetylene copper/bismuth catalyst, the mixing solutions of 4-butynediol and acetylene copper/bismuth catalyst, time initial, 1, the receipts rate of 4-butynediol is greater than 91%, when 1, when the receipts rate of 4-butynediol is reduced to 70%��80%, the activity decrease of acetylene copper/bismuth catalyst is obvious, now extraction part acetylene copper/bismuth catalyst suspension liquid, then the acetylene copper/bismuth catalyst added in reactor etc. mole or copper catalyst,
(3) continuous filtration
In reactor, the mixing solutions of the 1,4-butynediol that step (2) obtains and acetylene copper/bismuth catalyst filters through metal membrane filter device, and filtrate 1,4-butynediol enters subsequent technique and finally obtains finished product outside sending reactor; Acetylene copper/bismuth catalyst is trapped in reactor by metallic membrane, continues reaction; In filtration procedure, adopt the clear liquid of 1,4-butynediol to recoil a metallic membrane every 50��300S, remove the cake layer of metallic film surface, to ensure the continuity of separation.
2. the process of the acetylene copper/bismuth catalyst suspension liquid of (4) extraction
Outside reactor, the acetylene copper/bismuth catalyst suspension liquid of extraction after filtering clear liquid enter subsequent technique and finally obtain finished product, acetylene copper/bismuth catalyst cake reuse after step for regeneration.
3. method according to claim 1, it is characterised in that the mode adding catalyzer has two kinds:
A, outside reactor, configure a little catalyst activation tank, in catalyst activation tank, first prepare acetylene copper/bismuth catalyst, from catalyst activation tank, add the acetylene copper/bismuth catalyst needed in reactor;
B, directly to adding in reactor and the copper catalyst CuO-Bi of extraction catalyzer etc. mole2O3, limit coronite is added;
Method according to claim 1, it is characterised in that in reactor, in metal membrane filter device, the filtering accuracy of metallic membrane is 0.5��30 ��m.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106334580A (en) * | 2016-08-30 | 2017-01-18 | 中国成达工程有限公司 | 1,4-butanediol device BYD catalyst filtering and recovering device and method |
| CN113233959A (en) * | 2021-04-19 | 2021-08-10 | 邢彩虹 | BYD reaction and catalyst separation and regeneration method and device |
| CN113816839A (en) * | 2021-09-23 | 2021-12-21 | 中国成达工程有限公司 | Method for synthesizing butanedialdehyde by acetylene double-hydrogen formyl |
| WO2022041927A1 (en) * | 2020-08-25 | 2022-03-03 | Basf Corporation | Copper aluminum catalyst used for 1,4-butynediol production |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106334580A (en) * | 2016-08-30 | 2017-01-18 | 中国成达工程有限公司 | 1,4-butanediol device BYD catalyst filtering and recovering device and method |
| WO2022041927A1 (en) * | 2020-08-25 | 2022-03-03 | Basf Corporation | Copper aluminum catalyst used for 1,4-butynediol production |
| CN113233959A (en) * | 2021-04-19 | 2021-08-10 | 邢彩虹 | BYD reaction and catalyst separation and regeneration method and device |
| CN113816839A (en) * | 2021-09-23 | 2021-12-21 | 中国成达工程有限公司 | Method for synthesizing butanedialdehyde by acetylene double-hydrogen formyl |
| CN113816839B (en) * | 2021-09-23 | 2024-02-02 | 中国成达工程有限公司 | Method for synthesizing glyoxal through acetylene double hydroformylation |
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