KR100436173B1 - Manufacturing method of monoammonium phosphate using the deserted liquid produced by semiconductor etching process - Google Patents
Manufacturing method of monoammonium phosphate using the deserted liquid produced by semiconductor etching process Download PDFInfo
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- KR100436173B1 KR100436173B1 KR10-2004-0002075A KR20040002075A KR100436173B1 KR 100436173 B1 KR100436173 B1 KR 100436173B1 KR 20040002075 A KR20040002075 A KR 20040002075A KR 100436173 B1 KR100436173 B1 KR 100436173B1
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- South Korea
- Prior art keywords
- phosphoric acid
- etching process
- waste liquid
- ammonium phosphate
- reaction
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000004065 semiconductor Substances 0.000 title claims abstract description 28
- 238000005530 etching Methods 0.000 title claims abstract description 25
- 239000007788 liquid Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 title abstract description 9
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 title abstract description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 title abstract description 3
- 239000006012 monoammonium phosphate Substances 0.000 title abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002699 waste material Substances 0.000 claims abstract description 40
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 28
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 26
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 26
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 13
- 230000005484 gravity Effects 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000010789 controlled waste Substances 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 8
- 239000010452 phosphate Substances 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229930182555 Penicillin Natural products 0.000 description 2
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- -1 dyeing Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229940049954 penicillin Drugs 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-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
- 229930003268 Vitamin C Natural products 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AXFZAZQUMXZWJV-UHFFFAOYSA-N diazanium;phosphono phosphate Chemical compound [NH4+].[NH4+].OP(O)(=O)OP([O-])([O-])=O AXFZAZQUMXZWJV-UHFFFAOYSA-N 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000021107 fermented food Nutrition 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical group [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- 229940019931 silver phosphate Drugs 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229960005322 streptomycin Drugs 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47B—TABLES; DESKS; OFFICE FURNITURE; CABINETS; DRAWERS; GENERAL DETAILS OF FURNITURE
- A47B81/00—Cabinets or racks specially adapted for other particular purposes, e.g. for storing guns or skis
- A47B81/005—Devices for storing or displaying rifles, guns, pistols or elongated objects such as fishing rods storing fishing rods
-
- E—FIXED CONSTRUCTIONS
- E05—LOCKS; KEYS; WINDOW OR DOOR FITTINGS; SAFES
- E05B—LOCKS; ACCESSORIES THEREFOR; HANDCUFFS
- E05B65/00—Locks or fastenings for special use
- E05B65/08—Locks or fastenings for special use for sliding wings
-
- E—FIXED CONSTRUCTIONS
- E05—LOCKS; KEYS; WINDOW OR DOOR FITTINGS; SAFES
- E05D—HINGES OR SUSPENSION DEVICES FOR DOORS, WINDOWS OR WINGS
- E05D15/00—Suspension arrangements for wings
- E05D15/06—Suspension arrangements for wings for wings sliding horizontally more or less in their own plane
- E05D15/0621—Details, e.g. suspension or supporting guides
- E05D15/066—Details, e.g. suspension or supporting guides for wings supported at the bottom
- E05D15/0665—Details, e.g. suspension or supporting guides for wings supported at the bottom on wheels with fixed axis
-
- E—FIXED CONSTRUCTIONS
- E05—LOCKS; KEYS; WINDOW OR DOOR FITTINGS; SAFES
- E05D—HINGES OR SUSPENSION DEVICES FOR DOORS, WINDOWS OR WINGS
- E05D15/00—Suspension arrangements for wings
- E05D15/06—Suspension arrangements for wings for wings sliding horizontally more or less in their own plane
- E05D15/0621—Details, e.g. suspension or supporting guides
- E05D15/066—Details, e.g. suspension or supporting guides for wings supported at the bottom
- E05D15/0691—Top guides
-
- E—FIXED CONSTRUCTIONS
- E05—LOCKS; KEYS; WINDOW OR DOOR FITTINGS; SAFES
- E05Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES E05D AND E05F, RELATING TO CONSTRUCTION ELEMENTS, ELECTRIC CONTROL, POWER SUPPLY, POWER SIGNAL OR TRANSMISSION, USER INTERFACES, MOUNTING OR COUPLING, DETAILS, ACCESSORIES, AUXILIARY OPERATIONS NOT OTHERWISE PROVIDED FOR, APPLICATION THEREOF
- E05Y2900/00—Application of doors, windows, wings or fittings thereof
- E05Y2900/20—Application of doors, windows, wings or fittings thereof for furniture, e.g. cabinets
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- Removal Of Specific Substances (AREA)
Abstract
본 발명은 반도체 에칭공정에서 부생되는 반응폐액으로부터 제1인산암모늄 (monoammonium phosphate)을 제조하는 방법에 관한 것으로, 반도체 에칭공정 폐액을 인산의 함량이 70-80wt%가 되도록 정제한 다음, 정제된 폐액을 비중이 1.4-1.5가 되도록 조절하고, 비중 조절된 폐액에 인산과 암모니아가 제1인산암모늄으로 전환 될 수 있는 화학양론비에 해당하는 당량비로 구성하도록 암모니아를 투입하고 0-1기압의 압력과 50-110℃의 온도, 15-40rpm의 교반속도에서 반응시키는 것을 특징으로 하며, 본 발명의 방법에 의하여 반도체 에칭공정에서 대량 발생되고 있는 반응폐액을 효과적으로 재활용할 수 있다.The present invention relates to a method for producing monomonium phosphate (monoammonium phosphate) from the reaction waste solution by-produced in the semiconductor etching process, the semiconductor waste waste solution is purified to a phosphoric acid content of 70-80wt%, and then purified waste liquid Is adjusted to a specific gravity of 1.4-1.5, and ammonia is added to the equilibrium ratio of the equivalent stoichiometric ratio at which the phosphoric acid and ammonia can be converted into ammonium phosphate. It is characterized in that the reaction at a temperature of 50-110 ℃, a stirring speed of 15-40rpm, by the method of the present invention can effectively recycle a large amount of reaction waste generated in the semiconductor etching process.
Description
본 발명은 반도체 에칭공정에서 부생되는 반응폐액으로부터 제1인산암모늄 (monoammonium phosphate)을 제조하는 반도체 에칭공정 폐액을 이용한 제1인산암모늄의 제조방법에 관한 것이다.The present invention relates to a method for producing first ammonium phosphate using a semiconductor etching process waste liquid for producing monomonium phosphate from the reaction waste liquid by-produced in the semiconductor etching process.
현재 알려져 있는 반도체 에칭공정 용액은 대부분 인산, 질산, 불산, 유기산 등의 여러 산이 혼합된 혼산 형태로 반도체 제조원판인 웨이퍼(wafer)에 제어용 전극인 게이트를 만들기 위한 공정에서 산화규소부분을 깎아내기 위한 에칭액으로 사용된다. 최근 반도체 기술이 고집적화 됨에 따라 점점 초고순도 케미칼이 요구되고 있으며 이에 대한 유해 케미칼의 저감 및 재활용 기술개발이 시급한 실정이다.Currently known semiconductor etching solution is a mixed acid mixed with various acids such as phosphoric acid, nitric acid, hydrofluoric acid, organic acid, etc. to cut the silicon oxide part in the process for making a gate as a control electrode on a wafer, which is a semiconductor manufacturing plate. Used as an etchant. Recently, as semiconductor technology is highly integrated, ultra-high purity chemicals are required, and it is urgent to develop harmful chemical reduction and recycling technologies.
이들 혼산류는 공정처리 후 재래식 폐수처리 방법에 의하여 방출되거나 위탁 처리되고 있어 상당량의 처리비용을 증가시키므로 상기의 폐수에 대한 처리기술이 시급한 실정이다. 이에 따라 반도체 웨이퍼 에칭 공정에서 발생되는 질소 및 인 폐기물 등을 포함하는 처리기술과 재활용 기술개발이 수자원 오염방지와 제한된 수자원의 사용을 극대화하는 차원에서 시급하다. 이러한 취지에서 반도체 공정에서 발생하는 에칭폐액을 반도체 공정 또는 다른 산업에서 사용될 수 있는 산으로 재생하는 공정개발은 중요하다.Since these mixed acids are discharged or consigned by conventional wastewater treatment methods after the process treatment, a considerable amount of treatment costs are increased, so the treatment technology for the wastewater is urgently needed. Accordingly, development of treatment technology and recycling technology including nitrogen and phosphorous waste generated in the semiconductor wafer etching process is urgent in terms of preventing water pollution and maximizing the use of limited water resources. To this end, it is important to develop a process for regenerating the etching waste liquid generated in the semiconductor process into an acid that can be used in the semiconductor process or other industries.
특히 반도체 에칭용액 중 반응액의 배출방법에 따라 각기 다르나 대체로 인산, 질산, 초산이 혼합된 혼산 용액은 반도체 공업 분야의 중요약품으로 근래 반도체의 생산량이 증가함에 따라 에칭용액의 사용량도 증가되고 있고 따라서 반응폐액도 다량으로 부생되고 있으나 재활용하기 위한 기술은 현재까지 알려져 있는 바가 없다.In particular, mixed solutions of phosphoric acid, nitric acid, and acetic acid are important chemicals in the semiconductor industry. However, as the production of semiconductors increases, the amount of etching solutions is increasing. The reaction waste liquid is also produced by a large amount, but there is no known technique for recycling.
폐액의 대부분을 차지하는 인산은 건식법과 습식법으로 만들어지는데 건식법은 전기로 내지는 용광로에 인광석, 규석, 코오스크의 혼합물을 가열, 환원시켜 기체상의 황인을 얻어 이것을 공기와 함께 연소시켜 오산화인을 만들어 물에 흡수시켜 인산을 만든다. 습식법은 황산을 이용해 인광석을 분해하여 인산을 만든다.Phosphoric acid, which accounts for most of the waste liquid, is made by dry and wet methods. Drying method heats and reduces a mixture of phosphate, silica, and koosks in an electric furnace or a furnace to obtain gaseous yellow phosphorus, which is burned with air to form phosphorus pentoxide. Absorption produces phosphoric acid. The wet method uses sulfuric acid to break down phosphate ore to produce phosphoric acid.
인산은 도금, 인산염 및 축합인산 염료, 금속표면처리, 의약(페니실린, 비타민C등), 염색, 인산칼슘, 직물공업, 경화유리제조, 고무유액의 응고, 표백제, 과산화수소의 합성, 에틸렌가스의 제조, 분석시약, 세라믹, 비료, 농약, 전극연마제 등 광범위한 용도로 사용되고 있다.Silver phosphate plating, phosphate and condensed phosphate dyes, metal surface treatment, medicine (penicillin, vitamin C, etc.), dyeing, calcium phosphate, textile industry, hardened glass manufacturing, rubber emulsion coagulation, bleaching agent, hydrogen peroxide synthesis, ethylene gas production It is used in a wide range of applications, such as analytical reagents, ceramics, fertilizers, pesticides, and electrode polishing agents.
반도체용으로 사용되는 것에 대한 용도별 분류는 없으나 반도체 특수재료로 사용되고 있다. 반도체 제조공정에 이용되는 인산은 주로 알루미늄의 습식에칭용에 사용되고 있으며, 반도체 이외에는 연료전지용(인산형)에 고순도 인산이 사용되고 있다.There is no classification by use for semiconductors, but it is used as a special semiconductor material. Phosphoric acid used in the semiconductor manufacturing process is mainly used for wet etching of aluminum, and high purity phosphoric acid is used for fuel cells (phosphate type) other than semiconductors.
금속이나 폐산 등이 포함된 폐액의 경우, 상기 폐액중의 금속이나 폐산이 재자원화 될 수 있음에도 불구하고 기존의 처리방법에 의해서는 이들이 단순히 폐기되고 있어 자원의 엄청난 낭비일 뿐만 아니라 환경오염을 유발시키는 문제를 안고 있다.In the case of the waste liquid containing metal or waste acid, even though the waste metal or waste acid can be recycled, they are simply discarded by conventional treatment methods, which is not only a huge waste of resources but also causes environmental pollution. I have a problem.
반도체 에칭공정에서 부생되는 반응폐액을 처리하는 방법으로서 현재까지 알려져 있는 방법은 공해물질의 폐기차원에서 반응폐액을 배출하는 업체 및 위탁 처리업체에서는 에칭폐액을 알칼리 등으로 폐수를 중화처리한 후 하수도를 통하여 방류하였으나, 이 때 방류되는 폐수는 비록 화학적 산소요구량(COD)과 생화학적 산소요구량(BOD)이 낮기는 하나 금속과 산을 비롯한 각종 유해성분이 잔류하고 있어 중금속에 의한 수생생태계에서 서식하는 생물에게 악영향을 줄 수 있으며, 최근에 문제되는 질소성분으로 인한 부영양화의 중요 요인이 되고 이로 인하여 심각한 수질오염이 초래되는 원인이 되었다.As a method of treating the reaction waste liquid by-produced in the semiconductor etching process, methods known to date are used to discharge the reaction waste liquid in order to dispose of pollutants and consignment treatment companies to neutralize the waste water with alkali, etc. Although the wastewater discharged at this time has a low chemical oxygen demand (COD) and biochemical oxygen demand (BOD), it contains a variety of harmful components such as metals and acids. It may have an adverse effect and is an important factor of eutrophication due to nitrogen component, which is a problem recently, which causes serious water pollution.
에칭공정에서 부생되는 반응폐액을 효율적으로 처리하는 방법이 아직까지 개발되지 않고 있었던 이유는 그간 에칭공정 용액이 부산물 처리에 어려움을 겪을 정도로 많지가 않았고 또한 에칭용액이 고가이어서 경제적인 면에서도 반응폐액의 재활용에 대한 필요성을 느끼지 못한 것으로 추정된다.Efficient treatment of by-product reaction wastes in the etching process has not yet been developed because the etching process solution has not been so difficult to deal with by-products, and because the etching solution is expensive, it is economical. It is assumed that there is no need for recycling.
인산암모늄은 인산을 적당히 희석하여 반응조에 넣고 적당량의 암모니아를 가하여 반응시키고 이를 방냉, 결정시킨 후 탈수, 건조하여 제1인산암모늄이나 제3인산암모늄 형태로 수득된다. 제 2인산암모늄도 이와 같은 제조공정으로 얻어진다.Ammonium phosphate is appropriately diluted with phosphoric acid, added to an appropriate amount of ammonia and reacted. After cooling, crystallization, dehydration and drying are obtained in the form of monoammonium phosphate or triammonium phosphate. Ammonium diphosphate is also obtained by such a manufacturing process.
제1인산암모늄은 소화제, 염료분산제, 법랑용 유약, 난연제, 성냥탄화제, 방화재, 이스트배양제 등으로 사용되고, 의약용으로는 충치예방제, 페니실린, 스트렙토마이신, 배양제 등으로 사용되며, 식품첨가제로는 제2인산암모늄과 함께 효모의 증식, 발효증진, 발효식품 및 합성팽창제 원료로 사용된다.Ammonium monophosphate is used as a fire extinguishing agent, dye dispersant, enamel glaze, flame retardant, match carbonizing agent, fire retardant, yeast culture agent, etc.In medicine, it is used as caries preventive agent, penicillin, streptomycin, culture agent, etc. As an additive, it is used as a raw material for the growth of yeast, fermentation, fermented food, and synthetic expander together with diammonium diphosphate.
이처럼 인산암모늄은 습식인산을 암모니아와 반응시키는 방법으로 제조될 수 있음이 공지되어 있다{영국특허 제951,476호(고체인산암모늄 제조방법), 한국특허 제1979-0001375호(인산암모늄의 제법) 등}. 상기 공지된 모든 제조방법은 습식인산을 원료로 인산암모늄을 제조하는 것이나 본 발명은 반도체 에칭공정에서 부생되는 폐액을 정제하여 암모니아와 반응시켜 소화약제의 주원료로 사용될 수 있는 제1인산암모늄을 제조하는 방법이다.As such, it is known that ammonium phosphate can be prepared by a method of reacting wet phosphoric acid with ammonia (UK Patent No. 951,476 (Method for Producing Solid Ammonium Phosphate), Korean Patent No. 1979-0001375 (Method for Producing Ammonium Phosphate), etc.). . All known production methods are prepared by producing ammonium phosphate as a raw material of wet phosphoric acid, but the present invention purifies the by-products from the semiconductor etching process and reacts with ammonia to produce the first ammonium phosphate which can be used as a main raw material of the extinguishing agent. Way.
본 발명의 목적은 공정처리 후 재래식 폐수처리 방법에 의해 방출되어 질소질, 인, 유기물 등에 의한 하천, 해양의 부영양화 등의 2차 공해의 발생을 유발함으로써 처리에 어려움을 겪고 있을 뿐만 아니라, 상당한 폐기비용이 소요되고 있는 반도체 에칭공정에서 부생되는 반응폐액을 산업용으로 유용한 제1인산암모늄 제조용 원료물질로 활용하는 방법을 제공하는데 있다.The object of the present invention is not only difficult to treat by being discharged by conventional wastewater treatment method after processing, causing secondary pollution such as rivers, nitrogen and phosphorus, organic matters, eutrophication of the ocean, etc. The present invention provides a method of utilizing the reaction waste liquid by-produced in this semiconductor etching process as a raw material for preparing ammonium phosphate useful for industrial use.
도 1은 본 발명에 따른 반도체 에칭폐액을 재활용 가능하도록 처리하기 위한 방법의 공정도이다.1 is a process diagram of a method for treating a semiconductor etching waste solution to be recyclable according to the present invention.
* 도면의 주요 부분에 대한 부호의 설명 *Explanation of symbols on the main parts of the drawings
1 : 에칭 폐액 저장조 2 : 농축기1: etching waste storage tank 2: concentrator
3 : 농축인산 저장조 4 : 암모니아 반응조3: concentrated phosphoric acid storage tank 4: ammonia reactor
5 : 원심분리기 6 : 모액저장조5: centrifuge 6: mother liquor storage tank
7 : 건조기 8 : 인산암모늄7: dryer 8: ammonium phosphate
본 발명은 반도체 에칭공정에서 부생되는 폐액을 인산의 함량이 70-80wt%가 되도록 정제한 다음, 이 정제된 폐액에 인산과 당량비의 암모니아를 투입하고 0-1기압의 압력과 50-110℃의 온도, 15-40rpm의 교반속도로 반응시키는 것으로 구성된다.The present invention purifies the waste liquid by-produced in the semiconductor etching process so that the phosphoric acid content is 70-80wt%, and then adds ammonia of phosphoric acid and equivalent ratio to the purified waste liquid, and the pressure of 0-1 atm and the pressure of 50-110 ° C. It consists of reacting at a temperature, a stirring speed of 15-40rpm.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
반도체 공정중의 에칭폐액은 대부분 인산, 질산, 유기산 등의 여러 산이 혼합된 혼산 형태이다. 상기의 폐액은 에칭공정의 반응조건 및 반응상태에 따라 구성 성분의 함량이 차이가 있기는 하나 평균적으로 인산(H3PO4) 50-70wt%, 초산(CH3COOH) 10-20wt%, 질산(HNO3) 1-5wt%, 기타 1.0wt% 이하로 구성되어 있다.Etching wastes in the semiconductor process are mostly mixed acid forms of various acids such as phosphoric acid, nitric acid, and organic acid. Although the content of the constituents varies depending on the reaction conditions and the reaction conditions of the etching process, the average amount of phosphate (H 3 PO 4 ) 50-70wt%, acetic acid (CH 3 COOH) 10-20wt%, nitric acid (HNO 3 ) 1-5wt%, and other 1.0wt% or less.
본 발명의 제1인산암모늄을 제조하는 방법은 다음과 같다. 먼저 반응폐액으로부터 인산의 함량을 증가시키는 정제단계와, 정제단계를 거쳐 얻어진 폐액에 암모니아를 투입하여 인산암모늄을 제조하는 단계로 구성된다.Method for producing the first ammonium phosphate of the present invention is as follows. First, a purification step of increasing the content of phosphoric acid from the reaction waste liquid, and ammonia is added to the waste liquid obtained through the purification step to produce ammonium phosphate.
정제단계는 온도 120-150℃, 압력 0-1기압의 조건이며, 이러한 조건을 유지하면 폐액은 2개의 층으로 층 분리가 일어나게 되며, 상부 층은 초산의 함량이 30-50wt%, 질산의 함량이 10-30wt%, 나머지는 물인 구성이며, 하부 층은 인산의 함량이 70-80wt%, 초산의 함량이 3-8wt%, 질산 1wt% 이하인 구성을 하게 된다(잔량은 물임). 하부 층과 상부 층은 약 8 : 2의 비율로 분리된다.The purification step is the temperature 120-150 ℃, pressure 0-1 atm pressure, if the conditions are maintained, the waste liquid is separated into two layers, the upper layer is acetic acid content of 30-50wt%, nitric acid content The 10-30wt%, the remainder is water, the lower layer is composed of phosphoric acid content of 70-80wt%, acetic acid content of 3-8wt%, nitric acid 1wt% or less (the remaining amount is water). The lower layer and the upper layer are separated at a ratio of about 8: 2.
정제단계의 온도가 상기 범위 미만의 경우에는 층 분리가 잘 일어나지 아니하며, 상기 범위를 초과하는 경우에는 층 분리 향상효과는 더 이상 일어나지 아니하고 에너지 비용이 과다하게 소요된다.When the temperature of the purification step is less than the above range, the separation of the layer does not occur well, and when the temperature exceeds the above range, the effect of improving the separation of the layer no longer occurs and the energy cost is excessive.
본 발명에서는 하부 층의 조성물을 이용하여 인산암모늄을 얻는다. 하부 층의 조성물은 비중이 약 1.6이며, 반응 전 이 정제된 하부 조성물(폐액)을 비중이 1.4-1.5가 되도록 물을 가하여 조절하는 단계가 필요하다. 비중이 이 범위를 벗어날 경우에는 목적하는 인산암모늄의 석출량이 급격히 저하됨과 동시에 얻어진 인산암모늄의 순도가 저하된다. 그 이유는 정확히 알 수는 없으나 비중이 상기 범위 미만의 경우에는 인산의 농도가 적정량이 미치지 못하게 되어 반응이 느리게 일어나며, 상기 범위를 초과하는 경우에는 점도의 상승으로 역시 미반응 또는 부반응 물질이 생성되기 때문으로 여겨진다.In the present invention, ammonium phosphate is obtained using the composition of the lower layer. The composition of the lower layer has a specific gravity of about 1.6, and prior to the reaction, a step of adjusting the purified lower composition (waste solution) by adding water to have a specific gravity of 1.4-1.5 is necessary. If the specific gravity is out of this range, the amount of precipitation of the desired ammonium phosphate drops rapidly, and the purity of the obtained ammonium phosphate decreases. The reason for this is not known precisely, but if the specific gravity is less than the above range, the concentration of phosphoric acid does not reach the proper amount, and the reaction occurs slowly. It is considered because.
비중이 조절된 폐액에 인산과 당량비의 암모니아를 투입하고 0-1기압의 압력과 50-110℃의 온도, 15-40rpm의 교반속도로 반응시킴으로써 비교적 고순도의 인산암모늄을 얻을 수 있다.A relatively high purity ammonium phosphate can be obtained by injecting ammonia of phosphoric acid and equivalent ratio into the waste liquid with specific gravity control and reacting with a pressure of 0-1 atm, a temperature of 50-110 ° C., and a stirring speed of 15-40 rpm.
인산과 암모니아가 제1인산암모늄으로 전환될 수 있는 화학양론비에 해당하는 통상적으로 N:P 원자비라고 칭하는 함유된 질소 대 인의 원자비에 따라 특징을 갖는 바, 제1인산암모늄은 N:P원자비가 1.0이며 인산암모늄 이외의 기타 질소 또는 인 화합물을 함유하는 혼합물의 경우 N:P 원자비는 인산암모늄의 비율로만 표시된다.The ammonium monophosphate is characterized by the atomic ratio of nitrogen to phosphorus, commonly referred to as the N: P atomic ratio, which corresponds to the stoichiometric ratio at which phosphoric acid and ammonia can be converted to ammonium monophosphate. For mixtures containing an atomic ratio of 1.0 and containing nitrogen or phosphorus compounds other than ammonium phosphate, the N: P atomic ratio is expressed only in the proportion of ammonium phosphate.
반응온도가 상기 범위 미만의 경우에는 반응속도가 지나치게 낮으며, 상기 범위를 초과하는 경우에는 더 이상 반응속도의 향상은 없으나 에너지 비용이 과다하게 소요된다. 교반속도도 상기 범위 미만의 경우에는 반응속도가 부족하게 되며, 상기 범위를 초과하는 경우에도 더 이상의 반응속도의 향상은 없다.If the reaction temperature is less than the above range, the reaction rate is too low, and if it exceeds the above range, there is no further improvement of the reaction rate, but excessive energy costs are required. If the stirring speed is also lower than the above range, the reaction rate is insufficient, and even if the stirring rate is exceeded, there is no further improvement of the reaction rate.
이러한 과정을 거쳐 얻어지는 인산암모늄은 순도가 98% 이상으로, 현재 시판되는 공업용 인산암모늄의 순도와 별 다른 차이가 없다.The ammonium phosphate obtained through this process has a purity of 98% or more, and there is no difference from the commercial purity of commercial ammonium phosphate.
본 발명의 실시예는 아래와 같다.An embodiment of the present invention is as follows.
<실시예 1><Example 1>
* 폐액의 정제공정* Wastewater Purification Process
평균 인산 62wt%, 초산 16wt%, 질산 3wt% 기타 첨가제로 이루어진 반도체 에칭공정 부생 폐액을 정량펌프로 15ml/min 유량으로 박막유하식 농축기 상부로 투입하면서 온도 130℃, 압력 0.5기압을 유지하여 20초간 농축하여 하부 층을 분리하였다.Semiconductor etching process consisting of average 62wt% phosphoric acid, 16wt% acetic acid, 3wt% nitric acid and other additives were injected into the upper part of the thin film flow condenser at a flow rate of 15ml / min with a metering pump, maintaining a temperature of 130 ° C and a pressure of 0.5 atm for 20 seconds. Concentration separated the bottom layer.
이들 하부층의 조성은 인산 75wt%, 초산 5wt%, 질산 1wt% 였다.The compositions of these lower layers were 75 wt% phosphoric acid, 5 wt% acetic acid, and 1 wt% nitric acid.
<실시예 2><Example 2>
* 정제 폐액으로부터 인산암모늄의 제조Preparation of Ammonium Phosphate from Purified Wastewater
실시예 1에서 얻은 정제 폐액을 교반기가 달린 반응기에 넣고 물을 혼합하여 비중을 1.450/20℃로 맞춘 다음, 화학양론비에 해당하는 당량비를 구성하도록 암모니아를 투입하여 pH 3.8에 이르렀을 때 반응을 종료하여 제1인산암모늄으로 전환시켰다. 이때 반응기의 운전조건은 온도 100℃, 압력 0.5기압, 교반속도 30rpm을 유지하였고 이 용액을 50℃로 냉각하여 결정을 석출시키고, 얻어진 결정을 원심분리기에서 탈수한 다음 진공건조기에서 110-130℃로 2-3시간 건조하여 최종 제품을 얻었다.The purified waste liquid obtained in Example 1 was placed in a reactor equipped with a stirrer, water was mixed to adjust the specific gravity to 1.450 / 20 ° C., and ammonia was added to form an equivalence ratio corresponding to the stoichiometric ratio. Termination was carried out to the first ammonium phosphate. At this time, the operating conditions of the reactor were maintained at a temperature of 100 ° C., a pressure of 0.5 atm, and a stirring speed of 30 rpm. The solution was cooled to 50 ° C. to precipitate crystals, and the obtained crystals were dehydrated in a centrifuge and then 110-130 ° C. in a vacuum dryer. Drying for 2-3 hours gave the final product.
정량분석결과 순도 98%, 수분 0.15%의 제1인산암모늄을 얻었다.As a result of quantitative analysis, monobasic ammonium phosphate with 98% purity and 0.15% moisture was obtained.
<실시예 3><Example 3>
실시예 1에서 얻은 농축인산을 교반기가 달린 반응기에 넣고 물 그리고 실시예 2에서 원심분리기에 탈수된 여과액(모액)을 혼합하여 비중을 1.45/20℃로 맞춘 다음, 실시예 2와 같은 방법으로 조작한 후 내용물을 정량분석하여 실시예 2와 같은 동일한 분석결과를 얻었다.The concentrated phosphoric acid obtained in Example 1 was placed in a reactor equipped with a stirrer, water and a filtrate (mother liquor) dehydrated in a centrifuge in Example 2 were adjusted to 1.45 / 20 ° C., followed by the same method as in Example 2. After the operation, the contents were quantitatively analyzed to obtain the same analysis results as in Example 2.
<비교예 1>Comparative Example 1
실시예 1의 정제되지 아니한 폐액을 이용하여 실시예 2와 동일한 공정을 거쳐 제1인산암모늄을 얻었으며, 얻어진 제품의 정량분석결과 순도가 83%로 공업용으로 사용되기에는 부적합하였다.Ammonium phosphate monobasic was obtained by the same process as in Example 2 using the crude waste solution of Example 1, and the quantitative analysis of the obtained product was 83%, which is not suitable for industrial use.
<비교예 2>Comparative Example 2
실시예 1에 의하여 얻어진 폐액을 비중 조절하지 아니한 상태(1.62)에서 실시예 2와 동일하게 시행하여 제1인산암모늄을 얻었다. 얻어진 제품의 순도는 95% 이었으며, 수득율은 실시예 2의 82%에 불과하였다.Ammonium phosphate monobasic was obtained in the same manner as in Example 2 in the state where the waste liquid obtained in Example 1 was not adjusted to specific gravity (1.62). The purity of the obtained product was 95%, the yield was only 82% of Example 2.
<비교예 3>Comparative Example 3
실시예 1에 의하여 얻어진 폐액에 물을 가하여 비중이 1.3으로 조절한 다음, 실시예 2와 동일하게 시행하여 제1인산암모늄을 얻었다. 얻어진 제품의 순도는 82%이었으며, 수득율은 실시예2의 58%에 불과하였다.Water was added to the waste liquid obtained in Example 1 to adjust the specific gravity to 1.3, and then the same procedure as in Example 2 was carried out to obtain a first ammonium phosphate. The purity of the obtained product was 82%, and the yield was only 58% of Example 2.
본 발명의 방법은 반도체 에칭공정에서 대량 발생되고 있는 반응 폐액의 위탁 처리비용이 절감될 뿐 아니라, 에칭 폐액 중에 함유되어 있는 인산을 회수하여 전량 수입되고 있는 소화기약제의 주원료인 제1인산암모늄을 제조할 수 있는 방법을 제공함으로써 폐자원의 활용과 환경오염을 감소시켜 줄 수 있는 효과를 갖는다.The method of the present invention not only reduces the processing cost of the reaction waste liquid generated in a large amount in the semiconductor etching process, but also recovers the phosphoric acid contained in the etching waste liquid to prepare the first ammonium phosphate, which is the main raw material of the fire extinguishing agent, which is imported in its entirety. Providing a way to do this has the effect of reducing the utilization of waste resources and environmental pollution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100550829B1 (en) * | 2005-03-03 | 2006-02-10 | (주) 광진화학 | Method and apparatus for separating acetic acid and nitric salts |
| KR101256611B1 (en) | 2009-02-13 | 2013-04-19 | 재단법인 포항산업과학연구원 | Manufacturing of ammonium phosphate from mixed waste acid |
| KR101700437B1 (en) | 2015-08-19 | 2017-02-03 | (주) 솔코리젠트 | Refining method of ammonium phosphate and refined ammonium phosphate thereof |
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| KR100542969B1 (en) * | 2005-03-18 | 2006-01-20 | (주) 광진화학 | Method of refining high-purity phosphoric acid continuously using deserted liquid from process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100550829B1 (en) * | 2005-03-03 | 2006-02-10 | (주) 광진화학 | Method and apparatus for separating acetic acid and nitric salts |
| KR101256611B1 (en) | 2009-02-13 | 2013-04-19 | 재단법인 포항산업과학연구원 | Manufacturing of ammonium phosphate from mixed waste acid |
| KR101700437B1 (en) | 2015-08-19 | 2017-02-03 | (주) 솔코리젠트 | Refining method of ammonium phosphate and refined ammonium phosphate thereof |
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