CN113200828B - Refining method of vinyl isobutyl ether - Google Patents
Refining method of vinyl isobutyl ether Download PDFInfo
- Publication number
- CN113200828B CN113200828B CN202110487024.4A CN202110487024A CN113200828B CN 113200828 B CN113200828 B CN 113200828B CN 202110487024 A CN202110487024 A CN 202110487024A CN 113200828 B CN113200828 B CN 113200828B
- Authority
- CN
- China
- Prior art keywords
- parts
- filter membrane
- isobutyl ether
- vinyl isobutyl
- adsorption
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
Abstract
The invention relates to the field of chemical industry, and provides a refining method of vinyl isobutyl ether, which comprises the following steps: crude distillation, water washing, drying, adsorption filtration, rectification and the like; the invention provides a refining method of a high-purity vinyl isobutyl ether product, the purity of the vinyl isobutyl ether product is more than 99%, the market competitiveness of the product is greatly improved, and the application range of the product is widened. The invention uses a refined adsorption composite filter membrane to carry out adsorption filtration on a product which is preliminarily separated, the refined adsorption composite filter membrane contains a calcium hydroxy phosphate modified mesoporous silica material through composite modification, and can form hydrogen bonding with isobutanol impurities containing hydroxyl, so that the isobutanol impurities are adsorbed and intercepted on the filter membrane, and then the vinyl isobutyl ether product with high purity is obtained through rectification.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a refining method of vinyl isobutyl ether.
Background
Vinyl isobutyl ether is a chemical raw material used for producing polyvinyl ether by polymerization and copolymerization and also used for coating additives, and a plurality of industrial production methods are available.
CN105837407A relates to isobutyl vinyl ether. Injecting isobutanol solution containing a catalyst into a loop reactor from the bottom of a lifting pipe through a metering pump, and enabling mixed gas of acetylene and nitrogen to enter a gas ejector from the bottom of the lifting pipe after passing through a gas buffer tank, a compressor and an adsorption drying column; the material is driven to flow into a downcomer from the upper part of a lifting pipe, and circularly flows back to the lifting pipe after being subjected to heat exchange with heat conduction oil through a heat exchanger, and the sprayed micro bubbles are mixed with an isobutanol solution and contact with the isobutanol solution to react to obtain a reaction mixture; and the reaction mixture flows out from an outlet at the top of the riser, is cooled by a cooler and then enters a gas-liquid separator for gas-liquid separation, wherein a gas phase flows out from the top of the gas-liquid separator, is decompressed by a decompressor and then circulates back to a gas buffer tank, and the liquid flowing out from the bottom of the gas-liquid separator is the isobutyl vinyl ether. Good mass and heat transfer effect, simple device structure, safety, high efficiency, simple operation, low cost and easy industrialization.
CN1709847A relates to a continuous synthesis method of vinyl isobutyl ether, which takes acetylene and isobutanol as reaction raw materials, the synthesis reaction is carried out in a synthesis tower, the synthesis tower is filled with catalyst solution with the liquid level of 50-80%, the acetylene and isobutanol gas are evenly mixed from the bottom of the synthesis tower through a nozzle and then are led into the synthesis tower, the catalyst solution at the bottom of the tower is continuously pumped to the top of the tower through a circulating pump for circulation, the formed acetylene small bubbles and isobutanol are contacted in the synthesis tower for synthesis etherification reaction, and the temperature of the etherification reaction is as follows: and (2) at the temperature of 125-150 ℃, the reaction pressure of the synthesis tower is 0.3-0.6 Mpa, the catalyst is isobutanol solution containing KOH, the vinyl isobutyl ether generated by the reaction and unreacted acetylene and isobutanol are led out from the top of the synthesis tower, enter a receiving tank through a condenser and are subjected to post-treatment to obtain the finished product of the vinyl isobutyl ether. The method has the advantages of high reaction safety and reliability, high single-pass conversion rate of acetylene and high synthesis reaction yield, high purity of the reaction product vinyl isobutyl ether and low acetylene content discharged from tail gas.
CN102701920B discloses a purification method of vinyl isobutyl ether, which comprises the following steps: (1) carrying out reduced pressure rectification on a vinyl isobutyl ether solution with the mass percentage concentration of 50-90% to obtain a distillate taking the vinyl isobutyl ether as a main component and a kettle bottom solution taking isobutanol as a main component, wherein the rectification temperature is 50-95 ℃, and the pressure is 10-60 kPa; (2) washing and layering the distillate obtained in the step (1) by using deionized water to obtain an upper organic phase and a lower aqueous phase, and separating the organic phases to obtain 97-99.5% of vinyl isobutyl ether. The method reduces the using amount of deionized water during washing, saves the washing time, improves the production efficiency and reduces the production cost; materials can be recycled, the discharge of three wastes is reduced, and the environmental benefit is improved; the product has good quality, and the content of the vinyl isobutyl ether is more than 98.5 percent.
The purity of the vinyl ethers prepared by the above patents and the prior art can only be more than 98.5% or less, but this limits the expansion of the application field of the vinyl ethers.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for purifying vinyl isobutyl ether.
A refining method of vinyl isobutyl ether comprises the following operation steps:
step one, crude distillation, namely adding 100 parts of crude product of vinyl isobutyl ether into a primary crude distillation tower according to the mass parts, and carrying out vacuum distillation under the conditions of absolute pressure of 30-40kPa and kettle temperature of 70-80 ℃ to obtain a distillate liquid;
step two, washing, namely adding 180 parts of 100-180 parts of washing water into 50-80 parts of distillate according to parts by mass, fully stirring and washing for 30-60min, standing and layering, and separating liquid to obtain an upper organic layer;
step three, drying, namely adding 2-6 parts of drying agent into 40-70 parts of upper organic layer according to the mass parts, stirring and mixing at normal temperature for 30-60min, and filtering to obtain a dried organic layer;
step four, adsorption filtration, namely introducing the obtained dry organic layer into a refined adsorption device, and filtering the organic layer through a filter membrane under the pressure of 0.1-0.5MPa, wherein the filter membrane is a refined adsorption composite filter membrane;
and step five, rectifying, namely adding the crude product of the vinyl isobutyl ether into a rectifying tower, and carrying out vacuum evaporation under the conditions of the absolute pressure of 30-40kPa and the kettle temperature of 75-85 ℃ at the reflux ratio of 1.1-1.5 to obtain distillate, namely the refined vinyl isobutyl ether.
The preparation method of the refined adsorption composite filter membrane comprises the following steps: according to the mass portion of the components,
1) adding 20-50 parts of mesoporous silica into 40-60 parts of acetone, then adding 1-4.8 parts of methacryloxypropyltrimethoxysilane and 0.1-0.36 part of 1% sodium hydroxide solution, heating to 35-55 ℃ for reaction for 2-4h, then adding 0.03-0.05 part of methylphenyldimethylsiloxane, continuing to react for 3-8h under the condition of heat preservation, and carrying out reduced pressure distillation at 60 ℃ for 1-3h to obtain grafted mesoporous silica; adding 18-40 parts of grafted mesoporous silica into 36-60 parts of xylene, adding 5-15 parts of hydroxyethyl acrylate, 1-5 parts of vinyl isobutyl ether and 0.01-0.1 part of 4-vinylpyridine-nickel, heating to 60-80 ℃, adding 0.01-0.1 part of benzoyl peroxide and 0.005-0.008 part of dichloromethane, carrying out closed heat preservation reaction for 2-6 hours, cooling, and evaporating the solvent to obtain grafted active mesoporous silica;
2) adding 2.6-7.2 parts of phosphoric acid into 100-200 parts of deionized water, uniformly stirring and mixing, then adding 5-10 parts of grafted active mesoporous silica into the system, stirring and mixing at 40-60 ℃ for 30-60min, then slowly adding 100-120 parts of suspension containing 2.5-8.2 parts of calcium hydroxide into the reaction kettle, controlling the addition to be completed within 10-20min, then adjusting the pH value of the solution to be 9.6-10.5 by using a sodium hydroxide solution with the concentration of 0.05-0.5mol/L, continuously stirring for 60-120min, filtering after the completion, and washing to obtain the calcium hydroxy phosphate modified mesoporous silica;
3) adding 8-12 parts of polyimide into 80-100 parts of N, N-dimethylacetamide, fully and uniformly stirring, adding 0.5-2 parts of calcium hydroxy phosphate modified mesoporous silica, stirring and dispersing at the rotating speed of 1000-2000r/min for 10-60min, then continuing ultrasonic dispersion for 30-60min to obtain a casting solution, carrying out film scraping treatment on the casting solution by using a flat film scraper, wherein the film scraping thickness is 200-300 mu m, drying at normal temperature and normal pressure for 10-20min to obtain an adsorption film, then vertically irradiating the basic filter membrane and the adsorption film by using electron beams, and carrying out rolling compounding on the adhered basic filter membrane and the adsorption film by using a compression roller to obtain the refined adsorption composite filter membrane.
The basic filter membrane is a polysulfone membrane or a polyether sulfone membrane or a polyvinylidene fluoride membrane.
The energy of the electron beam is 0.2-0.8 MeV.
The refined adsorption composite filter membrane is prepared by modifying activated and grafted modified mesoporous silica with calcium hydroxy phosphate, the activated and modified grafted mesoporous silica reduces the binding force among particles, improves the agglomeration characteristic of mesoporous silica materials, and can be uniformly distributed on a basic filter membrane, so that the filtration and adsorption performance is improved. The washing water is deionized water or purified water.
The drying agent is anhydrous calcium chloride or sodium sulfate.
The theoretical plate number of the rectifying tower is 8-20.
The invention provides a refining method of vinyl isobutyl ether, and the refining method of a high-purity vinyl isobutyl ether product provided by the invention has the purity of more than 99%, greatly improves the market competitiveness of the product and widens the application range of the product. The invention uses a refined adsorption composite filter membrane to carry out adsorption filtration on a product which is preliminarily separated, the refined adsorption composite filter membrane is subjected to composite modification, hydroxyethyl acrylate, vinyl isobutyl ether and 4-vinylpyridine-nickel are used for surface polymerization to obtain a mesoporous silica material which can form hydrogen bond with isobutanol impurities containing hydroxyl, the isobutanol impurities are adsorbed and intercepted on the filter membrane, and the polymerization modification of the vinyl isobutyl ether can improve the compatibility of an adsorbent and the product; then rectifying to obtain a high-purity product.
Drawings
FIG. 1 is a gas chromatogram of the product vinyl isobutyl ether prepared in example 1.
FIG. 2 is a Fourier infrared spectrum of the product vinyl isobutyl ether prepared in example 1.
Detailed Description
The invention is further illustrated by the following specific examples:
the content of vinyl isobutyl ether in the product is analyzed by adopting a gas chromatography, and the retention rate of the refined adsorption composite filter membrane prepared in the example on the polyhydroxy compound glycerol is determined by the following method: 1g of glycerol was added to 1L of water, and the mixture was dissolved by stirring, passed through the purified adsorption composite filtration membranes prepared in examples 1 to 3 and multi-ratio 1 to 6, respectively, and the glycerol content in the filtered aqueous solution was measured to calculate the rejection rate of glycerol.
Example 1
A refining method of vinyl isobutyl ether comprises the following operation steps:
step one, crude distillation, namely adding 100kg of a crude product of vinyl isobutyl ether into a primary crude distillation tower, and performing vacuum distillation under the conditions of the absolute pressure of 30kPa and the kettle temperature of 70 ℃ to obtain a distillate liquid;
step two, washing, namely adding 100kg of washing water into 50kg of distillate, fully stirring and washing for 30min, standing for layering, and separating liquid to obtain an upper organic layer;
step three, drying, namely adding 2kg of drying agent into 40kg of the upper organic layer, stirring and mixing for 30min at normal temperature, and filtering to obtain a dried organic layer;
step four, adsorption filtration, namely introducing the obtained dry organic layer into a refined adsorption device, and filtering the organic layer through a filter membrane under the pressure of 0.1MPa, wherein the filter membrane is a refined adsorption composite filter membrane;
and step five, rectifying, namely adding the crude product of the vinyl isobutyl ether into a rectifying tower, and carrying out vacuum evaporation under the conditions of the absolute pressure of 30kPa and the kettle temperature of 75 ℃ with the reflux ratio of 1.1 to obtain distillate, namely the refined vinyl isobutyl ether.
The preparation method of the refined adsorption composite filter membrane comprises the following steps:
1) adding 20kg of mesoporous silica into 40kg of acetone, then adding 1kg of methacryloxypropyltrimethoxysilane and 0.36kg of 1% sodium hydroxide solution, heating to 55 ℃ for reaction for 4h, then adding 0.05kg of methyl phenyl dimethyl siloxane for continuous heat preservation reaction for 8h, and carrying out reduced pressure distillation at 60 ℃ for 3h to obtain grafted mesoporous silica; adding 40kg of grafted mesoporous silica into 36kg of xylene, adding 15kg of hydroxyethyl acrylate, 1kg of vinyl isobutyl ether and 0.1kg of 4-vinylpyridine-nickel, heating to 60 ℃, adding 0.1kg of benzoyl peroxide and 0.008kg of dichloromethane, carrying out closed heat preservation reaction for 2 hours, cooling, and evaporating a solvent to obtain grafted active mesoporous silica;
2) adding 2.6kg of phosphoric acid into 200kg of deionized water, uniformly stirring and mixing, adding 10kg of grafted active mesoporous silica into the system, stirring and mixing for 60min at 60 ℃, then slowly adding 120kg of suspension containing 8.2kg of calcium hydroxide into a reaction kettle, controlling the addition to be finished for 10min, then adjusting the pH value of the solution to be 9.6 by using a sodium hydroxide solution with the concentration of 0.5mol/L, continuously stirring for 60min, filtering after the completion, and washing to obtain the calcium hydroxy phosphate modified mesoporous silica;
3) adding 12kg of polyimide into 100kg of N, N-dimethylacetamide, fully and uniformly stirring, adding 2kg of calcium hydroxy phosphate modified mesoporous silica, stirring and dispersing at the rotating speed of 2000r/min for 10min, then continuing ultrasonic dispersion for 60min to obtain a casting solution, carrying out film scraping treatment on the casting solution by using a flat film scraper, drying at normal temperature and normal pressure for 10min to obtain an adsorption film, vertically irradiating the base filter membrane and the adsorption film by using an electron beam, and carrying out rolling compounding on the attached base filter membrane and the adsorption film by using a press roll to obtain the refined adsorption composite filter membrane.
The basic filter membrane is a polysulfone membrane.
The energy of the electron beam is 0.2 MeV.
The washing water is deionized water.
The drying agent is anhydrous calcium chloride.
The theoretical plate number of the rectifying tower is 8.
Example 2
A refining method of vinyl isobutyl ether comprises the following operation steps:
step one, crude distillation, namely adding 150kg of crude product of vinyl isobutyl ether into a primary crude distillation tower, and performing vacuum distillation under the conditions of absolute pressure of 35kPa and kettle temperature of 75 ℃ to obtain distillate liquid;
step two, washing, namely adding 140kg of washing water into 60kg of distillate, fully stirring and washing for 30min, standing for layering, and separating liquid to obtain an upper organic layer;
step three, drying, namely adding 4kg of drying agent into 50kg of the upper organic layer, stirring and mixing for 40min at normal temperature, and filtering to obtain a dried organic layer;
step four, adsorption filtration, namely introducing the obtained dry organic layer into a refined adsorption device, and filtering the organic layer through a filter membrane under the pressure of 0.3MPa, wherein the filter membrane is a refined adsorption composite filter membrane;
and step five, rectifying, namely adding the crude product of the vinyl isobutyl ether into a rectifying tower, and carrying out vacuum evaporation under the conditions of absolute pressure of 35kPa and kettle temperature of 75-85 ℃, wherein the reflux ratio is 1.3, and the obtained distillate is the refined vinyl isobutyl ether.
The preparation method of the refined adsorption composite filter membrane comprises the following steps:
1) adding 50kg of mesoporous silica into 60kg of acetone, then adding 4.8kg of methacryloxypropyltrimethoxysilane and 0.1kg of 1% sodium hydroxide solution, heating to 35 ℃ for reaction for 2 hours, then adding 0.03kg of methyl phenyl dimethyl siloxane for continuous heat preservation reaction for 3 hours, and carrying out reduced pressure distillation at 60 ℃ for 1 hour to obtain grafted mesoporous silica; adding 18kg of grafted mesoporous silica into 60kg of dimethylbenzene, adding 5kg of hydroxyethyl acrylate, 5kg of vinyl isobutyl ether and 0.01kg of 4-vinylpyridine-nickel, heating to 80 ℃, adding 0.01kg of benzoyl peroxide and 0.005kg of dichloromethane, carrying out closed heat preservation reaction for 6 hours, cooling, and evaporating a solvent to obtain grafted active mesoporous silica;
2) adding 7.2kg of phosphoric acid into 100kg of deionized water, uniformly stirring and mixing, adding 5kg of grafted active mesoporous silica into the system, stirring and mixing for 30min at 40 ℃, then slowly adding 100kg of suspension containing 2.5kg of calcium hydroxide into a reaction kettle, controlling the addition to be finished within 20min, then adjusting the pH value of the solution to 10.5 by using a sodium hydroxide solution with the concentration of 0.05mol/L, continuously stirring for 120min, filtering after the completion, and washing to obtain the calcium hydroxy phosphate modified mesoporous silica;
3) adding 8kg of polyimide into 80kg of N, N-dimethylacetamide, fully and uniformly stirring, adding 0.5kg of calcium hydroxy phosphate modified mesoporous silica, stirring and dispersing at the rotating speed of 1000r/min for 60min, then continuing ultrasonic dispersion for 30min to obtain a casting solution, carrying out film scraping treatment on the casting solution by using a flat film scraper, drying at normal temperature and normal pressure for 20min to obtain an adsorption film, vertically irradiating the base filter film and the adsorption film by using an electron beam, and rolling and compounding the attached base filter film and the adsorption film by using a press roller to obtain the refined adsorption composite filter film.
The basic filter membrane is a polyether sulfone membrane.
The energy of the electron beam is 0.5 MeV.
The washing water is purified water.
The drying agent is sodium sulfate.
The theoretical plate number of the rectifying tower is 14.
Example 3
A refining method of vinyl isobutyl ether comprises the following operation steps:
step one, crude distillation, namely adding 250kg of crude product of vinyl isobutyl ether into a primary crude distillation tower, and performing vacuum distillation under the conditions of absolute pressure of 40kPa and kettle temperature of 80 ℃ to obtain distillate liquid;
step two, washing, namely adding 180kg of washing water into 80kg of distillate, fully stirring and washing for 30min, standing for layering, and separating liquid to obtain an upper organic layer;
drying, namely adding 6kg of drying agent into 70kg of the upper organic layer, stirring and mixing at normal temperature for 60min, and filtering to obtain a dried organic layer;
step four, adsorption filtration, namely introducing the obtained dry organic layer into a refined adsorption device, and filtering the organic layer through a filter membrane under the pressure of 0.5MPa, wherein the filter membrane is a refined adsorption composite filter membrane;
and step five, rectifying, namely adding the crude product of the vinyl isobutyl ether into a rectifying tower, and carrying out vacuum evaporation under the conditions of absolute pressure of 40kPa and kettle temperature of 85 ℃, wherein the reflux ratio is 1.5, and the obtained distillate is the refined vinyl isobutyl ether.
The preparation method of the refined adsorption composite filter membrane comprises the following steps: according to the mass portion of the components,
1) adding 35 parts of mesoporous silica into 50 parts of acetone, then adding 3.6 parts of methacryloxypropyltrimethoxysilane and 0.22 part of 1% sodium hydroxide solution, heating to 40 ℃ for reaction for 3 hours, then adding 0.04 part of methyl phenyl dimethyl siloxane, continuing to perform heat preservation reaction for 5 hours, and performing reduced pressure distillation at 60 ℃ for 2 hours to obtain grafted mesoporous silica; adding 28 parts of grafted mesoporous silica into 45 parts of xylene, adding 10 parts of hydroxyethyl acrylate, 3 parts of vinyl isobutyl ether and 0.05 part of 4-vinylpyridine-nickel, heating to 72 ℃, adding 0.05 part of benzoyl peroxide and 0.006 part of dichloromethane, carrying out closed heat preservation reaction for 4 hours, cooling, and evaporating a solvent to obtain grafted active mesoporous silica;
2) adding 4.8 parts of phosphoric acid into 150 parts of deionized water, uniformly stirring and mixing, adding 7 parts of grafted active mesoporous silica into the system, stirring and mixing at 50 ℃ for 45min, then slowly adding 110 parts of suspension containing 4.8 parts of calcium hydroxide into a reaction kettle, controlling the addition to be finished for 15min, then adjusting the pH value of the solution to be 9.8 by using a sodium hydroxide solution with the concentration of 0.15mol/L, continuously stirring for 90min, filtering after the completion, and washing to obtain the calcium hydroxy phosphate modified mesoporous silica;
3) adding 10 parts of polyimide into 90 parts of N, N-dimethylacetamide, fully and uniformly stirring, adding 0.9 part of calcium hydroxy phosphate modified mesoporous silica, stirring and dispersing at the rotating speed of 1500r/min for 35min, then continuing ultrasonic dispersion for 50min to obtain a casting membrane solution, carrying out membrane scraping treatment on the casting membrane solution by using a flat membrane scraping machine, drying at normal temperature and normal pressure for 15min to obtain an adsorption membrane, vertically irradiating the base filter membrane and the adsorption membrane by using an electron beam, and rolling and compounding the attached base filter membrane and the adsorption membrane by using a press roll to obtain the refined adsorption composite filter membrane.
The basic filter membrane is a polyvinylidene fluoride membrane.
The energy of the electron beam is 0.8 MeV.
The washing water is purified water.
The drying agent is sodium sulfate.
The theoretical plate number of the rectifying tower is 20.
The statistical results of the content of the vinyl isobutyl ether prepared in the above examples and the retention rate of the refined adsorption composite filter membrane on glycerol are shown in the following table:
| content (%) | Glycerol retention (%) | |
| Example 1 | 99.75 | 91.72 |
| Example 2 | 99.89 | 93.87 |
| Example 3 | 99. 92 | 94.69 |
Comparative example 1
A refining method of vinyl isobutyl ether comprises the following operation steps:
step one, crude distillation, namely adding 100kg of a crude product of vinyl isobutyl ether into a primary crude distillation tower, and performing vacuum distillation under the conditions of the absolute pressure of 30kPa and the kettle temperature of 70 ℃ to obtain a distillate liquid;
step two, washing, namely adding 100kg of washing water into 50kg of distillate, fully stirring and washing for 30min, standing for layering, and separating liquid to obtain an upper organic layer;
step three, drying, namely adding 2kg of drying agent into 40kg of the upper organic layer, stirring and mixing for 30min at normal temperature, and filtering to obtain a dried organic layer;
step four, adsorption filtration, namely introducing the obtained dry organic layer into a refined adsorption device, and filtering the organic layer through a filter membrane under the pressure of 0.1MPa, wherein the filter membrane is a polysulfone membrane;
and step five, rectifying, namely adding the crude product of the vinyl isobutyl ether into a rectifying tower, and carrying out vacuum evaporation under the conditions of the absolute pressure of 30kPa and the kettle temperature of 75 ℃ with the reflux ratio of 1.1 to obtain distillate, namely the refined vinyl isobutyl ether.
The washing water is deionized water.
The drying agent is anhydrous calcium chloride.
The theoretical plate number of the rectifying tower is 8.
Comparative example 2
A refining method of vinyl isobutyl ether comprises the following operation steps:
step one, crude distillation, namely adding 100kg of a crude product of vinyl isobutyl ether into a primary crude distillation tower, and performing vacuum distillation under the conditions of the absolute pressure of 30kPa and the kettle temperature of 70 ℃ to obtain a distillate liquid;
step two, washing, namely adding 100kg of washing water into 50kg of distillate, fully stirring and washing for 30min, standing for layering, and separating liquid to obtain an upper organic layer;
and step three, drying, namely adding 2kg of drying agent into 40kg of the upper organic layer, stirring and mixing for 30min at normal temperature, and filtering to obtain a dried organic layer, namely the refined vinyl isobutyl ether.
The washing water is deionized water.
The drying agent is anhydrous calcium chloride.
Comparative example 3
A refining method of vinyl isobutyl ether comprises the following operation steps:
step one, crude distillation, namely adding 100kg of a crude product of vinyl isobutyl ether into a primary crude distillation tower, and performing vacuum distillation under the conditions of the absolute pressure of 30kPa and the kettle temperature of 70 ℃ to obtain a distillate liquid;
step two, washing, namely adding 100kg of washing water into 50kg of distillate, fully stirring and washing for 30min, standing for layering, and separating liquid to obtain an upper organic layer;
step three, drying, namely adding 2kg of drying agent into 40kg of the upper organic layer, stirring and mixing for 30min at normal temperature, and filtering to obtain a dried organic layer;
step four, adsorption filtration, namely introducing the obtained dry organic layer into a refined adsorption device, and filtering the organic layer through a filter membrane under the pressure of 0.1MPa, wherein the filter membrane is a refined adsorption composite filter membrane;
and step five, rectifying, namely adding the crude product of the vinyl isobutyl ether into a rectifying tower, and carrying out vacuum evaporation under the conditions of the absolute pressure of 30kPa and the kettle temperature of 75 ℃ with the reflux ratio of 1.1 to obtain distillate, namely the refined vinyl isobutyl ether.
The preparation method of the refined adsorption composite filter membrane comprises the following steps:
adding 8kg of polyimide into 80kgN, N-dimethylacetamide, fully and uniformly stirring, adding 0.5kg of mesoporous silica, stirring and dispersing at the rotating speed of 1000r/min for 10min, then continuing ultrasonic dispersion for 30min to obtain a casting solution, carrying out film scraping treatment on the casting solution by using a flat film scraper, wherein the thickness of the scraped film is 200 microns, drying at normal temperature and normal pressure for 10min to obtain an adsorption film, then vertically irradiating the base filter membrane and the adsorption film by using electron beams, and carrying out rolling compounding on the attached base filter membrane and the adsorption film by using a press roll to obtain the refined adsorption composite filter membrane.
The basic filter membrane is a polysulfone membrane.
The energy of the electron beam is 0.2 MeV.
The washing water is deionized water.
The drying agent is anhydrous calcium chloride.
The theoretical plate number of the rectifying tower is 8.
Comparative example 4
A refining method of vinyl isobutyl ether comprises the following operation steps:
step one, crude distillation, namely adding 100kg of a crude product of vinyl isobutyl ether into a primary crude distillation tower, and performing vacuum distillation under the conditions of the absolute pressure of 30kPa and the kettle temperature of 70 ℃ to obtain a distillate liquid;
step two, washing, namely adding 100kg of washing water into 50kg of distillate, fully stirring and washing for 30min, standing for layering, and separating liquid to obtain an upper organic layer;
step three, drying, namely adding 2kg of drying agent into 40kg of the upper organic layer, stirring and mixing for 30min at normal temperature, and filtering to obtain a dried organic layer;
step four, adsorption filtration, namely introducing the obtained dry organic layer into a refined adsorption device, and filtering the organic layer through a filter membrane under the pressure of 0.1MPa, wherein the filter membrane is a refined adsorption composite filter membrane;
and step five, rectifying, namely adding the crude product of the vinyl isobutyl ether into a rectifying tower, and carrying out vacuum evaporation under the conditions of the absolute pressure of 30kPa and the kettle temperature of 75 ℃ with the reflux ratio of 1.1 to obtain distillate, namely the refined vinyl isobutyl ether.
The preparation method of the refined adsorption composite filter membrane comprises the following steps:
1) adding 20kg of mesoporous silica into 40kg of acetone, then adding 0.36kg of 1% sodium hydroxide solution, heating to 55 ℃, then adding 0.05kg of methyl phenyl dimethyl siloxane, continuing to react for 8 hours under the condition of heat preservation, and distilling under reduced pressure at 60 ℃ for 3 hours to obtain grafted mesoporous silica; adding 40kg of grafted mesoporous silica into 36kg of xylene, adding 15kg of hydroxyethyl acrylate, 1kg of vinyl isobutyl ether and 0.1kg of 4-vinylpyridine-nickel, heating to 60 ℃, adding 0.1kg of benzoyl peroxide and 0.008kg of dichloromethane, carrying out closed heat preservation reaction for 2 hours, cooling, and evaporating a solvent to obtain grafted active mesoporous silica;
2) adding 2.6kg of phosphoric acid into 200kg of deionized water, uniformly stirring and mixing, adding 10kg of grafted active mesoporous silica into the system, stirring and mixing for 60min at 60 ℃, then slowly adding 120kg of suspension containing 8.2kg of calcium hydroxide into a reaction kettle, controlling the addition to be finished for 10min, then adjusting the pH value of the solution to be 9.6 by using a sodium hydroxide solution with the concentration of 0.5mol/L, continuously stirring for 60min, filtering after the completion, and washing to obtain the calcium hydroxy phosphate modified mesoporous silica;
3) adding 12kg of polyimide into 100kg of N, N-dimethylacetamide, fully and uniformly stirring, adding 2kg of calcium hydroxy phosphate modified mesoporous silica, stirring and dispersing at the rotating speed of 2000r/min for 10min, then continuing ultrasonic dispersion for 60min to obtain a casting solution, carrying out film scraping treatment on the casting solution by using a flat film scraper, drying at normal temperature and normal pressure for 10min to obtain an adsorption film, vertically irradiating the base filter membrane and the adsorption film by using an electron beam, and carrying out rolling compounding on the attached base filter membrane and the adsorption film by using a press roll to obtain the refined adsorption composite filter membrane.
The basic filter membrane is a polysulfone membrane.
The energy of the electron beam is 0.2 MeV.
The washing water is deionized water.
The drying agent is anhydrous calcium chloride.
The theoretical plate number of the rectifying tower is 8.
Comparative example 5
A refining method of vinyl isobutyl ether comprises the following operation steps:
step one, crude distillation, namely adding 100kg of a crude product of vinyl isobutyl ether into a primary crude distillation tower, and performing vacuum distillation under the conditions of the absolute pressure of 30kPa and the kettle temperature of 70 ℃ to obtain a distillate liquid;
step two, washing, namely adding 100kg of washing water into 50kg of distillate, fully stirring and washing for 30min, standing for layering, and separating liquid to obtain an upper organic layer;
step three, drying, namely adding 2kg of drying agent into 40kg of the upper organic layer, stirring and mixing for 30min at normal temperature, and filtering to obtain a dried organic layer;
step four, adsorption filtration, namely introducing the obtained dry organic layer into a refined adsorption device, and filtering the organic layer through a filter membrane under the pressure of 0.1MPa, wherein the filter membrane is a refined adsorption composite filter membrane;
and step five, rectifying, namely adding the crude product of the vinyl isobutyl ether into a rectifying tower, and carrying out vacuum evaporation under the conditions of the absolute pressure of 30kPa and the kettle temperature of 75 ℃ with the reflux ratio of 1.1 to obtain distillate, namely the refined vinyl isobutyl ether.
The preparation method of the refined adsorption composite filter membrane comprises the following steps:
1) adding 20kg of mesoporous silica into 40kg of acetone, then adding 1kg of methacryloxypropyltrimethoxysilane and 0.36kg of 1% sodium hydroxide solution, heating to 55 ℃ for reaction for 4h, then adding 0.05kg of methyl phenyl dimethyl siloxane for continuous heat preservation reaction for 8h, and carrying out reduced pressure distillation at 60 ℃ for 3h to obtain grafted mesoporous silica; adding 40kg of grafted mesoporous silica into 36kg of xylene, adding 1kg of vinyl isobutyl ether and 0.1kg of 4-vinylpyridine-nickel, heating to 60 ℃, adding 0.1kg of benzoyl peroxide and 0.008kg of dichloromethane, carrying out closed heat preservation reaction for 2 hours, cooling, and evaporating the solvent to obtain grafted active mesoporous silica;
2) adding 2.6kg of phosphoric acid into 200kg of deionized water, uniformly stirring and mixing, adding 10kg of grafted active mesoporous silica into the system, stirring and mixing for 60min at 60 ℃, then slowly adding 120kg of suspension containing 8.2kg of calcium hydroxide into a reaction kettle, controlling the addition to be finished for 10min, then adjusting the pH value of the solution to be 9.6 by using a sodium hydroxide solution with the concentration of 0.5mol/L, continuously stirring for 60min, filtering after the completion, and washing to obtain the calcium hydroxy phosphate modified mesoporous silica;
3) adding 12kg of polyimide into 100kg of N, N-dimethylacetamide, fully and uniformly stirring, adding 2kg of calcium hydroxy phosphate modified mesoporous silica, stirring and dispersing at the rotating speed of 2000r/min for 10min, then continuing ultrasonic dispersion for 60min to obtain a casting solution, carrying out film scraping treatment on the casting solution by using a flat film scraper, drying at normal temperature and normal pressure for 10min to obtain an adsorption film, vertically irradiating the base filter membrane and the adsorption film by using an electron beam, and carrying out rolling compounding on the attached base filter membrane and the adsorption film by using a press roll to obtain the refined adsorption composite filter membrane.
The basic filter membrane is a polysulfone membrane.
The energy of the electron beam is 0.2 MeV.
The washing water is deionized water.
The drying agent is anhydrous calcium chloride.
The theoretical plate number of the rectifying tower is 8.
Comparative example 6
A refining method of vinyl isobutyl ether comprises the following operation steps:
step one, crude distillation, namely adding 100kg of a crude product of vinyl isobutyl ether into a primary crude distillation tower, and performing vacuum distillation under the conditions of the absolute pressure of 30kPa and the kettle temperature of 70 ℃ to obtain a distillate liquid;
step two, washing, namely adding 100kg of washing water into 50kg of distillate, fully stirring and washing for 30min, standing for layering, and separating liquid to obtain an upper organic layer;
step three, drying, namely adding 2kg of drying agent into 40kg of the upper organic layer, stirring and mixing for 30min at normal temperature, and filtering to obtain a dried organic layer;
step four, adsorption filtration, namely introducing the obtained dry organic layer into a refined adsorption device, and filtering the organic layer through a filter membrane under the pressure of 0.1MPa, wherein the filter membrane is a refined adsorption composite filter membrane;
and step five, rectifying, namely adding the crude product of the vinyl isobutyl ether into a rectifying tower, and carrying out vacuum evaporation under the conditions of the absolute pressure of 30kPa and the kettle temperature of 75 ℃ with the reflux ratio of 1.1 to obtain distillate, namely the refined vinyl isobutyl ether.
The preparation method of the refined adsorption composite filter membrane comprises the following steps:
1) adding 20kg of mesoporous silica into 40kg of acetone, then adding 1kg of methacryloxypropyltrimethoxysilane and 0.36kg of 1% sodium hydroxide solution, heating to 55 ℃ for reaction for 4h, then adding 0.05kg of methyl phenyl dimethyl siloxane for continuous heat preservation reaction for 8h, and carrying out reduced pressure distillation at 60 ℃ for 3h to obtain grafted mesoporous silica; adding 40kg of grafted mesoporous silica into 36kg of xylene, adding 15kg of hydroxyethyl acrylate, 1kg of vinyl isobutyl ether and 0.1kg of 4-vinylpyridine-nickel, heating to 60 ℃, adding 0.1kg of benzoyl peroxide, carrying out closed heat preservation reaction for 2 hours, cooling, and evaporating a solvent to obtain grafted active mesoporous silica;
2) adding 2.6kg of phosphoric acid into 200kg of deionized water, uniformly stirring and mixing, adding 10kg of grafted active mesoporous silica into the system, stirring and mixing for 60min at 60 ℃, then slowly adding 120kg of suspension containing 8.2kg of calcium hydroxide into a reaction kettle, controlling the addition to be finished for 10min, then adjusting the pH value of the solution to be 9.6 by using a sodium hydroxide solution with the concentration of 0.5mol/L, continuously stirring for 60min, filtering after the completion, and washing to obtain the calcium hydroxy phosphate modified mesoporous silica;
3) adding 12kg of polyimide into 100kg of N, N-dimethylacetamide, fully and uniformly stirring, adding 2kg of calcium hydroxy phosphate modified mesoporous silica, stirring and dispersing at the rotating speed of 2000r/min for 10min, then continuing ultrasonic dispersion for 60min to obtain a casting solution, carrying out film scraping treatment on the casting solution by using a flat film scraper, drying at normal temperature and normal pressure for 10min to obtain an adsorption film, vertically irradiating the base filter membrane and the adsorption film by using an electron beam, and carrying out rolling compounding on the attached base filter membrane and the adsorption film by using a press roll to obtain the refined adsorption composite filter membrane.
The basic filter membrane is a polysulfone membrane.
The energy of the electron beam is 0.2 MeV.
The washing water is deionized water.
The drying agent is anhydrous calcium chloride.
The theoretical plate number of the rectifying tower is 8
The content of the vinyl isobutyl ether prepared in the above examples and the statistical results of the glycerol retention of the filters used are shown in the following table:
| content (%) | Glycerol retention (%) | |
| Comparative example 1 | 98.92 | 0.84 |
| Comparative example 2 | 98.57 | -- |
| Comparative example 3 | 99.28 | 20.41 |
| Comparative example 4 | 99.36 | 35.42 |
| Comparative example 5 | 99.41 | 30.56 |
| Comparative example 6 | 99.48 | 56.70 |
Claims (5)
1. A refining method of vinyl isobutyl ether comprises the following operation steps:
step one, crude distillation, namely adding 100 parts of crude product of vinyl isobutyl ether into a primary crude distillation tower according to the mass parts, and carrying out vacuum distillation under the conditions of absolute pressure of 30-40kPa and kettle temperature of 70-80 ℃ to obtain a distillate liquid;
step two, washing, namely adding 180 parts of 100-180 parts of washing water into 50-80 parts of distillate according to parts by mass, fully stirring and washing for 30-60min, standing and layering, and separating liquid to obtain an upper organic layer;
step three, drying, namely adding 2-6 parts of drying agent into 40-70 parts of upper organic layer according to the mass parts, stirring and mixing at normal temperature for 30-60min, and filtering to obtain a dried organic layer;
step four, adsorption filtration, namely introducing the obtained dry organic layer into a refined adsorption device, and filtering the organic layer through a filter membrane under the pressure of 0.1-0.5MPa, wherein the filter membrane is a refined adsorption composite filter membrane;
step five, rectification, namely adding the crude product of the vinyl isobutyl ether into a rectification tower, and carrying out vacuum evaporation under the conditions of the absolute pressure of 30-40kPa and the kettle temperature of 75-85 ℃, wherein the reflux ratio is 1.1-1.5, and the obtained distillate is refined vinyl isobutyl ether;
the preparation method of the refined adsorption composite filter membrane comprises the following steps: according to the mass portion of the components,
1) adding 20-50 parts of mesoporous silica into 40-60 parts of acetone, then adding 1-4.8 parts of methacryloxypropyltrimethoxysilane and 0.1-0.36 part of 1% sodium hydroxide solution, heating to 35-55 ℃ for reaction for 2-4h, then adding 0.03-0.05 part of methylphenyldimethylsiloxane, continuing to react for 3-8h under the condition of heat preservation, and carrying out reduced pressure distillation at 60 ℃ for 1-3h to obtain grafted mesoporous silica; adding 18-40 parts of grafted mesoporous silica into 36-60 parts of xylene, adding 5-15 parts of hydroxyethyl acrylate, 1-5 parts of vinyl isobutyl ether and 0.01-0.1 part of 4-vinylpyridine-nickel, heating to 60-80 ℃, adding 0.01-0.1 part of benzoyl peroxide and 0.005-0.008 part of dichloromethane, carrying out closed heat preservation reaction for 2-6 hours, cooling, and evaporating the solvent to obtain grafted active mesoporous silica;
2) adding 2.6-7.2 parts of phosphoric acid into 100-200 parts of deionized water, uniformly stirring and mixing, then adding 5-10 parts of grafted active mesoporous silica into the system, stirring and mixing at 40-60 ℃ for 30-60min, then slowly adding 100-120 parts of suspension containing 2.5-8.2 parts of calcium hydroxide into the reaction kettle, controlling the addition to be completed within 10-20min, then adjusting the pH value of the solution to be 9.6-10.5 by using a sodium hydroxide solution with the concentration of 0.05-0.5mol/L, continuously stirring for 60-120min, filtering after the completion, and washing to obtain the calcium hydroxy phosphate modified mesoporous silica;
3) adding 8-12 parts of polyimide into 80-100 parts of N, N-dimethylacetamide, fully and uniformly stirring, adding 0.5-2 parts of calcium hydroxy phosphate modified mesoporous silica, stirring and dispersing at the rotating speed of 1000-2000r/min for 10-60min, then continuing ultrasonic dispersion for 30-60min to obtain a casting solution, carrying out film scraping treatment on the casting solution by using a flat film scraper, wherein the film scraping thickness is 200-300 mu m, drying at normal temperature and normal pressure for 10-20min to obtain an adsorption film, then vertically irradiating a basic filter membrane and the adsorption film by using an electron beam, and carrying out rolling compounding on the adhered basic filter membrane and the adsorption film by using a compression roller to obtain a refined adsorption composite filter membrane;
the basic filter membrane is a polysulfone membrane or a polyether sulfone membrane or a polyvinylidene fluoride membrane.
2. The method according to claim 1, wherein: the energy of the electron beam is 0.2-0.8 MeV.
3. The method according to claim 1, wherein: the washing water is deionized water or purified water.
4. The method according to claim 1, wherein: the drying agent is anhydrous calcium chloride or sodium sulfate.
5. The method according to claim 1, wherein: the theoretical plate number of the rectifying tower is 8-20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110487024.4A CN113200828B (en) | 2021-05-04 | 2021-05-04 | Refining method of vinyl isobutyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110487024.4A CN113200828B (en) | 2021-05-04 | 2021-05-04 | Refining method of vinyl isobutyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113200828A CN113200828A (en) | 2021-08-03 |
| CN113200828B true CN113200828B (en) | 2022-04-26 |
Family
ID=77029059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110487024.4A Active CN113200828B (en) | 2021-05-04 | 2021-05-04 | Refining method of vinyl isobutyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113200828B (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709847A (en) * | 2005-06-21 | 2005-12-21 | 孟永华 | Continuous synthesizing method of vinyl isobutyl ether |
| JP5312133B2 (en) * | 2009-03-26 | 2013-10-09 | 丸善石油化学株式会社 | Production method of high purity vinyl ether |
| CN202290057U (en) * | 2011-11-07 | 2012-07-04 | 安徽省绩溪县天池化工有限公司 | Device for clearing attachments on molecular sieve for purifying GDR (Glycol Dimethyl Ether) rough product |
| CN102701920B (en) * | 2012-05-29 | 2015-03-18 | 浙江锦华新材料股份有限公司 | Method for purifying vinyl isobutyl ether |
| CN102976904B (en) * | 2012-12-24 | 2014-10-15 | 厦门大学 | Preparation device of isobutyl vinyl ether and preparation method thereof |
| CN105837407A (en) * | 2016-04-27 | 2016-08-10 | 厦门大学 | Preparation method of isobutyl vinyl ether |
| CN107737530B (en) * | 2017-11-15 | 2020-11-06 | 北京工业大学 | Modified graphene oxide/hyperbranched polymer composite membrane, preparation method and application |
| CN112299964B (en) * | 2020-11-16 | 2023-04-11 | 博爱新开源医疗科技集团股份有限公司 | Preparation method of ethylene glycol monovinyl ether |
-
2021
- 2021-05-04 CN CN202110487024.4A patent/CN113200828B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113200828A (en) | 2021-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105418368A (en) | Technology and device for producing high-purity ethyl alcohol | |
| KR20220086665A (en) | Gas-Liquid Bubble Bed Reactor, Reaction System, and Carbonate Synthesis Method | |
| CN114344932A (en) | Method and device for producing high-purity electronic grade acetone | |
| CN114307368A (en) | Method and device for producing high-purity electronic grade ethanol | |
| CN113200828B (en) | Refining method of vinyl isobutyl ether | |
| CN114506820A (en) | Method for directly producing electronic grade hydrogen peroxide from hydrogen and oxygen | |
| CN102199227A (en) | Method for producing high-purity poly-glucose through simulated moving bed chromatography | |
| CN107778139B (en) | Separation and purification method for energy-saving dehydration and impurity removal of ethylene glycol aqueous solution | |
| CN106883209A (en) | A kind of preparation technology of dioxolanes | |
| CN209210671U (en) | Steam infiltration-alkaline process coupling prepares the device of sodium methoxide | |
| CN111892525A (en) | N-methyl pyrrolidone for liquid crystal panel and production process thereof | |
| CN114797145B (en) | Differential pressure thermal coupling rectification process for coal-to-ethylene glycol byproduct | |
| CN114230608B (en) | Production process of reactive flame retardant THPO | |
| CN110683513A (en) | Preparation method of high-purity chlorine | |
| CN110668919A (en) | Method for purifying chromatographically pure methanol | |
| CN110294726A (en) | The preparation method of ISOASCORBIC ACID potassium | |
| WO2010130214A1 (en) | Method for two-stage production of dimethyl ether | |
| CN115028523A (en) | Pressure-variable-heterogeneous azeotropic rectification separation method for butanone dehydration | |
| CN114456222A (en) | Extraction process for cholesterol | |
| CN105771589B (en) | A kind of separator of ammonia and carbon dioxide | |
| CN112694401A (en) | Ethyl acetate production system and production method thereof | |
| CN111185070A (en) | NF removal using low temperature HF3System and method for removing impurities from electrolysis gas | |
| CN216259552U (en) | Membrane adsorption coupling device for preparing tetrahydrofuran with low water content | |
| CN105481660B (en) | The continuous production system and synthetic method of a kind of cyclopentyl methyl ether | |
| CN107400103B (en) | Preparation process of olefin epoxidation oxidation liquid, oxidation liquid and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |