CN113896614A - 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 64
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 112
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 21
- 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
- 239000002608 ionic liquid Substances 0.000 claims abstract description 19
- 238000000066 reactive distillation Methods 0.000 claims abstract description 19
- IPHBBZWQWUFXGR-UHFFFAOYSA-N 1-butyl-2H-pyridine hydrochloride Chemical compound CCCCN1CC=CC=C1.Cl IPHBBZWQWUFXGR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011552 falling film Substances 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 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 24
- 238000005507 spraying Methods 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 6
- 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 description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 21
- 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 9
- 238000004821 distillation Methods 0.000 description 8
- 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 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 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
- 230000001186 cumulative effect Effects 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
- 238000010586 diagram Methods 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
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000005086 pumping Methods 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
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- 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
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- 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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Abstract
A method for continuously synthesizing chlorobutane in a non-aqueous system, wherein the non-aqueous system consists of ionic liquid 1-butyl-3-methylimidazolium 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 continuous synthesis of chlorobutane, normal butanol and hydrogen chloride and the rectification of the reaction product 1-chlorobutane are synchronously and continuously carried out in a reaction rectifying tower. Introducing hydrogen chloride gas from the bottom of the reactive distillation column, introducing n-butanol and ionic liquid into the middle of the reactive distillation column, collecting 1-chlorobutane from the top of the reactive distillation column, and returning part of the ionic liquid collected from the bottom of the reactive distillation column into the system after water is evaporated in a falling film evaporator. The method has the advantages that the reaction and the rectification are carried out simultaneously, the operation is simple, the reaction rate is high, and the 1-chlorobutane is generated by almost instantaneous reaction after the gas phase and the liquid phase are contacted; 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 by the n-butyl alcohol.
Description
Technical Field
The invention relates to a method for continuously synthesizing chlorobutane in a non-aqueous system, belonging to the technical field of organic synthesis.
Background
The 1-chlorobutane is also called n-butyl chloride and n-butyl chloride, is a relatively important monohalogenated alkane, can be used as a solvent, an organic synthesis intermediate and a catalyst and is used in the fields of grease, rubber, resin and the like. The raw materials for synthesizing the 1-chlorobutane are many, and the 1-chlorobutane is mainly synthesized by taking low-price n-butanol and hydrogen chloride gas or concentrated hydrochloric acid as raw materials in industrial production, and the synthesis methods are disclosed in the following patents:
the preparation method of 1-chlorobutane disclosed in Chinese patent CN104326863A is characterized in that dimethyl sulfoxide is used as a catalyst to catalyze hydrogen chloride and n-butyl alcohol 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, the efficiency is low, and the energy consumption is high.
Chinese patent CN1440958 (CN1225440C) discloses a method for converting primary alcohol or cyclohexanol in acidic ionic liquid [ Hmim ] + X- (X = Cl, Br, I) into halogenated hydrocarbon, wherein N-butanol is reacted with N-methylimidazole hydrochloride ionic liquid, wherein N-methylimidazole hydrochloride is used as a solvent and chlorine is provided to participate in chlorination reaction, the process is intermittent, the reaction time is 12 hours, the efficiency is low, and after the reaction is finished, concentrated hydrochloric acid is needed to regenerate N-methylimidazole hydrochloride ionic liquid.
Disclosure of Invention
Aiming at the existing defects, the invention provides a method for continuously synthesizing chlorobutane in a nonaqueous system, which realizes the following purposes: the ionic liquid is used as a solvent and a catalyst to form a non-aqueous reaction system, so that the reaction time is greatly shortened, the continuous synthesis of high-purity 1-chlorobutane is realized in a reaction rectification mode, and the ionic liquid is regenerated by online simple falling film evaporation dehydration.
In order to realize the purpose, the invention adopts the following technical scheme:
a method for continuously synthesizing chlorobutane in a non-aqueous system, wherein the non-aqueous system consists of ionic liquid, n-butyl alcohol and hydrogen chloride, and the ionic liquid is a solvent and also serves as a catalyst for chlorination reaction; the ionic liquid is 1-butyl-3-methylimidazole chloride salt or 1-butylpyridine hydrochloride; the continuous synthesis of chlorobutane is characterized in that the chemical reaction of the raw material n-butyl alcohol and hydrogen chloride and the rectification of the 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 solution:
adding a proper amount of 1-butyl-3-methylimidazolium chloride or 1-butylpyridine hydrochloride at the bottom of the reactive distillation tower, heating the whole system of the reactive distillation tower to 88-152 ℃, and heating the falling film evaporator to 100-120 ℃. And starting a second circulating pump, allowing the ionic liquid to pass through a falling-film evaporator and enter the reactive distillation tower from the top end of the first tower section of the reactive distillation tower in a spraying mode, wherein the spraying flow rate is 205-210 g/min, then introducing n-butyl alcohol at the top end of the first tower section at the flow rate of 70-74 g/min, simultaneously introducing hydrogen chloride gas at the bottom of the tower at the flow rate of 29-31 g/min, allowing the tower top to reflux after 10 or 30 minutes, condensing the gas extracted from the tower top, and then allowing the condensed gas to enter 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 ℃. And accumulating the water-containing 1-butyl-3-methylimidazolium chloride or 1-butylpyridine hydrochloride at the bottom of the tower, pumping the water-containing 1-butyl-3-methylimidazolium chloride or 1-butylpyridine hydrochloride into a falling-film evaporator by a first circulating pump to evaporate water in the falling-film evaporator, collecting and concentrating the water, wherein the water content of the water-removed 1-butyl-3-methylimidazolium chloride or 1-butylpyridine hydrochloride is 1.3-1.7%, and spraying the water-removed 1-butyl-3-methylimidazolium chloride or 1-butylpyridine hydrochloride into the reactive distillation 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 the 1-chlorobutane;
2. the ionic liquid as the catalyst can realize the recovery of the catalytic performance only by removing part of water;
3. the method realizes the coupling of synthesis and refining of chlorobutane through reactive distillation, the reaction and the rectification are carried out simultaneously, the operation is simple, the process flow is shortened, after hydrogen chloride gas is introduced for 10-30 minutes, an immediate sample (initial distillation) at the top of the tower is taken for analysis, the content of 1-chlorobutane is 95.56-99.87%, the content of n-butyl alcohol is 0.049-2.87%, n-butyl ether is 0.0021-1.110%, isomers are 0.0009-0.082%, and the other components are 0.0204-0.378%; introducing hydrogen chloride gas for 1 hour and 45 minutes, taking an immediate sample (initial 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%; after the reaction is carried out for 10 hours, the accumulated sample is analyzed, 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 content of isomers is 0.006-0.173%, the content of other isomers is 0.0913-7.2306%, and the yield of 1-chlorobutane calculated by n-butyl alcohol is 90.3-98.2%.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a flow diagram of the synthetic process of the present invention.
In the figure, 1-reaction rectifying tower; 2-a condenser; 3-a reflux buffer tank; 4-a product storage tank; 5-falling film evaporator; 6-a reboiler; 7-a second circulation pump; 8-first circulation pump.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the 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 chlorine salt is added to the bottom of the reactive distillation tower 1 and introduced into a reboiler 6 for circulation, the reboiler 6 is opened to heat the whole system of the reactive distillation tower 1 to 120 +/-2 ℃, and then the 1-butyl-3-methylimidazole chlorine salt is introduced into a falling film evaporator 5 to heat the temperature to 110 ℃. And (3) starting a second circulating pump 7, allowing the ionic liquid to pass through a falling-film evaporator 5, then allowing the ionic liquid to enter the reactive rectifying tower 1 from the top end of the first tower section of the reactive rectifying tower 1 in a spraying mode, allowing the spraying flow rate to be 210g/min, introducing n-butyl alcohol at the top end of the first tower section at the flow rate of 74g/min, simultaneously introducing hydrogen chloride gas at the bottom of the tower at the flow rate of 30-31 g/min, allowing reflux to occur at the top of the tower after 10 minutes, controlling the reflux ratio of the top of the tower to be 6:1, allowing reflux temperature to be 70 +/-1 ℃, condensing gas extracted at the top of the tower into liquid through a condenser 2, allowing the liquid to flow into a reflux buffer tank 3, allowing liquid at the rear part of the reflux buffer tank to flow back into the reactive rectifying tower 1, and allowing part of the liquid to flow into a product storage tank 4 to obtain high-purity 1-chlorobutane. The water-containing 1-butyl-3-methylimidazole chlorine salt is accumulated at the bottom of the tower, and is respectively pumped into a reboiler 6 and a falling film evaporator 5 by a first circulating pump 8 according to the mass ratio of 1:1, the water-containing 1-butyl-3-methylimidazole chlorine salt in the falling film evaporator 5 is evaporated to remove water, the water is collected and then is treated in a centralized manner, the water content of the water-removed 1-butyl-3-methylimidazole chlorine salt is 1.5%, and the water-removed 1-butyl-3-methylimidazole chlorine salt is sprayed into the reactive distillation tower 1 from the top of the first tower section of the reactive distillation tower 1 again for recycling.
Example 1, after introducing hydrogen chloride gas for 10 minutes, an immediate sample (preliminary distillation) at the top of the column was taken for analysis, and the content of 1-chlorobutane was 99.67%, the content of n-butanol was 0.21%, n-butyl ether was 0.0021%, isomers were 0.009%, and others were 0.1089%; introducing 45 minutes after 1 hour, collecting accumulated samples, and analyzing, wherein the content of 1-chlorobutane is 99.80 percent, the content of n-butyl alcohol is 0.04 percent, the content of n-butyl ether is 0.0015 percent, the content of isomers is 0.009 percent, and the content of the other isomers is 0.1495 percent; after 10 hours of passing, the cumulative sample was analyzed to find that the 1-chlorobutane content was 99.84%, the n-butanol content was 0.036%, the n-butyl ether was 0.0018%, the isomer was 0.006%, and the other 0.1162%, and the 1-chlorobutane yield was 98.2% based on the n-butanol.
Example 2:
10 kg of 1-butyl-3-methylimidazolium chloride is added to the bottom of the reactive rectification tower 1, the temperature in the whole system of the reactive rectification 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 in example 1, and the hydrogen chloride gas begins to reflux at the top of the tower after being introduced for 30 minutes.
Example 2, after 30 minutes of introduction, an immediate sample (preliminary distillation) at the top of the column was taken and analyzed, and the content of 1-chlorobutane was 95.56%, the content of n-butanol was 2.87%, n-butyl ether was 1.110%, the content of isomers was 0.082%, and the other content was 0.378%; after the mixture is introduced for 1 hour and 45 minutes, an immediate sample at the top of the tower is taken for analysis, wherein the content of 1-chlorobutane is 87.13 percent, the content of n-butyl alcohol is 11.18 percent, the content of n-butyl ether is 0.48 percent, the content of isomers is 0.047 percent, and the content of the isomers is 1.163 percent; after 10 hours of introduction, the column top was sampled and analyzed, and the 1-chlorobutane content was 85.38%, the n-butanol content was 13.59%, the n-butyl ether was 0.51%, the isomer was 0.068%, the other was 0.452%, and the 1-chlorobutane yield was 93.7% in terms of n-butanol.
Example 3:
10 kg of 1-butyl-3-methylimidazolium chloride is added to the bottom of the reactive rectifying tower 1, the temperature in the whole system of the reactive rectifying tower 1 is raised to 150 +/-2 ℃, the temperature of the falling film evaporator 5 is raised to 120 ℃, the reflux temperature at the top of the tower is controlled to be 90 +/-1 ℃, other process conditions are the same as those of the example 1, and the reflux of the hydrogen chloride gas begins to appear at the top of the tower after 30 minutes of introduction.
Example 3, an immediate sample (preliminary distillation) at the top of the column was taken after 30 minutes had passed and analyzed, and the 1-chlorobutane content was 99.87%, the n-butanol content was 0.049%, the n-butyl ether was 0.0094%, the isomer was 0.0512%, and the others were 0.0204%; after the mixture is introduced for 1 hour and 45 minutes, an immediate sample at the top of the tower is taken for analysis, wherein the content of 1-chlorobutane is 98.74 percent, the content of n-butyl alcohol is 0.23 percent, n-butyl ether is 0.0113 percent, an isomer is 0.141 percent, and the rest is 0.8777 percent; after 10 hours of passing, the column top was sampled and analyzed, and the 1-chlorobutane content was 90.22%, the n-butanol content was 2.34%, the n-butyl ether was 0.0364%, the isomer was 0.173%, the other 7.2306%, and the 1-chlorobutane yield was 90.3% based on the n-butanol.
Example 4:
10 kg of 1-butylpyridine hydrochloride is added into the bottom of the reactive 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 other process conditions are the same as those in example 1, and the reflux at the top of the tower begins to appear after the hydrogen chloride gas is introduced for 30 minutes.
Example 4, an immediate sample (preliminary distillation) at the top of the column was taken after 30 minutes had passed through and analyzed, and the content of 1-chlorobutane was 98.11%, the content of n-butanol was 1.37%, n-butyl ether was 0.251%, the content of isomers was 0.0009%, and the remainder was 0.2681%; after the mixture is introduced for 1 hour and 45 minutes, an immediate sample at the top of the tower is taken for analysis, wherein the content of 1-chlorobutane is 99.35 percent, the content of n-butyl alcohol is 0.0281 percent, the content of n-butyl ether is 0.43 percent, the content of isomers is 0.054 percent, and the content of the isomers is 0.1379 percent; after 10 hours of introduction, the column top was sampled and analyzed, and the 1-chlorobutane content was 99.47%, the n-butanol content was 0.0307%, the n-butyl ether was 0.33%, the isomer was 0.078%, the other 0.0913%, and the 1-chlorobutane yield was 95.4% in terms of n-butanol.
Comparative example 1:
10 kg of n-butyl alcohol is added to the bottom of the reaction rectifying tower 1, and the temperature in the whole system of the reaction rectifying tower 1 is raised to 120 +/-2 ℃. And then introducing n-butanol at the top end of the first tower section at a flow rate of 74g/min, introducing hydrogen chloride gas at the bottom of the tower at a flow rate of 30-31 g/min, beginning to reflux at the top of the tower after 55 minutes, controlling the reflux ratio at the top of the tower to be 6:1, controlling the initial reflux temperature to be 110 +/-2 ℃, reducing the reflux temperature to 80 +/-2 ℃ after 1 hour and 30 minutes, and condensing gas extracted from the top of the tower and then entering a product storage tank 4.
Comparative example 1, after 55 minutes of introduction, an immediate sample (preliminary distillation) at the top of the column was taken for analysis, and the content of 1-chlorobutane was 0.08%, the content of n-butanol was 99.21%, n-butyl ether was 0.0011%, the content of isomers was 0.0019%, and the content of the others was 0.707%; after the reaction lasts for 1 hour and 25 minutes, an immediate sample at the top of the tower is taken for analysis, wherein the content of 1-chlorobutane is 29.46 percent, the content of n-butyl alcohol is 69.58 percent, n-butyl ether is 0.0021 percent, an isomer is 0.0039 percent, and the other content is 0.954 percent; after 10 hours of introduction, the tower top is taken for analysis, and the content of 1-chlorobutane is 98.87 percent, the content of n-butyl alcohol is 0.7824 percent, n-butyl ether is 0.0512 percent, the content of isomers is 0.0169 percent, and the content of the other isomers is 0.2795 percent; the yield of 1-chlorobutane calculated by n-butanol is 97.9%.
Comparative example 2:
10 kg of 35% hydrochloric acid is added to the bottom of the reaction rectifying tower 1, and the temperature in the whole system of the reaction rectifying tower 1 is raised to 120 +/-2 ℃. And (3) introducing n-butanol at the flow rate of 74g/min, refluxing the top of the tower after 30 minutes, controlling the reflux ratio of the top of the tower to be 6:1, controlling the reflux temperature to be 80 +/-1 ℃, and condensing gas extracted from the top of the tower and then entering a product storage tank 4.
Comparative example 2, an immediate sample (preliminary distillation) at the top of the column was taken after 30 minutes had passed and analyzed, and the 1-chlorobutane content was 19.89%, the n-butanol content was 79.24%, the n-butyl ether was 0.082%, the isomer was 0.061%, and the others were 0.727%; after the mixture is introduced for 1 hour and 45 minutes, an immediate sample at the top of the tower is taken for analysis, wherein the content of 1-chlorobutane is 27.49 percent, the content of n-butyl alcohol is 71.40 percent, n-butyl ether is 1.02 percent, isomers are 0.021 percent, and the other isomers are 0.069 percent; after 10 hours of passing, the column top was sampled and analyzed, and the 1-chlorobutane content was 96.22%, the n-butanol content was 0.913%, the n-butyl ether was 0.0231%, the isomer was 2.157%, the other was 0.6869%, and the 1-chlorobutane yield was 95.4% based on the n-butanol.
Claims (7)
1. A method for continuously synthesizing chlorobutane in a non-aqueous system is characterized by comprising the following steps: the non-aqueous system consists of ionic liquid, n-butyl alcohol and hydrogen chloride, wherein the ionic liquid is a solvent and is also used as a catalyst for chlorination reaction; the ionic liquid is 1-butyl-3-methylimidazole chloride salt or 1-butylpyridine hydrochloride; the continuous synthesis of chlorobutane is characterized in that the chemical reaction of the raw material n-butyl alcohol and hydrogen chloride and the rectification of the reaction product 1-chlorobutane are synchronously and continuously carried out in a reaction rectifying tower.
2. The method of claim 1, wherein the continuous synthesis of chlorobutane in a non-aqueous system comprises: 1-butyl-3-methylimidazolium chloride or 1-butylpyridine hydrochloride is introduced from the top end of the first tower section of the reactive distillation tower in a spraying 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.
3. The method of claim 2, wherein the continuous synthesis of chlorobutane in a non-aqueous system comprises: the flow rate of introducing the 1-butyl-3-methylimidazolium chloride or 1-butylpyridine hydrochloride is 205-210 g/min, the flow rate of introducing the n-butanol is 70-74 g/min, and the flow rate of introducing the hydrogen chloride gas is 29-31 g/min.
4. The method of claim 2, wherein the continuous synthesis of chlorobutane in a non-aqueous system comprises: the 1-butyl-3-methylimidazole chloride salt or 1-butylpyridine hydrochloride is introduced from the top end of a first tower section of the reactive distillation tower in a spraying 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 salt or 1-butylpyridine hydrochloride after moisture removal is sprayed from the top end of the first tower section again and enters the reactive distillation tower for recycling.
5. The method of claim 4, wherein the continuous synthesis of chlorobutane in a non-aqueous system comprises: the water content of the dehydrated 1-butyl-3-methylimidazole chloride salt or 1-butylpyridine hydrochloride is 1.3-1.7 wt%.
6. The method of claim 1, wherein the continuous synthesis of chlorobutane in a non-aqueous system comprises: after the reaction is carried out for 10-30 minutes, the reflux begins to appear at the top of the tower, the reflux ratio of 5-7: 1 and the reflux temperature of 69-92 ℃ are controlled at the top of the tower, and the gas extracted from the top of the tower flows into a product storage tank after being condensed by a condenser to obtain the high-purity 1-chlorobutane.
7. The method of claim 1, wherein the continuous synthesis of chlorobutane in a non-aqueous system comprises: when the reaction is started, adding 1-butyl-3-methylimidazolium chloride or 1-butylpyridine hydrochloride from the bottom of the reactive distillation column, raising the temperature in the whole system of the reactive distillation column to 88-152 ℃, and raising the temperature of the falling film evaporator to 100-120 ℃.
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