CN110713432A - Preparation method of anhydrous electronic grade ethanol - Google Patents
Preparation method of anhydrous electronic grade ethanol Download PDFInfo
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- CN110713432A CN110713432A CN201911187141.8A CN201911187141A CN110713432A CN 110713432 A CN110713432 A CN 110713432A CN 201911187141 A CN201911187141 A CN 201911187141A CN 110713432 A CN110713432 A CN 110713432A
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000012528 membrane Substances 0.000 claims abstract description 43
- 238000001179 sorption measurement Methods 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000005373 pervaporation Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 239000012466 permeate Substances 0.000 claims abstract description 5
- 239000012530 fluid Substances 0.000 claims abstract 5
- 230000000149 penetrating effect Effects 0.000 claims abstract 5
- 239000011347 resin Substances 0.000 claims description 33
- 229920005989 resin Polymers 0.000 claims description 33
- 239000003513 alkali Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 150000001450 anions Chemical class 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- 239000002031 ethanolic fraction Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- 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 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 5
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- 238000010306 acid treatment Methods 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims 2
- 239000003456 ion exchange resin Substances 0.000 claims 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 abstract description 54
- 230000018044 dehydration Effects 0.000 abstract description 4
- 238000006297 dehydration reaction Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 18
- 239000012535 impurity Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 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 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of anhydrous electronic grade ethanol, which comprises the following steps: feeding industrial grade ethanol into a rectifying tower, and removing light components and heavy components by adopting a rectifying mode; the ethanol distillate obtained after rectification is sent into a pervaporation membrane separation device for dehydration; separating with pervaporation membrane separation device to obtain anhydrous ethanol, allowing water and small amount of ethanol in solution at feed liquid side to permeate pervaporation membrane in vapor form to obtain penetrating fluid, condensing the penetrating fluid, returning to rectifying tower, and recovering ethanol; and (3) allowing the absolute ethyl alcohol obtained by the pervaporation separation device to enter an adsorption tower for adsorption, and removing ions in the ethyl alcohol to finally obtain the absolute electronic grade ethyl alcohol. In the preparation process, the ethanol has low water content, high purity, simple process, low operation energy consumption, high safety coefficient and no waste salt.
Description
Technical Field
The invention relates to a preparation method of anhydrous electronic grade ethanol, belonging to the field of pervaporation membrane application.
Background
Electronic grade chemicals, also known as ultra-clean and high-purity reagents (ultraclean and high-purity reagents), are also called as process chemicals internationally, and also called as wet chemicals in regions of europe and taiwan of china, and are one of key basic chemical materials in the manufacturing process of very large scale integrated circuits (commonly called as "chips"), wherein electronic grade ethanol is mainly used for ultra-clean cleaning and drying in the processing process of precision electronic components such as chips, liquid crystals, magnetic heads, circuit boards and the like, and ultra-clean organic solvents for cleaning workshop appliances. When the ethanol contains alkali metal impurities (sodium, potassium, calcium and the like), the impurities are dissolved into the oxide film, so that the insulation voltage is reduced; when heavy metals (copper, iron, chromium, silver, etc.) are present, the P-N junction withstand voltage is lowered. Therefore, purity and cleanliness have a significant impact on the yield, electrical performance, and reliability of integrated circuits.
The prior art for preparing ultra-clean high-purity ethanol comprises one or more of adsorption, rectification, sub-boiling distillation, drying and filtration processes. For example, Chinese patent "an apparatus for preparing ethanol with ultra-low metal ion concentration" describes that electronic grade ethanol with ultra-low metal ion concentration is obtained by sub-boiling distillation, but the method has low efficiency and is not suitable for industrial production. The Chinese patent 'a method for preparing ultra-clean high-purity alcohol reagents' describes that anhydrous ethanol is adsorbed by modified carbon fibers to obtain the ultra-clean high-purity alcohol reagents without ions, but the method is not suitable for directly treating industrial-grade hydrous ethanol as a raw material, and an oxidant is required to be used when the adsorbent is treated, so that certain potential safety hazards are caused. The Chinese patent 'purification method of ultra-pure absolute ethyl alcohol' describes that absolute ethyl alcohol passes through trace barium hydroxide, then is subjected to micro-membrane filtration, and is rectified after filtration. This method does not address the removal of anions and cations.
Disclosure of Invention
The invention aims to overcome the defects that the existing raw material for preparing electronic grade ethanol has high requirement and needs to introduce external compounds, and provides an industrial production method which takes industrial grade ethanol as a raw material, does not introduce other impurities, and has high stability and low water content.
The technical scheme of the invention is as follows:
and step 2, heating the ethanol obtained in the step 1, and then sending the heated ethanol into a pervaporation membrane separation device for separation to obtain anhydrous ethanol, wherein the water content of the ethanol is 0-0.5%, and the particle impurities (not less than 0.2 mu m and not more than 1 mu m) are less than 25/mL. Heating the ethanol distillate treated by the rectifying tower to 70-180 ℃ in an evaporator, and then feeding the ethanol distillate into a pervaporation membrane separation device, wherein the gauge pressure of the feed liquid side of a pervaporation membrane is 0.1-0.4 MPa; the permeation side is connected with a vacuum system, and the absolute pressure of the permeation side is 100-4000 Pa; the pervaporation membrane adopts a membrane which is a preferential permeable membrane, can be a molecular sieve membrane, an amorphous silica membrane and a PVA membrane, and is optimally a molecular sieve membrane.
And 3, feeding the dehydrated ethanol obtained in the step 2 into an adsorption tower for adsorption to obtain a finished product ethanol, wherein the water content of the ethanol is 0.1-0.5% when the ethanol enters the adsorption tower, the particle impurities (more than or equal to 0.2 mu m, more than or equal to 1 mu m, max) are lower than 25/mL, the operating pressure is 0.1-0.2MPa, the adsorption time is 60-120 minutes, the cation adsorption resin used for adsorption needs to be subjected to acid treatment before use and regeneration, the acid liquor concentration is controlled to be 1 ~ 10wt.%, the volume of the acid liquor used is 0.5-5 times of the volume of the cation resin, the acid can be hydrochloric acid, sulfuric acid, phosphoric acid and methanesulfonic acid, the resin can be of a gel type, a macroporous type and the like, the anion resin used for adsorption needs to be subjected to alkali treatment before use and regeneration, the alkali liquor concentration is controlled to be 1 ~ 10wt.%, the volume of the alkali liquor used is 0.5-5 times of the volume of the anion resin, the alkali can be sodium hydroxide, potassium hydroxide, tetramethylammonium fluoride, the resin can be a macroporous gel type gel, the macroporous type resin, the macroporous ethylene receiver and the finished product has a single polytetrafluoroethylene (single electron density) of no more than 150ppb, and the finished product has a single electron density of a single ppb standard electron polytetrafluoroethylene (1 ppb.
The device for preparing the anhydrous electronic grade ethanol comprises a raw material tank, a rectifying tower, a receiving tank, a pervaporation device, an adsorption tower and a finished product receiving tank, wherein an outlet of the pervaporation device is connected with an inlet of the adsorption tower, and an outlet of the adsorption tower is connected with an inlet of the finished product receiving tank.
Has the advantages that: in the preparation process, the ethanol has low water content, high purity, simple process, low operation energy consumption, high safety coefficient and no waste salt. The used process device has small occupied area, easy operation and stable quality and can be used for continuous production.
Drawings
FIG. 1 is a process flow diagram of the method for preparing anhydrous electronic grade ethanol according to the present invention. Wherein, 1 is a raw material tank, 2 is a rectifying tower, 3 is an evaporator, 4 is a pervaporation device, 5 is an adsorption tower, and 6 is a finished product receiver.
Detailed Description
The technical scheme of the invention is further specifically described by the following embodiments.
Example 1
Firstly, feeding an industrial-grade ethanol (95 percent and 5 percent of water) raw material into a raw material tank 1, setting the heating temperature of a tower kettle of a rectifying tower 2 to be 110 ℃, keeping the top of the rectifying tower 2 to be totally refluxed for 1 hour, removing light components accounting for 10 percent of the mass of the raw material, controlling the reflux ratio to be 2, collecting ethanol fraction accounting for 72-80 ℃, wherein the mass of the fraction accounts for 85 percent and 10 percent of the mass of the raw material. The ethanol distillate obtained from the rectifying tower 2 is delivered to a pervaporation device 4, and is heated by an evaporator 3, and the ethanol aqueous solution is heated to 110 ℃ and enters into 15 molecular sieve membranes, silicon dioxide membranes and PVA membrane modules (each stage of membrane module has an area of 10 m)2) The pervaporation membrane separation device 4 constructed in series performs dehydration separation. The feed liquid side pressure was 0.2MPa (gauge pressure), and the permeate side pressure was controlled at 1000 Pa. The water content of the feed liquid on the feed liquid side of the membrane is obviously reduced through the pervaporation membrane separation opportunity, anhydrous ethanol with the water content of 0.2wt.% is obtained, the permeation liquid on the permeation side is sucked by a vacuum pump, and the obtained permeation liquid is condensed by a permeation liquid condenser and then returns to the rectifying tower 2 to be treated and a small amount of ethanol is recovered. The absolute ethyl alcohol enters an adsorption tower 5, and is adsorbed by gel type adsorption resin, wherein the adsorption process is that the ethyl alcohol is firstly subjected to adsorption treatmentAdsorbing with cationic resin, and adsorbing with anionic resin. The cation resin is treated by acid before use and regeneration, the concentration of the acid liquid is controlled to be 10 wt%, the volume of the used acid liquid is 0.5 times of that of the cation resin, and the acid is hydrochloric acid, sulfuric acid, phosphoric acid or methanesulfonic acid. Before using and regenerating the anion resin, alkali solution concentration is controlled at 10wt.%, the volume of the alkali solution is 0.5 times of that of the anion resin, and the alkali is sodium hydroxide, potassium hydroxide or tetramethyl ammonium fluoride. The absorbed finished product enters a finished product receiver 6.
The content of the absolute electronic grade ethanol produced in example 1 was analyzed by gas chromatography, the cation by ICP-MS, the anion by ion chromatography, and the dust particles by laser particle counter. Specific data are shown in table 1.
TABLE 1
Example 2
Firstly, feeding industrial-grade ethanol (95 percent and 5 percent of water) into a raw material tank 1, setting the heating temperature of a tower kettle of a rectifying tower 2 to be 110 ℃, keeping the top of the rectifying tower 2 to be totally refluxed for 1 hour, removing light components accounting for 10 percent of the mass of the raw material, controlling the reflux ratio to be 6, collecting ethanol fraction with the temperature range of 74-76 ℃, wherein the mass of the fraction accounts for 60-70 percent of the mass of the raw material and the mass of the fraction accounts for 1.0 percent of the water. The ethanol distillate obtained from the rectifying tower 2 is delivered to a pervaporation device 4, and is heated by an evaporator 3, and the ethanol aqueous solution is heated to 70 ℃ and enters into 15 molecular sieve membranes, silicon dioxide membranes and PVA membrane modules (each stage of membrane module has an area of 10 m)2) The pervaporation membrane separation device 4 constructed in series performs dehydration separation. The feed liquid side pressure was 0.1MPa (gauge pressure), and the permeate side pressure was controlled at 100 Pa. The water content of the feed liquid on the feed liquid side of the membrane is obviously reduced through the pervaporation membrane separation opportunity, anhydrous ethanol with the water content of 0.5wt.% is obtained, the permeation liquid on the permeation side is sucked by a vacuum pump, and the obtained permeation liquid is condensed by a permeation liquid condenser and then returns to the rectifying tower 2 for treatment and recovery of a small amount of ethanol. The absolute ethyl alcohol enters an adsorption tower 5 and enters the adsorption tower through macroporous adsorption resinPerforming adsorption treatment, wherein the adsorption process is that ethanol is firstly adsorbed by cation resin and then adsorbed by anion resin. Before the cation resin is used and regenerated, acid treatment is needed, the concentration of the acid liquor is controlled to be 1 wt%, the volume of the used acid liquor is 5 times of that of the cation resin, and the acid is hydrochloric acid, sulfuric acid, phosphoric acid or methanesulfonic acid. Before using and regenerating the anion resin, alkali treatment is needed, the concentration of alkali liquor is controlled to be 1wt.%, the volume of the used alkali liquor is 5 times of that of the anion resin, and the alkali is sodium hydroxide, potassium hydroxide or tetramethyl ammonium fluoride. The absorbed finished product enters a finished product receiver 6.
The analysis results showed that the ethanol content was greater than 99.9wt.% and the moisture content was less than 0.1 wt.%. The specific data are shown in Table 2.
TABLE 2
。
Example 3
Firstly, feeding industrial-grade ethanol (95 percent and 5 percent of water) into a raw material tank 1, setting the heating temperature of a tower kettle of a rectifying tower 2 to be 110 ℃, keeping the top of the rectifying tower 2 to perform total reflux for 1 hour, removing light components accounting for 10 percent of the mass of the raw material, controlling the reflux ratio to be 10, collecting ethanol fractions accounting for 90 percent and 10 percent of the mass of the raw material, wherein the mass of the ethanol fractions is the mass of 90 percent and the water content of the raw material. The ethanol distillate obtained from the rectifying tower 2 is delivered to a pervaporation device 4, and is heated by an evaporator 3, and the ethanol aqueous solution is heated to 180 ℃ and enters into 15 molecular sieve membranes, silicon dioxide membranes and PVA membrane modules (each stage of membrane module has an area of 10 m)2) The pervaporation membrane separation device 4 constructed in series performs dehydration separation. The feed liquid side pressure was 0.4MPa (gauge pressure), and the permeate side pressure was controlled at 4000 Pa. The water content of the feed liquid on the feed liquid side of the membrane is obviously reduced through the pervaporation membrane separation opportunity, anhydrous ethanol with the water content of 0.1wt.% is obtained, the permeation liquid on the permeation side is sucked by a vacuum pump, and the obtained permeation liquid is condensed by a permeation liquid condenser and then returns to the rectifying tower 2 for treatment and recovery of a small amount of ethanol. The anhydrous ethanol enters an adsorption tower 5, and is adsorbed by chelating adsorption resin, wherein the adsorption process comprises the steps of adsorbing the ethanol by cationic resin and then passing the ethanol through the adsorption towerAdsorbing with anion resin. Before the cation resin is used and regenerated, acid treatment is needed, the concentration of the acid liquor is controlled to be 5 wt%, the volume of the used acid liquor is 2 times of that of the cation resin, and the acid is hydrochloric acid, sulfuric acid, phosphoric acid or methanesulfonic acid. Before using and regenerating the anion resin, alkali treatment is needed, the concentration of alkali liquor is controlled at 5wt.%, the volume of the alkali liquor is 2 times of that of the anion resin, and the alkali is sodium hydroxide, potassium hydroxide or tetramethyl ammonium fluoride. The absorbed finished product enters a finished product receiver 6.
The analysis results showed that the ethanol content was greater than 99.9wt.% and the moisture content was less than 0.1 wt.%. Specific data are shown in table 3.
TABLE 3
Claims (7)
1. A preparation method of anhydrous electronic grade ethanol is characterized by comprising the following steps:
step 1: conveying the industrial-grade ethanol to a rectifying tower to remove light components and heavy components, and recovering the ethanol in the light components after the light components return to the rectifying tower;
step 2: heating the ethanol distillate in the step 1, sending the heated ethanol distillate into a pervaporation membrane separation device for separation to obtain crude ethanol, allowing water and a small amount of ethanol in the solution on the feed liquid side to permeate the pervaporation membrane in a steam form to obtain a penetrating fluid, and returning the penetrating fluid after condensation to a rectifying tower to recover the ethanol in the penetrating fluid;
and 3, step 3: feeding the dehydrated ethanol obtained in the step 2 into an adsorption tower for adsorption to obtain a finished product ethanol, wherein the adsorption process comprises the steps of adsorbing the ethanol by cationic resin and then adsorbing the ethanol by anionic resin; the cation resin needs to be treated by acid before use and regeneration, and the anion resin needs to be treated by alkali before use and regeneration.
2. The method for preparing anhydrous electronic grade ethanol according to claim 1, wherein the reflux ratio of light components removal in step 1 is controlled to be 2-10, the ethanol fraction with the temperature range of 72-80 ℃ is collected, and the water content of the ethanol fraction is 1.0 ~ 10 wt.%.
3. The process for producing anhydrous electronic grade ethanol according to claim 1, wherein in step 2, the ethanol distillate is heated in an evaporator to 70 to 180 ℃ and the gauge pressure on the feed side of the pervaporation membrane is 0.1 to 0.4 MPa; the permeation side is connected with a vacuum system, and the absolute pressure of the permeation side is 100-4000 Pa; the pervaporation membrane separation device adopts a water permeable membrane, specifically a molecular sieve membrane, an amorphous silica membrane and a PVA membrane.
4. The method for preparing anhydrous electronic grade ethanol according to claim 1, wherein the water content of the anhydrous ethanol obtained in the step 2 is controlled to be 0.1-0.5 wt.%.
5. The method for preparing anhydrous electronic grade ethanol according to claim 1, wherein the material used for adsorption in step 3 is an ion exchange resin, specifically a gel-type, macroporous-type or chelate-type ion exchange resin.
6. The method for preparing anhydrous electronic grade ethanol according to claim 1, wherein the acid solution used in the acid treatment in step 3 is controlled to have a concentration of 1 ~ 10wt.%, the volume of the acid solution used is 0.5-5 times that of the cationic resin, and the acid is hydrochloric acid, sulfuric acid, phosphoric acid or methanesulfonic acid.
7. The method for preparing anhydrous electronic grade ethanol according to claim 1, wherein the concentration of the alkali solution used in the alkali treatment in step 3 is controlled to be 1 ~ 10wt.%, the volume of the alkali solution used is 0.5-5 times of the volume of the anion resin, and the alkali is sodium hydroxide, potassium hydroxide or tetramethylammonium fluoride.
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Cited By (6)
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| CN112194567A (en) * | 2020-11-03 | 2021-01-08 | 山东中盛药化设备有限公司 | Process and system for recovering absolute ethyl alcohol by combining rectification, vaporization membrane and MVR (mechanical vapor recompression) technology |
| CN113248376A (en) * | 2021-07-15 | 2021-08-13 | 山东海科新源材料科技股份有限公司 | Preparation method of electronic grade propionate, product obtained by preparation method and application of product |
| CN114307368A (en) * | 2022-02-15 | 2022-04-12 | 北京袭明科技有限公司 | Method and device for producing high-purity electronic grade ethanol |
| CN114504872A (en) * | 2022-02-15 | 2022-05-17 | 北京袭明科技有限公司 | Method and device for producing high-purity electronic grade ethylene glycol |
| CN114712884A (en) * | 2022-06-08 | 2022-07-08 | 北京化工大学 | Device and method for producing electronic grade ethanol by rectification-membrane separation |
| CN116041147A (en) * | 2022-12-27 | 2023-05-02 | 苏州东瑞制药有限公司 | Method for recovering ethanol in sulbactam sodium production |
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| CN112194567A (en) * | 2020-11-03 | 2021-01-08 | 山东中盛药化设备有限公司 | Process and system for recovering absolute ethyl alcohol by combining rectification, vaporization membrane and MVR (mechanical vapor recompression) technology |
| CN113248376A (en) * | 2021-07-15 | 2021-08-13 | 山东海科新源材料科技股份有限公司 | Preparation method of electronic grade propionate, product obtained by preparation method and application of product |
| CN114307368A (en) * | 2022-02-15 | 2022-04-12 | 北京袭明科技有限公司 | Method and device for producing high-purity electronic grade ethanol |
| CN114504872A (en) * | 2022-02-15 | 2022-05-17 | 北京袭明科技有限公司 | Method and device for producing high-purity electronic grade ethylene glycol |
| CN114712884A (en) * | 2022-06-08 | 2022-07-08 | 北京化工大学 | Device and method for producing electronic grade ethanol by rectification-membrane separation |
| CN116041147A (en) * | 2022-12-27 | 2023-05-02 | 苏州东瑞制药有限公司 | Method for recovering ethanol in sulbactam sodium production |
| CN116041147B (en) * | 2022-12-27 | 2024-04-12 | 苏州东瑞制药有限公司 | Method for recovering ethanol in sulbactam sodium production |
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