CN105347578A - Improved 2-naphthol synthesis technology - Google Patents
Improved 2-naphthol synthesis technology Download PDFInfo
- Publication number
- CN105347578A CN105347578A CN201510732648.2A CN201510732648A CN105347578A CN 105347578 A CN105347578 A CN 105347578A CN 201510732648 A CN201510732648 A CN 201510732648A CN 105347578 A CN105347578 A CN 105347578A
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- Prior art keywords
- beta naphthal
- waste water
- reaction
- bipolar membrane
- synthesis technique
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 57
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 57
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 title abstract description 20
- 238000005516 engineering process Methods 0.000 title abstract description 11
- 229950011260 betanaphthol Drugs 0.000 title abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 116
- 238000000034 method Methods 0.000 claims abstract description 101
- 239000002351 wastewater Substances 0.000 claims abstract description 89
- 239000000243 solution Substances 0.000 claims abstract description 83
- 239000012528 membrane Substances 0.000 claims abstract description 66
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 40
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000008569 process Effects 0.000 claims abstract description 34
- 239000012267 brine Substances 0.000 claims abstract description 31
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 24
- 230000020477 pH reduction Effects 0.000 claims abstract description 21
- 238000010612 desalination reaction Methods 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 230000004927 fusion Effects 0.000 claims abstract description 11
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 7
- 238000002203 pretreatment Methods 0.000 claims abstract description 7
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 3
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 claims description 106
- 238000006243 chemical reaction Methods 0.000 claims description 70
- 238000000909 electrodialysis Methods 0.000 claims description 54
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 238000005189 flocculation Methods 0.000 claims description 24
- 239000001117 sulphuric acid Substances 0.000 claims description 24
- 235000011149 sulphuric acid Nutrition 0.000 claims description 24
- 230000016615 flocculation Effects 0.000 claims description 23
- 238000009279 wet oxidation reaction Methods 0.000 claims description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 15
- 238000005868 electrolysis reaction Methods 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 230000006872 improvement Effects 0.000 claims description 12
- 235000010265 sodium sulphite Nutrition 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 11
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002594 sorbent Substances 0.000 claims description 6
- 238000012423 maintenance Methods 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000003814 drug Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 241000609240 Ambelania acida Species 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 235000019600 saltiness Nutrition 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 abstract description 13
- 239000002585 base Substances 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 5
- -1 and 3 Substances 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract description 2
- 238000005370 electroosmosis Methods 0.000 abstract 3
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 34
- 238000004519 manufacturing process Methods 0.000 description 18
- 230000001105 regulatory effect Effects 0.000 description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 239000011780 sodium chloride Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 238000012545 processing Methods 0.000 description 9
- 230000009102 absorption Effects 0.000 description 8
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 230000008878 coupling Effects 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005349 anion exchange Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 3
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 2
- 150000004782 1-naphthols Chemical class 0.000 description 1
- GWIAAIUASRVOIA-UHFFFAOYSA-N 2-aminonaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(N)=CC=C21 GWIAAIUASRVOIA-UHFFFAOYSA-N 0.000 description 1
- KSTGSVANFMJGGB-UHFFFAOYSA-N 2-ethylnaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(CC)=CC=C21 KSTGSVANFMJGGB-UHFFFAOYSA-N 0.000 description 1
- 150000005004 2-naphthylamines Chemical class 0.000 description 1
- TVYVQNHYIHAJTD-UHFFFAOYSA-N 2-propan-2-ylnaphthalene Chemical compound C1=CC=CC2=CC(C(C)C)=CC=C21 TVYVQNHYIHAJTD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000011284 combination treatment Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- VNEBWJSWMVTSHK-UHFFFAOYSA-L disodium;3-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=CC2=C1 VNEBWJSWMVTSHK-UHFFFAOYSA-L 0.000 description 1
- IEXIPYCHASVPFD-UHFFFAOYSA-L disodium;7-hydroxynaphthalene-1,3-disulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=CC(O)=CC=C21 IEXIPYCHASVPFD-UHFFFAOYSA-L 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical class C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- ZBNNKSSSCSTNNK-UHFFFAOYSA-M sodium;naphthalen-1-olate Chemical compound [Na+].C1=CC=C2C([O-])=CC=CC2=C1 ZBNNKSSSCSTNNK-UHFFFAOYSA-M 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses an improved 2-naphthol synthesis technology. Through sulfonation, hydrolysis, neutralization, alkali fusion, acidification and refining, a 2-naphthol product and waste water are prepared from refined naphthalene, and the waste water is treated. The waste water treatment process comprises 1, pre-treatment: pre-treating 2-naphthol waste water to remove organic impurities of the waste water and to obtain a salt-containing filtrate, 2, bipolar membrane desalination: carrying out bipolar membrane electroosmosis on the pretreated filtrate to obtain a sulfuric acid solution, a sodium hydroxide solution and dilute brine, carrying out electroosmosis condensation on the dilute brine and carrying out bipolar membrane electroosmosis on the concentrated brine, and 3, acid and base recycle: recycling the sulfuric acid and the sodium hydroxide solution in the 2-naphthol synthesis process and/or the step 1 so that use in the technology is realized. The improved 2-naphthol synthesis technology realizes standard discharge of 2-naphthol waste water, recovers and utilizes an effective resource in waste water by the bipolar membrane technology, and reduces a 2-naphthol synthesis cost.
Description
Technical field
The present invention relates to the technical field of dyestuff intermediate improvement in synthesis, be specifically related to a kind of beta naphthal synthesis technique of improvement.
Background technology
Beta naphthal has another name called 2-Naphthol, ethyl naphthol or 2 hydroxy naphthalene, is important Organic Chemicals and dyestuff intermediate, is all widely used in medicine, agricultural chemicals, rubber ingredients, spices and textile printing and dyeing etc.At dye industry, beta naphthal for the manufacture of organic dye and intermediate thereof, as R salt, G salt, γ salt, TOBIAS ACID 97MIN.& 98MIN., 2,3-acid etc.In recent years, beta naphthal derived product can be used for producing sensitive materials and liquid crystal material, has market outlook widely.
Beta naphthal synthetic process mainly contain the sulfonation-alkali fusion of naphthalene, 2-naphthylamines diazonium compound and dilute sulphuric acid azeotropic, 2-naphthylamines under stress with dilute acid hydrolysis, 2-isopropyl naphthalene through be oxidized and sourly decomposing.Consider the problem such as cost, environment, both at home and abroad the main sulfonation-alkali fusion adopting the naphthalene of comparison of technology maturation.The method is raw material with refined naphthalene, and through concentrated acid sulfonation, S-WAT neutralizes, alkali fusion, and sulfuric acid acidation obtains the thick product of beta naphthal, and through boiling, wash, drying, underpressure distillation obtains beta naphthal product.This technique can produce a large amount of waste water, and environmental problem is comparatively outstanding.
The beta naphthal waste water produced in production process is mainly containing a large amount of inorganic salt-sodium sulfate, S-WAT, 2-sodium naphthalene sulfonate and beta naphthal.If technological operation is improper, has refined naphthalene and run off.General often production 1 ton of beta naphthal, produces sodium sulfate waste liquid 8 ~ 10m
3(relative density about 1.14), containing sodium sulfate 14% ~ 17%, produces S-WAT waste liquid 1m
3left and right (relatively close about 1.12), containing S-WAT 13% ~ 16%, the contribution of S-WAT to COD is larger.There is larger unstable in the Contents of Main Components of sewage, changes along with the change of production operation.And naphthene sulfonic acid, sodium naphthalene sulfonate are soluble in water, also can run off with water section in production process.Therefore, beta naphthal direct discharging of waste water, can cause serious detrimentally affect to environment.
The patent of invention of application publication number CN103626637A describes a kind of environment-friendly production process of beta naphthal, and isolated waste liquid lixiviating neutralization uses when alkali lye by this technique, neutralizes the SO produced
2absorb with the soda ash aqueous solution and produce S-WAT, isolating the waste liquid sulfuric acid after 2-sodium naphthalene sulfonate adjusts pH to be 2 ± 1, three grades of extractions are carried out with extraction agent, extraction liquid uses diluted alkaline back extraction again, strip liquor is used for sulfonated liquid dilution, aqueous phase is oxidized through Fenton reagent or KMnO4, after activated carbon decolorizing, and MVR concentration technique reclaim(ed) sulfuric acid sodium.Present invention process is released without waste water substantially, but treating processes is comparatively loaded down with trivial details.The patent of invention of application publication number CN102603101A describes a kind of beta naphthal factory effluent combination treatment method, beta naphthal rich water is not by after complexometric extraction, liquid Membrane Separation Technique process, improve the biodegradability of waste water, loaded extractant and load emulsion reproducible utilization, concentrated solution, containing high density sodium naphtholate and sodium naphthalene sulfonate, can be back to production workshop section.But because of extraction and the problem such as liquid film technology cost of investment is large, processing power is limited, this method for combined use is promoted comparatively difficult.
The core component of electrodialytic technique is ion-exchange membrane, and it is divided into anion-exchange membrane, cationic exchange membrane and Bipolar Membrane three kinds.The membrane stack that common electrodialysis unit is alternately made up of anion and cation exchange membrane, its major function carries out concentrated desalination to electrolyte solution.Bipolar membrane electrodialysis is alternately formed membrane stack by anion and cation exchange membrane and Bipolar Membrane and formed.Wherein, the composite membrane that Bipolar Membrane is made up of anion exchange layer, cation exchange layer and middle layer, can be dissociated into H efficiently by water or alcohol
+and OH
-or alcohol root and do not produce gas.Bipolar membrane electrodialysis when not adding other any chemical reagent, can convert certain electrolytic salt to corresponding bronsted lowry acids and bases bronsted lowry, and therefore electrodialysis and bipolar membrane electrodialysis are a kind of clearer production technologies.
The present invention utilizes the feature of electrodialytic technique, is introduced into the processing wastewater produced in beta naphthal synthesis technique, reclaim the bronsted lowry acids and bases bronsted lowry of high-quality, and reuse is in beta naphthal synthesis technique, decreases the discharge of waste water and reduces beta naphthal synthesis cost.
Summary of the invention
The invention discloses a kind of beta naphthal synthesis technique of improvement, beta naphthal waste water is through pre-treatment and electrodialytic technique process, not only solve the governing problem of beta naphthal waste water, and valuable constituent in waste water is back in beta naphthal synthesis technique, reduce beta naphthal synthesis cost.
A beta naphthal synthesis technique for improvement, refined naphthalene mainly obtains beta naphthal product and waste water through sulfonation, hydrolysis, neutralization, alkali fusion, acidifying, purification step, finally processes waste water; It is characterized in that, method of wastewater treatment comprises the following steps:
(1) pre-treatment: beta naphthal waste water removes the organic impurity in waste water through pre-treatment, obtains brine waste;
(2) Bipolar Membrane desalination: by brine waste through bipolar membrane electrodialysis process, obtains corresponding sulphuric acid soln, sodium hydroxide solution and weak brine respectively, and weak brine proceeds to electrodialysis concentration;
(3) soda acid reuse: the sodium hydroxide solution that step (2) obtains and sulphuric acid soln are back in beta naphthal synthesis technique and/or step (1) regulates liquid pH value.
The present invention is that starting raw material synthesizes beta naphthal with refined naphthalene, refined naphthalene first after through continuous sulfonation, continuous hydrolysis, blow naphthalene, continuously neutralization continuously, catch up with sulfurous gas, continuous coo1ing, continuous filtration, alkali fusion (periodical operation), dilution (periodical operation), continuously acidizing continuously, be continuously separated and wash, successive drying, continuous still battery obtain beta naphthal product.Tight association between each operation, isolated SO
2, wash water, S-WAT etc. all can realize online recycled, the waste water of generation is separated through electrodialytic technique and obtains acid-base solution and can be back in beta naphthal synthesis technique, reduces production cost.
As preferably, pretreatment process is absorption, Fenton oxidation, Fe
2+the combination of one or more in/HClO oxidation, light electrolysis, wet oxidation, flocculation.
As preferably, adsorbing pretreated actual conditions is: add the sorbent material of 0.1% ~ 5.0%, stirring reaction 0.5 ~ 8h, and sorbent material can select gac, diatomite, organobentonite, resin or bagasse flying dust.
Micro electrolysis tech, having another name called internal electrolysis, iron-deoxidize, Zero-valence Iron Process, core-loss shape etc., is take iron as anode, carbonaceous material is negative electrode, ion in waste water as ionogen, thus defines cell reaction, has the effects such as reduction, flocculation adsorption, complexing and galvanic deposit.Light electrolysis not only can remove part hardly degraded organic substance, and the organic Morphology and structure of energy changing section, improve the biodegradability of waste water.Can the industrial wastes such as waste iron filing be adopted in iron-carbon micro-electrolysis process, can processing costs be saved, reach the object of " treatment of wastes with processes of wastes against one another ".Following electrode reaction is there is in acid condition in light electrolysis by galvanic effect:
Anode (Fe): Fe-2e → Fe
2+
Eθ＝-0.44V
Negative electrode (C): 2H
++ 2e → 2 [H] → H
2
Eθ＝0V
As preferably, the reaction conditions of light electrolysis: adjust wastewater pH to 2 ~ 4, add 0.1 ~ 0.5% gac and 0.5 ~ 4% iron powder, maintenance system pH is constant, stirring reaction 2 ~ 6h.
As preferably, the reaction conditions of flocculation: add 0.05 ~ 1.0% flocculation agent in beta naphthal waste water, regulate wastewater pH to 8 ~ 11, stir 5 ~ 10min soon, rotating speed is 300 ~ 500rpm; Slowly stir 10 ~ 20min, rotating speed is 1 ~ 200rpm.Preferably, flocculation agent can select the one or more combination in ferrous sulfate, bodied ferric sulfate, polyaluminium sulfate, polymerize aluminum chloride, poly-ferric chloride or PAFS, and dosage is 0.05 ~ 1.0%.Further preferably, can add PAM or gac carries out drainage in flocculation process, the dosage of PAM is 0.0001% ~ 0.01%, and the dosage of gac is 0.05% ~ 1.0%.
Fenton oxidation reagent is by Fe
2+and H
2o
2composition, it can generate the HO with strong oxidizing property in acid condition, there is higher electronegativity or electron affinity (569.3KJ), by capturing the H in organic pollutant molecule, filling the reaction paths such as unsaturated C-C key makes pollutent degrade rapidly, and principal degradation mechanism is as follows:
RH+HO·→R·+H
2O
R·+O
2→ROO·
ROO·+HO·+O
2→···→CO
2+H
2O
As preferably, the reaction conditions of Fenton oxidation: adjust wastewater pH to 3 ~ 5, add 0.1% ~ 1%Fe
2+and/or Fe
3+, then add 0.5% ~ 2% hydrogen peroxide, in 40 ~ 60 DEG C of stirring reaction 60 ~ 120min, then refilter after adjusting reaction solution pH8 ~ 11 to flocculate.
Hypochlorous acid has strong oxidizing property, and easily decomposition, instability, therefore adopt and generate HClO with hypochlorite in acid condition.As preferably, Fe
2+/ HClO oxidation style reaction conditions: adjust wastewater pH to 1 ~ 3, add 0.1% ~ 2%NaClO solution (massfraction of NaClO solution is 5%), then add 0.1% ~ 1%Fe
2+, in 40 ~ 60 DEG C of stirring reaction 1 ~ 3h, regulate reaction solution pH8 ~ 11, refilter after flocculation.
Wet oxidation (WAO) technology is under high-temperature and high-pressure conditions, pass into air (or O
2, H
2o
2deng), the organic pollutant of Coal Gas Washing Cycling Water difficult degradation is oxidized in the liquid phase small organic molecule, the CO of readily biodegradable
2with inorganicss such as water.Part is contained to the various industrial organic waste waters of the compound of high chemical oxygen demand or bio-refractory, COD and NH
3-N clearance reaches more than 99%, without the need to carrying out aftertreatment, only gets final product qualified discharge through primary treatment.Compared with ordinary method, have applied widely, processing efficiency is high, and rate of oxidation is fast, rarely secondary pollution, the feature such as recoverable energy and useful material.
As preferably, the reaction conditions of wet oxidation: treatment solution pH2 ~ 11, pressure 2 ~ 8MPa, temperature 150 ~ 280 DEG C, reaction times 30 ~ 150min.Wet oxidation reaction still uses for a long time, can cause damage to equipment, in order to take into account the treatment effect of wet oxidation, further preferably, and pH3 ~ 10 of wet oxidation treatment solution, pressure 2 ~ 5MPa, temperature 180 ~ 260 DEG C.
Catalytic Wet Oxidation (CWAO) is by adding suitable catalyzer, to reduce temperature needed for reaction and pressure, reduces the reaction times, improves oxidative decomposition capacity, extends wet oxidation reaction still work-ing life.As preferably, the optional Cu-series catalyst of wet oxidizing catalyst and/or Fe-series catalyst, dosage is 0.01 ~ 2.0%.
Above-mentioned fine electrolyser, sorbent material, flocculation agent, Fe
2+and/or Fe
3+, hydrogen peroxide, the medicament such as NaClO solution dosage all with the quality of beta naphthal waste water for benchmark.
As preferably, pre-treatment adopts wet oxidation, Catalytic Wet Oxidation or light electrolysis-Fenton oxidation-flocculation-absorption coupling technique process beta naphthal waste water effect better.
Bipolar membrane electrodialysis is the electrodialytic technique be combined to form in different ways by Bipolar Membrane regulating YIN and YANG ion-exchange membrane, being dissociated by common electrodialytic salt dissociates with the water molecules of Bipolar Membrane combines, and makes the H that in solution, corresponding salt ion and Bipolar Membrane water decomposition produce
+and OH
-in conjunction with being converted into corresponding bronsted lowry acids and bases bronsted lowry.
As preferably, the reaction conditions of Bipolar Membrane desalting plant: 1-5% conductive soln is pole liquid, current density is 100-700A/m
2, temperature of reaction is 0 ~ 40 DEG C.Run after for some time, functional quality mark be 2% sulfuric acid Bipolar Membrane system is cleaned.
As preferably, the sodium hydroxide solution that bipolar membrane electrodialysis prepares is for absorbing the SO produced in beta naphthal synthesis technique
2, for the production of S-WAT, the sodium sulfite solution of generation be used for washing room in beta naphthal synthesis technique and in and workshop section; The sulphuric acid soln obtained is for the acidification of acidification section in beta naphthal synthesis technique.
As preferably, the salt solution that step (2) obtains after carrying out electrodialysis concentration to weak brine carries out bipolar membrane electrodialysis process again, electrodialysis concentrate adopt saltiness be the conductive soln of 0.1 ~ 5% as pole liquid, current density is 100 ~ 600A/m
2, inflow temperature is lower than 40 DEG C.
Compared with existing Technology, advantage of the present invention is, present invention process flow process is simple, reaction conditions is gentle, be easy to popularization; Secondly, the present invention utilizes electrodialytic technique, extracts the useful component in beta naphthal waste water, and reuse, in beta naphthal synthesis technique, is synthesized and cost for wastewater treatment to reduce beta naphthal.
Accompanying drawing explanation
Fig. 1 is the schema of the beta naphthal synthesis technique of a kind of improvement of the present invention.
Embodiment
Below in conjunction with Fig. 1 and embodiment, the present invention is described in further detail.
Refined naphthalene obtains beta naphthal product and waste water through sulfonation, hydrolysis, neutralization, alkali fusion, acidifying, the step such as refining.This route mainly produces two strands of waste water, and one is the mother liquor after naphthalene sulfonate salt suction strainer; Another strand is the aqueous phase after crude phenols boil layering, through the mother liquor of cooling, press filtration gained.Mainly contain a large amount of inorganic salt sodium sulfate and S-WAT in waste water, also containing 1-naphthalene sulfonic aicd sodium, 2-sodium naphthalene sulfonate, 1-naphthols, beta naphthal etc., belong to the wastewater from chemical industry of high salt, high COD, high chroma.
Embodiment 1
Beta naphthal waste water, COD is about 37000mg/L, and pH is about 5, SO
4 2-concentration is about 76g/L, SO
3 2-concentration is about 30g/L, C
10h
7sO
3 2-concentration is about 17g/L.
Step 1, pre-treatment-wet oxidation: beta naphthal waste water is placed in wet oxidation reaction still and passes into oxygen, in 260 DEG C, under the condition of 5.5MPa, oxidizing reaction 120min, filtering separation obtains saline solns, and the COD of saline solns is about 1201mg/L after measured.
Step 2, Bipolar Membrane desalination: utilize bipolar membrane electrodialysis to process saline solns, obtain massfraction be 9% sulphuric acid soln, massfraction be 10% sodium hydroxide solution and weak brine.Bipolar Membrane reaction conditions: adopt 1% sodium sulfate sodium solution to be pole liquid, current density is 500A/m
2, temperature of reaction is 30 DEG C.
Weak brine carries out soda acid preparation through bipolar membrane electrodialysis again after electrodialysis is concentrated.Electrodialysis reaction conditions: adopt 1% metabisulfite solution to be pole liquid, current density is 200A/m
2, temperature of reaction is 30 DEG C.
Step 3, soda acid reuse: the sodium hydroxide solution obtained is for absorbing the SO produced in beta naphthal synthesis technique
2, for the production of S-WAT, the sodium sulfite solution of generation can be used for again washing room in beta naphthal synthesis technique and in and workshop section, sodium hydroxide addition solution also can be used for regulating wastewater pH in step 1.The sulphuric acid soln obtained is for regulating wastewater pH in the acidification of acidification section in beta naphthal synthesis technique and/or step 1.
Embodiment 2
Beta naphthal waste water, COD is about 37000mg/L, and pH is about 5, SO
4 2-concentration is about 76g/L, SO
3 2-concentration is about 30g/L, C
10h
7sO
3 2-concentration is about 17g/L.
Step 1, pre-treatment-Catalytic Wet Oxidation: get beta naphthal waste water and add 0.5% copper sulfate (with beta naphthal wastewater quality for benchmark), be placed in wet oxidation reaction still, in pressure 3MPa, at temperature 220 DEG C, wet oxidation reaction 90min, filters and obtains filtrate, and its COD is about 1018mg/L after measured.
Step 2, Bipolar Membrane desalination: utilize bipolar membrane electrodialysis to process saline solns, obtain massfraction be 9% sulphuric acid soln (sulfurous acid containing a small amount of), massfraction be 10% sodium hydroxide solution and weak brine.Bipolar Membrane reaction conditions: adopt 1% sodium sulfate sodium solution to be pole liquid, current density is 500A/m
2, temperature of reaction is 30 DEG C.
Weak brine carries out soda acid preparation through bipolar membrane electrodialysis again after electrodialysis is concentrated.Electrodialysis reaction conditions: adopt 1% metabisulfite solution to be pole liquid, current density is 200A/m
2, temperature of reaction is 30 DEG C.
Step 3, soda acid reuse: the sodium hydroxide solution obtained is for absorbing the SO2 produced in beta naphthal synthesis technique, for the production of S-WAT, the sodium sulfite solution produced can be used for again washing room in beta naphthal synthesis technique and in and workshop section, sodium hydroxide addition solution also can be used for regulating wastewater pH in step 1.The sulphuric acid soln obtained is for regulating wastewater pH in the acidification of acidification section in beta naphthal synthesis technique and/or step 1.
Embodiment 3
Beta naphthal waste water, COD is about 37000mg/L, and pH is about 5, SO
4 2-concentration is about 76g/L, SO
3 2-concentration is about 30g/L, C
10h
7sO
3 2-concentration is about 17g/L.
Step 1, pre-treatment-light electrolysis, flocculation coupling
Light electrolysis: adjust beta naphthal wastewater pH to 3 with sulfuric acid, then add 0.3% gac and 0.2% iron powder (with beta naphthal wastewater quality for benchmark), stirring reaction 4h under normal temperature, all the time maintenance system about pH=3, filtering separation.
Flocculation: adjust above-mentioned filtrate pH to 8 ~ 9 with sodium hydroxide solution, 300 ~ 500rpm stirs 5 ~ 10min soon, and 1 ~ 200rpm stirs 10 ~ 20min slowly, adds 0.1% gac and helps solidifying, filtering and collecting filter liquid, and the COD of filtrate is 5254mg/L after measured.
Step 2, Bipolar Membrane desalination: utilize bipolar membrane electrodialysis to process saline solns, obtain massfraction be 9% sulphuric acid soln (sulfurous acid containing a small amount of), massfraction be 10% sodium hydroxide solution and weak brine.Bipolar Membrane reaction conditions: adopt 1% sodium sulfate sodium solution to be pole liquid, current density is 500A/m
2, temperature of reaction is 30 DEG C.
Weak brine carries out soda acid preparation through bipolar membrane electrodialysis again after electrodialysis is concentrated.Electrodialysis reaction conditions: adopt 1% metabisulfite solution to be pole liquid, current density is 200A/m
2, temperature of reaction is 30 DEG C.
Step 3, soda acid reuse: the sodium hydroxide solution obtained is for absorbing the SO2 produced in beta naphthal synthesis technique, for the production of S-WAT, the sodium sulfite solution produced can be used for again washing room in beta naphthal synthesis technique and in and workshop section, sodium hydroxide addition solution also can be used for regulating wastewater pH in step 1.The sulphuric acid soln obtained is for regulating wastewater pH in the acidification of acidification section in beta naphthal synthesis technique and/or step 1.
Embodiment 4
Beta naphthal waste water, COD is about 37000mg/L, and pH is about 5, SO
4 2-concentration is about 76g/L, SO
3 2-concentration is about 30g/L, C
10h
7sO
3 2-concentration is about 17g/L.
Step 1, pre-treatment-Fenton oxidation, flocculation coupling
Fenton oxidation: add 0.5% ferrous sulfate (with beta naphthal wastewater quality for benchmark) in beta naphthal waste water, then add 1% hydrogen peroxide, in 50 DEG C of stirring reaction 1h.
Flocculation: adjust above-mentioned reaction solution pH to 8 ~ 9 with sodium hydroxide solution, 300 ~ 500rpm stirs 5 ~ 10min soon, and 1 ~ 200rpm stirs 10 ~ 20min slowly, and add 0.1% gac and help solidifying, filtering and collecting filter liquid, the COD of filtrate is about 5013mg/L after measured.
Step 2, Bipolar Membrane desalination: utilize bipolar membrane electrodialysis to process saline solns, obtain massfraction be 9% sulphuric acid soln (sulfurous acid containing a small amount of), massfraction be 10% sodium hydroxide solution and weak brine.Bipolar Membrane reaction conditions: adopt 1% sodium sulfate sodium solution to be pole liquid, current density is 500A/m
2, temperature of reaction is 30 DEG C.
Weak brine carries out soda acid preparation through bipolar membrane electrodialysis again after electrodialysis is concentrated.Electrodialysis reaction conditions: adopt 1% metabisulfite solution to be pole liquid, current density is 200A/m
2, temperature of reaction is 30 DEG C.
Step 3, soda acid reuse: the sodium hydroxide solution obtained is for absorbing the SO2 produced in beta naphthal synthesis technique, for the production of S-WAT, the sodium sulfite solution produced can be used for again washing room in beta naphthal synthesis technique and in and workshop section, sodium hydroxide addition solution also can be used for regulating wastewater pH in step 1.The sulphuric acid soln obtained is for regulating wastewater pH in the acidification of acidification section in beta naphthal synthesis technique and/or step 1.
Embodiment 5
Beta naphthal waste water, COD is about 37000mg/L, and pH is about 5, SO
4 2-concentration is about 76g/L, SO
3 2-concentration is about 30g/L, C
10h
7sO
3 2-concentration is about 17g/L.
Step 1, pre-treatment-light electrolysis, Fenton oxidation, flocculation and absorption coupling
Light electrolysis: get beta naphthal waste water, regulates wastewater pH to 3 with sodium hydroxide solution, adds 0.3% gac and 2% iron powder (with beta naphthal wastewater quality for benchmark), stirring reaction 4h, all the time maintenance system about pH=3.
Fenton oxidation: with sodium hydroxide solution regulation system pH to 4 ~ 5, add 1% hydrogen peroxide, in 50 DEG C of stirring reaction 1h.
Flocculation: adjust system pH to 8 ~ 9 with potassium hydroxide solution, 300 ~ 500rpm stirs 5 ~ 10min soon, and 1 ~ 200rpm stirs 10 ~ 20min slowly, adds 0.1% gac and helps solidifying, filtering and collecting filter liquid.
Absorption: add 0.3% gac, stirring reaction 30min under normal temperature in the filtrate obtained toward flocculating, namely filtering separation obtains filtrate, and its COD is 1674mg/L after measured.
Step 2, Bipolar Membrane desalination: utilize bipolar membrane electrodialysis to process saline solns, obtain massfraction be 9% sulphuric acid soln (sulfurous acid containing a small amount of), massfraction be 10% sodium hydroxide solution and weak brine.Bipolar Membrane reaction conditions: adopt 1% sodium sulfate sodium solution to be pole liquid, current density is 500A/m
2, temperature of reaction is 30 DEG C.
Weak brine carries out soda acid preparation through bipolar membrane electrodialysis again after electrodialysis is concentrated.Electrodialysis reaction conditions: adopt 1% metabisulfite solution to be pole liquid, current density is 200A/m
2, temperature of reaction is 30 DEG C.
Step 3, soda acid reuse: the sodium hydroxide solution obtained is for absorbing the SO2 produced in beta naphthal synthesis technique, for the production of S-WAT, the sodium sulfite solution produced can be used for again washing room in beta naphthal synthesis technique and in and workshop section, sodium hydroxide addition solution also can be used for regulating wastewater pH in step 1.The sulphuric acid soln obtained is for regulating wastewater pH in the acidification of acidification section in beta naphthal synthesis technique and/or step 1.
Embodiment 6
Beta naphthal waste water, COD is about 37000mg/L, and pH is about 5, SO
4 2-concentration is about 76g/L, SO
3 2-concentration is about 30g/L, C
10h
7sO
3 2-concentration is about 17g/L.
Step 1, pre-treatment-Fe
2+/ HClO oxidation, flocculation and absorption coupling
Fe
2+/ HClO is oxidized: adjust beta naphthal wastewater pH to 2 with sulfuric acid, add 1% chlorine bleach liquor (chlorine bleach liquor's massfraction is 5%), then add 0.5% ferrous sulfate, in 50 DEG C of stirring reaction 2h.
Flocculation: adjust above-mentioned reaction solution pH to 8 ~ 9 with sodium hydroxide solution, 300 ~ 500rpm stirs 5 ~ 10min soon, and 1 ~ 200rpm stirs 10 ~ 20min slowly, adds 0.1% gac and helps solidifying, filtering and collecting filter liquid.
Absorption: add 0.4% gac in the filtrate of flocculation gained, under normal temperature, stirring reaction 30min, filters to get filtrate, and its COD is 2198mg/L after measured.
Step 2, Bipolar Membrane desalination: utilize bipolar membrane electrodialysis to process saline solns, obtain massfraction be 9% sulphuric acid soln (sulfurous acid containing a small amount of), massfraction be 10% sodium hydroxide solution and weak brine.Bipolar Membrane reaction conditions: adopt 1% sodium sulfate sodium solution to be pole liquid, current density is 500A/m
2, temperature of reaction is 30 DEG C.
Weak brine carries out soda acid preparation through bipolar membrane electrodialysis again after electrodialysis is concentrated.Electrodialysis reaction conditions: adopt 1% metabisulfite solution to be pole liquid, current density is 200A/m
2, temperature of reaction is 30 DEG C.
Step 3, soda acid reuse: the sodium hydroxide solution obtained is for absorbing the SO2 produced in beta naphthal synthesis technique, for the production of S-WAT, the sodium sulfite solution produced can be used for again washing room in beta naphthal synthesis technique and in and workshop section, sodium hydroxide addition solution also can be used for regulating wastewater pH in step 1.The sulphuric acid soln obtained is for regulating wastewater pH in the acidification of acidification section in beta naphthal synthesis technique and/or step 1.
Embodiment 7
Beta naphthal waste water, COD is about 37000mg/L, and pH is about 5, SO
4 2-concentration is about 76g/L, SO
3 2-concentration is about 30g/L, C
10h
7sO
3 2-concentration is about 17g/L.
Step 1, pre-treatment-absorption
Charcoal absorption: add 0.5% gac in beta naphthal waste water, under normal temperature, stirring reaction 30min, filters to get filtrate.
Resin absorption: add the CHA-111 macroporous resin of 0.5% in above-mentioned filtrate, stirring reaction a few hours, timing sampling analytical reaction liquid COD, until absorption reaches saturated.Filter to get filtrate, its COD is 3847mg/L after measured.
Step 2, Bipolar Membrane desalination: utilize bipolar membrane electrodialysis to process saline solns, obtain massfraction be 9% sulphuric acid soln (sulfurous acid containing a small amount of), massfraction be 10% sodium hydroxide solution and weak brine.Bipolar Membrane reaction conditions: adopt 1% sodium sulfate sodium solution to be pole liquid, current density is 500A/m
2, temperature of reaction is 30 DEG C.
Weak brine carries out soda acid preparation through bipolar membrane electrodialysis again after electrodialysis is concentrated.Electrodialysis reaction conditions: adopt 1% metabisulfite solution to be pole liquid, current density is 200A/m
2, temperature of reaction is 30 DEG C.
Step 3, soda acid reuse: the sodium hydroxide solution obtained is for absorbing the SO2 produced in beta naphthal synthesis technique, for the production of S-WAT, the sodium sulfite solution produced can be used for again washing room in beta naphthal synthesis technique and in and workshop section, sodium hydroxide addition solution also can be used for regulating wastewater pH in step 1.The sulphuric acid soln obtained is for regulating wastewater pH in the acidification of acidification section in beta naphthal synthesis technique and/or step 1.
Embodiment 1 ~ 7 shows that the treatment effect of different pretreatment processs to beta naphthal waste water is not quite similar, and according to concrete requirement, can select suitable pretreatment process.
Embodiment 8
Beta naphthal synthesis technique after improvement is as follows:
Step 1, sulfonation: add 1t melting refined naphthalene and 1.05t98% sulfuric acid in sulphonation kettle, carry out sulfonation reaction, qualified sulfonated bodies enters hydrolyzing process.
Step 2, hydrolysis: sulfonation material continuously flows in hydrolysis kettle, and water and sulfonated bodies add by 1:1 throughput ratio Automatic continuous.
Step 3, blows naphthalene: hydrolyzate pump is sent in tower by blowing naphthalene tower top continuously, and uses naphthalene water separator by naphthalene Separation and Recovery, applies mechanically most in sulfonation reaction.
Step 4, neutralizes, catches up with SO
2, cooling, filter: adopt sodium sulfite solution neutralization blow naphthalene thing, unnecessary SO
2carry out the acidifying of alkali fusion thing towards acidifying still, realize applying mechanically in technique.In and desulfurization material obtain naphthalene sulfonate salt crystallisate through cold filtration.
Step 5, alkali fusion: the caustic soda adding 0.7t fusing in alkali-melting vessel, opens and stirs, add 2-naphthalene sulfonate salt paste, stirring and dissolving.
Step 6, dilution, acidifying: alkali fusion thing, after washing water or clear water dilution, passes into SO
2or in sulphuric acid soln and acidifying.
Step 7, washing, drying: the material after acidifying is continuously separated and washing through sodium sulfite solution, then dry through thick naphthols moisture eliminator.
Step 8, dehydrogenation, distillation, steaming slag and section: thick naphthols first after through de-light, distillation continuously with steam slag and obtain qualified beta naphthal, squeeze into section header tank with pump and go section.The light constituent produced in process, heavy constituent get back to washing procedure reprocessing above.Final beta naphthal product and beta naphthal processing wastewater.
Step 9, pre-treatment-wet oxidation: beta naphthal waste water is placed in wet oxidation reaction still and passes into oxygen, in 260 DEG C, under the condition of 5.5MPa, oxidizing reaction 120min, filtering separation obtains saline solns, and the COD of saline solns is about 1201mg/L after measured.
Step 10, Bipolar Membrane desalination: utilize bipolar membrane electrodialysis to process saline solns, obtain massfraction be 9% sulphuric acid soln, massfraction be 10% sodium hydroxide solution and weak brine.Bipolar Membrane reaction conditions: adopt 1% sodium sulfate sodium solution to be pole liquid, current density is 500A/m
2, temperature of reaction is 30 DEG C.
Weak brine carries out soda acid preparation through bipolar membrane electrodialysis again after electrodialysis is concentrated.Electrodialysis reaction conditions: adopt 1% metabisulfite solution to be pole liquid, current density is 200A/m
2, temperature of reaction is 30 DEG C.
Step 11, soda acid reuse: the sodium hydroxide solution obtained is for absorbing the SO produced in beta naphthal synthesis technique
2, for the production of S-WAT, the sodium sulfite solution of generation can be used for again washing room in beta naphthal synthesis technique and in and workshop section, sodium hydroxide addition solution also can be used for regulating wastewater pH in step 1.The sulphuric acid soln obtained is for regulating wastewater pH in the acidification of acidification section in beta naphthal synthesis technique and/or step 1.
Comparative example 1
Beta naphthal waste water, COD is about 37000mg/L, and pH is about 5, SO
4 2-concentration is about 76g/L, SO
3 2-concentration is about 30g/L, C
10h
7sO
3 2-concentration is about 17g/L.
Compared with embodiment 1, other condition remains unchanged, and saves electrodialysis and concentrates salt solution step, causes Bipolar Membrane process weak brine efficiency on the low side, increases the weak brine treatment time, and cost increases.
Comparative example 2
Beta naphthal waste water, COD is about 37000mg/L, and pH is about 5, SO
4 2-concentration is about 76g/L, SO
3 2-concentration is about 30g/L, C
10h
7sO
3 2-concentration is about 17g/L.
Compared with embodiment 1, other condition remains unchanged, and changes the parameter of electrodialysis unit, current density is down to 100A/m
2, research finds, the processing efficiency of electrodialysis unit reduces 47%, and the treatment time significantly increases, and improves the processing cost of waste water.
Comparative example 3
Beta naphthal waste water, COD is about 37000mg/L, and pH is about 5, SO
4 2-concentration is about 76g/L, SO
3 2-concentration is about 30g/L, C
10h
7sO
3 2-concentration is about 17g/L.
Compared with embodiment 1, other reaction conditions remains unchanged, and changes the parameter of bipolar membrane electrodialysis device, current density is down to 250A/m
2, from experiment, the processing efficiency of bipolar membrane electrodialysis device reduces by 51%, and the treatment time extends, and adds the processing cost of waste water.
Claims (6)
1. the beta naphthal synthesis technique improved, refined naphthalene mainly obtains beta naphthal product and waste water through sulfonation, hydrolysis, neutralization, alkali fusion, acidifying, purification step, finally processes waste water; It is characterized in that, method of wastewater treatment comprises the following steps:
Pre-treatment: beta naphthal waste water removes the organic impurity in waste water through pre-treatment, obtains brine waste;
(2) Bipolar Membrane desalination: by brine waste through bipolar membrane electrodialysis process, obtains corresponding sulphuric acid soln, sodium hydroxide solution and weak brine respectively, and weak brine carries out electrodialysis concentration;
(3) soda acid reuse: the sodium hydroxide solution that step (2) obtains and sulphuric acid soln are back in beta naphthal synthesis technique and/or step (1) regulates liquid pH value.
2. the beta naphthal synthesis technique of a kind of improvement according to claim 1, is characterized in that pretreatment process described in step (1) is absorption, Fenton oxidation, Fe
2+the combination of one or more in/HClO oxidation, light electrolysis, wet oxidation, flocculation.
3. the beta naphthal synthesis technique of a kind of improvement according to claim 2, is characterized in that, described absorption, Fenton oxidation, Fe
2+the actual conditions of/HClO oxidation style, light electrolysis, wet oxidation, flocculation is as follows:
Absorption: add the sorbent material of 0.1% ~ 5.0%, whip attachment 0.5 ~ 8h, sorbent material selects gac, diatomite, resin, organobentonite or bagasse flying dust;
Flocculation: add 0.05 ~ 1.0% flocculation agent in waste water, regulate wastewater pH to 8 ~ 11, rotating speed 300 ~ 500rpm stirs 5 ~ 10min soon, and rotating speed 1 ~ 200rpm stirs 10 ~ 20min slowly;
Fenton oxidation: adjust wastewater pH to 3 ~ 5, add 0.1% ~ 1%Fe
2+and/or Fe
3+, add 0.5% ~ 2% hydrogen peroxide, in 40 ~ 60 DEG C of stirring reaction 1 ~ 2h, regulate reaction solution pH8 ~ 11, refilter after flocculation;
Fe
2+/ HClO oxidation style: adjust wastewater pH to 1 ~ 3, add 0.1% ~ 2%NaClO solution (massfraction of NaClO solution is 5%), then add 0.1% ~ 1%Fe
2+, in 40 ~ 60 DEG C of stirring reaction 1 ~ 3h, regulate reaction solution pH8 ~ 11, refilter after flocculation;
Light electrolysis: adjust wastewater pH to 2 ~ 4, add 0.1 ~ 0.5% gac and 0.5 ~ 4% iron powder, maintenance system pH stablizes, stirring reaction 2 ~ 6h;
Wet oxidation: waste water is dropped into wet oxidation reaction still, the reaction conditions of wet oxidation: pH2 ~ 11, pressure 2 ~ 8MPa, temperature 150 ~ 280 DEG C, reaction times 30 ~ 150min;
Above-mentioned fine electrolyser, sorbent material, flocculation agent, Fe
2+and/or Fe
3+, hydrogen peroxide, the medicament such as NaClO solution dosage all with the quality of beta naphthal waste water for benchmark.
4. the beta naphthal synthesis technique of a kind of improvement according to claim 1, it is characterized in that, the salt solution obtained after step (2) weak brine carries out electrodialysis concentration carries out bipolar membrane electrodialysis process again, electrodialysis is concentrated adopt saltiness be the conductive soln of 0.1 ~ 5% as pole liquid, current density 100 ~ 600A/m
2, inflow temperature is lower than 40 DEG C.
5. the beta naphthal synthesis technique of a kind of improvement according to claim 1, is characterized in that, in step (2), Bipolar Membrane desalination reaction condition is: 1-5% conductive soln is pole liquid, and current density is 100-700A/m
2, temperature of reaction is 0 ~ 40 DEG C.
6. the beta naphthal synthesis technique of a kind of improvement according to claim 1, is characterized in that, the sodium hydroxide solution that step (2) obtains is for absorbing the SO produced in beta naphthal synthesis technique
2produce S-WAT, sodium sulfite solution is used in beta naphthal synthesis technique and workshop section and washing room; The sulphuric acid soln obtained, for the acidification of acidification section in beta naphthal synthesis technique, realizes applying mechanically in technique.
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