CN117820135A - Method for continuously preparing tert-butylaminoethoxyethanol - Google Patents
Method for continuously preparing tert-butylaminoethoxyethanol Download PDFInfo
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- CN117820135A CN117820135A CN202311713376.2A CN202311713376A CN117820135A CN 117820135 A CN117820135 A CN 117820135A CN 202311713376 A CN202311713376 A CN 202311713376A CN 117820135 A CN117820135 A CN 117820135A
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- butylamine
- butylaminoethoxyethanol
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- 238000000034 method Methods 0.000 title claims abstract description 35
- AHXXIYFEJGGBMG-UHFFFAOYSA-N 1-[2-(tert-butylamino)ethoxy]ethanol Chemical compound CC(O)OCCNC(C)(C)C AHXXIYFEJGGBMG-UHFFFAOYSA-N 0.000 title claims description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 23
- HUTXVUPGARJNHM-UHFFFAOYSA-N 1-(2-chloroethoxy)ethanol Chemical compound CC(O)OCCCl HUTXVUPGARJNHM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- VJRXEJXVFJDYJH-UHFFFAOYSA-N 1-ethoxyethanol;2-methylpropan-2-amine Chemical compound CC(C)(C)N.CCOC(C)O VJRXEJXVFJDYJH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012043 crude product Substances 0.000 claims abstract description 9
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 6
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 12
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000005576 amination reaction Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- 235000009518 sodium iodide Nutrition 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000011085 pressure filtration Methods 0.000 claims description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims 2
- 239000003513 alkali Substances 0.000 abstract description 5
- 238000005112 continuous flow technique Methods 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- -1 haloalkyl alcohol Chemical compound 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YDEDDFNFQOPRQJ-UHFFFAOYSA-N 2-[2-(tert-butylamino)ethoxy]ethanol Chemical compound CC(C)(C)NCCOCCO YDEDDFNFQOPRQJ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005913 hydroamination reaction Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910001504 inorganic chloride Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KTWPNGDSFIQDBU-UHFFFAOYSA-N 2-methylpropan-2-amine;morpholine Chemical compound CC(C)(C)N.C1COCCN1 KTWPNGDSFIQDBU-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical group N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical group NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for continuously preparing tert-butylamine ethoxyethanol, which adopts tert-butylamine and 2-chloroethoxyethanol as raw materials, adds a catalyst, continuously transmits the raw materials to a dynamic tubular reactor with a process set temperature through pulse, controls the feeding quantity, the reaction pressure and the reaction time, continuously discharges and transmits the raw materials to a crude product receiving kettle, then carries out alkali neutralization treatment and distillation to recycle the tert-butylamine, and finally carries out rectification to obtain the high-purity tert-butylamine ethoxyethanol. The invention adopts dynamic tubular continuous flow process to replace traditional kettle type process, so that the reaction high temperature residence time is short, the reaction selectivity and the molar yield are greatly improved, the product quality index reaches foreign level, and the invention has obvious improvement and innovation to the prior art.
Description
Technical Field
The invention belongs to the technical field of new material synthesis, and particularly relates to a method for continuously preparing tert-butylaminoethoxyethanol.
Background
Tert-butylaminoethoxyethanol (TBEE), CAS: [87787-67-5], english name: 2- (2-tert-butyl-hydrochloride) ethanol. TBEE is a secondary aminoether alcohol with strong steric hindrance and is a clear transparent liquid with ammonia taste, readily soluble in water and boiling at about: 233.8+/-15.0 ℃ or 123-127 ℃/20mmHg, and the chemical structural formula is as follows:
because the amino nitrogen atom in the molecular structure is connected with a nonlinear carbon chain group (tertiary butyl) with larger volume, a strong steric hindrance effect can be generated, and the strong steric hindrance effect makes the bond energy of the nonlinear carbon chain group and carbon dioxide weaker so as to weaken the reaction of the nonlinear carbon chain group and the carbon dioxide. The stronger alkalinity leads the acid gas capacity of the TBEE to be larger, the activity coefficient of the TBEE reacting with hydrogen sulfide is PKa=10.3, and the TBEE has higher hydrogen sulfide reactivity and selectivity. The above properties make it desirable for use in the selective desulfurization of acid gases.
Tert-butylamine ethoxyethanol (TBEE) is used as a novel efficient selective desulfurization solvent, has remarkable energy-saving effect in the process of purifying acid gas, does not corrode equipment in the application process, and is widely applied to selective desulfurization of natural gas, oilfield associated gas and synthesis gas.
Currently, the synthetic route of tert-butylaminoethoxyethanol (TBEE) is mainly 2 of the following:
the method comprises the following steps:
1. exxon (Exxon) research and engineering company in US4471138A and US4405585A report that tert-butylamine and 2-chloroethoxyethanol are used as raw materials, and the tert-butylamine ethoxyethanol is obtained by reacting for 3 hours at 150 ℃ in a high-temperature pressure-resistant kettle, and the yield is about 77%.
2. The Sichuan institute of fine chemical engineering, CN1623978A discloses a process for preparing tert-butylaminoethoxyethanol with steric hindrance, which comprises charging tert-butylamine and 2-chloroethoxyethanol into a reaction vessel, reacting under heating and self-pressurizing conditions, neutralizing with alkali, distilling to recover excessive tert-butylamine, filtering, rectifying the filtrate to obtain high-purity tert-butylaminoethoxyethanol with yield of 72%.
The reaction equation is as follows:
the preparation method has the following defects: when the haloalkyl alcohol is used as a reactant, excessive alkali liquor needs to be added in the subsequent treatment process to convert the byproduct amine hydrochloride into inorganic chloride, and corrosion-resistant reaction equipment needs to be used. The high temperature causes a lot of reaction impurities, the yield is low, the complicated purification operation causes higher production cost, and the by-products such as inorganic chloride and the like can also cause unavoidable environmental problems in the treatment process.
The second method is as follows:
1. U.S. patent No. 4487967a reports for the first time the synthesis of severely sterically hindered amino-ether alcohols TBEE from diethylene glycol and tert-butylamine as reaction raw materials, in which catalysts of various metals Ni, co, pt, pd, rh and Cr as active components were constructed and their catalytic activity for the amination reaction was examined in tank reactors as well as in fixed bed reactors. The result shows that the catalytic activity of the Ni component is optimal, and the TBEE yield can reach 54% in the reaction for 6 hours.
2. Pasteur European company in China patent CN102906061B discloses a process for preparing 2- (2-tert-butylaminoethoxy) ethanol by reacting diethylene glycol (DEG) with tert-butylamine (TBA) in the presence of hydrogen and copper catalyst using advanced hydroamination techniques, with a conversion of 70%, selectivity 85% and a yield of 60% at optimum conditions.
3. Chinese patent CN10890601a employs Ni-based catalysts with different supports (SiO 2, al2O3, activated carbon, tiO2, mgO, SBA-15, ZSM-5, etc.), the DEG conversion in a fixed bed reactor can reach 49.4% under optimal reaction conditions, and TBEE selectivity is 83.3%.
The reaction equation is as follows:
the basf european company adopts the advanced technology of hydro-amination, diethylene glycol and tert-butylamine are used as raw materials for amination reaction, the main byproducts are tert-butylamine morpholine (TBM) and water, and various aliphatic amines are synthesized by an alcohol catalytic amination method, so that the synthesis method is currently considered as an economic, green and safe synthesis method. However, the prior art has the defects of complicated purification process operation and very high production cost due to the problems of low selectivity and low yield.
In summary, finding a continuous preparation method of tert-butylaminoethoxy ethanol with the advantages of low raw material cost, high product purity and yield and less three wastes becomes a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a method for continuously preparing tert-butylamine ethoxyethanol, which takes tert-butylamine and 2-chloroethoxyethanol as raw materials, and the catalyst is respectively and continuously conveyed into a dynamic tubular reactor with a process set temperature through pulse, and the reaction is finished, and a high-purity tert-butylamine ethoxyethanol (TBEE) product is obtained through rectification.
For this purpose, the technical scheme of the invention is as follows:
a method for continuously preparing tert-butylaminoethoxyethanol, comprising the following steps:
(1) Preparation of reaction raw material A: 2-chloroethoxyethanol and 5% of a catalyst aqueous solution in weight ratio of 5:1, mixing;
(2) Continuous flow reaction operation:
continuously conveying the reaction raw material A and tert-butylamine obtained in the step (1) into a dynamic tubular reactor with a process set temperature through pulses, controlling the feeding quantity to be the process set value, the reaction pressure to be 0.5-3.0MPa, the reaction temperature to be 230-250 ℃, and the reaction time to be 1-5 minutes. After the product is discharged through a pressure reducing valve under reduced pressure, the product is analyzed by GC, and the amination product contains less than 5 percent of raw materials of 2-chloroethoxy ethanol.
(3) And (3) reaction treatment:
continuously discharging under reduced pressure through a reducing valve, feeding the discharged material into a crude product receiving kettle, adding sodium hydroxide for neutralization treatment, removing sodium chloride salt through positive pressure filtration, recovering tert-butylamine through reduced pressure distillation of filtrate to obtain a crude product, and obtaining high-purity tert-butylamine ethoxyethanol through reduced pressure rectification.
Preferably, the reaction catalyst in the step (1) is at least one of sodium iodide, sodium bromide, potassium bromide, 18-crown-6 and tetrabutylammonium bromide, preferably sodium iodide, sodium bromide, more preferably sodium bromide.
Preferably, the flow rate ratio of the reaction raw material A to the tert-butylamine in the step (2) is 1: (2-10), preferably 1: (3-6).
Preferably, the internal temperature of the dynamic tubular reactor in step (2) is 238-240 ℃.
Preferably, the reaction time in step (2) is 1 to 3 minutes, preferably 3 minutes.
The sources and theoretical basis of the innovative technical process of the invention are described in detail below, aiming at the drawbacks of the existing synthetic processes.
The current production process adopts batch kettle operation, the reaction temperature is about 150 ℃, the reaction pressure reaches about 5-8 kg, and the high-temperature long-time reaction leads to a plurality of impurities of the product and great purification difficulty, which is a key technical problem to be solved by the invention.
From the analysis of the reaction mechanism, the reaction mainly has the following side reactions:
side reaction:
1.
2.
3.
the reactive activity of chlorine atoms of the polyoxyalkylene halide is low, and hydroxyl and chlorine atoms can be subjected to nucleophilic substitution reaction with tert-butylamine; at high temperature, the 2-chloroethoxy ethanol can be condensed or etherified with the target product TBEE, and the generation of the impurities seriously reduces the yield and increases the cost of the rectification process.
From the theory of organic chemistry, the reaction of tert-butylamine and 2-chloroethoxyethanol belongs to SN of amino-to-chlorine substitution 2 Nucleophilic substitution reaction, leaving ability of halogen atom: iodine > bromine > chlorine, so that bromine or iodine atoms are introduced into the reaction system, thereby greatly enhancing the nucleophilic substitution capability, and further accelerating the reaction speed or reducing the harsh conditions of the reaction.
In addition, according to the related documents, 18 kinds of dangerous chemical processes are mainly supervised.
The continuous flow technology is a new technology which is produced in the chemical industry field in recent years, is regarded as a revolutionary technology capable of changing the chemical industry field, and the continuous flow technology is also becoming a trend to replace the traditional kettle type technology. The continuous flow channel reaction is taken as a new reaction technology, and is increasingly favored in chemical industry by the characteristics of intrinsically safe process, high-efficiency mass and heat transfer, easy integration and self control and the like.
The continuous flow channel equipment needs to be flexibly selected and designed according to the characteristics of the reaction and the physicochemical properties of materials, and the like, and is suitable for various high-risk reaction processes, in particular ammonification, hydrogenation, nitration, and the like.
According to the preparation method, tert-butylamine, 2-chloroethoxyethanol and a catalyst solution are continuously conveyed into a dynamic tubular reactor with a process set temperature through pulses, the feeding amount, the reaction pressure and the reaction time are controlled, the materials are continuously discharged under reduced pressure through a reducing valve, the materials are conveyed into a crude product receiving kettle, then alkali is added for neutralization treatment, and high-purity tert-butylamine ethoxyethanol is prepared through rectification, so that the preparation method of the step (1) is formed.
The invention has the beneficial effects that:
1. the invention adopts tert-butylamine and 2-chloroethoxy ethanol as raw materials, adds a catalyst, continuously transmits the raw materials to a dynamic tubular reactor with the process set temperature through pulse, controls the feeding quantity, the reaction pressure and the reaction time, continuously discharges the raw materials under reduced pressure through a reducing valve, transmits the raw materials to a crude product receiving kettle, then adds alkali for neutralization treatment, and prepares the high-purity tert-butylamine ethoxyethanol through rectification.
2. The invention adopts dynamic tubular continuous flow process to replace traditional kettle type process, so that the reaction high temperature residence time is short, the reaction selectivity and the molar yield are greatly improved, the product quality index reaches foreign level, and the invention has obvious improvement and innovation to the prior art.
Drawings
Fig. 1 is a process flow diagram of the present invention.
Detailed Description
The following examples will help the scientific researchers understand the technical gist of the present invention, but are not intended to limit the scope of the present invention.
The preparation method of the continuous flow dynamic tubular tert-butylaminoethoxyethanol adopted in the following example comprises the following steps:
(1) Preparation of reaction raw material A: 2-chloroethoxyethanol and 5% of a catalyst aqueous solution in weight ratio of 5:1, mixing;
(2) Continuous flow reaction operation:
continuously conveying the reaction raw material A and tert-butylamine into a dynamic tubular reactor with a process set temperature by pulse, controlling the feeding quantity to be set values specified by the process, and controlling the reaction pressure to be 0.5-3.0MPa and the reaction time to be 2 minutes. After the product is discharged through a pressure reducing valve under reduced pressure, the product is analyzed by GC, and the amination product contains less than 5 percent of raw materials of 2-chloroethoxy ethanol.
(3) And (3) reaction treatment:
continuously discharging under reduced pressure through a reducing valve, feeding the discharged material into a crude product receiving kettle, adding sodium hydroxide for neutralization treatment, removing sodium chloride salt through positive pressure filtration, performing reduced pressure distillation on filtrate to recover tert-butylamine to obtain a crude product, and performing reduced pressure distillation to obtain tert-butylamine ethoxyethanol, wherein the conversion rate of 2-chloroethoxyethanol is more than 85%, and the purity is more than 99.2%.
Example 1 catalyst selection for the reaction System
The data set forth in Table 1 below were obtained using a comparison of the different catalysts, with other conditions unchanged:
TABLE 1
Example 2 internal temperature selection of dynamic tubing:
based on other conditions, different process temperatures were used to obtain the data set forth in table 2 below:
TABLE 2
Example 3 selection of flow rate of reaction system:
the flow rate ratio of the reaction raw material a to t-butylamine was adjusted on the basis of other conditions, to obtain the data listed in table 3 below:
TABLE 3 Table 3
Comparative example 1
An experiment was performed using example 1 described in chinese patent application CN1623978A, the specific steps being as follows:
A. 2 liters of ethanol with the purity of 97 percent and 657g of tert-butylamine with the content of 95 percent or more and 450g of 2-chloroethoxy ethanol are put into a reaction kettle, heated to 100-120 ℃ and subjected to self-pressure reaction for 2.0 hours;
B. cooling the reactants to 60 ℃, adding 220g of KOH with the content of 95%, neutralizing for 1.0 hour under the reflux condition, and cooling to less than or equal to 30 ℃ to recover excessive tert-butylamine;
C. the filtrate obtained after the filtration of the solution is placed at 160 ℃ and is subjected to rough distillation under the vacuum of 0.03 MPa;
D. and (3) rectifying the crude distillate obtained in the step C under the conditions of 190 ℃ and 0.03MPa of empty vacuum to obtain 442g of tert-butylaminoethoxyethanol product, wherein the molar conversion rate of the 2-chloroethoxyethanol is 75.87% and the purity of the product is 95.8%.
The invention is not limited to the above embodiments, and based on the technical solution disclosed in the invention, a person skilled in the art may make some substitutions and modifications to some technical features thereof without creative effort according to the technical content disclosed, and all the substitutions and modifications are within the protection scope of the invention.
Claims (5)
1. A method for continuously preparing tert-butylaminoethoxyethanol, which is characterized by comprising the following steps:
(1) Preparation of reaction raw material A: 2-chloroethoxyethanol and 5% of a catalyst aqueous solution in weight ratio of 5:1, mixing;
(2) Continuous flow reaction operation:
continuously conveying the reaction raw material A and tert-butylamine obtained in the step (1) into a dynamic tubular reactor with a process set temperature through pulses, controlling the feeding quantity to be the process set value, the reaction pressure to be 0.5-3.0MPa, the reaction temperature to be 230-250 ℃, and the reaction time to be 1-5 minutes. After the product is discharged through a pressure reducing valve under reduced pressure, the product is analyzed by GC, and the amination product contains less than 5 percent of raw materials of 2-chloroethoxy ethanol.
(3) And (3) reaction treatment:
continuously discharging under reduced pressure through a reducing valve, feeding the discharged material into a crude product receiving kettle, adding sodium hydroxide for neutralization treatment, removing sodium chloride salt through positive pressure filtration, recovering tert-butylamine through reduced pressure distillation of filtrate to obtain a crude product, and obtaining high-purity tert-butylamine ethoxyethanol through reduced pressure rectification.
2. A continuous process for the preparation of tert-butylaminoethoxyethanol according to claim 1, wherein the reaction catalyst in step (1) is at least one of sodium iodide, sodium bromide, potassium bromide, 18-crown-6, tetrabutylammonium bromide, preferably sodium iodide, sodium bromide, more preferably sodium bromide.
3. The continuous process for preparing tert-butylaminoethoxyethanol according to claim 1, wherein the ratio of flow rates of the reaction material a to tert-butylamine in step (2) is 1: (2-10), preferably 1: (3-6).
4. A process for the continuous preparation of tert-butylaminoethoxyethanol according to claim 1, wherein the internal temperature of the dynamic tubular reactor in step (2) is 238-240 ℃.
5. A process for the continuous preparation of tert-butylaminoethoxyethanol according to claim 1, wherein the reaction time in step (2) is 1-3 minutes, preferably 3 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311713376.2A CN117820135A (en) | 2023-12-13 | 2023-12-13 | Method for continuously preparing tert-butylaminoethoxyethanol |
Applications Claiming Priority (1)
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| CN119330841A (en) * | 2024-11-11 | 2025-01-21 | 山东达民化工股份有限公司 | Process for the efficient catalytic synthesis of tert-butylaminoethoxyethanol |
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