CN113121622A - Method for removing trace anions and cations in organic matter - Google Patents
Method for removing trace anions and cations in organic matter Download PDFInfo
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- CN113121622A CN113121622A CN201911397725.8A CN201911397725A CN113121622A CN 113121622 A CN113121622 A CN 113121622A CN 201911397725 A CN201911397725 A CN 201911397725A CN 113121622 A CN113121622 A CN 113121622A
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- resin
- anion
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- anions
- removal method
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- 150000001450 anions Chemical class 0.000 title claims abstract description 84
- 150000001768 cations Chemical class 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000005416 organic matter Substances 0.000 title claims description 12
- 239000011347 resin Substances 0.000 claims abstract description 111
- 229920005989 resin Polymers 0.000 claims abstract description 111
- 238000005498 polishing Methods 0.000 claims abstract description 18
- 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 abstract description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 55
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 32
- 239000012498 ultrapure water Substances 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000003729 cation exchange resin Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003957 anion exchange resin Substances 0.000 claims description 6
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 229930195725 Mannitol Natural products 0.000 claims description 5
- 229920001429 chelating resin Polymers 0.000 claims description 5
- 239000000594 mannitol Substances 0.000 claims description 5
- 235000010355 mannitol Nutrition 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 4
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 claims description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 4
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims description 4
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 claims description 4
- 229960000367 inositol Drugs 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 claims description 4
- 239000000845 maltitol Substances 0.000 claims description 4
- 235000010449 maltitol Nutrition 0.000 claims description 4
- 229940035436 maltitol Drugs 0.000 claims description 4
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- UIKQNMXWCYQNCS-UHFFFAOYSA-N 2-hydroxybutanal Chemical compound CCC(O)C=O UIKQNMXWCYQNCS-UHFFFAOYSA-N 0.000 claims description 2
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940023913 cation exchange resins Drugs 0.000 claims description 2
- 229940120503 dihydroxyacetone Drugs 0.000 claims description 2
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical compound OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 239000003456 ion exchange resin Substances 0.000 abstract description 8
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 description 36
- 238000011049 filling Methods 0.000 description 23
- 238000005406 washing Methods 0.000 description 19
- 230000001172 regenerating effect Effects 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 11
- -1 organic acid salts Chemical class 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 9
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 9
- 239000000811 xylitol Substances 0.000 description 9
- 235000010447 xylitol Nutrition 0.000 description 9
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 9
- 229960002675 xylitol Drugs 0.000 description 9
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 8
- 235000011149 sulphuric acid Nutrition 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229940116333 ethyl lactate Drugs 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- 229960001855 mannitol Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000013014 purified material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- RFSUNEUAIZKAJO-VRPWFDPXSA-N D-Fructose Natural products OC[C@H]1OC(O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-VRPWFDPXSA-N 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BJHIKXHVCXFQLS-UYFOZJQFSA-N keto-D-fructose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C(=O)CO BJHIKXHVCXFQLS-UYFOZJQFSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229960002920 sorbitol Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/02—Monosaccharides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Biotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention relates to a method for removing trace anions and cations in organic matters. The invention can obtain the product with the ion content less than 1ppb and the anion less than 10ppb by processing the organic raw material with the ion resin and the polishing resin. The ion exchange resin can be repeatedly used after being adsorbed and saturated, and compared with rectification, no phase change occurs in the purification process of the ion exchange resin, so that the energy is saved. And the operation at room temperature is safer, and is beneficial to large-scale production.
Description
Technical Field
The invention relates to a method for removing trace anions and cations in organic matters.
Background
The content of impurities in the electronic-grade reagent can directly influence the electrical property and the yield of the integrated circuit. With the rapid development of the integrated circuit industry, in which the size of the integrated circuit is reduced from 90nm to 28nm, the latest process has been able to reduce the size of the integrated circuit to 7 nm. The distance between the components is smaller and smaller, and trace impurities inevitably influence the product yield, so that higher requirements are put forward on the electronic-grade reagent.
Conventional electronic grade reagents can be obtained by rectification. CN102898275A discloses a preparation method of high-purity isopropanol, which comprises the preparation steps of molecular sieve dehydration, resin dehydration, reverse osmosis, high-temperature rectification, ion exchange and circulating filtration, and finally obtains an isopropanol reagent with metal ion concentration less than 10ppt and single anion concentration less than 1 ppb. CN109251143A discloses a preparation method of electronic grade ethyl lactate, which takes food grade ethyl lactate as raw material, and the raw material is absorbed by ion exchange resin, rectified and sub-boiled distilled, the content of metal ions is less than 1ppb, and the acidity is less than 65 ppm. From this, it is known that rectification is an effective method for removing metal ions, but has a limited effect on the residual acid. Since the metal compounds are not volatile, the acid will be volatile along with the desired purified material during the rectification. Therefore, lowering the acid in the product requires a higher tray or a greater reflux ratio, which in turn increases production costs and reduces production efficiency. In addition, the purified materials required for rectification generally need to be stable at high temperature under normal pressure or negative pressure, and as mentioned above, materials such as isopropanol and ethyl lactate are heated to boiling point under normal pressure and are not decomposed, and substances with poor stability need to be rectified under reduced pressure. CN103450101A discloses a continuous purification process of methylbenzotriazole, wherein the methylbenzotriazole needs to be purified under the condition of high vacuum degree (190-210Pa), and the methylbenzotriazole can be rapidly decomposed by heating under normal pressure. Therefore, the distillation method cannot be used to remove metal ions from the high-temperature decomposed substances such as xylitol, mannitol, L-ascorbic acid, etc.
For the pyrolysis material, an ion exchange resin may be used to remove metal ions. CN101643755B discloses a method for producing electronic grade gallic acid, which can obtain gallic acid with metal ion less than or equal to 20ppb by anion and cation resin treatment, but does not disclose the condition of residual anions in the product. The metal ions are present in the form of salts, such as chloride, sulfate, nitrate, organic acid salts, which are present in the product in the form of acids after removal of the metal ions by the cation exchange resin. The final total acidity of the product disclosed in CN109251143A is less than or equal to 65ppm, and the final acidity of the product disclosed in CN109160876A is less than or equal to 100 ppm.
While in semiconductor cleaning, ppm levels of anions are not negligible, the anions need to be reduced to a low enough concentration to avoid adverse effects on the semiconductor device, such as: the nonmetal activity of the chloride ions is very strong, and if the concentration of the chloride ions is not reduced to be low enough, the chloride ions can form a potential difference on the surface of the device, so that a chemical reaction occurs, the corrosion speed of the surface of the device is accelerated, and the conditions of open circuit and electric leakage are easily generated inside the device, so that the problem of the residue of anions needs to be paid sufficient attention. The prior published documents do not have a method of directly passing through ion exchange resin to enable the content of metal ions in the product to be less than 1ppb and the content of anions to be less than 10 ppb. In addition, the methods reported in the current patents are limited to the removal of metal ions. As mentioned above, the anions also need to be reduced to very low concentrations to avoid affecting product yield.
The anions in the product are mainly inorganic acid radicals and organic acid radicals, the inorganic acid radicals are mainly sulfate radicals, nitrate radicals and chloride ions, the organic acid radicals are mainly carboxylate radicals, and the part has no universal method for treatment.
Disclosure of Invention
The invention aims to provide a general method for preparing an electronic grade reagent, namely a product with metal ion content less than 1ppb and anion less than 10ppb can be obtained through the treatment of an ionic resin and a polishing resin. The ion exchange resin can be repeatedly used after being adsorbed and saturated, and compared with rectification, no phase change occurs in the purification process of the ion exchange resin, so that the energy is saved. And the operation at room temperature is safer, and is beneficial to large-scale production.
The invention is realized by the following technical scheme:
(1) dissolving organic matters in water;
(2) adsorption is carried out by using anion and cation exchange resins;
(3) purifying the organic solution obtained in (2) with a polishing resin;
(4) and obtaining a solution of the target organic matter.
Preferably, in the step (1), the organic substance is an organic substance such as alcohol, ketone, aldehyde, etc.;
preferably, the alcoholic organics include, but are not limited to, monohydric alcohols such as methanol, ethanol, isopropanol, and the like, or polyhydric alcohols such as mannitol, sorbitol, inositol, pentaerythritol, maltitol, hexitol, and the like;
preferably, the ketone organic includes, but is not limited to, acetone, butanone, dihydroxyacetone, 3-hydroxybutanone, and the like;
preferably, the aldehyde organic compounds include, but are not limited to, formaldehyde, acetaldehyde, propionaldehyde, hydroxybutyraldehyde, D (+) -glucose, and the like;
preferably, the adsorption of the anion and cation resins in the step (2) can be performed by first adsorbing with a cation resin and then adsorbing with an anion resin, or first adsorbing with an anion resin and then adsorbing with a cation resin;
preferably, the anion resin in the step (2) is strong-base anion exchange resin, and pretreatment is carried out before the step (2), namely the anion resin is converted into an OH type by alkali, and then the resin is washed by ultrapure water until the metal ions of the resin receiving liquid are less than 1ppb and the anions are less than 10 ppb;
preferably, the alkali in the above steps is selected from one or more of sodium hydroxide and potassium hydroxide;
preferably, the cation resin described in the above step (2) comprises a strong acid cation exchange resin, a chelating resin or a mixture of both, and is subjected to a pretreatment before step (2), comprising: the resin is converted into H type by acid, and then the resin is cleaned by ultrapure water until the metal ion of the resin receiving liquid is less than 1ppb and the anion is less than 10 ppb;
preferably, the acid in the above step is selected from one or more of nitric acid, sulfuric acid and hydrochloric acid.
Detailed Description
The advantages of the invention are explained in detail below with reference to specific embodiments.
Example 1
(1) Dissolving 25kg of D (+) -glucose in 75kg of ultrapure water;
(2) filling 6L Rohm and Haas 4500CL anion resin into an ion exchange column with the diameter of 10cm and the height of 1m, regenerating by NaOH, and washing by ultrapure water until the metal ions of the resin receiving liquid are less than 1ppb and the anions are less than 10 ppb;
(3) filling 6L Rohm and Haas 1500H cation resin into an ion exchange column with the diameter of 10cm and the height of 1m, regenerating by using HCl, and washing by using ultrapure water until metal ions of a resin receiving liquid are less than 1ppb and anions are less than 10 ppb;
(4) 6L of Rohm and Hass polishing resin UP6150 resin is filled in an ion exchange column with the diameter of 10cm and the height of 1 m;
(5) d (+) -glucose aqueous solution passes through three ion exchange columns in turn at the speed of 2BV/h, the content of metal ions in the product is measured by ICP-MS, and the content of anions such as sulfate radical, nitrate radical and chloride ion is measured by IC.
Example 2
(1) Dissolving 25kg of mannitol in 75kg of ultrapure water;
(2) filling 14L of blanc C104E cation resin into an ion exchange column with the diameter of 15cm and the height of 1m, regenerating by using H2SO4, and washing by using ultrapure water until metal ions of a resin receiving liquid are less than 1ppb and anions are less than 10 ppb;
(3) filling 14L of blanc A400 anion resin into an ion exchange column with the diameter of 15cm and the height of 1m, regenerating by using KOH, and washing by using ultrapure water until metal ions of a resin receiving liquid are less than 1ppb and anions are less than 10 ppb;
(4) filling 14L of bleached-grade MB400 polishing resin into an ion exchange column with the diameter of 15cm and the height of 1 m;
(5) sequentially passing the mannitol aqueous solution through three ion exchange columns at a speed of 5BV/h, measuring the content of metal ions by ICP-MS, and testing the content of anions such as sulfate radical, nitrate radical and chloride ion by IC.
Example 3
(1) Dissolving inositol 10kg in 90kg ultrapure water;
(2) filling 30L of blanc A600 anion resin into an ion exchange column with the diameter of 15cm and the height of 2m, regenerating by using KOH, and washing by using ultrapure water until metal ions of a resin receiving liquid are less than 1ppb and anions are less than 10 ppb;
(3) filling 20L of blanc C100E cation resin and blanc 10L S930 chelate resin into an ion exchange column with the diameter of 15cm and the height of 2m, regenerating by HNO3, and washing by using ultrapure water until metal ions in a resin receiving liquid are less than 1ppb and anions are less than 10 ppb;
(4) filling 30L of bleached-ite MB400 polishing resin into an ion exchange column with the diameter of 10cm and the height of 1 m;
(5) sequentially passing inositol aqueous solution through three ion exchange columns at a speed of 10BV/h, measuring the content of metal ions by ICP-MS, and testing the content of anions such as sulfate radical, nitrate radical and chloride ion by IC.
Example 4
(1) Dissolving 70kg of D-fructose in 30kg of ultrapure water;
(2) filling 23L Rohm and Haas 1500H resin in an ion exchange column with the diameter of 15cm and the height of 1.5m, regenerating by using H2SO4, and washing by using ultrapure water until the metal ions of the resin receiving liquid are less than 1ppb and the anions are less than 10 ppb;
(3) filling 23L of Rohm and Haas 4500CL resin into an ion exchange column with the diameter of 15cm and the height of 1.5m, regenerating by using KOH, and washing by using ultrapure water until metal ions in resin receiving liquid are less than 1ppb and anions are less than 10 ppb;
(4) filling 23L of Rohm and Hass polishing resin UP6150 resin into an ion exchange column with the diameter of 15cm and the height of 1.5 m;
(5) d-fructose aqueous solution is sequentially passed through three ion exchange columns at the speed of 5BV/h, the content of metal ions in the product is measured by ICP-MS, and the content of anions such as sulfate radical, nitrate radical and chloride ion is measured by IC.
Example 5
(1) Dissolving 50kg of sorbitol in 50kg of ultrapure water;
(2) filling 25L of Langshan M800 anion 0 resin into an ion exchange column with the diameter of 20cm and the height of 1M, regenerating the ion exchange column by using NaOH, and washing the ion exchange column by using ultrapure water until metal ions in a resin receiving liquid are less than 1ppb and anions are less than 10 ppb;
(3) filling 25L of Langshan S80 cation resin into an ion exchange column with the diameter of 20cm and the height of 1m, regenerating by using H2SO4, and washing by using ultrapure water until the metal ions of the resin receiving liquid are less than 1ppb and the anions are less than 10 ppb;
(4) filling 25L of Langshan NM60 polishing resin in an ion exchange column with the diameter of 20cm and the height of 1 m;
(5) sorbitol aqueous solution is sequentially passed through three ion exchange columns at the speed of 4BV/h, the content of metal ions in the product is measured by ICP-MS, and the content of anions such as sulfate radical, nitrate radical and chloride ion is measured by IC.
Example 6
(1) Dissolving 15kg of maltitol in 85kg of ultrapure water;
(2) filling 8L of Langshan M800 anion resin into an ion exchange column with the diameter of 10cm and the height of 1.5M, regenerating by using KOH, and washing by using ultrapure water until metal ions in a resin receiving liquid are less than 1ppb and anions are less than 10 ppb;
(3) filling 4L of Langshan S80 cation resin and 4L of Langshan TP207 resin into an ion exchange column with the diameter of 10cm and the height of 1.5m, regenerating by using H2SO4, and washing by using ultrapure water until metal ions in a resin receiving liquid are less than 1ppb and anions are less than 10 ppb;
(4) packing 8L of Langshan NM60 polishing resin in an ion exchange column with a diameter of 10cm and a height of 1.5 m;
(5) sequentially passing the maltitol aqueous solution through three ion exchange columns at the speed of 15BV/h, measuring the content of metal ions by ICP-MS, and testing the content of anions such as sulfate radical, nitrate radical and chloride ion by IC.
Example 7
(1) Dissolving 50kg of xylitol in 50kg of ultrapure water;
(2) filling 12L Rohm and Haas 4500CL anion resin into an ion exchange column with the diameter of 10cm and the height of 2m, regenerating by NaOH, and washing by ultrapure water until the metal ion of the resin receiving liquid is less than 1ppb and the anion is less than 10 ppb;
(3) filling 6L Rohm and Haas 1300H cation resin and 6L Rohm and Haas IRC748 chelating resin into an ion exchange column with the diameter of 10cm and the height of 2m, regenerating by using H2SO4, and washing by using ultrapure water until metal ions in resin receiving liquid are less than 1ppb and anions are less than 10 ppb;
(4) filling 12L of Rohm and Haas polishing resin UP6150 resin into an ion exchange column with the diameter of 10cm and the height of 2 m;
(5) the xylitol aqueous solution is sequentially passed through three ion exchange columns at the speed of 20BV/h, the content of metal ions in the product is measured by ICP-MS, and the content of anions such as sulfate radical, nitrate radical and chloride ion is measured by IC.
Comparative example 1
(1) Dissolving 50kg of xylitol in 50kg of ultrapure water;
(2) filling 12L Rohm and Haas 4500CL anion resin into an ion exchange column with the diameter of 10cm and the height of 2m, regenerating by NaOH, and washing by ultrapure water until the metal ion of the resin receiving liquid is less than 1ppb and the anion is less than 10 ppb;
(3) filling 6L Rohm and Haas 1300H cation resin and 6L Rohm and Haas IRC748 chelating resin into an ion exchange column with the diameter of 10cm and the height of 2m, regenerating by using H2SO4, and washing by using ultrapure water until metal ions in resin receiving liquid are less than 1ppb and anions are less than 10 ppb;
(4) the xylitol aqueous solution is sequentially passed through two ion exchange columns at the speed of 20BV/h, the content of metal ions in the product is measured by ICP-MS, and the content of anions such as sulfate radical, nitrate radical and chloride ion is measured by IC.
Comparative example 2
(1) Dissolving 50kg of xylitol in 50kg of ultrapure water;
(2) filling 12L Rohm and Haas 1300H cation resin and 12L Rohm and Haas IRC748 chelating resin into two ion exchange columns with the diameter of 15cm and the height of 2m, regenerating by using H2SO4, and washing by using ultrapure water until the metal ions and the anions of resin receiving liquid are less than 1ppb and less than 10 ppb;
(3) the xylitol aqueous solution is passed through two cation exchange columns at the speed of 20BV/h, and the product is measured for the content of metal ions and for the content of anions such as sulfate, nitrate and chloride by using ICP-MS.
Comparative example 3
(1) Dissolving 50kg of xylitol in 50kg of ultrapure water;
(2) filling 24L Rohm and Haas 4500CL anion resin into two ion exchange columns with the diameter of 15cm and the height of 2m, regenerating by NaOH, and washing by ultrapure water until the metal ions of the resin receiving liquid are less than 1ppb and the anions are less than 10 ppb;
(3) the xylitol aqueous solution is passed through an anion exchange column at a speed of 20BV/h, and the product is measured for metal ion content and IC content of anions such as sulfate, nitrate and chloride by ICP-MS.
Table 1: ICP-MS and IC detection results of organic matters before and after treatment in examples 1-7 and comparative examples 1-3
As shown in the table, the raw materials contain not only a trace amount of chloride ions, nitrate ions and sulfate ions, but also organic carboxylate groups in the section of others, and the cations are mainly sodium ions. After the treatment of anion resin, cation resin and polishing resin, the metal ions contained in the purified organic matter in the embodiment are all less than 1ppb, and the anions are lower than the detection limit, which shows that the technical scheme in the application can effectively remove the balance impurities in the organic matter.
In comparative example 1, in order to purify the organic matter only by anion exchange resin, further purification by polishing resin was not carried out. The detection result shows that most of metal ions in the purified organic solution are less than 20ppb, and anions are not reduced to ppb level, which indicates that the organic product with metal ions less than 1ppb and anions less than 10ppb can not be obtained by only ion exchange resin. Taking a cationic resin as an example, although the cationic resin is subjected to acid washing, the acid used in the present application is not an electronic grade acid, and the resin is not an ultra-clean resin, and the metal ions originally contained in the resin are not reduced to ppb level. After the ion resin adsorbs the metal ions in the raw materials, the metal ions on the ion resin are further enriched. The cation resin is used for removing metal ions, which are basically H + ions dissociated by sulfonic groups on the resin and used for exchanging the metal ions in raw materials, and the metal ions on the resin cannot be guaranteed not to be exchanged under extremely low concentration.
In comparative example 2, which uses only the cation exchange resin, but the cation exchange resin was twice as much as in comparative example 1, as compared with comparative example 1, it was found that the concentration of the metal ions was decreased, but was not decreased below 1ppb, and the anions were hardly changed. For the reasons described above, at such an extremely low concentration, there is a limit in the effect depending on the amount of the resin used, and it is difficult to further reduce the ion concentration in the organic matter to 1ppb or less by merely increasing the amount of the resin used, indicating the necessity of polishing the resin.
Comparative example 3 used only an anion exchange resin compared to comparative example 1, but the cation exchange resin was twice as much as comparative example 1, and likewise, the anion could not be reduced to less than 1 ppm. Therefore, at very low concentrations, neither anions nor cations can be reduced further to trace amounts by simply increasing the amount of resin used.
Comparing example 7 with comparative example 1, it can be seen that the organic material in example 7 is treated with anion resin, cation resin and polishing resin, respectively, and the anion and cation contents in the purified organic material meet the required requirements. It is known that the use of anionic resins and cationic resins alone is not sufficient to reduce the content of anions and cations in organic materials to the desired content, and that the use of polishing resins in combination is required to obtain products having a metal ion content of less than 1ppb and an anion content of less than 10 ppb.
Wherein, the polishing resin is an ultra-clean anion and cation resin mixed bed, can synchronously remove anions and cations, and can avoid the problem of precipitation. Meanwhile, the polishing resin has extremely high cleanliness and cannot pollute raw materials to be purified. Therefore, the ultra-clean reagent can be obtained by treating with anion and cation resins and then passing through the resin mixed bed. And the anions and cations of the raw materials entering the mixed bed are very low, so that the service life of the mixed bed is prolonged, and the service life of the resin is prolonged. In addition, the method for removing the trace anions and cations in the organic matters has mild operation conditions, can complete operation at room temperature, is safe and reliable, and is beneficial to large-scale production.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (10)
1. A method for removing trace anions and cations in organic matters is characterized by comprising the following steps:
(1) dissolving organic matters in water;
(2) adsorption is carried out by using anion and cation exchange resins;
(3) purifying the organic solution obtained in (2) with a polishing resin;
(4) and obtaining a solution of the target organic matter.
2. The removal method according to claim 1,
the organic matter is alcohol, ketone or aldehyde.
3. The removal method according to claim 2,
the alcohol organic matter is selected from one or more of methanol, ethanol, isopropanol, mannitol, sorbitol, inositol, pentaerythritol, maltitol and hexitol.
4. The removal method according to claim 2,
the ketone organic matter is selected from one or more of acetone, butanone, dihydroxyacetone and 3-hydroxy butanone.
5. The removal method according to claim 2,
the aldehyde organic matter is one or more of formaldehyde, acetaldehyde, propionaldehyde, hydroxybutyraldehyde and D (+) -glucose.
6. The removal method according to claim 1,
the adsorption is carried out by using anion-cation exchange resin to remove partial metal ions and anions in the organic solution, and the method comprises the following steps:
firstly, using anion resin for adsorption, and then using cation resin for adsorption;
or firstly using cation resin for adsorption and then using anion resin for adsorption.
7. The removal method according to claim 1,
the anion resin is strong-base anion exchange resin,
the removal method further comprises the step of removing the substrate,
performing pretreatment before the step (2), wherein the pretreatment comprises the following steps: firstly, the anion resin is converted into OH type by alkali, and then the resin is cleaned by ultrapure water until the resin bears metal ions less than 1ppb and anions less than 10 ppb.
8. The removal method as set forth in claim 7,
the alkali is sodium hydroxide or potassium hydroxide.
9. The removal method according to claim 1,
the cation resin is strong acid cation exchange resin and/or chelating resin, and is pretreated before the step (2), and the pretreatment comprises the following steps: the resin is converted into H type by acid, and then the resin is cleaned by ultrapure water until the metal ion of the resin receiving liquid is less than 1ppb and the anion is less than 10 ppb.
10. The removal method as set forth in claim 9,
the acid is nitric acid, sulfuric acid or hydrochloric acid.
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Cited By (1)
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