CN114213364A - Industrial continuous production method of ethyl tetrahydrofurfuryl ether - Google Patents
Industrial continuous production method of ethyl tetrahydrofurfuryl ether Download PDFInfo
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- VUFKMYLDDDNUJS-UHFFFAOYSA-N 2-(ethoxymethyl)oxolane Chemical compound CCOCC1CCCO1 VUFKMYLDDDNUJS-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000010924 continuous production Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 239000003513 alkali Substances 0.000 claims abstract description 64
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims abstract description 36
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims abstract description 36
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000003842 bromide salts Chemical class 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000007790 solid phase Substances 0.000 claims abstract description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 239000012071 phase Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000010533 azeotropic distillation Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000005373 pervaporation Methods 0.000 claims description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- 238000006959 Williamson synthesis reaction Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 238000007670 refining Methods 0.000 abstract description 8
- 238000012824 chemical production Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 10
- 239000002994 raw material Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- -1 tetrahydrofurfuryl alkoxide Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/12—Radicals substituted by oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an industrialized continuous production method of ethyl tetrahydrofurfuryl ether, belongs to the technical field of fine chemical production, and solves the problems that the industrialized production of the ethyl tetrahydrofurfuryl ether cannot realize continuity, the yield is low, the product purity is low, and the refining difficulty is high. The industrial continuous production method comprises the following steps: dissolving alkali in tetrahydrofurfuryl alcohol in an alkali dissolving tank to obtain an alkali solution; continuously conveying the alkali solution to a multi-phase reactor to react with the continuously added bromoethane; continuously discharging reaction liquid containing bromide salt crystals into filtering and separating equipment to separate solid-phase bromide salt and mixed liquid; the mixed solution continuously returns to the alkali dissolving tank to dissolve alkali continuously and circularly participate in the reaction; when the ether content of the mixed solution is 80-97 wt%, stopping adding the alkali and the ethyl bromide; and after the reaction is completed, distilling and permeating the mixed solution separated by the filtering and separating equipment in sequence to obtain the tetrahydrofurfuryl ethyl ether. The method has the advantages of high product conversion rate, continuous reaction process batch, safe and reliable reaction process, and closed and environment-friendly process.
Description
Technical Field
The invention belongs to the technical field of fine chemical production, and particularly relates to an industrial continuous production method of ethyl tetrahydrofurfuryl ether.
Background
The structural formula of the ethyl tetrahydrofurfuryl ether (ETFE) is shown in a formula I.
The ethyl tetrahydrofurfuryl ether is an important compound, has excellent solubility on a plurality of organic matters, and can be used as a high-quality solvent. The ethyl tetrahydrofurfuryl ether is also used as a structure regulator for synthesizing the polybutadiene rubber with high 1, 2-structure by diene monomers, and comprises solution polymerized styrene-butadiene rubber (SSBR), Butadiene Rubber (BR), thermoplastic styrene-butadiene rubber and the like. The content of polybutadiene 1, 2-structure in the styrene butadiene rubber regulated by the ethyl tetrahydrofurfuryl ether can reach 60-80%.
In 1977 Henry R Nychka et al used tetrahydrofurfuryl alcohol (THFA) and chloroethane as raw materials to synthesize ethyl tetrahydrofurfuryl ether; in 2008, the literature reports that scholars adopt tetrahydrofurfuryl alcohol (THFA), sodium hydroxide and ethyl bromide (EtBr) as raw materials and aliphatic hydrocarbon as a dehydration solvent to synthesize sodium tetrahydrofurfuryl alcohol in the first step and synthesize ethyl tetrahydrofurfuryl ether in the second step by a Williamson method, wherein the yield is 50-55%, and ethyl tetrahydrofurfuryl ether with the purity of 98% is obtained by reacting metal sodium with residual tetrahydrofurfuryl alcohol in reactants and rectifying, wherein the content of harmful substances such as tetrahydrofurfuryl alcohol is less than 150mg/kg, but the method has the advantages of low yield, high energy consumption, high refining difficulty and low product purity, and is not suitable for subsequent industrial application.
Patent application CN 106928165 of the petrochemical Beijing chemical research institute in 2015 discloses a method for carrying out enol etherification by using tetrahydrofurfuryl alcohol and C2-C8 olefin as raw materials and concentrated sulfuric acid as a catalyst. The waste acid treatment generated by the method has the restriction on environmental protection, and simultaneously, the self-polymerization of olefin in a concentrated sulfuric acid environment also brings certain product refining problems.
At present, the petrochemical industry in China continuously expands the capacity of solution polymerized styrene butadiene rubber, and a main structure regulator is imported abroad, so that the industrial production method of the ethyl tetrahydrofurfuryl ether is provided, the industrial production of the ethyl tetrahydrofurfuryl ether with high batch conversion rate, energy conservation, safety and high quality is realized, and the problem to be solved by technical personnel in the field is solved urgently.
Disclosure of Invention
One of the purposes of the invention is to provide an industrial continuous production method of the tetrahydrofurfuryl ethyl ether, which solves the problems that the industrial production of the tetrahydrofurfuryl ethyl ether in the prior art can not realize continuity, the yield is low, the product purity is low and the refining difficulty is large.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides an industrial continuous production method of ethyl tetrahydrofurfuryl ether, which comprises the following steps:
s1, dissolving alkali in tetrahydrofurfuryl alcohol in an alkali dissolving tank to obtain an alkali solution;
s2, continuously conveying the alkali solution to a multi-phase reactor, and carrying out multiphase Williamson reaction with continuously added bromoethane to generate ethyl tetrahydrofurfuryl ether and bromide salt;
s3, continuously discharging reaction liquid containing bromide salt crystals into filtering and separating equipment through a control valve for continuous separation, and separating solid phase bromide salt and mixed liquid; the mixed solution comprises tetrahydrofurfuryl alcohol, ethyl tetrahydrofurfuryl ether, water and dissolved sodium hydroxide;
s4, continuously returning the mixed solution to the alkali dissolving tank to continuously dissolve alkali and circularly participate in the reaction; when the water content of the mixed solution reaches 4%, separating a part of solution to an evaporation kettle for distillation, performing osmotic dehydration, and returning the mixed solution after distillation and dehydration to an alkali dissolving tank for raw material dissolution; when the ether content in the mixed solution is 80-97 wt.%, stopping adding the alkali into the alkali dissolving tank and adding bromoethane into the multiphase reactor;
and S5, after the reaction is completed, distilling and permeating the mixed solution separated by the filtering and separating equipment in sequence to obtain the tetrahydrofurfuryl ethyl ether.
The invention adopts tetrahydrofurfuryl alcohol (THFA), alkali and ethyl bromide (EtBr) as raw materials to synthesize the ethyl tetrahydrofurfuryl ether with the structural formula shown in the formula I in one step without solvent. The method provided by the invention overcomes the problems of complex process, low target product conversion rate and low safety caused by the auxiliary two-step method for synthesizing the tetrahydrofurfuryl ethyl ether with the aqueous solvent.
In the invention, the reaction of tetrahydrofurfuryl alcohol and alkali to generate tetrahydrofurfuryl alkoxide is equilibrium reversible reaction, after bromoethane is added to react with tetrahydrofurfuryl alkoxide to carry out Williamson reaction, the reaction equilibrium of the former stage can be broken, and the movement to the reaction direction of generating the ethyl tetrahydrofurfuryl ether is promoted.
In one embodiment of the present invention, the alkali is sodium hydroxide, and apparently, the sodium hydroxide shows an evolution process from solid sodium hydroxide → dissolved sodium hydroxide → tetrahydrofurfuryl alcohol sodium → sodium bromide in the system.
By adopting the method, the ethyl tetrahydrofurfuryl ether with the purity of more than 97 wt.% can be obtained.
The ethyl tetrahydrofurfuryl ether obtained by the method can be further refined, and the refining method is the prior art and can adopt conventional methods such as washing, distillation, rectification, chemical reaction refining and the like.
In the invention, the solid phase bromide salt separated by the filtering and separating equipment is washed and dried to obtain a purified bromide salt product; the purification process of solid phase bromide salts is prior art.
In some embodiments of the invention, the molar ratio of tetrahydrofurfuryl alcohol, bromoethane and alkali in the materials participating in the reaction is 0.8-1.2: 0.8-1.2: 0.8-1.2, preferably 1:1: 1.
In some embodiments of the invention, in S1, tetrahydrofurfuryl alcohol is added into the alkali dissolving tank according to the feeding amount, and the concentration of the alkali solution is greater than or equal to 4g/100 g;
in the S2, bromoethane is added according to the complete average reaction amount in 5-10 hours in a balanced way, and preferably, the adding speed of the bromoethane is controlled to be 0.1-0.12 theoretical mole number/hour;
preferably, the rate of addition of the alkali solution to the multiphase reactor is controlled to be 15 to 30 times, more preferably 20 times, the rate of addition of the bromoethane.
In some embodiments of the invention, the base comprises at least one of sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium metal, potassium metal.
In some embodiments of the invention, the S1 or S4 is dissolved with alkali in an alkali dissolving tank at 30-90 ℃.
In some embodiments of the invention, in the step S2, the reaction temperature is controlled to be 30-90 ℃, and the operation pressure is 0.01-0.5 MPa; preferably, the reaction temperature is 60-80 ℃, and the operation pressure is 0.05-0.35 MPa.
In some embodiments of the invention, the bromide crystal content in the multiphase reactor is controlled to be 1-15 wt.% by continuously discharging the reaction solution containing bromide salt crystals to a filtration separation apparatus; preferably 1-8 wt.%.
In the invention, bromide salt (sodium bromide or potassium bromide) has certain solubility in raw material tetrahydrofurfuryl alcohol, reaction product water and product ethyl tetrahydrofurfuryl ether, wherein the solubility in water is more than 150g/100g, the bromide salt is saturated and crystallized and separated out in reaction liquid along with the reaction, excessive accumulated bromide salt crystals can bring adverse effects to reaction stirring and material circulating transportation, the stable reaction can be ensured by adopting continuous centrifugal separation bromide salt crystals, and the salt crystal content in a reactor is controlled to be 1-15 wt.%, preferably 1-8 wt.%.
In some embodiments of the invention, when the water content of the mixed liquid separated by the filtering and separating device is more than or equal to 4%, part of the alkali liquor in the alkali dissolving tank is divided and enters a distillation kettle for water-ether azeotropic distillation, the distillate enters a pervaporation membrane separation device for dehydration or is dried and dehydrated by a molecular sieve, the dehydrated distillate is pumped back to the alkali dissolving tank and then sent to the multi-phase reactor for continuous reaction; the water content of the reaction system is adjusted to 2.0-4.0%.
In some embodiments of the present invention, when the water content of the mixed solution separated by the filtering and separating device is greater than or equal to 4%, half of the alkali solution in the alkali dissolving tank is divided and enters the distillation kettle to perform azeotropic distillation of water and ether.
In the present invention, the accumulation of water produced by the reaction reduces the process Williamson reaction conversion. Therefore, the water content of the reaction system was controlled to 2.0 to 4.0 wt.% by azeotropic dehydration.
In the present invention, by adding ethyl bromide in a balanced manner, water produced by the reaction and crystals of bromide salt are removed from the reaction system by azeotropic distillation and separation by filtration, and the raw tetrahydrofurfuryl alcohol and the product ethyltetrahydrofurfuryl ether function as solvents in the system, so that a water-carrying solvent such as toluene is not introduced in the present invention.
In some embodiments of the invention, the S1-S4 is carried out under nitrogen or inert atmosphere, preferably, the nitrogen or inert gas in the multiphase reactor is replaced and pressurized to 0.01-0.1MPa, and the nitrogen or inert gas sealing pressure in the alkali dissolving tank and the filtering separation equipment is 1.0-4.0 KPa.
In some embodiments of the present invention, the alkali dissolving tank is a device with a stirrer, a material outlet screen and a gas sealing facility.
In the present invention, the type of the filtration and separation apparatus is not particularly limited, and may be various types of filters, centrifuges. According to a particular embodiment of the invention, the filtration separation is carried out in the following manner: the reaction liquid containing bromide salt crystals at the bottom of the multiphase reactor automatically flows into an automatic continuous centrifugal filter, solid-liquid separation is carried out at the rotation speed of 400-1200 r/min, the mixed liquid obtained by separation automatically flows into an alkali dissolving tank, and after a certain amount of solid-phase bromide salt is accumulated, the solid-phase bromide salt is washed by a solvent and centrifugally dewatered and then transferred into drying equipment for drying.
Compared with the prior art, the invention has the following beneficial effects:
the invention has scientific design, ingenious conception, simple method and simple and convenient operation. The method has the advantages of high conversion rate of the product ethyl tetrahydrofurfuryl ether, continuous reaction process batches, safe and reliable reaction process, closed and environment-friendly process and contribution to refining of subsequent product byproducts.
The ethyl tetrahydrofurfuryl ether obtained by adopting the method and subsequent refining is tried in a solution polymerized butadiene styrene rubber device in a certain petrochemical plant in China, has excellent quality and reaches the quality level of imported products at abroad.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a graph showing the relationship between the water content of the reaction system and the instantaneous conversion rate of the newly added tetrahydrofurfuryl alcohol.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The embodiment discloses a method for industrial continuous production of ethyl tetrahydrofurfuryl ether, which comprises the following steps: 1500L alkali dissolving tank, 2500L horizontal multiphase stirring reactor, PGZ-1250 program control centrifuge, 500L reaction distillation still, 2000kg/h pervaporation device, auxiliary pump, pipeline and electric automatic control equipment. The specific method comprises the following steps:
performing nitrogen replacement on ethyl tetrahydrofurfuryl ether (ETFE) synthesis equipment and a pipeline flow, adjusting the nitrogen sealing pressure after the replacement is qualified, and ensuring that the nitrogen pressure in a multiphase reactor is 0.01MPa and the nitrogen pressure in an alkali dissolving tank and a centrifugal machine is 1.0 KPa.
50kg of sodium hydroxide flake caustic soda (600 kg of sodium hydroxide flake caustic soda is added in a stirring alkali dissolving tank in a single time, 1500kg of commercial tetrahydrofurfuryl alcohol is added, a stirrer is started to stir and dissolve the caustic soda for 20 minutes, and a delivery pump is started to stably convey the tetrahydrofurfuryl alcohol solution dissolved with the sodium hydroxide into a multiphase reactor according to the flow rate of 2000 kg/h.
Then starting a stirrer of the multiphase reactor, starting a bromoethane pump to stably convey the bromoethane into the multiphase reactor according to the flow of 100kg/h, gradually raising the material temperature of an alkali dissolving tank and the reactor along with the dissolution of sodium hydroxide and the beginning of reaction, raising the pressure in the reactor, starting jacket cooling water when the temperature in the reactor reaches 60 ℃, controlling the reaction temperature to be 60-80 ℃, controlling the adding amount of bromoethane, and controlling the pressure in the reactor to be 0.3-0.35MPa (G).
When the liquid level of the reactor rises to more than 50 percent, opening a bottom outlet valve, continuously transferring the reactor to a centrifugal machine, separating solid-phase crystallized sodium bromide, controlling the crystallized content of the sodium bromide in the multiphase reactor to be 1-15 wt.%, stopping feeding the reactor for 10 minutes every 3 hours by the centrifugal machine, discharging the centrifuged and liquid-removed crystallized sodium bromide, and transferring the reactor to subsequent washing and drying equipment; the mixed solution obtained by centrifugal separation automatically flows into an alkali dissolving tank to continuously dissolve alkali and circularly participate in the reaction.
Analyzing the water content of the mixed liquor to reach 4 wt.%, shunting 1000kg/h mixed liquid phase at the outlet of a transfering pump of the alkali dissolving tank, feeding the mixed liquid phase into a distillation kettle with a stirrer for water ether azeotropic distillation, feeding the distillate into a pervaporation membrane separation device for dehydration, pumping the dehydrated distillate back to the alkali dissolving tank, and then feeding the dehydrated distillate into a multi-phase reactor for continuous reaction.
And after the ether content of the mixed liquid phase is analyzed to reach more than 92 wt%, stopping adding the alkali into the alkali dissolving tank and adding the bromoethane into the reactor, and after the pressure of the reactor is reduced from 0.3-0.35MPa (G) to 0.1-0.15MPa (G), basically completely reacting the bromoethane in the liquid phase. And transferring the mixed liquid phase after filtration into a distillation and pervaporation membrane separator to obtain crude ethyl tetrahydrofurfuryl ether with the purity of more than 97 wt.%.
The total conversion rate of tetrahydrofurfuryl alcohol is 94 percent, and the selectivity of the ethyl tetrahydrofurfuryl ether is 97 percent. And distilling residual alcohol and transferring unreacted sodium hydroxide to the reactor for next batch production.
The crude ethyl tetrahydrofurfuryl ether is further refined to obtain a finished product of ethyl tetrahydrofurfuryl ether with the purity of 99.2 wt.% and the alcohol content of less than 150 ppm.
Example 2
This example examines the influence of the water content of the reaction system on the conversion of tetrahydrofurfuryl alcohol.
Ethyl tetrahydrofurfuryl ether is produced by the process of example 1, with the difference that there is no dehydration step and the mixed solution is reacted in a multiphase reactor without dehydration after dissolving the alkali.
The water content of the reaction system and the instantaneous conversion rate of the newly added tetrahydrofurfuryl alcohol are respectively measured at different time points, and the influence of the water content of the reaction system on the instantaneous conversion rate of the newly added tetrahydrofurfuryl alcohol is measured. The results are shown in the following table:
TABLE 1 reaction system water-fresh tetrahydrofurfuryl alcohol instantaneous conversion relationship
The relation chart of the water-newly added tetrahydrofurfuryl alcohol instantaneous conversion rate of the reaction system is shown in the attached figure 2. When the water content of the system at the initial time of the reaction is 1.0 wt.%, the instantaneous conversion rate of the added tetrahydrofurfuryl alcohol reaches 96.2%, and when the water content of the reaction system reaches 8.0 wt.%, the instantaneous conversion rate of the added tetrahydrofurfuryl alcohol is reduced to 77.0%.
It can be seen that the lower the water content in the reaction system, the higher the instantaneous conversion of the fresh tetrahydrofurfuryl alcohol. In combination with the practical situation of industrial production, the invention controls the water content in the reaction system to be 2-4 wt.%.
Example 3
The embodiment discloses a method for industrial continuous production of ethyl tetrahydrofurfuryl ether, compared with the embodiment 1, the temperature of a multiphase reactor is controlled to be 70-90 ℃, the pressure is controlled to be 0.05-0.1 MPa (G), and the rest conditions are the same. Finally, crude tetrahydrofurfuryl ethyl ether with the purity of 98.2 wt.% is obtained, the total conversion rate of tetrahydrofurfuryl alcohol is 95.1 percent, and the selectivity of tetrahydrofurfuryl ethyl ether is 97.5 percent.
Example 4
The embodiment discloses a method for industrial continuous production of ethyl tetrahydrofurfuryl ether, compared with the embodiment 1, the temperature of a multiphase reactor is controlled to be 30-60 ℃, the pressure is controlled to be 0.45-0.5 MPa (G), and the other conditions are the same. Finally, crude tetrahydrofurfuryl ethyl ether with the purity of 98.7 wt.% is obtained, the total conversion rate of tetrahydrofurfuryl alcohol is 93.9 percent, and the selectivity of tetrahydrofurfuryl ethyl ether is 96.2 percent.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. An industrial continuous production method of the tetrahydrofurfuryl ethyl ether is characterized by comprising the following steps:
s1, dissolving alkali in tetrahydrofurfuryl alcohol in an alkali dissolving tank to obtain an alkali solution;
s2, continuously conveying the alkali solution to a multi-phase reactor, and carrying out multiphase Williamson reaction with continuously added bromoethane to generate ethyl tetrahydrofurfuryl ether and bromide salt;
s3, continuously discharging reaction liquid containing bromide salt crystals into filtering and separating equipment through a control valve for continuous separation, and separating solid phase bromide salt and mixed liquid;
s4, continuously returning the mixed solution to the alkali dissolving tank to continuously dissolve alkali and circularly participate in the reaction; when the ether content in the mixed solution is 80-97 wt.%, stopping adding the alkali into the alkali dissolving tank and adding bromoethane into the multiphase reactor;
and S5, after the reaction is completed, distilling and permeating the mixed solution separated by the filtering and separating equipment in sequence to obtain the tetrahydrofurfuryl ethyl ether.
2. The industrial continuous production method of the tetrahydrofurfuryl ethyl ether according to claim 1, characterized in that the molar ratio of tetrahydrofurfuryl alcohol, ethyl bromide and alkali in the materials participating in the reaction is 0.8-1.2: 0.8-1.2: 0.8-1.2, preferably 1:1: 1.
3. The industrial continuous production method of the tetrahydrofurfuryl ethyl ether according to claim 2, wherein in S1, tetrahydrofurfuryl alcohol is added into the alkali dissolving tank according to the dosage, and the concentration of the alkali solution is greater than or equal to 4g/100 g;
in the S2, bromoethane is added according to the complete average reaction amount in 5-10 hours in a balanced way, and preferably, the adding speed of the bromoethane is controlled to be 0.1-0.12 theoretical mole number/hour;
preferably, the rate of addition of the alkali solution to the multiphase reactor is controlled to be 15 to 30 times, more preferably 20 times, the rate of addition of the bromoethane.
4. The industrial continuous production method of tetrahydrofurfuryl ethyl ether according to claim 1, characterized in that the base comprises at least one of sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium metal, and potassium metal.
5. The industrial continuous production method of ethyltetrahydrofurfuryl ether according to any one of claims 1 to 4, characterized in that in S1 or S4, alkali is dissolved in an alkali dissolving tank at 30 to 90 ℃.
6. The industrial continuous production method of ethyltetrahydrofurfuryl ether according to any one of claims 1 to 4, characterized in that in S2, the reaction temperature is controlled to 30 to 90 ℃, and the operating pressure is controlled to 0.01 to 0.5 MPa; preferably, the reaction temperature is 60-80 ℃, and the operation pressure is 0.05-0.35 MPa.
7. The industrial continuous production method of ethyltetrahydrofurfuryl ether according to any one of claims 1 to 4, characterized in that the bromide crystal content in the multiphase reactor is controlled to 1 to 15 wt.% by continuously discharging the reaction liquid containing bromide salt crystals into the filtration separation apparatus; preferably 1-8 wt.%.
8. The industrial continuous production method of the tetrahydrofurfuryl ethyl ether according to claim 1, characterized in that when the water content of the mixed liquor separated by the filtering separation equipment is more than or equal to 4 wt.%, part of the alkali liquor in the alkali dissolving tank is branched and enters a distillation still for azeotropic distillation of water and ether, the distillate enters a pervaporation membrane separation device for dehydration or is dried and dehydrated by a molecular sieve, the dehydrated distillate is pumped back to the alkali dissolving tank and then is sent to a multi-phase reactor for continuous reaction; the water content of the reaction system was adjusted to 2.0 to 4.0 wt.%.
9. The industrial continuous production method of tetrahydrofurfuryl ethyl ether according to claim 8, characterized in that when the water content of the mixed liquid separated by the filtering and separating device is not less than 4%, half of the alkali liquor in the alkali dissolving tank is branched and enters the distillation still for azeotropic distillation of water and ether.
10. The industrial continuous production method of ethyltetrahydrofurfuryl ether according to claim 1, characterized in that said S1-S4 is performed under nitrogen or inert atmosphere; preferably, the nitrogen or inert gas in the multiphase reactor is replaced and pressurized to 0.01-0.1MPa, and the nitrogen or inert gas sealing pressure in the alkali dissolving tank and the filtering separation equipment is 1.0-4.0 KPa.
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