CN109336793A - A kind of method of liquid-solid phase continuous catalytic reaction synthesis 2- thiophenyl ethyl alcohol - Google Patents
A kind of method of liquid-solid phase continuous catalytic reaction synthesis 2- thiophenyl ethyl alcohol Download PDFInfo
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- benzenethiol
- potassium
- ethylene carbonate
- thiophenyl
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
Abstract
A kind of method of liquid-solid phase continuous catalytic reaction synthesis 2- thiophenyl ethyl alcohol, it is related to organic sulfide work technical field, using inorganic porous material carrying alkali metal salt as catalyst, at normal pressure, 120 DEG C, the volume space velocity of ethylene carbonate and benzenethiol mixed solution is 0.75 ~ 1.5 h‑1, benzenethiol conversion ratio 99.9%, 2- thiophenyl ethanol selectivity 99.9%.Catalyst continuously runs 168 h, and the selectivity of benzenethiol conversion ratio and 2- thiophenyl ethyl alcohol is 99% or more.Vacuum distillation is carried out to product and removes the unconverted benzenethiol and ethylene carbonate of denier by Alkali absorption, obtains the 2- thiophenyl alcohol product that purity is higher than 99%.
Description
Technical field
The present invention relates to organic sulfur chemical technology fields, belong to the preparation method of aryl ethoxy thioether, more specifically,
The present invention is a kind of method of selectivity synthesis 2- thiophenyl ethyl alcohol.
Background technique
In aromatic yl sulfide, 2- thiophenyl ethyl alcohol is a kind of important industrial chemicals, can be used for synthesis of phenyl vinyl
Sulfone, high refractive index epoxy resin diluent (phenylthio ethyl -2,3- epoxy -1- dipropyl sulfide), liquid phenolic ester type antioxidant
(KY505) and the small molecule Bcl-2 inhibitor of inducible Apoptosis.
Seen that 2- thiophenyl ethyl alcohol synthetic method reported in the literature mainly has: first method is benzenethiol and ethylene oxide
Reaction generates benzene sulphur ethyl alcohol [Liu J, Qian C, Chen X. A green synthesis of phenyl vinyl
sulfoxide[J]. Research on Chemical Intermediates, 2009, 35(2): 137-144]；Second
Kind method is that benzenethiol is reacted [WO2016138988] with β-ethylene halohydrin in NaOH aqueous solution；The third method is 2- hydroxyl
Ethylphenyl sulfoxide deoxidation and reduction [Zarei M, Ameri M A, Jamaleddini A. NaI/silica sulfuric
acid as an efficient reducing system for deoxygenation of sulfoxides in poly
ethylene glycol (PEG-200)[J]. Journal of Sulfur Chemistry, 2013, 34(3): 259-
263.]；Fourth method be NiBr2 or CuI catalysis aryl bromide reacted with mercaptoethanol [Dubey A V, Gharat S B,
Vijay Kumar A. Glycerol as a Recyclable Solvent for Copper-Mediated Ligand-
Free C‐S Cross‐Coupling Reaction: Application to Synthesis of Gemmacin
Precursor[J]. ChemistrySelect, 2017, 2(17): 4852-4856.]；Fifth method is diphenyl iodine
Fluoroform sulphonate, ethylene glycol and potassium rhodanide microwave one pot process [Vaddula B R, Varma R S, Leazer
J. One‐Pot Catalyst‐Free Synthesis of β‐and γ‐Hydroxy Sulfides Using
Diaryliodonium Salts and Microwave Irradiation[J]. European Journal of
Organic Chemistry, 2012, 2012(35): 6852-6855.]；6th kind of method is nano cupric oxide catalysis ethyl
Potassium xanthate, Beta-bromo ethyl alcohol react [Akkilagunta V K, Kakulapati R R. Synthesis of with iodobenzene
unsymmetrical sulfides using ethyl potassium xanthogenate and recyclable
copper catalyst under ligand-free conditions[J]. The Journal of organic
chemistry, 2011, 76(16): 6819-6824.]
Although the first synthetic method belongs to atomic economy reaction, but ethylene oxide low boiling point (10.8 DEG C), flash-point low (- 29
DEG C), it stores, there are security risks in transport and use process；When reaction temperature is higher than 11 DEG C, reacting must band press operation；
When improving reaction temperature, although reaction speed increases, there is more side reaction, generate more benzene sulphur ethyl alcohol
With the addition product of ethylene oxide so that product quality decline；Using 20% sodium hydroxide solution of mass fraction as catalyst,
Its subsequent separation process is cumbersome.
Second of synthetic method does not meet atomic economy reaction, and 2- the problem is that a large amount of bromination sodium salt of by-product
The separating-purifying of thiophenyl alcohol product is difficult, higher cost.
Third ~ six kind synthetic method does not obviously meet atomic economy reaction, and cost of material is too high, has a large amount of wastes to arrange
It puts, does not have commercial value, be only limitted to laboratory synthesis.
Use benzenethiol and ethylene carbonate considerably less for the document report of Material synthesis 2- thiophenyl ethyl alcohol.The two of early stage
Piece document uses K2CO3For catalyst [Lissel M, Schmidt S, Neumann B. Use of Dimethyl
Carbonate as a Methylating Agent Under Phase Transfer Catalysed Conditions
[J]. Synthesis, 1986, 17(43): 382~383.][Carlson, W.W. Process of
Hydroxyethylation. US Patent 2,448,767,1948-09-07.], 2- thiophenyl alcohol yied about 70%.Closely
The document report of phase reacted with ethylene carbonate using Na-X zeolite catalysis benzenethiol [Upare P P, Kinage A K,
Shingote S K, et al. Environmentally benign synthesis of β-hydroxy sulfides
using cyclic carbonates catalyzed by large-pore zeolites[J]. Green Chemistry
Letters and Reviews, 2012,5 (1): 19-26.], Na-X zeolite catalyst is by the method for filtering from product
It separates and reusable, but the problem is that the reaction time is too long (24 hours), reaction temperature is higher (140 DEG C).
The catalyst separated three times, is dried 2 hours, and calcine again at 400 DEG C 2 hours with acetone washing at 100 DEG C, and
It is reused after being cooled to room temperature, it is clear that the removal process of catalyst is cumbersome.
The vapour pressure of benzenethiol is 260 Pa at 25 DEG C, is higher by nearly 5 times than the vapour pressure of phenol (55 Pa).The gas of PhSH
Taste aerial concentration is very faint when being 0.26 ppb, is easy to arouse people's attention in 0.72 ppm, 8 hours TWA
PEL(allows to expose limit to the weighted average of time) and TLV(threshold value) it is 0.5 ppm.The U.S. NIOSH(employment security with
Health association) recommend exposure concentrations maximum be 0.1 ppm.Oral Administration in Rats LD50For 46.2 mg/kg, in rat abdominal cavity
LD50For 9.8 mg/kg, rat skin LD50For 300 mg/kg, rabbit is 134 mg/kg.All administration routes and all species
Clinical symptoms include that breathing increases, lacks coordination, muscle inability, bony segment myoparalysis, cyanosis and drowsiness.By above-mentioned toxicity
Data are learned it is found that benzenethiol belongs to severe poisonous chemicals, must be prevented from evaporating, emitting, dripping or leaking of liquid or gas in use, are easy using intermittently operated
Air pollution is caused, it is harmful to human health and environment.
Summary of the invention
The purpose of the present invention is seeking some solid base catalysts, in fixed bed reactors, in a mild condition (often
Pressure, temperature are lower than 140 DEG C), continuous catalysis benzenethiol is reacted with ethylene carbonate, obtains 2- thiophenyl ethyl alcohol in high yield, together
When avoid Batch reaction processes that benzenethiol occurs leaking in air to cause the harm of human health and environment.
The purpose of the present invention is what is be achieved through the following technical solutions:
Solid base catalyst, in fixed bed reactors, in a mild condition (normal pressure, temperature are lower than 140 DEG C), continuous catalysis benzene
Thiophenol is reacted with ethylene carbonate, is included the following steps:
(1) solid base catalyst is inorganic porous carrier loaded alkali metal salt, using equi-volume impregnating by alkali metal salt water
Solution is impregnated on porous carrier, 120 DEG C dry 24 hours, or continue 400~600 DEG C Muffle kiln roasting 3 hours, alkali gold
The load capacity for belonging to salt is 5~20%(mass percent)；
(2) ethylene carbonate measured is previously laid into preparing tank, benzenethiol is pumped to from storage tank with metering pump and is matched
It is stirred in tank processed and is configured to solution；
(3) solid base catalyst is seated in reaction tube, both ends are with silica wool and quartz sand filling for maintaining bed height
Degree, assembling obtain fixed bed reactors；
(4) benzenethiol and ethylene carbonate mixed solution are passed through in reaction tube with metering pump and are reacted, reaction temperature is
100~140 DEG C, every 12 hours sampling analyses, the product 2- thiophenyl ethyl alcohol reacted was collected by cooler, titanium dioxide
The emptying of carbon gaseous by-product；
(5) vacuum distillation is carried out to product and removes the unconverted benzenethiol and ethylene carbonate of denier by Alkali absorption,
Finally obtain the 2- thiophenyl alcohol product that purity is 99% or more.
In above scheme, in the step (1) alkali metal salt be sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium fluoride,
Potassium fluoride, rubidium fluoride RbF, cesium fluoride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, sodium bromide, potassium bromide, rubidium bromide, cesium bromide,
Sodium iodide, potassium iodide, rubidium iodide, cesium iodide, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, potassium nitrate, potassium sulfate, tricresyl phosphate
Potassium, potassium formate, potassium oxalate, potassium citrate, potassium tartrate, sodium potassium tartrate tetrahydrate, potassium tungstate.Inorganic porous carrier is active oxidation
Aluminium, silica gel, molecular sieve, active carbon.
In above scheme, breather valve and Alkali absorption system is arranged in preparing tank sealing part in the step (2), to prevent benzene sulphur
Phenol leaks in surrounding air.Benzenethiol is got in preparing tank from storage tank with metering pump, EC and benzenethiol in molar ratio 1:1 ~
1.05:1 is uniformly mixed and is configured to solution.
In above scheme, catalysis reaction is specific as follows in step (3): quartz tube reactor length 530mm, interior diameter
9.0mm, catalyst fill 8.0mL(and load height 12.5cm), both ends are with silica wool and quartz sand filling for maintaining bed height
Degree, assembling obtain fixed bed reactors, the vertical installation of reactor, with open electric heating furnace (Shandong Juancheng China Shandong electric heating instrument
Co., Ltd, 220 mm of outer diameter, 16 mm of internal diameter, height 390 mm, 300 mm of bringing-up section height, 1.0 kW of power), using journey
Sequence warm-up controller temperature control.Catalysis reaction carries out under normal pressure, and 100 ~ 140 DEG C of reaction temperature.Benzenethiol and ethylene carbonate
Mixed solution (molar ratio of ethylene carbonate and benzenethiol is 1/1 ~ 1.05/1) is with 0.1 mL/min(volume space velocity, 0.75 h-1)
Or 0.2 mL/min(volume space velocity, 1.5 h-1) metering pump (Hangzhou Pu Pu Science and Technology Ltd., PPS-100A) is used to be passed through fixed bed
Reactor.Product, the emptying of by-product carbon dioxide gas are collected by cooler.Reaction equation is as follows:
In above scheme, the volume space velocity of benzenethiol and ethylene carbonate mixed solution is 0.75~1.5 in the step (4)
h-1。
In above scheme, product is evaporated under reduced pressure in the step (5), 15 mmHg of vacuum degree, vapo(u)rizing temperature 60
DEG C, distillation time 2 hours, the unconverted benzenethiol that solid sodium hydroxide bed absorbs removal denier was arranged in vacuum pump front end
And ethylene carbonate, finally obtain the 2- thiophenyl alcohol product that purity is higher than 99%.
When system needs to stop work or switch for a long time, metering pump, preparing tank can be cleaned with toluene, it is residual by what is washed down
Redistillation recycling toluene and product after staying material to convert in fixed bed reactors.Therefore, fixed bed liquid-solid phase continuous catalysis is anti-
Technique is answered largely to solve operational safety issue.
Using gas chromatographic analysis product, chromatographic column is WAX ETR capillary column (Perkin-Elmer, 30 m*0.32
MmID*0.25 μm of df, Crossbond Carbowax-PEG), fid detector, 280 DEG C of temperature of vaporization chamber, detector temperature
260 DEG C, chromatographic condition: temperature programming, 140 C of initial column temperature stop 2 min, rise to 200 with 10 C/min heating rates
DEG C, stop 2 min.High pure nitrogen is carrier gas, 4 mL/min of flow rate of carrier gas.
The advantages and effects of the present invention are:
(1) condensation reaction of benzenethiol and ethylene carbonate carries out in fixed bed reactors in the present invention, compared to tradition side
Method, the present invention have the reaction condition of milder, product easily collecting, and catalyst has high stability, can be used continuously.Continuous fortune
Turn 168 h benzenethiol conversion ratios and is still higher than the selectivity of 99%, 2- thiophenyl ethyl alcohol higher than 99%.
(2) since reaction process is carried out continuously, and the preparation and conveying of reaction mass are under conditions of closed
Operation, avoids in batch process procedures benzenethiol leakage and distributes into air and come to harm so as to cause operator's health.
(3) since reaction carries out under solvent-free conditions, ethylene carbonate and benzenethiol molar ratio close to theoretical value,
Vacuum distillation is carried out to product and removes the unconverted benzenethiol and ethylene carbonate of denier by Alkali absorption, obtains purity
2- thiophenyl alcohol product higher than 99%.Without the lock out operation of subsequent complexity, product can directly as commodity selling, because
This technical process has potential commercial value.
(4) when system needs to stop work for a long time or switching produces other products, metering pump can be cleaned with toluene, is prepared
Tank, redistillation recycling toluene and product after the residual material washed down is converted in fixed bed reactors.Therefore, fixed bed
Liquid-solid phase continuous catalytic reaction technique largely solves operational safety issue.
(5) the advantages of fixed bed heterogeneous catalytic reaction is to allow continuous operation, thus allows for cytotoxic compound with most
Big safety is handled.Using benzenethiol and ethylene carbonate (EC) to synthesize 2- thiophenyl ethyl alcohol for catalytic material is to belong to
The new way of green syt.Since benzenethiol belongs to severe poisonous chemicals, human health and environment are damaged using intermittently operated, because
This, carries out serialization to catalyze and synthesize 2- thiophenyl ethyl alcohol being preferably to select using fixed bed reactors.
Specific embodiment
In the following embodiments, catalysis reaction is used uniformly following process: 530 mm of quartz tube reactor length, interior diameter
9.0 mm, catalyst fill 8.0 mL(and load 12.5 cm of height), both ends are with silica wool and quartz sand filling for maintaining bed
Highly, assembling obtains fixed bed reactors, the vertical installation of reactor, with open electric heating furnace (Shandong Juancheng China Shandong electric heating instrument
Device Co., Ltd, 220 mm of outer diameter, 16 mm of internal diameter, height 390 mm, 300 mm of bringing-up section height, 1.0 kW of power) to quartz
Pipe reactor heating, using programmed temperature-rising controller temperature control.Catalysis reaction carries out under normal pressure, and 100 ~ 140 DEG C of reaction temperature.
The mixed solution (molar ratio of ethylene carbonate and benzenethiol is 1:1 ~ 1.05:1) of benzenethiol and ethylene carbonate is with 0.1 mL/
0.75 h of min(volume space velocity-1) or 0.2 mL/min(volume space velocity, 1.5 h-1) use metering pump (the general limited public affairs of science and technology in Hangzhou
Department, PPS-100A) it is passed through fixed bed reactors.Product, the emptying of by-product carbon dioxide gas are collected by cooler.Using gas
The conversion ratio of analysis of hplc benzenethiol and the selectivity of product 2- thiophenyl ethyl alcohol.Product is evaporated under reduced pressure, vacuum degree
15 mmHg, 60 DEG C of vapo(u)rizing temperature, distillation time 2 hours, it is atomic that the absorption removal of solid sodium hydroxide bed is arranged in vacuum pump front end
The unconverted benzenethiol and ethylene carbonate of amount finally obtain the 2- thiophenyl alcohol product that purity is higher than 99%.
Embodiment 1
2.10 g Anhydrous potassium carbonates are dissolved in 24mL distilled water and are configured to wet chemical, are weighed by dry 40.0
G activated alumina (10 ~ 20 mesh, 440 m2/g of specific surface area, 0.56 mL/g of pore volume) is carried to activated alumina under stiring
Wet chemical is sprayed on body, is obtained in 120 DEG C of 24 h of drying then in 500 DEG C of Muffle kiln roasting 3h after standing 5 h
The supported potassium carbonate catalysts that mass percent load capacity is 5%.
The mixed solution (molar ratio of ethylene carbonate and benzenethiol is 1.05/1) of benzenethiol and ethylene carbonate is with 0.1
0.75 h-1 of mL/min(volume space velocity) with metering pump it is passed through fixed bed reactors, 120 DEG C of reaction temperature are controlled, every 12 hours
Sampling analysis, continuously runs 168h, and the conversion ratio of benzenethiol is the selectivity 99.9% of 99.7%, 2- thiophenyl ethyl alcohol.To product
It carries out vacuum distillation and removes the unconverted benzenethiol and ethylene carbonate of denier by Alkali absorption, obtain purity and be higher than
99% 2- thiophenyl alcohol product.
Embodiment 2
4.44 g Anhydrous potassium carbonates are dissolved in 24mL distilled water and are configured to wet chemical, are weighed by dry 40.0
G activated alumina (10 ~ 20 mesh, 440 m2/g of specific surface area, 0.56 mL/g of pore volume) is carried to activated alumina under stiring
Wet chemical is sprayed on body, is obtained in 120 DEG C of 24 h of drying then in 500 DEG C of Muffle kiln roasting 3h after standing 5 h
The supported potassium carbonate catalysts that mass percent load capacity is 10%.
The mixed solution (molar ratio of ethylene carbonate and benzenethiol is 1.02/1) of benzenethiol and ethylene carbonate is with 0.2
1.5 h of mL/min(volume space velocity-1) with metering pump it is passed through fixed bed reactors, 110 DEG C of reaction temperature are controlled, was taken every 12 hours
Sample analysis, continuously runs 168 h, and the conversion ratio of benzenethiol is the selectivity 99.8% of 99.9%, 2- thiophenyl ethyl alcohol.To product into
Row vacuum distillation and the unconverted benzenethiol and ethylene carbonate that denier is removed by Alkali absorption obtain purity higher than 99%
2- thiophenyl alcohol product.
Embodiment 3
11.44 g bis- hydration potassium fluoride is dissolved in 24mL distilled water and is configured to potassium fluoride aqueous solution, is weighed by dry
40.0 g activated aluminas (10 ~ 20 mesh, 440 m2/g of specific surface area, 0.56 mL/g of pore volume), under stiring to active oxidation
It sprays potassium fluoride aqueous solution on alumina supporter, stands after 5 h in 120 DEG C of 24 h of drying, then in 550 DEG C of 3 h of Muffle kiln roasting,
Obtain the support type Compounds Catalyzed by Potassium Fluoride agent that mass percent load capacity is 15%.
The mixed solution (molar ratio of ethylene carbonate and benzenethiol is 1.05/1) of benzenethiol and ethylene carbonate is with 0.1
0.75 h of mL/min(volume space velocity-1) with metering pump it is passed through fixed bed reactors, 120 DEG C of reaction temperature are controlled, every 12 hours
Sampling analysis, continuously runs 168h, and the conversion ratio of benzenethiol is the selectivity 99.8% of 99.7%, 2- thiophenyl ethyl alcohol.To product
It carries out vacuum distillation and removes the unconverted benzenethiol and ethylene carbonate of denier by Alkali absorption, obtain purity and be higher than
99% 2- thiophenyl alcohol product.
Embodiment 4
2.10 g Carbon Dioxide caesiums are dissolved in 24mL distilled water and are configured to cesium carbonate aqueous solution, are weighed by dry 40.0
G gross porosity microsphere silica gel (100 ~ 200 mesh, 355 m of specific surface area2/ g, 0.99 mL/g of pore volume), under stiring to gross porosity microballoon
It sprays cesium carbonate aqueous solution on silica-gel carrier, stands after 5 h in 120 DEG C of 24 h of drying, then in 550 DEG C of Muffle kiln roastings 3
H obtains the support type carbonic acid cesium-promoted catalyst that mass percent load capacity is 5%.
The mixed solution (molar ratio of ethylene carbonate and benzenethiol is 1.02/1) of benzenethiol and ethylene carbonate is with 0.2
1.5 h of mL/min(volume space velocity-1) with metering pump it is passed through fixed bed reactors, 100 DEG C of reaction temperature are controlled, was taken every 12 hours
Sample analysis, continuously runs 168 h, and the conversion ratio of benzenethiol is the selectivity 99.9% of 99.7%, 2- thiophenyl ethyl alcohol.To product into
Row vacuum distillation and the unconverted benzenethiol and ethylene carbonate that denier is removed by Alkali absorption obtain purity higher than 99%
2- thiophenyl alcohol product.
Embodiment 5
7.06 g anhydrous acetic acid potassium are dissolved in 24mL distilled water and are configured to potassium acetate solution, are weighed by dry 40.0
G gross porosity microsphere silica gel (100 ~ 200 mesh, 355 m of specific surface area2/ g, 0.99 mL/g of pore volume), under stiring to gross porosity microballoon
It sprays potassium acetate solution on silica-gel carrier, stands after 5 h in 120 DEG C of 24 h of drying, obtaining mass percent load capacity is 15%
Support type potassium acetate catalyst.
The mixed solution (molar ratio of ethylene carbonate and benzenethiol is 1.05/1) of benzenethiol and ethylene carbonate is with 0.1
0.75 h of mL/min(volume space velocity-1) with metering pump it is passed through fixed bed reactors, 130 DEG C of reaction temperature are controlled, every 12 hours
Sampling analysis, continuously runs 168h, and the conversion ratio of benzenethiol is the selectivity 99.8% of 99.7%, 2- thiophenyl ethyl alcohol.To product
It carries out vacuum distillation and removes the unconverted benzenethiol and ethylene carbonate of denier by Alkali absorption, obtain purity and be higher than
99% 2- thiophenyl alcohol product.
Embodiment 6
7.06 g natrium carbonicum calcinatums are dissolved in 25 mL distilled water and are configured to aqueous sodium carbonate, are weighed by dry
40.0 g particle cocoanut active charcoals (10 ~ 20 mesh, 1115 m of specific surface area2/ g, 0.76 mL/g of pore volume), under stiring to work
Property high-area carbon on spray aqueous sodium carbonate, stand after 5 h in 120 DEG C of 24 h of drying, obtaining mass percent load capacity is 15%
Support type sodium carbonate catalyst.
The mixed solution (molar ratio of ethylene carbonate and benzenethiol is 1.02/1) of benzenethiol and ethylene carbonate is with 0.1
0.75 h of mL/min(volume space velocity-1) with metering pump it is passed through fixed bed reactors, 120 DEG C of reaction temperature are controlled, every 12 hours
Sampling analysis, continuously runs 168h, and the conversion ratio of benzenethiol is the selectivity 99.8% of 99.2%, 2- thiophenyl ethyl alcohol.To product
It carries out vacuum distillation and removes the unconverted benzenethiol and ethylene carbonate of denier by Alkali absorption, obtain purity and be higher than
99% 2- thiophenyl alcohol product.
Embodiment 7
7.06 g anhydrous acetic acid potassium are dissolved in 25 mL distilled water and are configured to potassium acetate solution, are weighed by dry
40.0 g particle cocoanut active charcoals (10 ~ 20 mesh, 1115 m of specific surface area2/ g, 0.76 mL/g of pore volume), under stiring to work
Property high-area carbon on spray potassium acetate solution, stand after 5 h in 120 DEG C of 24 h of drying, obtaining mass percent load capacity is 15%
Support type potassium acetate catalyst.
The mixed solution (molar ratio of ethylene carbonate and benzenethiol is 1.02/1) of benzenethiol and ethylene carbonate is with 0.1
0.75 h of mL/min(volume space velocity-1) with metering pump it is passed through fixed bed reactors, 120 DEG C of reaction temperature are controlled, every 12 hours
Sampling analysis, continuously runs 168 h, and the conversion ratio of benzenethiol is the selectivity 99.7% of 99.4%, 2- thiophenyl ethyl alcohol.To product
It carries out vacuum distillation and removes the unconverted benzenethiol and ethylene carbonate of denier by Alkali absorption, obtain purity and be higher than
99% 2- thiophenyl alcohol product.
Embodiment 8
4.44 g anhydrous oxalic acid potassium are dissolved in 25 mL distilled water and are configured to oxalic acid aqueous solutions of potassium, are weighed by dry
40.0 g particle cocoanut active charcoals (10 ~ 20 mesh, 1115.4 m of specific surface area2/ g, 0.76 mL/g of pore volume), under stiring to
On absorbent charcoal carrier spray oxalic acid aqueous solutions of potassium, stand 5 h after in 120 DEG C of 24 h of drying, obtaining mass percent load capacity is
10% support type potassium oxalate catalyst.
The mixed solution (molar ratio of ethylene carbonate and benzenethiol is 1.02/1) of benzenethiol and ethylene carbonate is with 0.1
0.75 h of mL/min(volume space velocity-1) with metering pump it is passed through fixed bed reactors, 130 DEG C of reaction temperature are controlled, every 12 hours
Sampling analysis, continuously runs 168 h, and the conversion ratio of benzenethiol is the selectivity 99.1% of 99.6%, 2- thiophenyl ethyl alcohol.To product
It carries out vacuum distillation and removes the unconverted benzenethiol and ethylene carbonate of denier by Alkali absorption, obtain purity and be higher than
99% 2- thiophenyl alcohol product.
Embodiment 9
2.10 g Anhydrous potassium carbonates are dissolved in 20 mL distilled water and are configured to wet chemical, are weighed by dry
40.0 g NaY molecular sieves (10 ~ 20 mesh, silica alumina ratio 5.2,715 m of specific surface area2/ g), under stiring to NaY molecular sieve carrier
Upper spray wet chemical in 120 DEG C of 24 h of drying obtains matter then in 450 DEG C of 3 h of Muffle kiln roasting after standing 5 h
Measure the supported potassium carbonate catalysts that percentage load capacity is 5%.
The mixed solution (molar ratio of ethylene carbonate and benzenethiol is 1.02/1) of benzenethiol and ethylene carbonate is with 0.2
1.5 h of mL/min(volume space velocity-1) with metering pump it is passed through fixed bed reactors, 120 DEG C of reaction temperature are controlled, was taken every 12 hours
Sample analysis, continuously runs 168 h, and the conversion ratio of benzenethiol is the selectivity 99.7% of 99.5%, 2- thiophenyl ethyl alcohol.To product into
Row vacuum distillation and the unconverted benzenethiol and ethylene carbonate that denier is removed by Alkali absorption obtain purity higher than 99%
2- thiophenyl alcohol product.
Embodiment 10
7.06 g natrium carbonicum calcinatums are dissolved in 25 mL distilled water and are configured to aqueous sodium carbonate, are weighed by dry
40.0 g sodium form 13X molecular sieve (10 ~ 20 mesh, silica alumina ratio 2.0,650 m of specific surface area2/ g), under stiring to sodium form 13X molecule
Aqueous sodium carbonate is sprayed on sieve carrier, is stood after 5 h in 120 DEG C of 24 h of drying, then in 500 DEG C of 3 h of Muffle kiln roasting,
Obtain the support type sodium carbonate catalyst that mass percent load capacity is 15%.
The mixed solution (molar ratio of ethylene carbonate and benzenethiol is 1.02/1) of benzenethiol and ethylene carbonate is with 0.2
1.5 h of mL/min(volume space velocity-1) with metering pump it is passed through fixed bed reactors, 130 DEG C of reaction temperature are controlled, was taken every 12 hours
Sample analysis, continuously runs 168 h, and the conversion ratio of benzenethiol is the selectivity 99.9% of 99.3%, 2- thiophenyl ethyl alcohol.To product into
Row vacuum distillation and the unconverted benzenethiol and ethylene carbonate that denier is removed by Alkali absorption obtain purity higher than 99%
2- thiophenyl alcohol product.
Claims (5)
1. a kind of method of liquid-solid phase continuous catalytic reaction synthesis 2- thiophenyl ethyl alcohol, which is characterized in that this method is in fixation
The method that progress ethylene carbonate and benzenethiol condensation reaction prepare 2- thiophenyl ethyl alcohol in bed reactor, includes the following steps:
(1) using inorganic porous material as carrier, aqueous solution of alkali metal salt is impregnated by inorganic porous load using equi-volume impregnating
On body, 120 DEG C dry 24 hours, or continue 400~600 DEG C Muffle kiln roasting 3 hours, obtain alkali metal salt load capacity 5
~20%(mass percent) solid base catalyst；
(2) ethylene carbonate measured is previously laid into preparing tank, benzenethiol is added to from storage tank with metering pump and is matched
It is stirred in tank processed and is configured to solution；
(3) solid base catalyst being seated in reaction tube, both ends are clogged with silica wool and quartz sand for maintaining bed height,
Assembling obtains fixed bed reactors；
(4) benzenethiol and ethylene carbonate mixed solution are passed through in reaction tube with metering pump and are reacted, reaction temperature 100
~140 DEG C, the product 2- thiophenyl ethyl alcohol reacted is collected by cooler, the emptying of carbon dioxide by-product object；
(5) vacuum distillation is carried out to product and removes the unconverted benzenethiol and ethylene carbonate of denier by Alkali absorption,
Finally obtain the 2- thiophenyl alcohol product that purity is 99% or more.
2. preparation method described in accordance with the claim 1, it is characterised in that: alkali metal salt is sodium carbonate, carbonic acid in step (1)
Potassium, rubidium carbonate, cesium carbonate, sodium fluoride, potassium fluoride, rubidium fluoride RbF, cesium fluoride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, bromination
Sodium, potassium bromide, rubidium bromide, cesium bromide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, sodium acetate, potassium acetate, rubidium acetate, acetic acid
Caesium, potassium nitrate, potassium sulfate, tripotassium phosphate, potassium formate, potassium oxalate, potassium citrate, potassium tartrate, sodium potassium tartrate tetrahydrate, in potassium tungstate
One kind.
3. preparation method described in accordance with the claim 1, it is characterised in that: the alkali gold that inorganic porous material loads in step (1)
Belonging to inorganic porous material carrier in salt catalyst is one of activated alumina, silica gel, molecular sieve, active carbon.
4. preparation method described in accordance with the claim 1, it is characterised in that: ethylene carbonate and benzenethiol mole in step (2)
Than for 1:1~1.05:1.
5. preparation method described in accordance with the claim 1, it is characterised in that: benzenethiol and ethylene carbonate mixing in step (4)
The volume space velocity of solution is 0.75~1.5 h-1。
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| CN111944619A (en) * | 2020-08-17 | 2020-11-17 | 无锡卡仕精密科技有限公司 | Cleaning agent for oil stain on surface of artificial joint wax mould and treatment method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2448767A (en) * | 1942-12-05 | 1948-09-07 | Mellon Inst Of Ind Res | Process of hydroxyethylation |
| US4341905A (en) * | 1979-07-18 | 1982-07-27 | The Dow Chemical Company | Inorganic halide salt catalysts for hydroxyalkylation of phenols or thiophenols |
| EP0478073A2 (en) * | 1990-09-20 | 1992-04-01 | Union Carbide Chemicals And Plastics Company, Inc. | Processes for the preparation of carboxylated compounds |
| EP0478075A2 (en) * | 1990-09-20 | 1992-04-01 | Union Carbide Chemicals And Plastics Company, Inc. | Decarboxylation processes |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2448767A (en) * | 1942-12-05 | 1948-09-07 | Mellon Inst Of Ind Res | Process of hydroxyethylation |
| US4341905A (en) * | 1979-07-18 | 1982-07-27 | The Dow Chemical Company | Inorganic halide salt catalysts for hydroxyalkylation of phenols or thiophenols |
| EP0478073A2 (en) * | 1990-09-20 | 1992-04-01 | Union Carbide Chemicals And Plastics Company, Inc. | Processes for the preparation of carboxylated compounds |
| EP0478075A2 (en) * | 1990-09-20 | 1992-04-01 | Union Carbide Chemicals And Plastics Company, Inc. | Decarboxylation processes |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111944619A (en) * | 2020-08-17 | 2020-11-17 | 无锡卡仕精密科技有限公司 | Cleaning agent for oil stain on surface of artificial joint wax mould and treatment method |
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