CN115322074B - Purification method of isopropanol - Google Patents
Purification method of isopropanol Download PDFInfo
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- CN115322074B CN115322074B CN202210796333.4A CN202210796333A CN115322074B CN 115322074 B CN115322074 B CN 115322074B CN 202210796333 A CN202210796333 A CN 202210796333A CN 115322074 B CN115322074 B CN 115322074B
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 238000000034 method Methods 0.000 title claims abstract description 78
- 238000000746 purification Methods 0.000 title claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 77
- 239000002245 particle Substances 0.000 claims abstract description 55
- 239000012528 membrane Substances 0.000 claims abstract description 39
- 239000002808 molecular sieve Substances 0.000 claims abstract description 32
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001450 anions Chemical class 0.000 claims abstract description 30
- 239000012535 impurity Substances 0.000 claims abstract description 28
- 150000001768 cations Chemical class 0.000 claims abstract description 25
- 238000001728 nano-filtration Methods 0.000 claims abstract description 20
- -1 then Substances 0.000 claims abstract description 13
- 238000005373 pervaporation Methods 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 7
- 238000005342 ion exchange Methods 0.000 claims abstract description 6
- 238000002407 reforming Methods 0.000 claims description 38
- 238000010992 reflux Methods 0.000 claims description 17
- 229920001721 polyimide Polymers 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 208000005156 Dehydration Diseases 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 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 description 10
- 238000000605 extraction Methods 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 claims description 7
- 239000003456 ion exchange resin Substances 0.000 claims description 7
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 6
- 239000012510 hollow fiber Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 241001550224 Apha Species 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000003729 cation exchange resin Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 239000011162 core material Substances 0.000 claims 2
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 238000010276 construction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000011164 primary particle Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920001429 chelating resin Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000003827 glycol group Chemical group 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000004934 PuraMem® Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a purification method of isopropanol, which adopts a construction multistage treatment procedure to treat the raw materials step by step, each stage of treatment procedure removes partial impurities respectively, industrial grade isopropanol is taken as the raw material, firstly, the raw material is dehydrated through a pervaporation membrane and a molecular sieve, then, metal cations are controlled through primary particles, light components and heavy components are removed through a two-stage rectifying tower, anions are removed through anion resin, the product is reformed through low-temperature treatment and rectification, then, the metal cations are removed through an ion exchange filter element, and finally, particles are controlled through a nanofiltration filter element, so that the semiconductor grade isopropanol can be obtained; the method can avoid the operation mode of repeatedly carrying out each purification step for reaching the index in the prior art, can progressively and continuously obtain high-quality products, and has reasonable process flow, high production efficiency, stable product quality and relatively low cost.
Description
Technical Field
The invention relates to the technical field of ultra-high purity reagent purification, in particular to a purification method of isopropanol.
Background
With the continuous increase of wafer size in semiconductor production, the chip integration level is higher and higher, and the requirement on high-purity solvent is also higher and higher. The ultra-high purity reagent is an important raw material in the production process of integrated circuits, wherein the ultra-high purity isopropanol is used as an organic solvent and is mainly used for cleaning organic matters on the surface of a wafer and removing water in the semiconductor industry.
With the increase in integrated circuit integration, the purity requirements for electronic chemicals are also increasing. The method for purifying the isopropyl alcohol commonly adopted at present comprises the following steps: the industrial grade isopropanol is directly rectified after being treated by a molecular sieve, the used device mainly comprises a rectifying tower and a micro-filter, the molecular sieve can bring ion pollution to subsequent purification, the cost of the subsequent purification is increased, and the requirement of a high-purity product cannot be met; meanwhile, the current scheme basically takes results as guidance, namely index requirements are provided for each step, then each step is repeatedly carried out without counting the cost until indexes are reached, the cost is too high, the product quality is not stable enough, and the method is difficult to be suitable for industrial application.
Disclosure of Invention
The present invention aims to overcome one or more of the deficiencies of the prior art and to provide a method for purifying modified isopropyl alcohol.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the method takes industrial grade isopropanol as a raw material, and adopts a construction multistage treatment process to treat the raw material step by step, wherein each stage of treatment process is used for removing part of impurities respectively, and the multistage treatment process at least comprises a dehydration treatment process, a particle treatment process and an impurity combined treatment process;
wherein the particle treatment procedure comprises a particle pretreatment step and a nanofiltration step;
the dehydration treatment process, the particle pretreatment process, the impurity combined treatment process and the nanofiltration process are sequentially and continuously performed;
the dehydration treatment process comprises the steps of sequentially passing the raw materials through a pervaporation membrane and a molecular sieve for dehydration treatment; the particle pretreatment step adopts a filter element to carry out filtration treatment;
the impurity combined treatment process at least comprises the following steps which are sequentially and continuously carried out:
membrane treatment: allowing the raw material treated by the particle pretreatment step to enter an organosilicone modified polyimide film for removing metal cations and particles;
(ii) rectification and purification: sequentially carrying out light removal rectification and heavy removal rectification on the raw materials subjected to the membrane treatment in the step (i); the extractant adopted by the dehydrogenation and rectification is glycol, and the extractant adopted by the de-duplication and rectification is triethylene glycol;
(iii) anion removal: removing anions from the raw material subjected to the rectification and purification treatment in the step (ii) through anion resin;
(iv) reforming: subjecting the anion-removed feedstock of step (iii) to low temperature reforming and rectification reforming;
the low-temperature reforming adopts low temperature of minus 60 ℃ to minus 40 ℃ to cool the raw material so as to solidify part of impurities in the raw material, and then filtering and removing the impurities;
the rectification reforming process extracts isopropanol from the side line, and the process parameters are as follows: the number of the tower plates is 70-80, the feeding port of the raw material is positioned at the 50-60 th tower plate, the temperature of the tower top is 75-85 ℃, the temperature of the side line is 77-83 ℃, the temperature of the tower kettle is 140-220 ℃, and the reflux ratio is 2-6;
(v) cation removal: and (3) removing metal cations in the reformed raw material obtained in the step (iv) through an ion exchange filter element or ion exchange resin.
The method can avoid the operation mode of repeatedly carrying out each purification step for reaching the index in the prior art, can progressively and continuously obtain high-quality products, and has reasonable process flow, high production efficiency, stable product quality and relatively low cost.
According to some preferred aspects of the invention, the pervaporation membrane is a NaA-type membrane.
According to some preferred aspects of the invention, the molecular sieve is a 3 angstrom aluminosilicate molecular sieve or a4 angstrom aluminosilicate molecular sieve.
According to some preferred aspects of the invention, the particle pretreatment step employs a filter element with a pore size of 1-40 μm and a material of polypropylene or polytetrafluoroethylene. According to a specific aspect of the invention, the particle pretreatment step adopts filter elements with different pore diameters to carry out multiple times of filtration, for example, filter elements with pore diameters of 40 μm and 10 μm can be respectively adopted to carry out 2-level filtration, and large particles separated by a molecular sieve and large particle impurities carried by isopropyl alcohol raw materials can be filtered.
According to some preferred aspects of the invention, the nanofiltration step is carried out by using a hollow fiber nanofiltration membrane, wherein the hollow fiber nanofiltration membrane is made of polytetrafluoroethylene and has a pore size of 1-40nm, and the nanofiltration step is carried out by using multi-stage hollow fiber nanofiltration membranes with different pore sizes. According to a specific aspect of the invention, the nanofiltration step is carried out by: the raw materials after cation removal are sequentially subjected to five-grade polytetrafluoroethylene filter cores of 40nm, 10nm, 5nm, 2nm and 1nm for particle removal.
According to some preferred aspects of the invention, the membrane treatment is performed at a flow rate of 100 to 500L/h and at a pressure of 1 to 5MPa.
In some embodiments of the invention, the membrane treatment is performed sequentially with a series of multistage organosilicone-modified polyimide membranes.
In some embodiments of the invention, the organosilicone-modified polyimide film is PuraMem Performance available from winning technology.
According to some preferred aspects of the present invention, in the rectification purification, the solvent ratio of the rectification purification is 0.6 to 1.4, the reflux ratio is 1 to 3, the number of trays is 40 to 60, the feed port of the raw material is at the position of 35 to 45 of the number of trays (i.e., the feed port of the raw material is at any one of the 35 to 45 th trays), the temperature of the top of the column is 76 to 84 ℃, the temperature of the bottom of the column is 160 to 180 ℃, and the feed port of the extractant is at the position of 10 to 20 of the number of trays.
Further, in the rectification and purification, the inner container of the extraction and rectification tower adopts 316L stainless steel, the surface is subjected to electrolytic polishing, and the filler adopts carbon fiber tetrafluoro filler.
Further, in the light component removal rectification, the solvent ratio is 0.6-1.0, the reflux ratio is 1.0-2, the number of plates is 45-60, the feed inlet of the raw material is positioned at the position of 35-45 of the number of plates, the feed inlet of the extractant is positioned at the position of 10-14 of the number of plates, the temperature of the top of the tower is 80-83 ℃, and the temperature of the bottom of the tower is 160-165 ℃.
Further, in the heavy-removal rectification, the solvent ratio is 0.6-1.2, the reflux ratio is 1-2.2, the number of plates is 45-60, the feed inlet of the raw material is positioned at the position of the number of plates which is 42-44, the feed inlet of the extractant is positioned at the position of the number of plates which is 12-14, the tower top temperature is 82.5-84.5 ℃, and the tower bottom temperature is 168-180 ℃.
According to some preferred aspects of the invention, the operating pressure in the light ends rectification is from 0.07 to 0.09MPa.
According to some preferred aspects of the invention, the operating pressure in the de-duplication rectification is 0.10-0.12MPa.
According to some preferred aspects of the invention, in the anion removal, the anion resin is a strongly basic gel-type ion exchange resin, for example Amberlite IRA402 Cl may be selected.
According to some preferred aspects of the invention, in the cation removal, the ion exchange resin is a gel styrene-based cation exchange resin, and the ion exchange resin may be DuPont AmberYST 36WET, duPont AmberTec UP 1400H, or the like.
According to some preferred aspects of the invention, in the cation removal, the ion exchange filter core adopts a polytetrafluoroethylene membrane modified by surface sulfonic acid groups, and for example, the ion exchange filter core can be Kebert Chemphobic ultrapure chemical filter and the like.
According to some preferred aspects of the invention, the rectification reforming operates at a pressure of 0.05-0.09MPa.
According to some preferred aspects of the invention, in the low-temperature reforming, a filter element adopted by the filtration is made of polyimide, and the pore size is 10-40nm.
According to the invention, in the purified isopropanol product, the weight content of isopropanol is more than or equal to 99.990%, the chromaticity APHA is less than or equal to 3, the moisture is less than or equal to 50ppm, each single metal ion is less than or equal to 50ppt, each single non-metal ion is less than or equal to 8ppb, and the particle size (particle size is more than 0.04 μm) is less than 55pcs/mL.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, industrial isopropanol is taken as a raw material, a plurality of purification processes are combined, the raw material is treated step by adopting a plurality of purification processes, partial impurities are removed in each stage of treatment process, the treatment pressure of a subsequent filter element is greatly relieved by the pretreatment of particles in the particle pretreatment step, the precision advantage of a nanofiltration filter element is better exerted, especially, a specific impurity combined treatment process is constructed and adopted, metal cations and particles are treated by using an organosilicone modified polyimide film before light removal and heavy removal rectification, the rectification pressure is reduced, the efficiency of removing organic impurities is improved, the anions of the raw material are removed by using anions before low-temperature reforming and rectification, the removal efficiency of the organic impurities is further improved, the low-temperature reforming is further beneficial to the removal of high-boiling organic impurities and moisture, the whole process is in cooperation, the impurities can be efficiently removed with high quality, the single operation is not required to be repeated for a certain index without cost, the continuous production is easy to realize, the product quality is stable, and the product quality can exceed the standard requirements of a semiconductor electronic chemical TiMI (D) in large scale.
Drawings
FIG. 1 is a process flow diagram of a method for purifying isopropyl alcohol according to an embodiment of the present invention.
Detailed Description
The above-described aspects are further described below in conjunction with specific embodiments; it should be understood that these embodiments are provided to illustrate the basic principles, main features and advantages of the present invention, and that the present invention is not limited by the scope of the following embodiments; the implementation conditions employed in the examples may be further adjusted according to specific requirements, and the implementation conditions not specified are generally those in routine experiments.
All starting materials, not specifically illustrated in the examples below, may be obtained from commercial sources or prepared by methods conventional in the art.
NaA molecular sieve membrane, purchased from national science and technology, brand GC-PV-003; the 3 angstrom molecular sieve is purchased in Shanghai long-time universe; an organosilicone modified polyimide film (PuraMem Performance), available from winning technology; the anionic resin Amberlite IRA402 Cl, available from dupont; cation exchange resin, amberTec UP 1400H, available from dupont; a40 μm, 10 μm PP filter cartridge, available from Kebaite; the inner containers of the light extraction rectifying tower and the heavy extraction rectifying tower are respectively made of 316L stainless steel, the surface is subjected to electrolytic polishing, and the filler is carbon fiber tetrafluoro filler; technical grade isopropanol is commercially available (performance standard GB/T7814-2017).
Example 1
The method adopts industrial grade isopropanol as a raw material, and adopts a construction multi-stage treatment process to treat the raw material step by step, and each stage of treatment process is used for removing part of impurities respectively.
Specifically, in connection with process flow diagram 1, the method comprises:
dehydration treatment procedure: industrial grade isopropanol with the weight content of 99.0 percent is taken as an isopropanol raw material and passes through a molecular sieve pervaporation membrane and a molecular sieve tank at the flow of 120L/h, wherein the pervaporation membrane is a NaA molecular sieve membrane, the molecular sieve is a 3 angstrom molecular sieve, and the water content is less than or equal to 50ppm after treatment;
particle pretreatment: carrying out particle pretreatment on the dehydrated isopropanol raw material, and sequentially filtering large particles falling off a molecular sieve and large particle impurities carried by the isopropanol raw material by using a filter element (PP material) with the particle size of 40 mu m and 10 mu m;
film treatment: the filtered isopropanol raw material enters an organic silicone modified polyimide film, the flow rate is 100L/h, and the pressure is 1.5MPa;
and (3) rectifying and purifying: the isopropanol raw material after membrane treatment is subjected to light removal rectification and heavy removal rectification in sequence, the light removal rectification adopts a light removal extraction rectification tower, an extractant is glycol, the solvent ratio is 0.6, the number of tower plates is 50, the reflux ratio is 1.0, the feeding port of the isopropanol raw material is positioned at the 40 th tower plate, the feeding port of the extractant is positioned at the 10 th tower plate, the tower top temperature is 82 ℃, the tower bottom temperature is 162 ℃, and the operating pressure is 0.08MPa; the heavy removal rectification adopts a heavy removal extraction rectifying tower, wherein an extractant is triethylene glycol, the solvent ratio is 0.6, the number of tower plates is 50, the reflux ratio is 1.5, a feed inlet of an isopropyl alcohol raw material is positioned at a 42 th tower plate, a feed inlet of the extractant is positioned at a 12 th tower plate, the tower top temperature is 83 ℃, the tower bottom temperature is 170 ℃, and the operating pressure is 0.11MPa;
anion removal: the isopropanol raw material treated by the light and heavy removal rectifying tower enters an anion treatment tank, and is subjected to anion removal by using Amberlite IRA402 Cl;
reforming: the solution after anion removal enters a reforming unit (low-temperature reforming and rectification reforming are sequentially carried out), in the low-temperature reforming, the temperature is-40 ℃, after cooling treatment is carried out to solidify part of impurities in the raw materials, filtering is sequentially carried out by adopting a40 nm filter core and a 10nm filter core (the material is polyimide, purchased from Yu Kogyo chemical);
rectifying and reforming, wherein the tower plate number is 80, the reflux ratio is 2, the feeding port of the isopropanol raw material is positioned at the 60 th tower plate, the tower top temperature is 80 ℃, the tower kettle temperature is 170 ℃, the pressure is 0.07MPa, the side line temperature is 82.2 ℃, and the reformed isopropanol raw material is taken out from the side line of the rectifying tower;
cation removal: the reformed isopropanol raw material enters a cation removal tank, and resin, amberTec UP 1400H is adopted for cation removal.
Nanofiltration: after cation removal, particle removal was performed sequentially through five-stage polytetrafluoroethylene cartridges (purchased from the company Poer, the same shall apply below) of 40nm, 10nm, 5nm, 2nm, and 1nm, and after particle control, ultra-pure isopropanol was obtained, reaching the semiconductor grade.
Comparative example 1
Compared with example 1, the difference is only that: the removal reforming step, specifically, the removal of low-temperature reforming and rectification reforming, was performed by directly introducing the mixture into a cation removal tank for treatment after treatment with an anion treatment tank, and was otherwise the same as in example 1.
Comparative example 2
Compared with example 1, the difference is only that: the removal of low temperature reforming, specifically, rectification reforming directly after anion removal, was performed as in example 1.
Comparative example 3
Compared with example 1, the difference is only that: the sequence of anion removal and reforming steps is reversed, i.e. the reforming step is first followed by anion removal, otherwise as in example 1.
Example 2
The method adopts industrial grade isopropanol as a raw material, and adopts a construction multi-stage treatment process to treat the raw material step by step, and each stage of treatment process is used for removing part of impurities respectively.
Specifically, in connection with process flow diagram 1, the method comprises:
dehydration treatment procedure: industrial grade isopropanol with the weight content of 99.0 percent is taken as an isopropanol raw material and passes through a molecular sieve pervaporation membrane and a molecular sieve tank at the flow of 200L/h, wherein the pervaporation membrane is a NaA molecular sieve membrane, the molecular sieve is a 3 angstrom molecular sieve, and the water content is less than or equal to 50ppm after treatment;
particle pretreatment: the dehydrated isopropanol raw material enters particle pretreatment, and large particles falling off by a molecular sieve and large particle impurities carried by the isopropanol raw material are sequentially filtered by using a filter element (PP material) with the particle diameter of 40 mu m and a filter element (PP material) with the particle diameter of 10 mu m;
film treatment: the filtered isopropanol raw material enters an organic silicone modified polyimide film, the flow rate is 200L/h, and the pressure is 1.5MPa;
and (3) rectifying and purifying: the isopropanol raw material after membrane treatment is subjected to light removal rectification and heavy removal rectification in sequence, the light removal rectification adopts a light removal extraction rectification tower, an extractant is glycol, the solvent ratio is 1.0, the tower plate number is 60, the reflux ratio is 2, the feeding port of the isopropanol raw material is positioned at the 35 th tower plate, the feeding port of the extractant is positioned at the 14 th tower plate, the tower top temperature is 80 ℃, the tower bottom temperature is 170 ℃, and the operation pressure is 0.08MPa; the heavy removal rectification adopts a heavy removal extraction rectifying tower, wherein an extractant is triethylene glycol, the solvent ratio is 1.0, the tower plate number is 60, the reflux ratio is 2, a feed inlet of an isopropyl alcohol raw material is positioned at a 44 th tower plate, a feed inlet of the extractant is positioned at a 12 th tower plate, the tower top temperature is 84 ℃, the tower bottom temperature is 172 ℃, and the operation pressure is 0.11MPa;
anion removal: the isopropanol raw material treated by the light and heavy removal rectifying tower enters an anion treatment tank, and is subjected to anion removal by using Amberlite IRA402 Cl;
reforming: the solution after anion removal enters a reforming unit (low-temperature reforming and rectification reforming are sequentially carried out), the temperature is minus 60 ℃, and after cooling treatment is carried out to solidify part of impurities in the raw materials, a40 nm filter element and a 10nm filter element (the material is polyimide) are sequentially adopted for filtering; rectifying and reforming, wherein the tower plate number is 80, the reflux ratio is 3, the feeding port of the isopropanol raw material is positioned at the 50 th tower plate, the tower top temperature is 82 ℃, the tower kettle temperature is 140 ℃, the pressure is 0.07MPa, the side line temperature is 82.4 ℃, and the reformed isopropanol raw material is taken out from the side line of the rectifying tower;
cation removal: the reformed isopropanol raw material enters a cation removal tank, a membrane filter core with a surface grafted exchange group is adopted for cation removal, and the filter core is selected from Ionkleen SL series and purchased from quite company;
nanofiltration: after cation removal, particle removal is carried out through five-grade polytetrafluoroethylene filter cores of 40nm, 10nm, 5nm, 2nm and 1nm in sequence, and ultra-pure isopropanol is obtained after particle control is carried out, so that the semiconductor grade is achieved.
Example 3
The method adopts industrial grade isopropanol as a raw material, and adopts a construction multi-stage treatment process to treat the raw material step by step, and each stage of treatment process is used for removing part of impurities respectively.
Specifically, in connection with process flow diagram 1, the method comprises:
dehydration treatment procedure: industrial grade isopropanol with the weight content of 99.0 percent is taken as an isopropanol raw material and passes through a molecular sieve pervaporation membrane and a molecular sieve tank at the flow rate of 150L/h, wherein the pervaporation membrane is a NaA molecular sieve membrane, the molecular sieve is a 3 angstrom molecular sieve, and the water content is less than or equal to 50ppm after treatment;
particle pretreatment: the dehydrated isopropanol raw material enters particle pretreatment, and large particles which are separated from a molecular sieve and large particle impurities carried by an isopropanol solution are sequentially filtered by using a filter element (PP material) with the particle diameter of 40 mu m and a filter element (PP material) with the particle diameter of 10 mu m;
film treatment: the filtered isopropanol raw material enters an organic silicone modified polyimide film, the flow rate is 150L/h, and the pressure is 1.25MPa;
and (3) rectifying and purifying: the isopropanol raw material after membrane treatment is subjected to light removal rectification and heavy removal rectification in sequence, the light removal rectification adopts a light removal extraction rectification tower, an extractant is glycol, the solvent ratio is 0.8, the number of tower plates is 50, the reflux ratio is 0.8, the feeding port of the isopropanol raw material is positioned at the 45 th tower plate, the feeding port of the extractant is positioned at the 12 th tower plate, the temperature of the tower top is 83 ℃, the temperature of the tower bottom is 164 ℃, and the operating pressure is 0.08MPa; the heavy removal rectification adopts a heavy removal extraction rectifying tower, wherein an extractant is triethylene glycol, the solvent ratio is 0.8, the number of tower plates is 50, the reflux ratio is 1.0, a feed inlet of an isopropyl alcohol raw material is positioned at a 42 th tower plate, a feed inlet of the extractant is positioned at a 14 th tower plate, the tower top temperature is 83 ℃, the tower bottom temperature is 180 ℃, and the operating pressure is 0.11MPa;
anion removal: the isopropanol raw material treated by the light and heavy removal rectifying tower enters an anion treatment tank, and is subjected to anion removal by using Amberlite IRA402 Cl;
reforming: the solution after anion removal enters a reforming unit (low-temperature reforming and rectification reforming are sequentially carried out), the temperature is minus 50 ℃, and after cooling treatment is carried out to solidify part of impurities in the raw materials, a40 nm filter element and a 10nm filter element (the material is polyimide) are sequentially adopted for filtering; rectifying and reforming, wherein the tower plate number is 80, the reflux ratio is 2, the feeding port of the isopropanol raw material is positioned at the 60 th tower plate, the tower top temperature is 80 ℃, the tower kettle temperature is 220 ℃, the pressure is 0.07MPa, the side line temperature is 82.0 ℃, and the reformed isopropanol raw material is taken out from the side line of the rectifying tower;
cation removal: the reformed isopropanol raw material enters a cation removal tank, the cation removal adopts resin, and the resin adopts AmberTec UP 1400H;
nanofiltration: after cation removal, particle removal is carried out through five-grade polytetrafluoroethylene filter cores of 40nm, 10nm, 5nm, 2nm and 1nm in sequence, and ultra-pure isopropanol is obtained after particle control is carried out, so that the semiconductor grade is achieved.
Performance testing
Tables 1-2 below show the results of the detection of isopropyl alcohol obtained in examples 1-3 and comparative examples 1-3, respectively.
Wherein, the mass content of the product is analyzed by gas chromatography, the weight content of the water is analyzed by Karl Fischer water analyzer, the anion is analyzed by liquid Ion Chromatography (IC), and the weight content of the metal ion is analyzed by inductively coupled plasma mass spectrometer (ICP-MS). The particles are tested by a laser particle tester, the chromaticity is tested by a colorimetric method, and the acidity is tested by a titration method.
TABLE 1
TABLE 2
In the purified isopropanol product, the weight content of the isopropanol is more than or equal to 99.990 percent, the chromaticity APHA is less than or equal to 3, the moisture is less than or equal to 50ppm, each single metal ion is less than or equal to 50ppt, each single non-metal ion is less than or equal to 8ppb, and the particle size (particle size is more than 0.04 mu m) is less than 55pcs/mL.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (9)
1. The method is characterized in that the method adopts a multi-stage treatment process to treat the raw materials step by step, each stage of treatment process is used for removing part of impurities, and the multi-stage treatment process at least comprises a dehydration treatment process, a particle treatment process and an impurity combined treatment process;
wherein the particle treatment procedure comprises a particle pretreatment step and a nanofiltration step;
the dehydration treatment process, the particle pretreatment process, the impurity combined treatment process and the nanofiltration process are sequentially and continuously performed;
the dehydration treatment process comprises the steps of sequentially passing the raw materials through a pervaporation membrane and a molecular sieve for dehydration treatment; the particle pretreatment step adopts a filter element to carry out filtration treatment;
the impurity combined treatment process at least comprises the following steps which are sequentially and continuously carried out:
membrane treatment: allowing the raw material treated by the particle pretreatment step to enter an organosilicone modified polyimide film for removing metal cations and particles;
(ii) rectification and purification: sequentially carrying out light removal rectification and heavy removal rectification on the raw materials subjected to the membrane treatment in the step (i); the extractant adopted by the light component removal and rectification is glycol, and the extractant adopted by the heavy component removal and rectification is triethylene glycol; wherein, the solvent ratio of rectification and purification is 0.6-1.4, the reflux ratio is 1-3, and the column plate number is 40-60;
(iii) anion removal: removing anions from the raw material subjected to the rectification and purification treatment in the step (ii) through anion resin; wherein the anion resin is a strong alkaline gel type ion exchange resin;
(iv) reforming: subjecting the anion-removed feedstock of step (iii) to low temperature reforming and rectification reforming;
the low-temperature reforming is carried out by adopting low temperature of minus 60 to minus 40 ℃ to cool the raw materials so as to solidify part of impurities in the raw materials, and then the raw materials are filtered and removed; wherein, the filter core material adopted by the filtration is polyimide, and the aperture is 10-40nm;
the rectification reforming process extracts isopropanol from the side line, and the process parameters are as follows: the number of the tower plates is 70-80, the feeding port of the raw material is positioned at the 50-60 th tower plate, the temperature of the tower top is 75-85 ℃, the temperature of the side line is 77-83 ℃, the temperature of the tower kettle is 140-220 ℃, and the reflux ratio is 2-6;
(v) cation removal: removing metal cations in the reformed raw material obtained in the step (iv) through an ion exchange filter element or ion exchange resin; wherein the ion exchange resin adopts gel styrene-based cation exchange resin, and the ion exchange filter core adopts polytetrafluoroethylene membrane modified by surface sulfonic acid groups.
2. The method for purifying isopropanol according to claim 1, wherein the pervaporation membrane is a NaA type membrane, and the molecular sieve is a 3 angstrom aluminosilicate molecular sieve or a4 angstrom aluminosilicate molecular sieve; the pore diameter of the filter element adopted in the particle pretreatment step is 1-40 mu m, and the filter element is made of polypropylene or polytetrafluoroethylene; the nanofiltration step is carried out by adopting a hollow fiber nanofiltration membrane, the hollow fiber nanofiltration membrane is made of polytetrafluoroethylene, the pore diameter is 1-40nm, and the nanofiltration step is carried out by adopting a multi-stage hollow fiber nanofiltration membrane with different pore diameters.
3. The method for purifying isopropyl alcohol according to claim 1, wherein in the membrane treatment, the flow rate is 100 to 500L/h, and the pressure is 1 to 5MPa; in the membrane treatment, multistage organosilicone modified polyimide membranes are adopted to carry out serial connection and sequential treatment.
4. The method for purifying isopropyl alcohol according to claim 1, wherein in the rectifying purification, the feed port of the raw material is at the position of 35-45 in number of trays, the temperature of the top of the column is 76-84 ℃, the temperature of the bottom of the column is 160-180 ℃, and the feed port of the extractant is at the position of 10-20 in number of trays.
5. The method according to claim 4, wherein in the rectification and purification, the inner container of the extraction and rectification tower is made of 316L stainless steel, the surface is subjected to electrolytic polishing, and the filler is carbon fiber tetrafluoro filler.
6. The method for purifying isopropyl alcohol according to claim 4, wherein in the light ends removal rectification, the solvent ratio is 0.6 to 1.0, the reflux ratio is 1.0 to 2, the number of trays is 45 to 60, the feed inlet of the raw material is at the position of 35 to 45, the feed inlet of the extractant is at the position of 10 to 14, the temperature at the top of the column is 80 to 83 ℃, and the temperature at the bottom of the column is 160 to 165 ℃;
in the heavy-removal rectification, the solvent ratio is 0.6-1.2, the reflux ratio is 1-2.2, the column plate number is 45-60, the feed inlet of the raw material is positioned at the position of the column plate number of 42-44, the feed inlet of the extractant is positioned at the position of the column plate number of 12-14, the temperature of the column top is 82.5-84.5 ℃, and the temperature of the column bottom is 168-180 ℃.
7. The method for purifying isopropyl alcohol according to claim 6, wherein in the light ends removal rectification, the operation pressure is 0.07 to 0.09MPa; in the heavy removal rectification, the operation pressure is 0.10-0.12MPa.
8. The method for purifying isopropyl alcohol according to claim 1, wherein the operation pressure of rectification reforming is 0.05 to 0.09MPa.
9. The method for purifying isopropyl alcohol according to claim 1, wherein the isopropyl alcohol product obtained after the purification has a weight content of isopropyl alcohol of 99.990% or more, a chromaticity APHA of 3 or less, a moisture of 50ppm or less, individual metal ions of 50ppt or less, individual nonmetallic ions of 8ppb or less, and particles with a particle size of >0.04 μm of < 55pcs/mL.
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