CN105622336B - A kind of method for preparing 1,4- butynediols - Google Patents
A kind of method for preparing 1,4- butynediols Download PDFInfo
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- CN105622336B CN105622336B CN201610114205.1A CN201610114205A CN105622336B CN 105622336 B CN105622336 B CN 105622336B CN 201610114205 A CN201610114205 A CN 201610114205A CN 105622336 B CN105622336 B CN 105622336B
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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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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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
- 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
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Abstract
The invention discloses a kind of method for preparing 1,4 butynediols.Including：Copper catalyst is activated first to obtain acetylene copper/bismuth catalyst, acetylene and formaldehyde react under the action of acetylene copper/bismuth catalyst obtains 1, the mixed solution of 4 butynediols and acetylene copper/bismuth catalyst, in reaction kettle, above-mentioned mixed solution obtains 1 after metal film filter filters, 4 butynediols clear liquids, send out and handle to obtain finished product through subsequent technique outside reaction kettle.During the reaction, periodically extraction acetylene copper/bismuth catalyst suspension, then equimolar acetylene copper/bismuth catalyst or copper catalyst are added, clear liquid is handled through subsequent technique after the acetylene copper of extraction/bismuth catalyst suspension filtering finally obtains finished product, acetylene copper/bismuth catalyst cake reuse after step for regeneration；Periodically recoiled to metal film filter using 1,4 butynediols clear liquids.The present invention, the regular extraction of catalyst avoid often production loss caused by parking, improve product yield and yield with adding.
Description
Technical field
The present invention relates to a kind of method for preparing organic compound, is particularly a kind of method for preparing Isosorbide-5-Nitrae-butynediols,
Belong to Organic chemical products production technical field.
Background technology
1,4- butynediols（C4H6O2）, white oblique square crystal, water-soluble, sour, ethanol and acetone, insoluble in benzene, second
Ether, has stimulation to eye mucous membranes, skin and the upper respiratory tract.Available for preparing butylene glycol, butanediol, n-butanol, dihydro
A series of important Organic chemical products such as furans, tetrahydrofuran, also act as brightening agent.Industrially, Isosorbide-5-Nitrae-butine
The main production process of glycol is Reppe methods：I.e. acetylene generates third with a molecule formaldehyde addition under the action of copper catalyst
Alkynol, the latter with a formaldehyde molecule addition, generate Isosorbide-5-Nitrae-butynediols again.Catalyst is used as main using copper in reaction process
Active component, using bismuth as co-catalyst, that is, copper catalyst, main component CuO-Bi2O3,（Cu contents about 20%, Bi contents about 2
~3%）.Before reaction, in reaction kettle, copper catalyst is added（CuO-Bi2O3）, and 25~35% formalins, temperature for 60~
100 DEG C, the acetylene gas for being passed through 0.10~0.15MPa is activated, and after 8~12h, active ingredient copper is converted into acetylene copper,
Obtain acetylene copper/bismuth catalyst.Then formalin and acetylene are continuously added to again, control reacting kettle inner pressure for 0.05~
0.15MPa, temperature are 80~100 DEG C, make formaldehyde and acetylene reacted to obtain under the action of acetylene copper/bismuth catalyst Isosorbide-5-Nitrae-
Butynediols crude product, bag filter of the reaction material liquid again in reacted kettle are filtered, filter liquor Isosorbide-5-Nitrae-butynediols crude product
It is concentrated to be refining to obtain finished product.The preparation method, during the reaction, with the increase in reaction time, catalyst acetylene copper/bismuth
Activity can reduce, the yield of Isosorbide-5-Nitrae-butynediols can also reduce, and General reactions are after 3~6 months, catalyst acetylene copper/bismuth
Activity can thoroughly be lost, the catalyst for needing parking more to renew at this time.In whole reaction process, since catalyst activity is more next
It is lower, cause that acetylene and formaldehyde reaction process are unstable, and reaction safety is poor, and yield is more and more lower.Wherein bag filter
Since its intensity is low and resistance tocrocking is poor, it is also required within general 3 months parking and replaces.Therefore traditional 1,4- butynediols production work
Skill is interval, needs replacing a filter bag and catalyst at quarterly intervals, during filter bag and catalyst is replaced, can be made
Leak into material, influence continuous production, cause that the production cost increases, yield reduces, and influences the economic benefit of enterprise.
The content of the invention
The object of the present invention is to provide a kind of method for preparing Isosorbide-5-Nitrae-butynediols, is produced with solving Isosorbide-5-Nitrae-butynediols
The problem of catalyst and filter bag are frequently replaced in journey, realizes production continuous and steady operation.
Its technical problem of present invention solution adopts the technical scheme that such.A kind of side for preparing 1,4- butynediols
Method, comprises the following steps：
(1) catalyst activates first
Using the reaction kettle of built-in metal film filter, drive first, with mass ratio 1 in reaction kettle：（8~12）Ratio
Example adds copper catalyst CuO-Bi2O3With the formalin of mass fraction 25%~35%, it is 60~100 DEG C in temperature, is passed through 0.10
The acetylene gas of~0.15MPa is activated, and after 8~12h, active ingredient copper is converted into acetylene copper, is obtained acetylene copper/bismuth and is urged
Agent；
(2) successive reaction
It is 0.05~0.15MPa to control reacting kettle inner pressure, and temperature is 80~100 DEG C, and second is continuously passed through into reaction kettle
Alkynes gas, acetylene air speed are 4~5min-1, are continuously added to the formalin of mass fraction 25%~35%, acetylene and formaldehyde are in second
Reaction obtains the mixed solution of Isosorbide-5-Nitrae-butynediols and acetylene copper/bismuth catalyst under the action of alkynes copper/bismuth catalyst, when initial,
The yield of Isosorbide-5-Nitrae-butynediols is more than 91%, when the yield of Isosorbide-5-Nitrae-butynediols is reduced to 70%~80%, acetylene copper/bismuth catalysis
The activity of agent declines substantially, produces part acetylene copper/bismuth catalyst suspension at this time, is then added into reaction kettle equimolar
Acetylene copper/bismuth catalyst or copper catalyst；
Adding the mode of catalyst has two kinds：
A, outside reaction kettle, a small activation of catalyst tank is configured, prepares acetylene in activation of catalyst tank first
Copper/bismuth catalyst, is added from activation of catalyst tank into the acetylene copper/bismuth catalyst needed in reaction kettle；
B, added directly into reaction kettle and the equimolar copper catalyst CuO-Bi of extraction catalyst2O3, side border ring benefit
Add；
(3) continuous filtering
In reaction kettle, the Isosorbide-5-Nitrae-butynediols and the mixed solution of acetylene copper/bismuth catalyst that step (2) obtains are through metal
Film filter is filtered, and filter liquor Isosorbide-5-Nitrae-butynediols is sent out and finally obtains finished product into subsequent technique outside reaction kettle；Acetylene
Copper/bismuth catalyst is trapped in reaction kettle by metal film, and the reaction was continued；In filter process, every 50~300S using Isosorbide-5-Nitrae-
A butynediols clear liquid metal film of recoil, removes the cake layer of metallic film surface, to ensure separated continuity.
(4) processing of acetylene copper/bismuth catalyst suspension is produced
Outside reaction kettle, clear liquid obtains acetylene copper/bismuth catalyst suspension of extraction into subsequent technique is final after filtering
To finished product, acetylene copper/bismuth catalyst cake reuse after step for regeneration；
In the present invention, the filtering accuracy of metal film is 0.5~30 μm in metal film filter in reaction kettle.
What the present invention obtained has the beneficial effect that：
(1) in reaction process of the present invention, the periodically quantitative extraction of catalyst is with adding, it is ensured that reaction process it is continuous steady
Fixed operation, improves Isosorbide-5-Nitrae-butynediols yield；
(2) compared with traditional handicraft, in the present invention, in reaction kettle, bag filter is substituted using metal film filter,
Its mechanical strength and antifouling property are better than bag filter, and parking regeneration in general 2~3 years once, can be continuing with；
(3) while ensure that the long-term safety stable operation of Isosorbide-5-Nitrae-butynediols production, caused by avoiding parking
Loss, improves product yield.
Brief description of the drawings
Fig. 1, Fig. 2 are the process flow diagram of the different additional ways of two kinds of catalyst of the present invention.
Embodiment
Following embodiments are used to illustrate the present invention.
Embodiment 1
The preparation method of Isosorbide-5-Nitrae-butynediols, process flow chart is as shown in Figure 1.Preparation method step is as follows：
(1) catalyst activates first
Using the reaction kettle of built-in metal film filter, drive first, 6t copper catalysts are added in reaction kettle（CuO-
Bi2O3, Cu contents about 20%, Bi contents about 3%）With 27t formalins（Mass fraction 28%）, it is 80 DEG C in temperature, is passed through
The acetylene gas of 0.13MPa is activated, and after 9h, active ingredient copper is converted into acetylene copper, obtains acetylene copper/bismuth catalyst；
(2) successive reaction
Reacting kettle inner pressure 0.08MPa is controlled, temperature is 90 DEG C, and acetylene gas is continuously passed through into reaction kettle, and acetylene is empty
Speed is 4min-1, is continuously added to formalin（Mass fraction 28%）, in reaction medium, acetylene copper/bismuth catalyst content is 10%,
Acetylene and formaldehyde react under the action of acetylene copper/bismuth catalyst obtains the mixed of 1,4- butynediols and acetylene copper/bismuth catalyst
Solution is closed, the yield of Isosorbide-5-Nitrae-butynediols is more than 91% at this time, when the yield of Isosorbide-5-Nitrae-butynediols is reduced to 73%, acetylene copper/
The activity of bismuth catalyst declines substantially, produces part acetylene copper/bismuth catalyst suspension at this time, is then added into reaction kettle
Mole acetylene copper/bismuth catalyst；
Wherein, catalyst is added into reaction kettle in the following ways：
Outside reaction kettle, a small activation of catalyst tank is configured, acetylene copper/bismuth is first prepared in activation of catalyst tank
Catalyst, adds acetylene copper/bismuth catalyst into requirement in reaction kettle from activation of catalyst tank；
(3) continuous filtering
In reaction kettle, the Isosorbide-5-Nitrae-butynediols and the mixed solution of acetylene copper/bismuth catalyst that step (2) obtains are through metal
Film filter is filtered, and filter liquor Isosorbide-5-Nitrae-butynediols is sent out and finally obtains finished product into subsequent technique outside reaction kettle；Acetylene
Copper/bismuth catalyst is trapped in reaction kettle by metal film, and the reaction was continued；In filter process, Isosorbide-5-Nitrae-butine two is used every 80S
An alcohol clear liquid metal film of recoil, removes the cake layer of metallic film surface, to ensure separated continuity；
(4) after acetylene copper/bismuth catalyst solution of extraction is filtered, clear liquid is sent into subsequent technique and finally obtains finished product,
Acetylene copper/bismuth catalyst cake reuse after step for regeneration.
The filtering accuracy of metal film is 5 μm in metal film filter in reaction kettle used.
Embodiment 2
The preparation method of Isosorbide-5-Nitrae-butynediols, process flow chart is as shown in Figure 2.Preparation process is as follows：
(1) catalyst activates first
Using the reaction kettle of built-in metal film filter, drive first, 12t copper catalysts are added in reaction kettle（CuO-
Bi2O3, Cu contents about 20%, Bi contents about 2.5%）With 50t formalins（Mass fraction 33%）, it is 70 DEG C in temperature, is passed through
The acetylene gas of 0.15MPa is activated, and after 10h, active ingredient copper is converted into acetylene copper, obtains acetylene copper/bismuth catalyst；
(2) successive reaction
It is 0.10MPa to control reacting kettle inner pressure, and temperature is 85 DEG C, and acetylene gas, acetylene are continuously passed through into reaction kettle
Air speed is 4.5min-1, is continuously added to formalin（Mass fraction 33%）, in reaction medium, acetylene copper/bismuth catalyst content is
9%, acetylene and formaldehyde react under the action of acetylene copper/bismuth catalyst obtains Isosorbide-5-Nitrae-butynediols and acetylene copper/bismuth catalyst
Mixed solution；The yield of Isosorbide-5-Nitrae-butynediols is more than 91%, when the yield of Isosorbide-5-Nitrae-butynediols is reduced to 76%, acetylene at this time
The activity of copper/bismuth catalyst declines substantially, produces partial catalyst suspension at this time, is then added into reaction kettle equimolar
Copper catalyst CuO-Bi2O3；
Wherein, catalyst mode is added into reaction kettle is：
Added directly into reaction kettle and extraction acetylene copper/equimolar copper catalyst CuO-Bi of bismuth catalyst2O3, side is anti-
Side is answered to add；
(3) continuous filtering
In reaction kettle, the Isosorbide-5-Nitrae-butynediols and the mixed solution of acetylene copper/bismuth catalyst that step (2) obtains are through metal
Film filter is filtered, and filter liquor Isosorbide-5-Nitrae-butynediols is sent out and finally obtains finished product into subsequent technique outside reaction kettle；Acetylene
Copper/bismuth catalyst is trapped in reaction kettle by metal film, and the reaction was continued；In filter process, Isosorbide-5-Nitrae-butine is used every 200S
A glycol clear liquid metal film of recoil, removes the cake layer of metallic film surface, to ensure separated continuity；
(4) processing of acetylene copper/bismuth catalyst suspension is produced
Outside reaction kettle, clear liquid obtains acetylene copper/bismuth catalyst suspension of extraction into subsequent technique is final after filtering
To finished product, acetylene copper/bismuth catalyst cake reuse after step for regeneration.
The filtering accuracy of metal film is 1 μm in metal film filter in reaction kettle used.
Claims (2)
- A kind of 1. method for preparing Isosorbide-5-Nitrae-butynediols, it is characterised in that comprise the following steps：(1) catalyst activates firstUsing the reaction kettle of built-in metal film filter, drive first, with mass ratio 1 in reaction kettle：The ratio of (8~12) adds Enter copper catalyst CuO-Bi2O3It is 60~100 DEG C in temperature with the formalin of mass fraction 25%~35%, it is passed through 0.10~ The acetylene gas of 0.15MPa is activated, and after 8~12h, active ingredient copper is converted into acetylene copper, obtains acetylene copper/bismuth catalysis Agent；(2) successive reactionIt is 0.05~0.15MPa to control reacting kettle inner pressure, and temperature is 80~100 DEG C, and acetylene gas is continuously passed through into reaction kettle Body, acetylene air speed are 4~5min-1, are continuously added to the formalin of mass fraction 25%~35%, acetylene and formaldehyde are in acetylene Reaction obtains the mixed solution of Isosorbide-5-Nitrae-butynediols and acetylene copper/bismuth catalyst under the action of copper/bismuth catalyst, when initial, 1, The yield of 4- butynediols is more than 91%, when the yield of Isosorbide-5-Nitrae-butynediols is reduced to 70%~80%, acetylene copper/bismuth catalysis The activity of agent declines substantially, produces part acetylene copper/bismuth catalyst suspension at this time, is then added into reaction kettle equimolar Acetylene copper/bismuth catalyst or copper catalyst；(3) continuous filteringIn reaction kettle, the Isosorbide-5-Nitrae-butynediols and the mixed solution of acetylene copper/bismuth catalyst that step (2) obtains are through metal film mistake Filter is filtered, and filter liquor Isosorbide-5-Nitrae-butynediols is sent out and finally obtains finished product into subsequent technique outside reaction kettle；Acetylene copper/bismuth Catalyst is trapped in reaction kettle by metal film, and the reaction was continued；In filter process, Isosorbide-5-Nitrae-butine two is used every 50~300S An alcohol clear liquid metal film of recoil, removes the cake layer of metallic film surface, to ensure separated continuity；The filtering accuracy of metal film is 0.5~30 μm in metal film filter in the reaction kettle；(4) processing of acetylene copper/bismuth catalyst suspension of extractionOutside reaction kettle, clear liquid is finally obtained into acetylene copper/bismuth catalyst suspension of extraction into subsequent technique after filtering Product, acetylene copper/bismuth catalyst cake reuse after step for regeneration.
- 2. according to the method described in claim 1, it is characterized in that the mode for adding catalyst has two kinds：A, outside reaction kettle, a small activation of catalyst tank is configured, prepares acetylene copper/bismuth in activation of catalyst tank first Catalyst, is added from activation of catalyst tank into the acetylene copper/bismuth catalyst needed in reaction kettle；B, add directly into reaction kettle and added with the extraction equimolar copper catalyst CuO-Bi2O3 of catalyst, side border ring.
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| 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 |
| CN111939919A (en) * | 2020-08-25 | 2020-11-17 | 巴斯夫公司 | Copper-aluminum catalyst for preparing 1, 4-butynediol |
| CN113233959B (en) * | 2021-04-19 | 2023-01-24 | 邢彩虹 | BYD reaction and catalyst separation and regeneration method and device |
| 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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| CN1130102A (en) * | 1995-10-27 | 1996-09-04 | 化学工业部北京化工研究院 | Catalyst regenerating method for synthesizing 1,4-butynediol from formaldehyde and acetylene by slurry-bed reaction |
| CN1171388A (en) * | 1996-06-21 | 1998-01-28 | 林德股份公司 | Process for synthesizing butynediol |
| US20100084350A1 (en) * | 2008-10-06 | 2010-04-08 | Jing Liu | Systems and Methods for Continuous Multiphase Reaction and Separation |
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2016
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| CN1130102A (en) * | 1995-10-27 | 1996-09-04 | 化学工业部北京化工研究院 | Catalyst regenerating method for synthesizing 1,4-butynediol from formaldehyde and acetylene by slurry-bed reaction |
| CN1171388A (en) * | 1996-06-21 | 1998-01-28 | 林德股份公司 | Process for synthesizing butynediol |
| US20100084350A1 (en) * | 2008-10-06 | 2010-04-08 | Jing Liu | Systems and Methods for Continuous Multiphase Reaction and Separation |
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