CN113896614B - Method for continuously synthesizing chlorobutane in non-aqueous system - Google Patents
Method for continuously synthesizing chlorobutane in non-aqueous system Download PDFInfo
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- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 112
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002608 ionic liquid Substances 0.000 claims abstract description 18
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011552 falling film Substances 0.000 claims abstract description 15
- IPHBBZWQWUFXGR-UHFFFAOYSA-N 1-butyl-2H-pyridine hydrochloride Chemical compound CCCCN1CC=CC=C1.Cl IPHBBZWQWUFXGR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 230000018044 dehydration Effects 0.000 claims abstract description 3
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 3
- 238000010992 reflux Methods 0.000 claims description 22
- 238000000066 reactive distillation Methods 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims 2
- 239000007788 liquid Substances 0.000 abstract description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 21
- 238000004821 distillation Methods 0.000 description 9
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 7
- WUNVTWGPFJFCPH-UHFFFAOYSA-N [Cl].C(CCC)N1CN(C=C1)C Chemical compound [Cl].C(CCC)N1CN(C=C1)C WUNVTWGPFJFCPH-UHFFFAOYSA-N 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- STCBHSHARMAIOM-UHFFFAOYSA-N 1-methyl-1h-imidazol-1-ium;chloride Chemical compound Cl.CN1C=CN=C1 STCBHSHARMAIOM-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000011831 acidic ionic liquid Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for continuously synthesizing chlorobutane in a nonaqueous system, wherein the nonaqueous system consists of ionic liquid 1-butyl-3-methylimidazole chloride or 1-butylpyridine hydrochloride, n-butyl alcohol and hydrogen chloride, and the ionic liquid is a solvent and a catalyst for chlorination reaction; the chemical reaction of the n-butyl alcohol and the hydrogen chloride and the rectification of the reaction product 1-chlorobutane are synchronously and continuously carried out in a reaction rectifying tower. Hydrogen chloride gas is introduced from the bottom of the reactive rectifying tower, n-butyl alcohol and ionic liquid are introduced from the middle part, 1-chlorobutane is extracted from the top of the tower, and part of ionic liquid extracted from the bottom of the tower is distilled in a falling film evaporator to remove water and then returned to the system. The method has the advantages of simultaneous reaction and rectification, simple operation, high reaction rate and almost instantaneous reaction after gas-liquid two phases are contacted to generate 1-chlorobutane; the ionic liquid can be regenerated after simple dehydration; the purity of the 1-chlorobutane is more than or equal to 99.5 percent, and the product yield is 90.3-98.2 percent based on n-butanol.
Description
Technical Field
The invention relates to a method for continuously synthesizing chlorobutane in a nonaqueous system, belonging to the technical field of organic synthesis.
Background
1-chlorobutane is also called n-butyl chloride and chloro-n-butane, is an important monobasic halogenated hydrocarbon, and can be used as a solvent, an organic synthesis intermediate and a catalyst in the fields of grease, rubber, resin and the like. The raw materials for synthesizing the 1-chlorobutane are numerous, the raw materials mainly comprise low-cost n-butanol and hydrogen chloride gas or concentrated hydrochloric acid in industrial production, and the synthesis method comprises the following patent publications:
the preparation method of 1-chlorobutane disclosed in Chinese patent CN104326863A takes dimethyl sulfoxide as a catalyst to catalyze hydrogen chloride and n-butanol to react to generate 1-chlorobutane, the yield can reach 89.6-93.5%, the purity can reach 99.5-99.7%, the reaction time of the method needs 20 hours, and the method is low in efficiency and high in energy consumption.
Chinese patent CN1440958 (CN 1225440C) discloses a method for converting primary alcohol or cyclohexanol in acidic ionic liquid [ Hmim ] +x- (x=cl, br, I) into halogenated hydrocarbon, using N-butanol and N-methylimidazole hydrochloride ionic liquid to react, wherein N-methylimidazole hydrochloride is used as solvent and provides chlorine element to participate in chlorination reaction, the process is batch process, the reaction time is 12 hours, the efficiency is low, and concentrated hydrochloric acid is needed to regenerate N-methylimidazole hydrochloride ionic liquid after the reaction is finished.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a method for continuously synthesizing chlorobutane in a non-aqueous system, which realizes the following aims: the ionic liquid is used as a solvent and a catalyst to form a nonaqueous reaction system, so that the reaction time is greatly shortened, the continuous synthesis of the high-purity 1-chlorobutane is realized in a reactive distillation mode, and the ionic liquid is regenerated by on-line simple falling film evaporation and dehydration.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a method for continuously synthesizing chlorobutane in a nonaqueous system, wherein the nonaqueous system consists of ionic liquid, n-butanol and hydrogen chloride, and the ionic liquid is used as a solvent and a catalyst for chlorination reaction at the same time; the ionic liquid is 1-butyl-3-methylimidazole chloride or 1-butylpyridine hydrochloride; the chemical reaction of raw material n-butyl alcohol and hydrogen chloride and the rectification of reaction product 1-chlorobutane are synchronously and continuously carried out in a reaction rectifying tower.
The following is a further improvement of the above technical scheme:
and adding a proper amount of 1-butyl-3-methylimidazole chloride or 1-butylpyridine hydrochloride at the bottom of the reaction rectifying tower, heating to 88-152 ℃ in the whole system of the reaction rectifying tower, and heating to 100-120 ℃ in a falling film evaporator. Starting a second circulating pump, enabling the ionic liquid to enter the reaction rectifying tower from the top end of a first tower section of the reaction rectifying tower in a spraying mode after passing through a falling film evaporator, wherein the spraying flow rate is 205-210g/min, then introducing n-butyl alcohol into the top end of the first tower section at the flow rate of 70-74g/min, simultaneously introducing hydrogen chloride gas into the tower bottom at the flow rate of 29-31g/min, starting to flow back at the tower top after 10 or 30 minutes, condensing the gas extracted from the tower top, entering a product storage tank to obtain high-purity 1-chlorobutane, controlling the reflux ratio of the tower top to be 5-7:1, and controlling the reflux temperature to be 69-92 ℃. The 1-butyl-3-methylimidazole chloride or 1-butylpyridine hydrochloride containing water is accumulated at the bottom of the tower, the water is pumped into a falling film evaporator by a first circulating pump, the water is evaporated, the water is collected and concentrated, the 1-butyl-3-methylimidazole chloride or 1-butylpyridine hydrochloride containing water is removed, the water content is 1.3-1.7%, and the 1-butyl-3-methylimidazole chloride or 1-butylpyridine hydrochloride containing water is sprayed into the reaction rectifying tower from the top end of the first tower section again for recycling.
Compared with the prior art, the invention has the following beneficial effects:
1. the method has short reaction time, and almost instantaneous reaction occurs after the gas phase and the liquid phase are contacted to generate 1-chlorobutane;
2. according to the invention, the ionic liquid is used as a catalyst, and the recovery of the catalytic performance can be realized only by removing part of water;
3. according to the invention, coupling of synthesis and refining of chlorobutane is realized through reactive distillation, the reaction and the distillation are carried out simultaneously, the operation is simple, the process flow is shortened, an immediate sample (primary distillation) at the top of the tower is taken for analysis after hydrogen chloride gas is introduced for 10-30 minutes, the content of 1-chlorobutane is 95.56-99.87%, the content of n-butanol is 0.049-2.87%, the content of n-butyl ether is 0.0021-1.110%, the isomer is 0.0009-0.082%, and the other content is 0.0204-0.378%; introducing hydrogen chloride gas for 1 hour and 45 minutes, taking an immediate sample (primary distillation) at the top of the tower for analysis, wherein the content of 1-chlorobutane is 87.13-99.82%, the content of n-butyl alcohol is 0.0281-11.18%, the content of n-butyl ether is 0.0015-0.48%, the content of isomers is 0.009-0.141%, and the content of other isomers is 0.1379-1.163%; and after 10 hours of introduction, taking a cumulative sample for analysis, wherein the content of 1-chlorobutane is 87.13-99.84%, the content of n-butyl alcohol is 0.0307-13.59%, the content of n-butyl ether is 0.0018-0.51%, the isomer is 0.006-0.173%, the other 0.0913-7.2306%, and the 1-chlorobutane yield is 90.3-98.2% based on n-butyl alcohol.
Drawings
The invention will be further described with reference to the drawings and examples.
FIG. 1 is a flow chart of the synthesis process of the present invention.
In the figure, a 1-reaction rectifying tower; a 2-condenser; 3-a reflux buffer tank; 4-a product storage tank; 5-falling film evaporator; 6-reboiler; 7-a second circulation pump; 8-a first circulation pump.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and explanation only and is not intended to limit the present invention.
Example 1: method for continuously synthesizing chlorobutane in non-aqueous system
The method comprises the following steps:
10 kg of 1-butyl-3-methylimidazole chloride is added at the bottom of the reaction rectifying tower 1, and is introduced into a reboiler 6 for circulation, the reboiler 6 is opened to heat the whole system of the reaction rectifying tower 1 to 120+/-2 ℃, and then the 1-butyl-3-methylimidazole chloride is introduced into a falling film evaporator 5 to heat the whole system to 110 ℃. The second circulating pump 7 is started, the ionic liquid enters the reactive distillation column 1 from the top end of a first tower section of the reactive distillation column 1 in a spraying mode after passing through the falling film evaporator 5, the spraying flow rate is 210g/min, then n-butyl alcohol is introduced into the top end of the first tower section at the flow rate of 74g/min, meanwhile, hydrogen chloride gas is introduced into the bottom of the tower at the flow rate of 30-31 g/min, reflux starts to occur at the top of the tower after 10 minutes, the reflux ratio of the top of the tower is controlled to be 6:1, the reflux temperature is 70+/-1 ℃, the gas extracted from the top of the tower is condensed into liquid through the condenser 2, part of the liquid flows back into the reactive distillation column 1 after flowing into the reflux buffer tank 3, and part of the liquid flows into the product storage tank 4, so that the high-purity 1-chlorobutane is obtained. The 1-butyl-3-methylimidazole chlorine salt containing water is accumulated at the bottom of the tower, the 1-butyl-3-methylimidazole chlorine salt containing water is pumped into a reboiler 6 and a falling film evaporator 5 respectively according to the mass ratio of 1:1 by a first circulating pump 8, the 1-butyl-3-methylimidazole chlorine salt containing water enters the falling film evaporator 5, the water in the falling film evaporator is distilled out, the water is collected and concentrated, the 1-butyl-3-methylimidazole chlorine salt containing water is removed, the water content is 1.5%, and the 1-butyl-3-methylimidazole chlorine salt containing water is sprayed into the reaction rectifying tower 1 from the top end of the first tower section of the reaction rectifying tower 1 again for recycling.
Example 1, after 10 minutes of hydrogen chloride gas is introduced, an immediate sample (primary distillation) at the top of the column is taken for analysis, wherein the content of 1-chlorobutane is 99.67%, the content of n-butyl alcohol is 0.21%, the content of n-butyl ether is 0.0021%, the content of isomers is 0.009%, and the other content is 0.1089%; introducing 45 minutes to collect a cumulative sample for analysis, wherein the content of 1-chlorobutane is 99.80%, the content of n-butyl alcohol is 0.04%, the content of n-butyl ether is 0.0015%, the content of isomers is 0.009%, and the other content is 0.1495%; after 10 hours of introduction, a cumulative sample was taken and analyzed, and the 1-chlorobutane content was 99.84%, the n-butanol content was 0.036%, the n-butyl ether content was 0.0018%, the isomer content was 0.006%, and the other 0.1162%, based on n-butanol, was 98.2%.
Example 2:
10 kg of 1-butyl-3-methylimidazole chloride is added at the bottom of the reaction rectifying tower 1, the temperature in the whole system of the reaction rectifying tower 1 is raised to 90+/-2 ℃, the temperature of the falling film evaporator 5 is raised to 100 ℃, other process conditions are the same as those of the embodiment 1, and after 30 minutes of hydrogen chloride gas is introduced, the reflux starts to occur at the top of the tower.
Example 2, after 30 minutes of introduction, an immediate sample (primary distillation) at the top of the column was taken and analyzed, the content of 1-chlorobutane was 95.56%, the content of n-butanol was 2.87%, the content of n-butyl ether was 1.110%, the isomer was 0.082%, and the others were 0.378%; taking an immediate sample at the top of the tower after 1 hour and 45 minutes for analysis, wherein the content of 1-chlorobutane is 87.13%, the content of n-butyl alcohol is 11.18%, the content of n-butyl ether is 0.48%, the content of isomers is 0.047%, and the other content is 1.163%; after 10 hours of introduction, the column top instant sample is taken and analyzed, the content of 1-chlorobutane is 85.38%, the content of n-butyl alcohol is 13.59%, the content of n-butyl ether is 0.51%, the isomer is 0.068%, the other 0.452%, and the yield of 1-chlorobutane is 93.7% based on n-butyl alcohol.
Example 3:
10 kg of 1-butyl-3-methylimidazole chloride is added at the bottom of the reaction rectifying tower 1, the temperature in the whole system of the reaction rectifying tower 1 is raised to 150+/-2 ℃, the temperature of the falling film evaporator 5 is raised to 120 ℃, the reflux temperature of the tower top is controlled to 90+/-1 ℃, other process conditions are the same as those in the embodiment 1, and after 30 minutes of the hydrogen chloride gas is introduced, the reflux of the tower top begins.
Example 3, after 30 minutes of introduction, an immediate sample (primary distillation) was taken from the top of the column and analyzed, with a 1-chlorobutane content of 99.87%, an n-butanol content of 0.049%, an n-butyl ether content of 0.0094%, an isomer 0.0512%, and others of 0.0204%; taking an immediate sample at the top of the tower after 1 hour and 45 minutes for analysis, wherein the content of 1-chlorobutane is 98.74%, the content of n-butyl alcohol is 0.23%, the content of n-butyl ether is 0.0113%, the content of isomers is 0.141%, and the other content is 0.8777%; after 10 hours of introduction, the column top instant sample was taken and analyzed, the 1-chlorobutane content was 90.22%, the n-butanol content was 2.34%, the n-butyl ether 0.0364%, the isomer 0.173%, the other 7.2306%, and the 1-chlorobutane yield was 90.3% based on n-butanol.
Example 4:
10 kg of 1-butylpyridine hydrochloride is added at the bottom of the reaction rectifying tower 1, the spraying flow rate is 206g/min, the reflux temperature at the top of the tower is controlled at 80+/-1 ℃, the rest process conditions are the same as those in the example 1, and after 30 minutes of hydrogen chloride gas is introduced, the reflux starts to appear at the top of the tower.
Example 4, after 30 minutes of introduction, an immediate sample (primary distillation) was taken from the top of the column and analyzed, with a 1-chlorobutane content of 98.11%, an n-butanol content of 1.37%, an n-butyl ether content of 0.251%, an isomer content of 0.0009% and other 0.2681%; taking an immediate sample at the top of the tower after 1 hour and 45 minutes for analysis, wherein the content of 1-chlorobutane is 99.35%, the content of n-butyl alcohol is 0.0281%, the content of n-butyl ether is 0.43%, the content of isomers is 0.054%, and the other content is 0.1379%; after 10 hours of introduction, the column top instant sample was taken and analyzed, the content of 1-chlorobutane was 99.47%, the content of n-butanol was 0.0307%, the content of n-butyl ether was 0.33%, the isomer was 0.078%, the other 0.0913%, and the yield of 1-chlorobutane was 95.4% based on n-butanol.
Comparative example 1:
10 kg of n-butanol is added into the bottom of the reaction rectifying tower 1, and the temperature is raised to 120+/-2 ℃ in the whole system of the reaction rectifying tower 1. Then, n-butyl alcohol is introduced at the top end of the first tower section at the flow rate of 74g/min, hydrogen chloride gas is introduced at the bottom of the tower at the flow rate of 30-31 g/min, reflux starts to occur at the top of the tower after 55 min, the reflux ratio of the top of the tower is controlled to be 6:1, the initial reflux temperature is controlled to be 110+/-2 ℃, the reflux temperature is reduced to 80+/-2 ℃ after 1 hour for 30 min, and the gas extracted from the top of the tower enters a product storage tank 4 after being condensed.
Comparative example 1, after 55 minutes of introduction, an immediate sample (primary distillation) at the top of the column was taken and analyzed, wherein the content of 1-chlorobutane was 0.08%, the content of n-butanol was 99.21%, the content of n-butyl ether was 0.0011%, the isomer was 0.0019%, and the other was 0.707%; taking an immediate sample at the top of the tower after 1 hour and 25 minutes for analysis, wherein the content of 1-chlorobutane is 29.46%, the content of n-butyl alcohol is 69.58%, the content of n-butyl ether is 0.0021%, the content of isomers is 0.0039%, and the other content is 0.954%; taking a tower top instant sample after 10 hours, and analyzing the sample, wherein the content of 1-chlorobutane is 98.87%, the content of n-butyl alcohol is 0.7824%, the content of n-butyl ether is 0.0512%, the isomer is 0.0169%, and the other 0.2795%; the yield of 1-chlorobutane was 97.9% based on n-butanol.
Comparative example 2:
10 kg of 35% hydrochloric acid is added into the bottom of the reaction rectifying tower 1, and the temperature is raised to 120+/-2 ℃ in the whole system of the reaction rectifying tower 1. N-butanol is introduced at a flow rate of 74g/min, reflux starts to appear at the top of the tower after 30 minutes, the reflux ratio of the top of the tower is controlled to be 6:1, the reflux temperature is 80+/-1 ℃, and the gas extracted from the top of the tower enters a product storage tank 4 after being condensed.
Comparative example 2, after 30 minutes of introduction, an immediate sample (primary distillation) at the top of the column was taken and analyzed, and the content of 1-chlorobutane was 19.89%, the content of n-butanol was 79.24%, the content of n-butyl ether was 0.082%, the isomer was 0.061%, and the others were 0.727%; introducing the mixture for 1 hour and 45 minutes, taking a tower top instant sample for analysis, wherein the content of 1-chlorobutane is 27.49%, the content of n-butyl alcohol is 71.40%, the content of n-butyl ether is 1.02%, the isomer is 0.021%, and the other content is 0.069%; after 10 hours of introduction, the column top instant sample was taken and analyzed, the content of 1-chlorobutane was 96.22%, the content of n-butanol was 0.913%, the content of n-butyl ether was 0.0231%, the isomer was 2.157%, the other 0.6869%, and the yield of 1-chlorobutane was 95.4% based on n-butanol.
Claims (2)
1. A method for continuously synthesizing chlorobutane in a non-aqueous system is characterized in that: the non-aqueous system consists of ionic liquid, n-butanol and hydrogen chloride, wherein the ionic liquid is a solvent and also serves as a catalyst for chlorination reaction; the ionic liquid is 1-butyl-3-methylimidazole chloride or 1-butylpyridine hydrochloride; the chemical reaction of raw material n-butyl alcohol and hydrogen chloride and the rectification of reaction product 1-chlorobutane are synchronously and continuously carried out in a reaction rectifying tower;
1-butyl-3-methylimidazole chloride or 1-butylpyridine hydrochloride is introduced from the top end of a first tower section of the reactive distillation tower in a spray mode, n-butanol is introduced from the top end of the first tower section, and hydrogen chloride gas is introduced from the bottom of the tower;
the flow rate of the 1-butyl-3-methylimidazole chloride or 1-butylpyridine hydrochloride is 205-210g/min, the flow rate of the n-butyl alcohol is 70-74g/min, and the flow rate of the hydrogen chloride gas is 29-31g/min;
the 1-butyl-3-methylimidazole chloride or 1-butylpyridine hydrochloride is introduced from the top end of a first tower section of the reaction rectifying tower in a spray mode, falls and accumulates at the bottom of the tower, is pumped into a falling film evaporator through a first circulating pump for dehydration, and the 1-butyl-3-methylimidazole chloride or 1-butylpyridine hydrochloride after moisture removal is sprayed from the top end of the first tower section into the reaction rectifying tower for recycling;
after reacting for 10-30 minutes, reflux starts to appear at the tower top, the reflux ratio of 5-7:1 and the reflux temperature of 69-92 ℃ are controlled at the tower top, and the gas extracted from the tower top flows into a product storage tank after being condensed by a condenser to obtain high-purity 1-chlorobutane;
when the reaction starts, 1-butyl-3-methylimidazole chloride or 1-butylpyridine hydrochloride is added from the bottom of the reaction rectifying tower, the temperature in the whole system of the reaction rectifying tower is raised to 88-152 ℃, and the temperature of the falling film evaporator is raised to 100-120 ℃.
2. The method for continuously synthesizing chlorobutane in a non-aqueous system according to claim 1, wherein: the content of the water content of the 1-butyl-3-methylimidazole chloride or 1-butylpyridine hydrochloride after the water removal is 1.3 to 1.7 weight percent.
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| CN202111310167.4A CN113896614B (en) | 2021-11-08 | 2021-11-08 | Method for continuously synthesizing chlorobutane in non-aqueous system |
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| CN202111310167.4A CN113896614B (en) | 2021-11-08 | 2021-11-08 | Method for continuously synthesizing chlorobutane in non-aqueous system |
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