CN115044001A - Method for producing water-soluble phenolic resin and co-producing aqueous calcium carbonate suspension by using white carbon black wastewater - Google Patents
Method for producing water-soluble phenolic resin and co-producing aqueous calcium carbonate suspension by using white carbon black wastewater Download PDFInfo
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- CN115044001A CN115044001A CN202210694830.3A CN202210694830A CN115044001A CN 115044001 A CN115044001 A CN 115044001A CN 202210694830 A CN202210694830 A CN 202210694830A CN 115044001 A CN115044001 A CN 115044001A
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- China
- Prior art keywords
- reaction
- calcium carbonate
- carbon black
- white carbon
- speed
- 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.)
- Pending
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 172
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 86
- 239000002351 wastewater Substances 0.000 title claims abstract description 58
- 239000000725 suspension Substances 0.000 title claims abstract description 56
- 239000006229 carbon black Substances 0.000 title claims abstract description 54
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 33
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 134
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 102
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000012065 filter cake Substances 0.000 claims abstract description 44
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001868 water Inorganic materials 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 17
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 15
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims description 65
- 239000008098 formaldehyde solution Substances 0.000 claims description 41
- 238000004321 preservation Methods 0.000 claims description 38
- 239000002002 slurry Substances 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 28
- 238000004537 pulping Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 21
- 239000002270 dispersing agent Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 18
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 18
- 239000004576 sand Substances 0.000 claims description 17
- 239000002518 antifoaming agent Substances 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000003755 preservative agent Substances 0.000 claims description 15
- 230000002335 preservative effect Effects 0.000 claims description 14
- 229920000570 polyether Polymers 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- -1 alkyl naphthalene sulfonate formaldehyde Chemical compound 0.000 claims description 9
- 238000009690 centrifugal atomisation Methods 0.000 claims description 9
- 238000004806 packaging method and process Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 238000000889 atomisation Methods 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 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 claims description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims description 5
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 claims description 5
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 239000004334 sorbic acid Substances 0.000 claims description 5
- 229940075582 sorbic acid Drugs 0.000 claims description 5
- 235000010199 sorbic acid Nutrition 0.000 claims description 5
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 claims description 4
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 claims description 4
- 229960004419 dimethyl fumarate Drugs 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 239000002480 mineral oil Substances 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 229950009390 symclosene Drugs 0.000 claims description 4
- 239000000230 xanthan gum Substances 0.000 claims description 4
- 235000010493 xanthan gum Nutrition 0.000 claims description 4
- 229920001285 xanthan gum Polymers 0.000 claims description 4
- 229940082509 xanthan gum Drugs 0.000 claims description 4
- XEGMDUOAESTQCC-UHFFFAOYSA-N 1-(naphthalen-1-ylmethyl)naphthalene;sodium Chemical compound [Na].C1=CC=C2C(CC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 XEGMDUOAESTQCC-UHFFFAOYSA-N 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229920002907 Guar gum Polymers 0.000 claims description 3
- 229920002396 Polyurea Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 3
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 3
- PYCBFXMWPVRTCC-UHFFFAOYSA-N ammonium metaphosphate Chemical compound N.OP(=O)=O PYCBFXMWPVRTCC-UHFFFAOYSA-N 0.000 claims description 3
- 229940077388 benzenesulfonate Drugs 0.000 claims description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- IPGANOYOHAODGA-UHFFFAOYSA-N dilithium;dimagnesium;dioxido(oxo)silane Chemical compound [Li+].[Li+].[Mg+2].[Mg+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O IPGANOYOHAODGA-UHFFFAOYSA-N 0.000 claims description 3
- OPGYRRGJRBEUFK-UHFFFAOYSA-L disodium;diacetate Chemical compound [Na+].[Na+].CC([O-])=O.CC([O-])=O OPGYRRGJRBEUFK-UHFFFAOYSA-L 0.000 claims description 3
- 239000000665 guar gum Substances 0.000 claims description 3
- 235000010417 guar gum Nutrition 0.000 claims description 3
- 229960002154 guar gum Drugs 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 235000017454 sodium diacetate Nutrition 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims 1
- LYYSMBDYBWUXFG-UHFFFAOYSA-N piperazine;triazine Chemical compound C1CNCCN1.C1=CN=NN=C1 LYYSMBDYBWUXFG-UHFFFAOYSA-N 0.000 claims 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims 1
- 230000018044 dehydration Effects 0.000 abstract description 7
- 238000006297 dehydration reaction Methods 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 30
- 235000011121 sodium hydroxide Nutrition 0.000 description 29
- 238000000034 method Methods 0.000 description 21
- 239000001569 carbon dioxide Substances 0.000 description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- 238000009775 high-speed stirring Methods 0.000 description 13
- 238000001704 evaporation Methods 0.000 description 11
- 239000012528 membrane Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 239000011268 mixed slurry Substances 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000000872 buffer Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- 150000003839 salts Chemical group 0.000 description 4
- 238000010517 secondary reaction Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229960005141 piperazine Drugs 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BEBXIKIXVLRHEM-UHFFFAOYSA-N [Na].C1=CC2=CC=CC=C2C(S(=O)(=O)O)=C1CC1=CC=C(C=CC=C2)C2=C1S(O)(=O)=O Chemical compound [Na].C1=CC2=CC=CC=C2C(S(=O)(=O)O)=C1CC1=CC=C(C=CC=C2)C2=C1S(O)(=O)=O BEBXIKIXVLRHEM-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000009993 causticizing Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007130 inorganic reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- LCRMGUFGEDUSOG-UHFFFAOYSA-N naphthalen-1-ylsulfonyloxymethyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(OCOS(=O)(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 LCRMGUFGEDUSOG-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a method for producing water-soluble phenolic resin and co-producing aqueous calcium carbonate suspension by using white carbon black wastewater, which comprises the following specific production process steps: the white carbon black wastewater is treated by a concentration system, and steam condensate water generated in the system is recovered. Slowly adding the prepared calcium hydroxide suspension into the white carbon black wastewater concentrated solution through a conveying system to perform causticization reaction. After the reaction is finished, the material is processed by dehydration equipment to obtain a sodium hydroxide solution, and the obtained filter cake is washed by clear water. The obtained sodium hydroxide solution reacts with phenol and formaldehyde in sequence to obtain the water-soluble phenolic resin. The invention solves the problem of environmental pollution caused by the discharge of white carbon black wastewater, and prepares the water-soluble phenolic resin and the nano calcium carbonate suspension which are commonly used in industry and have higher added value, thereby improving the added value of the whole production process. And the production equipment is mature, the equipment is simple to operate, and the industrial production is easy to realize.
Description
Technical Field
The invention belongs to the technical field of wastewater reclamation, and particularly relates to a method for producing water-soluble phenolic resin and co-producing aqueous calcium carbonate suspension by using white carbon black wastewater.
Background
White carbon black is a general term for white powdery X-ray amorphous silicic acid and silicate products, mainly referring to silicon dioxide, fumed silica and ultrafine silica gel, and also including powdery synthetic aluminum silicate, calcium silicate and the like, and the manufacturing methods thereof are classified into three types, namely a fumed method, a precipitation method and a non-metallic mineral separation method. The 'precipitated silica' is prepared by reacting water glass with acid to generate silicic acid, and then filtering, washing and drying. The white carbon black is porous material, and its composition can be SiO 2 ·nH 2 O represents, wherein nH 2 O exists in the form of surface hydroxyl, can be dissolved in caustic alkali and hydrofluoric acid, is not dissolved in water, solvent and acid (except hydrofluoric acid), is high-temperature resistant, non-combustible and tasteless, has good electric insulation, and is mainly used as a reinforcing agent of natural rubber and synthetic rubber, a toothpaste friction agent and the like.
The main raw materials for producing the white carbon black by the precipitation method are quartz sand, calcined soda, industrial hydrochloric acid or sulfuric acid or nitric acid or carbon dioxide. The process route is mainly as follows: the industrial water glass is prepared by reacting quartz sand with soda ash at high temperature by adopting fuel oil or high-quality coal, the industrial water glass is prepared into a dilute solution with a certain concentration by using water, then certain acid is added under a certain condition to precipitate silicon dioxide, and then the product white carbon black is prepared by cleaning, filtering, drying and crushing. The process can be known as follows: the production of white carbon black by precipitation method is basically an inorganic reaction process, and because alkali and acid are used in the production process, the main component of waste water is salts attached by neutralization, and the most important salt is Na 2 SO 4 、NaNO 3 Or Na 2 CO 3 And NaHCO 3 Others mainly contain K + 、Na + 、Mg 2+ 、Na 2 Inorganic salts and solid insoluble and suspended substances of S plasma. The project is mainly a production process for preparing white carbon black by the reaction of water glass and carbon dioxide, so Na is mainly used in production wastewater 2 CO 3 And NaHCO 3 Inorganic salts as main component. For the wastewater generated by the precipitation method, the current treatment methods mainly comprise direct evaporation and membrane separation concentration and evaporation. However, the direct evaporation method has the disadvantages of large investment and high operation cost. For the membrane separation concentration and evaporation method, because the precipitated white carbon black wastewater contains a certain amount of silicon dioxide, mainly colloidal silica and soluble silica, especially because of the existence of the soluble silica, silica scale is formed on the membrane after the membrane separation equipment operates for several hours, and silicon blockage is caused. No matter the ultrafiltration membrane or the reverse osmosis membrane is used, once the silicon plug is formed, the prior art means cannot be cleaned, and only a new membrane can be discarded and replaced, so that a pure membrane separation and concentration mode is fundamentally infeasible. Even if the flocculation precipitation is carried out by adding the chemical silicon removal agent before the membrane separation, the soluble silicon in the wastewater cannot be fully removed, and in addition, the chemical silicon removal agent has high cost, and enterprises cannot bear high operating cost, so far, no production enterprise at home and abroad really realizes the zero discharge of the white carbon black wastewater treatment.
From the above, how to provide a low-cost wastewater treatment method for the project and realize zero discharge of wastewater treatment is a technical problem to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a method for producing water-soluble phenolic resin and co-producing aqueous calcium carbonate suspension by using white carbon black wastewater, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a method for producing water-soluble phenolic resin and co-producing aqueous calcium carbonate suspension by using white carbon black wastewater comprises the following specific steps:
step 1: firstly, concentrating raw white carbon black wastewater, then transferring the raw white carbon black wastewater into a causticization reaction tank, stirring and heating the raw white carbon black wastewater, and gradually adding a calcium hydroxide suspension until no substance is precipitated, namely, after the reaction is finished, dehydrating the raw white carbon black wastewater by using a plate and frame filter press to obtain a filtrate and a washed filter cake;
the conductivity of the white carbon black raw wastewater is less than or equal to 6 multiplied by 10 4 us/cm, preferably, the conductivity is (4-6). times.10 4 us/cm。
The conductivity of the concentrated raw white carbon black wastewater is (10-15) multiplied by 10 5 us/cm。
The wastewater concentration conditions are as follows: the steam inlet pressure of the shell and tube evaporator is 0.8-1.0 MPa; the temperature of the raw wastewater inlet is 70-100 ℃; the outlet temperature of the concentrated solution is 100-120 ℃.
The stirring frequency of the causticization reaction tank is 20-100r/min, and the causticization reaction temperature is 40-80 ℃.
Preferably, the calcium hydroxide suspension has a solid content of 20-40% and a feed rate of 5-25m 3 /h。
Further, the filtrate is 10-15% sodium hydroxide solution.
Further, the filter cake is a mixture of calcium carbonate and calcium hydroxide with the solid content of 20-50%.
Step 2: adding a phenol solution into a reaction kettle, stirring and heating, then carrying out heat preservation reaction for 30min after the reaction of the filtrate obtained in the step 1 is finished, then adding a formaldehyde solution with the concentration of 37%, carrying out heat preservation reaction for 30min after the reaction is finished, carrying out heat preservation reaction for 30min after the secondary temperature rise, carrying out heat preservation reaction for 30min again, adding the rest formaldehyde solution with the concentration of 37%, continuing the heat preservation reaction for 30min after the reaction is finished, cooling to room temperature through circulating cooling water after the viscosity is detected to be qualified, and adding a dispersing agent, an anti-settling agent, a preservative and a defoaming agent into the mixture to obtain a finished product of the aqueous calcium carbonate suspension;
the molar ratio of the phenol to the sodium hydroxide is (1-1.05): 1.
preferably, the reaction temperature of the phenol and the sodium hydroxide is 43-50 ℃, the stirring frequency is 20-100r/min, and the feeding flow rate of the sodium hydroxide solution is 1-10m 3 /h。
Further, the dosage of the formaldehyde solution with the concentration of 37 percent which is put in for the first time is 50 to 80 percent, and the feeding flow is 0.5 to 5m 3 /h。
The secondary heating temperature is 80-95 ℃.
Preferably, the molar ratio of formaldehyde to phenol is (1-5): 1.
furthermore, the dosage of the formaldehyde solution with the concentration of 37 percent for the second time is20-50% and the feeding flow rate is 0.5-5m 3 /h。
The viscosity of the qualified water-soluble phenolic resin product is (100-200) mPa.
And step 3: processing the filter cake in the step 1 into slurry through high-speed pulping, adding a dispersing agent to control the viscosity of the slurry, then putting the slurry into a centrifugal atomization tower for atomization, conveying the atomized slurry into a plate and frame type filter press after an atomization reaction, and performing filter pressing again to obtain a filter cake;
the solid content of the calcium carbonate filter cake is (30-50)%.
Further, the low-speed operation rotating speed of the high-speed beater is (10-100) r/min, and the high-speed operation rotating speed is (1000-.
Further, the weight part ratio of the calcium carbonate and calcium hydroxide mixed slurry to the dispersing agent is (95-99): (5-1).
Further, the viscosity of the mixed slurry of the calcium carbonate and the calcium hydroxide is (10-100) mPa.s.
The temperature in the centrifugal atomization tower is 30-100 ℃, and the pressure in the centrifugal atomization tower is 0.1-0.5 MPa.
Furthermore, the running speed of the atomizer of the atomizing tower is (1000-0000) r/min, and the feeding flow of the atomizing tower is (1-5) m 3/h.
The pressing pressure of the plate and frame filter press is (0.5-2.0) MPa, and the pressing time is (5-60) min.
And 4, step 4: and (4) processing the filter cake obtained in the step (3) into slurry by a high-speed beater, sequentially adding a surfactant, a viscosity reducer, an anti-settling agent, a preservative and a defoaming agent, mixing at a high speed for 30min, processing the calcium carbonate with a ball mill until the particle size D97 is (10-20) um, processing the calcium carbonate with a sand mill until the particle size D97 is (0.5-3) um, packaging and warehousing.
The low-speed operation rotating speed of the high-speed beater is (10-100), and the high-speed operation rotating speed is (1000-2000) r/min.
Further, the conditions of the ball milling treatment include: the ball milling speed is 50-100r/min, the ball milling time is 10-60min, and the ball-to-material ratio is (1-2.5): 1.
The aqueous calcium carbonate suspension is mainly prepared from the following components in parts by weight: 90-98 parts of calcium carbonate slurry, 0.3-2.7 parts of dispersing agent, 0.5-4.0 parts of anti-settling agent, 0.1-0.3 part of preservative and 0.2-0.5 part of defoaming agent.
Further, the aqueous calcium carbonate suspension product has a viscosity of < 200 mpa.s.
In a specific embodiment of the present invention, the dispersant is any one of sodium dodecyl sulfate, linear alkyl benzene sulfonate, fatty alcohol-polyoxyethylene ether sodium sulfate, methylene dinaphthalene sodium sulfonate, polyvinylpyrrolidone, sodium tripolyphosphate, ammonium metaphosphate, alkyl naphthalene sulfonate formaldehyde condensate, fatty alcohol-polyoxyethylene ether ammonium sulfate, stearic acid monoglyceride, polyvinyl alcohol, heavy alkylbenzene sulfonate, nonylphenol polyoxyethylene ether, alkylsulfonate, fatty alcohol-polyoxyethylene ether, sodium polyacrylate, ammonium polyacrylate, sodium metaaluminate, and sodium pyrophosphate.
In a specific embodiment of the present invention, the anti-settling agent is any one of magnesium aluminum silicate, lithium magnesium silicate, sodium carboxymethylcellulose, xanthan gum, guar gum, aqueous polyacrylamide, organobentonite, fumed silica, aqueous polyurea, and associative polyurethane.
In a specific embodiment of the present invention, the preservative is any one of isothiazolinone, benzimidazole, piperazine, sorbic acid, dimethyl fumarate, trichloroisocyanuric acid and sodium diacetate.
In a specific embodiment of the present invention, the defoaming agent is any one of silicones, mineral oils, non-silicones, polyethers, and modified silicon polyethers.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention effectively solves the problem of difficult treatment of the white carbon black wastewater by the carbon dioxide precipitation method and can realize the purpose of zero discharge of the white carbon black wastewater.
(2) The invention can prepare aqueous phenolic resin and calcium carbonate suspension with higher industrial value, has wide application range and can be used in the industries of adhesives, coatings, paper making and the like.
The method has the advantages of high maturity of equipment, simple operation and easy realization of industrial production.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The method for producing the water-soluble phenolic resin and co-producing the water-based calcium carbonate suspension by using the white carbon black wastewater, provided by the embodiment of the invention, comprises the following steps:
step 1: firstly, concentrating raw white carbon black wastewater, then transferring the raw white carbon black wastewater into a causticization reaction tank, stirring and heating the raw white carbon black wastewater, and gradually adding a calcium hydroxide suspension until no substance is precipitated, namely, after the reaction is finished, dehydrating the raw white carbon black wastewater by using a plate and frame filter press to obtain a filtrate and a washed filter cake;
step 2: adding a phenol solution into a reaction kettle, stirring and heating, then carrying out heat preservation reaction for 30min after the reaction of the filtrate obtained in the step 1 is finished, then adding a formaldehyde solution with the concentration of 37%, carrying out heat preservation reaction for 30min after the reaction is finished, carrying out heat preservation reaction for 30min after the secondary temperature rise, carrying out heat preservation reaction for 30min again, adding the rest formaldehyde solution with the concentration of 37%, continuing the heat preservation reaction for 30min after the reaction is finished, cooling to room temperature through circulating cooling water after the viscosity is detected to be qualified, and adding a dispersing agent, an anti-settling agent, a preservative and a defoaming agent into the mixture to obtain a finished product of the aqueous calcium carbonate suspension;
and step 3: processing the filter cake in the step 1 into slurry through high-speed pulping, adding a dispersing agent to control the viscosity of the slurry, then putting the slurry into a centrifugal atomizing tower for atomization, after the atomization reaction, conveying the atomized slurry into a plate-and-frame type filter press, and performing filter pressing again to obtain a filter cake;
and 4, step 4: and (3) processing the filter cake in the step (3) into slurry by a high-speed beater, sequentially adding a surfactant, a viscosity reducer, an anti-settling agent, a preservative and a defoaming agent, mixing at a high speed for 30min, processing the calcium carbonate with a ball mill until the particle size D97 is (10-20) um, processing the calcium carbonate with a sand mill until the particle size D97 is (0.5-3) um, packaging and warehousing.
The application provides a method for utilizing the white carbon black wastewater with high added value, and simultaneously, the aim of zero discharge of the wastewater is also fulfilled. Solves the problems of comprehensive utilization and zero discharge of the wastewater generated in the prior production process. According to the invention, white carbon black wastewater containing sodium carbonate and sodium bicarbonate and calcium oxide are subjected to causticization reaction to obtain caustic soda solution with a certain concentration, and the caustic soda solution is a main raw material for preparing the water-soluble phenolic resin, so that the caustic soda solution is sequentially reacted with phenol and formaldehyde to produce the water-soluble phenolic resin commonly used in the fields of adhesives, coatings and plastic stools. The obtained filter cake reacts with carbon dioxide to obtain a calcium carbonate product with higher purity, and then the calcium carbonate product is ground to obtain the common pollution-free calcium carbonate suspension liquid in the industries of coating, printing ink, papermaking and the like. Not only solves the aim of zero discharge of the white carbon black wastewater, but also realizes the high added value recycling of waste materials. Compared with the existing processes such as evaporation concentration, membrane treatment and the like, the method greatly reduces the wastewater treatment environment, reduces the equipment investment and production operation cost, and produces products with considerable economic benefits.
As in different embodiments, the conductivity of the white carbon black raw wastewater after adjustment is 4 x 10 4 us/cm、4.5×10 4 us/cm、5×10 4 us/cm、5.5×10 4 us/cm、6×10 4 us/cm。
As in different embodiments, the conductivity of the concentrated raw silica wastewater is 10 x 10 5 us/cm、11×10 5 us/cm、12×10 5 us/cm、13×10 5 us/cm、14×10 5 us/cm、15×10 5 us/cm。
As in the different embodiments, the vapor inlet pressure of the shell and tube evaporator may be 0.8MPa, 0.85MPa, 0.9MPa, 0.95MPa, 1.0MPa in the concentrating conditions; the original wastewater inlet temperature can be 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, 100 deg.C; the outlet temperature of the concentrated solution can be 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C, and 120 deg.C.
As in the different embodiments, the causticizing reaction tank has the stirring frequency of 20r/min, 30r/min, 40r/min, 50r/min, 60r/min, 70r/min, 80r/min, 90r/min and 100 r/min.
As in the different embodiments, the causticization reaction temperature is 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃.
As in the different embodiments, the calcium hydroxide suspension has a solids content of 20%, 25%, 30%, 35%, 40%.
As in the different embodiments, the feed rate of the calcium hydroxide suspension during the causticization reaction was 5m 3 /h、10m 3 /h、15m 3 /h、20m 3 /h、25m 3 /h。
As in the different embodiments, the filtrate is a 10%, 11%, 12%, 13%, 14%, 15% sodium hydroxide solution.
As in the different embodiments, the solids content of the filter cake is 20%, 25%, 30%, 35%, 40%, 45%, 50%.
As in the various embodiments, the molar ratio of phenol to sodium hydroxide is 1:1. 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1: 1.05.
As in various embodiments, the phenol and sodium hydroxide reaction conditions are: inverse direction
The temperature is 43 deg.C, 44 deg.C, 45 deg.C, 46 deg.C, 47 deg.C, 48 deg.C, 49 deg.C, 50 deg.C;
the stirring frequency is 20r/min, 30r/min, 40r/min, 50r/min, 60r/min, 70r/min, 80r/min, 90r/min and 100 r/min; the feed rate of the sodium hydroxide solution was 1m 3 /h、2m 3 /h、3m 3 /h、4m 3 /h、5m 3 /h、6m 3 /h、7m 3 /h、8m 3 /h、9m 3 /h、10m 3 /h。
As in the various embodiments, the molar ratio of formaldehyde to phenol is 1:1. 1: 2.1: 3. 1: 4. 1: 5.
as in the different embodiments, the primary reaction conditions of the 37% formaldehyde solution and sodium phenolate are: the dosage of the formaldehyde solution in the first reaction is 50 percent, 60 percent, 70 percent and 80 percent of the total weight of formaldehyde; the feed flow of the formaldehyde solution during the reaction is 0.5m 3 /h、1.0m 3 /h、1.5m 3 /h、2.0m 3 /h、2.5m 3 /h、3.0m 3 /h、3.5m 3 /h、4.0m 3 /h、4.5m 3 /h、5m 3 /h。
As in the different embodiments, the secondary reaction conditions of 37% formaldehyde solution and sodium phenolate
Comprises the following steps: the secondary reaction temperature is 80 deg.C, 81 deg.C, 82 deg.C, 83 deg.C, 84 deg.C, 85 deg.C, 86 deg.C, 87 deg.C, 88 deg.C, 89 deg.C, 90 deg.C, 91 deg.C, 92 deg.C, 93 deg.C, 94 deg.C, 95 deg.C; the dosage of the formaldehyde solution in the secondary reaction is 20%, 30%, 40% and 50% of the total formaldehyde weight; the feed flow of the formaldehyde solution during the reaction is 0.5m 3 /h、1.0m 3 /h、1.5m 3 /h、2.0m 3 /h、2.5m 3 /h、3.0m 3 /h、3.5m 3 /h、4.0m 3 /h、4.5m 3 /h、5m 3 /h。
As in the different embodiments, the acceptable water-soluble phenolic resin product has a viscosity of 100mpa.s, 110mpa.s, 120mpa.s, 130mpa.s, 140mpa.s, 150mpa.s, 160mpa.s, 170mpa.s, 180mpa.s, 190mpa.s, 200 mpa.s.
As in the different embodiments, the operating conditions of the high speed pulper are: the low-speed stirring speed is 10r/min, 20r/min, 30r/min, 40r/min, 50r/min, 60r/min, 70r/min, 80r/min, 90r/min and 100 r/min; the high-speed stirring speed is 1000r/min, 1100r/min, 1200r/min, 1300r/min, 1400r/min, 1500r/min, 1600r/min, 1700r/min, 1800r/min, 1900r/min and 2000 r/min.
As in the different embodiments, the weight parts of the filter cake are 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts; further, the weight parts of the dispersing agent are 0 part, 1 part, 2 parts, 3 parts, 4 parts and 5 parts.
As in the different embodiments, the mixture will have a viscosity of 10mpa.s, 20mpa.s, 30mpa.s, 40mpa.s, 50mpa.s, 60mpa.s, 70mpa.s, 80mpa.s, 90mpa.s, 100 mpa.s.
As in various embodiments, the conditions of the centrifugal atomization reaction are: the temperature in the centrifugal atomization tower is 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ and 90 ℃; the pressure in the tower is 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa and 0.5 MPa; the running rotating speed of the atomizer is 10000r/min, 11000r/min, 12000r/min, 13000r/min, 14000r/min, 15000r/min, 16000r/min, 17000r/min, 18000r/min, 19000r/min and 20000 r/min; the atomization feed flow is 1m 3 /h、1.5m 3 /h、2m 3 /h、2.5m 3 /h、3m 3 /h、3.5m 3 /h、4m 3 /h、4.5m 3 /h、5m 3 /h。
As in the different embodiments, the pressing conditions of the plate and frame filter press are: the squeezing pressure is 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1.0MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa, 1.6MPa, 1.7MPa, 1.8MPa, 1.9MPa and 2.0 MPa; the squeezing time is 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60 min.
In a specific embodiment of the present invention, the aqueous calcium carbonate suspension is mainly prepared from the following components in parts by weight:
92-99 parts of calcium carbonate slurry, 0.3-3.0 parts of dispersing agent, 0.5-4.0 parts of anti-settling agent, 0.1-0.5 part of preservative and 0.1-0.5 part of defoaming agent.
The aqueous calcium carbonate suspension has high solid content, low viscosity and good dispersion stability, can be stored for a long time, is suitable for large-scale industrialization, and is suitable to be used as a flatting agent in the coating industry, a reinforcing agent in the latex industry and the like.
As in the various embodiments, the calcium carbonate slurry may be used in amounts of 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, etc., in parts by weight; the dispersant may be used in amounts of 0.3 parts, 0.6 parts, 0.9 parts, 1.2 parts, 1.5 parts, 1.8 parts, 2.1 parts, 2.4 parts, 2.7 parts, 3.0 parts, and the like; the anti-settling agent may be used in an amount of 0.5 parts, 1.0 part, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, etc.; 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.45 part, 0.5 part, etc. of a preservative; the defoaming agent may be used in an amount of 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts, 0.5 parts, etc. Other values not listed in the above numerical ranges are equally applicable.
In a particular embodiment of the invention, the calcium carbonate slurry has a solids content of 30 to 50%
As in the different embodiments, the solids content of the calcium carbonate slurry may be 30%, 35%, 40%, 45%, 50%.
In a particular embodiment of the invention, the viscosity of the calcium carbonate suspension is from 20 to 200 mpa.s.
As in the different embodiments, the viscosity of the calcium carbonate suspension may be 20mpa.s, 40mpa.s, 60mpa.s, 80mpa.s, 100mpa.s, 120mpa.s, 140mpa.s, 160mpa.s, 180mpa.s, 200 mpa.s.
In a specific embodiment of the present invention, the dispersant is any one of sodium dodecyl sulfate, linear alkyl benzene sulfonate, fatty alcohol-polyoxyethylene ether sodium sulfate, methylene dinaphthalene sodium sulfonate, polyvinylpyrrolidone, sodium tripolyphosphate, ammonium metaphosphate, alkyl naphthalene sulfonate formaldehyde condensate, fatty alcohol-polyoxyethylene ether ammonium sulfate, stearic acid monoglyceride, polyvinyl alcohol, heavy alkylbenzene sulfonate, nonylphenol polyoxyethylene ether, alkylsulfonate, fatty alcohol-polyoxyethylene ether, sodium polyacrylate, ammonium polyacrylate, sodium metaaluminate, and sodium pyrophosphate.
In a specific embodiment of the present invention, the anti-settling agent is any one of magnesium aluminum silicate, lithium magnesium silicate, sodium carboxymethylcellulose, xanthan gum, guar gum, aqueous polyacrylamide, organobentonite, fumed silica, aqueous polyurea, and associative polyurethane.
In a specific embodiment of the present invention, the preservative is any one of isothiazolinone, benzimidazole, piperazine, sorbic acid, dimethyl fumarate, trichloroisocyanuric acid and sodium diacetate.
In a specific embodiment of the present invention, the defoaming agent is any one of silicones, mineral oils, non-silicones, polyethers, and modified silicon polyethers.
In a particular embodiment of the invention, the preparation of the calcium carbonate suspension mixture comprises: adding the dispersing agent, the anti-settling agent, the preservative and the defoaming agent into the calcium carbonate slurry, and mixing for 20-60 min.
In a specific embodiment of the present invention, the grinding process includes a ball milling process and a sand milling process.
In a particular embodiment of the invention, the calcium carbonate suspension mixture is subjected to the ball milling treatment until the average particle size of the calcium carbonate in the system is 4 to 8 μm.
In a specific embodiment of the present invention, the conditions of the ball milling process include: the ball milling speed is 50-100r/min, the ball milling time is 10-60min, and the ball-to-material ratio is (1-2.5): 1.
In a specific embodiment of the invention, the ball-milled material is subjected to the sand milling treatment until the average particle size of calcium carbonate in the system is 0.5-2 μm,
in a specific embodiment of the present invention, the conditions of the sanding process include: the sanding rotating speed is 1000-3000r/min, and the sanding time is 5-60 min.
Example 1
(a) The conductivity of the white carbon black raw wastewater is 4.2 multiplied by 10 4 us/cm, steam pressure of the tubular evaporator is 0.8MPa, water inlet temperature is 95 deg.C, water outlet temperature is 105 deg.C, and electric conductivity after evaporation is 10.5 × 10 4 us/cm, transferring to a concentration buffer tank, and circularly cooling. And (3) putting 8.5 cubic cubes of concentrated solution into the causticization reaction tank, starting stirring, setting the stirring speed to be 40r/min, simultaneously starting a heating system, heating to 63 ℃, and carrying out heat preservation treatment. Mixing 5.2m 3 30% of calcium hydroxide of solid contentThe suspension was likewise heated to 63 ℃ and then at 12m 3 The flow of the reaction solution per hour is transferred into a causticization reaction tank for reaction, and after the feeding is finished, the heat preservation treatment is carried out for 30 min. Filtering the solution by a plate and frame filter to obtain a sodium hydroxide solution with the concentration of 13 wt%, and washing the solution to obtain a filter cake with the solid content of 36%.
(b) To 30m 3 The reactor is charged by 5.5m 3 And (3) starting stirring and heating the pre-melted phenol solution, wherein the stirring speed is 50r/min, and the heat preservation temperature is 44 ℃. Adding 7.8m of phenol and sodium hydroxide into the reaction kettle according to the molar ratio of 1:1.01 3 13% strength by weight sodium hydroxide solution with a feed rate of 6m 3 And h, after the reaction is finished, keeping the temperature for reaction for 30 min. Then, mixing the mixture in a molar ratio of formaldehyde to phenol of 1: 2 preparation 6.5m 3 37% formaldehyde solution and heated to 44 ℃. In the course of one-time reaction, 3.25m of catalyst is added 3 The flow rate of the formaldehyde solution (50% of the total formaldehyde solution) was set to 3.0m 3 H, preserving the temperature for reaction for 30min after the reaction is finished. Then, the temperature of the reaction kettle and the rest of the formaldehyde solution are both raised to 83 ℃, the rest 50 percent of the formaldehyde solution is added, and the flow rate is set to be 3.0m 3 And h, after the reaction is finished, keeping the temperature for reaction for 30min, and sampling to detect that the viscosity of the water-soluble phenolic resin product is 123 mPa.s. Cooling to room temperature after the product is qualified, packaging and warehousing.
(c) Starting high-speed pulping, setting the low-speed stirring rotation speed to be 50r/min and the high-speed stirring rotation speed to be 1200r/min, slowly adding 0.96 ton of filter cake obtained in the step (a) into the high-speed pulping machine, slowly adding 40 kg of sodium methylene dinaphthalene sulfonate, detecting the viscosity to be 42mPa.s, transferring the mixture to a feeding tank of a centrifugal atomizing tower, and carrying out heat preservation stirring at 60 ℃. Starting the centrifugal atomizing tower, setting the rotating speed to be 12000r/min, and throwing 7m 3 Then introducing carbon dioxide until the pressure in the tower is 0.2MPa, after the carbon dioxide is stabilized, starting a feeding pump of an atomizing tower, and setting the flow rate to be 1.5m 3 And h, simultaneously transferring the atomized slurry into a plate and frame filter for dehydration. After the feeding is finished, the squeezing pressure of the plate-and-frame filter press is set to be 0.8MPa, the squeezing treatment time is 10min, and the solid content of the calcium carbonate filter cake is 37%.
(d) And (c) starting high-speed pulping, setting the low-speed stirring speed to be 60r/min, setting the high-speed stirring speed to be 1100r/min, and slowly adding 0.96 ton of filter cakes obtained in the step (c) into the high-speed pulping machine. Then, 15 kg of methylene bis-naphthalene sulfonic acid sodium, 12 kg of magnesium aluminum silicate, 2 kg of isothiazolinone preservatives and 1 kg of polyether defoamer were slowly and sequentially fed, and mixed at a high speed for 30 min. Conveying the calcium carbonate mixed slurry into a ball mill through a screw pump, wherein the ball-material ratio is 2:1, starting a circulating pump and a stirring motor, stirring the ball mill at a rotating speed of 53r/min, and ball-milling until the average particle size of calcium carbonate in the system is 6.2 mu m; and then conveying the ball-milled materials to a horizontal sand mill through a pneumatic diaphragm pump, wherein the rotational speed of the sand mill is 2200r/min, circularly grinding for 18min until the particle size of calcium carbonate in the system is 0.68 mu m, and finally obtaining the aqueous calcium carbonate suspension.
Example 2
(a) The conductivity of the white carbon black raw wastewater is 5.1 multiplied by 10 4 us/cm, steam pressure of the tubular evaporator is 0.82MPa, water inlet temperature is 89 deg.C, water outlet temperature is 107 deg.C, and electric conductivity after evaporation is 10.8 × 10 4 us/cm, transferring to a concentration buffer tank, and circularly cooling. Adding 8.5 cubic of concentrated solution into a causticization reaction tank, starting stirring, setting the speed at 50r/min, simultaneously starting a heating system, heating to 70 ℃, and carrying out heat preservation treatment. 4.8m 3 The 25% solids calcium hydroxide suspension was likewise heated to 70 ℃ and then at 15m 3 The flow of the reaction solution per hour is transferred into a causticization reaction tank for reaction, and after the feeding is finished, the heat preservation treatment is carried out for 30 min. Filtering the solution by a plate and frame filter to obtain a sodium hydroxide solution with the concentration of 15 wt%, and washing the solution to obtain a filter cake with the solid content of 35%.
(b) To 30m 3 The reactor is charged by 5.5m 3 And (3) starting stirring and heating the pre-melted phenol solution, wherein the stirring speed is 60r/min, and the heat preservation temperature is 43 ℃. 6.5m of phenol and sodium hydroxide are put into the reaction kettle according to the molar ratio of 1:1 3 Of 15% strength by weight sodium hydroxide solution, feed rate 8m 3 And h, after the reaction is finished, keeping the temperature for reaction for 30 min. Then, mixing the mixture in a molar ratio of formaldehyde to phenol of 1: 1.5 preparation of 6.1m 3 37% formaldehyde solution and heated to 43 ℃. At one endIn the secondary reaction process, 3.355m is added 3 The flow rate of the formaldehyde solution (55% of the total formaldehyde solution) of (2) was set to 5.0m 3 H, preserving the temperature for reaction for 30min after the reaction is finished. Then, the reaction kettle and the rest of the formaldehyde solution are heated to 80 ℃, the rest 45 percent of the formaldehyde solution is added, and the flow rate is set to be 5.0m 3 And h, after the reaction is finished, keeping the temperature for reaction for 30min, and sampling to detect that the viscosity of the water-soluble phenolic resin product is 137 mPa.s. Cooling to room temperature after the product is qualified, packaging and warehousing.
(c) And (3) starting high-speed pulping, setting the low-speed stirring rotation speed to be 70r/min and the high-speed stirring rotation speed to be 1000r/min, slowly adding 0.98 ton of filter cakes obtained in the step (a) into the high-speed pulping machine, slowly adding 20 kg of sodium polyacrylate, detecting that the viscosity is 37mPa.s, transferring the mixture to a feeding tank of a centrifugal atomizing tower, and carrying out heat preservation and stirring at 53 ℃. Starting the centrifugal atomization tower, setting the rotating speed at 15000r/min, and feeding 7m 3 Introducing carbon dioxide until the pressure in the tower is 0.1MPa, starting a feeding pump of an atomizing tower after the carbon dioxide is stabilized, and setting the flow rate to be 2.3m 3 And h, simultaneously transferring the atomized slurry into a plate and frame filter for dehydration. After the feeding is finished, the squeezing pressure of the plate and frame filter press is set to be 1.2MPa, the squeezing treatment time is 30min, and the solid content of the calcium carbonate filter cake is 42%.
(d) And (c) starting high-speed pulping, setting the low-speed stirring rotation speed to be 60r/min, setting the high-speed stirring rotation speed to be 1300r/min, and slowly adding 0.93 ton of filter cake obtained in the step (c) into the high-speed pulping machine. Then, 30 kg of sodium polyacrylate, 33 kg of aqueous polyacrylamide, 4 kg of sorbic acid and 3 kg of silicone defoamer were slowly and sequentially fed, and after finishing, the mixture was mixed at a high speed for 20 min. Conveying the calcium carbonate mixed slurry into a ball mill through a screw pump, wherein the ball-to-material ratio is 1.8:1, starting a circulating pump and a stirring motor, stirring the ball mill at the rotating speed of 65r/min, and ball-milling until the average particle size of calcium carbonate in the system is 4.7 mu m; and then conveying the ball-milled materials to a horizontal sand mill through a pneumatic diaphragm pump, wherein the rotational speed of the sand mill is 2450r/min, circularly grinding for 21min until the particle size of calcium carbonate in the system is 1.24 mu m, and finally obtaining the aqueous calcium carbonate suspension.
Example 3
(a) The conductivity of the white carbon black raw wastewater is 5.3 multiplied by 10 4 us/cm, the steam pressure treated by the tubular evaporator is 0.91MPa, the water inlet temperature is 84 ℃, the water outlet temperature is 109 ℃, and the electric conductivity after evaporation is 12.3 multiplied by 10 4 us/cm, transferring to a concentration buffer tank, and circularly cooling. And (3) putting 8.5 cubic cubes of concentrated solution into the causticization reaction tank, starting stirring, setting the stirring speed to be 65r/min, simultaneously starting a heating system, heating to 62 ℃, and carrying out heat preservation treatment. Mixing 5.6m 3 Is likewise heated to 62 ℃ and then at 22m 3 The flow of the reaction solution/h is transferred into a causticization reaction tank for reaction, and after the feeding is finished, the reaction solution is subjected to heat preservation treatment for 30 min. Filtering the solution by a plate and frame filter to obtain a sodium hydroxide solution with the concentration of 17 wt%, and washing the solution to obtain a filter cake with the solid content of 40%.
(b) To 30m 3 The reactor is charged by 5.5m 3 And (3) starting stirring and heating the pre-melted phenol solution, wherein the stirring speed is 60r/min, and the heat preservation temperature is 43 ℃. 5.8m of phenol and sodium hydroxide are put into the reaction kettle according to the molar ratio of 1:1.04 3 Of a sodium hydroxide solution having a concentration of 17% by weight, the feed rate being 10m 3 And h, after the reaction is finished, keeping the temperature for reaction for 30 min. Then, mixing the mixture in a molar ratio of formaldehyde to phenol of 1: 1.2 preparation of 5.1m 3 37% formaldehyde solution and heated to 45 ℃. In the course of one reaction, 3.6m of the solution was added 3 With the flow rate set at 5.3m, based on 60% of the total formaldehyde solution 3 H, preserving the temperature for reaction for 30min after the reaction is finished. Then, the temperature of the reaction kettle and the rest of the formaldehyde solution are both raised to 83 ℃, the rest 40 percent of the formaldehyde solution is added, and the flow rate is set to be 5.3m 3 And h, after the reaction is finished, keeping the temperature for reaction for 30min, and sampling to detect that the viscosity of the water-soluble phenolic resin product is 167 mPa.s. Cooling to room temperature after the product is qualified, packaging and warehousing.
(c) And (2) starting high-speed pulping, setting the low-speed stirring rotation speed to be 30r/min, setting the high-speed stirring rotation speed to be 1400r/min, slowly adding 0.99 ton of filter cake obtained in the step (a) into the high-speed pulping machine, slowly adding 10 kg of nonylphenol polyoxyethylene ether, detecting the viscosity to be 50mPa.s, transferring the mixture to a feeding tank of a centrifugal atomizing tower, and carrying out heat preservation and stirring at 60 ℃. Opening the centrifugal atomization tower at a rotation speed set to19000r/min, 7m of input 3 Then introducing carbon dioxide until the pressure in the tower is 0.15MPa, after the carbon dioxide is stabilized, starting a feeding pump of an atomizing tower, and setting the flow rate to be 3.0m 3 And h, simultaneously transferring the atomized slurry into a plate and frame filter for dehydration. After the feeding is finished, the squeezing pressure of the plate-and-frame filter press is set to be 1.0MPa, the squeezing treatment time is 40min, and the solid content of the calcium carbonate filter cake is 35%.
(d) And (c) starting high-speed pulping, setting the low-speed stirring rotation speed to be 65r/min and the high-speed stirring rotation speed to be 1200r/min, and slowly adding 0.96 ton of filter cake obtained in the step (c) into the high-speed pulping machine. And then slowly adding 22 kg of nonylphenol polyoxyethylene ether, 10 kg of xanthan gum, 5 kg of sorbic acid and 3 kg of polyether antifoaming agent, and mixing at a high speed for 30 min. Conveying the calcium carbonate mixed slurry into a ball mill through a screw pump, wherein the ball-material ratio is 2.0:1, starting a circulating pump and a stirring motor, stirring the ball mill at the rotating speed of 50r/min, and ball-milling until the average particle size of calcium carbonate in the system is 5.8 mu m; and then conveying the ball-milled materials to a horizontal sand mill through a pneumatic diaphragm pump, wherein the rotational speed of the sand mill is 2250r/min, circularly grinding for 20min until the particle size of calcium carbonate in the system is 0.95 μm, and finally obtaining the aqueous calcium carbonate suspension.
Example 4
(a) The conductivity of the white carbon black raw wastewater is 5.8 multiplied by 10 4 us/cm, the steam pressure treated by the tubular evaporator is 0.82MPa, the water inlet temperature is 91 ℃, the water outlet temperature is 110 ℃, and the electrical conductivity after evaporation is 11.5 multiplied by 10 4 us/cm, transferring to a concentration buffer tank, and circularly cooling. And (3) putting 8.5 cubic cubes of concentrated solution into the causticization reaction tank, starting stirring, setting the stirring speed to be 40r/min, simultaneously starting a heating system, heating to 50 ℃, and carrying out heat preservation treatment. Will be 7.1m 3 The 25% solids calcium hydroxide suspension was likewise heated to 40 ℃ and then at 15m 3 The flow of the reaction solution per hour is transferred into a causticization reaction tank for reaction, and after the feeding is finished, the heat preservation treatment is carried out for 30 min. Filtering the solution by a frame filter to obtain a sodium hydroxide solution with the concentration of 12 wt%, and washing the solution to obtain a filter cake with the solid content of 20%.
(b) To 30m 3 The reactor is charged by 5.5m 3 And (3) starting stirring and heating the pre-melted phenol solution, wherein the stirring speed is 40r/min, and the heat preservation temperature is 48 ℃. Adding 7.4m of phenol and sodium hydroxide into the reaction kettle according to the molar ratio of 1:1.03 3 12% strength by weight sodium hydroxide solution, feed rate 8m 3 And h, after the reaction is finished, keeping the temperature for reaction for 30 min. Then, mixing the mixture in a molar ratio of formaldehyde to phenol of 1: 1.3 preparation of 4.7m 3 And heated to 48 ℃. In the course of one-time reaction, 3.76m of catalyst was added 3 The flow rate of the formaldehyde solution (80% of the total formaldehyde solution) was set to 5.3m 3 H, preserving the temperature for reaction for 30min after the reaction is finished. Then, the temperature of the reaction kettle and the rest of the formaldehyde solution are both raised to 83 ℃, the rest 20 percent of the formaldehyde solution is added, and the flow rate is set to be 4.5m 3 And h, after the reaction is finished, keeping the temperature for reaction for 30min, and sampling to detect that the viscosity of the water-soluble phenolic resin product is 125 mPa.s. Cooling to room temperature after the product is qualified, packaging and warehousing.
(c) And (3) starting high-speed pulping, setting the low-speed stirring rotation speed to be 70r/min and the high-speed stirring rotation speed to be 1800r/min, slowly adding 1.00 ton of the filter cake obtained in the step (a) into the high-speed pulping machine, detecting that the viscosity is 80mPa.s, transferring the filter cake into a feeding tank of a centrifugal atomizing tower, and carrying out heat preservation and stirring at 90 ℃. Starting the centrifugal atomization tower, setting the rotating speed to 14000r/min, and adding 7m 3 Introducing carbon dioxide until the pressure in the tower is 0.2MPa, and after the carbon dioxide is stabilized, starting a feeding pump of an atomizing tower, wherein the flow is set to be 2.5m 3 And h, simultaneously transferring the atomized slurry into a plate and frame filter for dehydration. After the feeding is finished, the squeezing pressure of the plate-and-frame filter press is set to be 1.2MPa, the squeezing treatment time is 25min, and the solid content of the calcium carbonate filter cake is 30%.
(d) And (c) starting high-speed pulping, setting the low-speed stirring rotation speed to be 70r/min and the high-speed stirring rotation speed to be 1800r/min, and slowly adding 0.98 ton of filter cakes in the step (c) into the high-speed pulping machine. Then, 10 kg of the alkyl naphthalene sulfonic acid sodium formaldehyde condensation compound, 5 kg of the organic bentonite, 4 kg of the dimethyl fumarate and 1 kg of the mineral oil antifoaming agent are slowly and sequentially fed, and then the mixture is mixed for 40min at a high speed. Conveying the calcium carbonate mixed slurry into a ball mill through a screw pump, wherein the ball-material ratio is 1.8:1, starting a circulating pump and a stirring motor, stirring the mixture by the ball mill at a rotating speed of 40r/min, and ball-milling until the average particle size of calcium carbonate in the system is 6.7 mu m; and then conveying the ball-milled materials to a horizontal sand mill through a pneumatic diaphragm pump, wherein the rotational speed of the sand mill is 1850r/min, circularly grinding for 30min until the particle size of calcium carbonate in the system is 1.84 mu m, and finally obtaining the aqueous calcium carbonate suspension.
Example 5
(a) The conductivity of the white carbon black raw wastewater is 4.1 multiplied by 10 4 us/cm, steam pressure of the tubular evaporator is 0.95MPa, water inlet temperature is 89 deg.C, water outlet temperature is 107 deg.C, and electric conductivity after evaporation is 10.7 × 10 4 us/cm, transferring to a concentration buffer tank, and circularly cooling. Adding 8.5 cubic of concentrated solution into a causticization reaction tank, starting stirring, setting the speed at 80r/min, simultaneously starting a heating system, heating to 80 ℃, and carrying out heat preservation treatment. Mixing 5.8m 3 Is likewise heated to 90 ℃ and then at 20m 3 The flow of the reaction solution per hour is transferred into a causticization reaction tank for reaction, and after the feeding is finished, the heat preservation treatment is carried out for 30 min. Filtering the solution by a plate and frame filter to obtain a sodium hydroxide solution with the concentration of 14 wt%, and washing the solution to obtain a filter cake with the solid content of 21%.
(b) To 30m 3 The reactor is charged by 5.5m 3 Stirring and heating the pre-melted phenol solution at the stirring speed of 70r/min at the heat preservation temperature of 46 ℃. 5.4m of phenol and sodium hydroxide are put into the reaction kettle according to the molar ratio of 1:1.05 3 With a feed rate of 10m of a 14% strength by weight sodium hydroxide solution 3 And h, after the reaction is finished, keeping the temperature for reaction for 30 min. Then, mixing the mixture in a molar ratio of formaldehyde to phenol of 1: 1.4 preparation of 7.2m 3 37% formaldehyde solution and heated to 46 ℃. In the course of one reaction, 3.51m of the reaction solution was fed 3 With the flow rate set at 2.5m, based on 50% of the total formaldehyde solution 3 H, preserving the temperature for reaction for 30min after the reaction is finished. Then, the temperature of the reaction kettle and the rest formaldehyde solution are both raised to 92 ℃, the rest 50 percent formaldehyde solution is added, and the flow is set to be 2.5m 3 H, keeping the temperature for reaction for 30min after the reaction is finished, and sampling to detect that the viscosity of the water-soluble phenolic resin product is 167 mpa.s. Cooling to room temperature after the product is qualified, packaging and warehousing.
(c) And (3) starting high-speed pulping, setting the low-speed stirring rotation speed to be 50r/min and the high-speed stirring rotation speed to be 1900r/min, slowly adding 1.00 ton of the filter cake obtained in the step (a) into the high-speed pulping machine, detecting that the viscosity is 83mPa.s, transferring the filter cake into a feeding tank of a centrifugal atomizing tower, and carrying out heat preservation and stirring at 85 ℃. Starting the centrifugal atomizing tower, setting the rotating speed to 13000r/min, and adding 7m 3 Introducing carbon dioxide until the pressure in the tower is 0.22MPa, after the process water is stable, starting a feed pump of an atomizing tower, and setting the flow at 2.0m 3 And h, simultaneously transferring the atomized slurry into a plate and frame filter for dehydration. After the feeding is finished, the squeezing pressure of the plate-and-frame filter press is set to be 1.4MPa, the squeezing treatment time is 20min, and the solid content of the calcium carbonate filter cake is 40%.
(d) And (c) starting high-speed pulping, setting the low-speed stirring rotation speed to be 50r/min and the high-speed stirring rotation speed to be 1800r/min, and slowly adding 0.96 ton of filter cakes in the step (c) into the high-speed pulping machine. And then, slowly adding 20 kg of fatty alcohol-polyoxyethylene ether sodium sulfate, 15 kg of water-based polyamide wax, 3 kg of trichloroisocyanuric acid and 2 kg of modified silicone polyether defoamer in sequence, and then mixing at high speed for 50 min. Conveying the calcium carbonate mixed slurry into a ball mill through a screw pump, wherein the ball-material ratio is 2.1:1, starting a circulating pump and a stirring motor, stirring the ball mill at the rotating speed of 30r/min, and ball-milling until the average particle size of calcium carbonate in the system is 4.1 mu m; and then conveying the ball-milled materials to a horizontal sand mill through a pneumatic diaphragm pump, wherein the rotational speed of the sand mill is 2400r/min, circularly grinding for 25min until the particle size of calcium carbonate in the system is 0.82 mu m, and finally obtaining the aqueous calcium carbonate suspension.
Example 6
(a) The conductivity of the white carbon black raw wastewater is 5.6 multiplied by 10 4 us/cm, steam pressure of the tubular evaporator is 0.90MPa, water inlet temperature is 90 deg.C, water outlet temperature is 110 deg.C, and electric conductivity after evaporation is 13.4 × 10 4 us/cm, transferring to a concentration buffer tank, and circularly cooling. Adding 8.5 cubic cubes of concentrated solution into a causticization reaction tank, starting stirring, setting the stirring speed to be 90r/min, simultaneously starting a heating system,heating to 85 deg.C, and maintaining the temperature. Will be 6.5m 3 The 30% solids calcium hydroxide suspension was likewise heated to 85 ℃ and then at 15m 3 The flow of the reaction solution per hour is transferred into a causticization reaction tank for reaction, and after the feeding is finished, the heat preservation treatment is carried out for 30 min. Filtering the solution by a plate and frame filter to obtain a sodium hydroxide solution with the concentration of 15 wt%, and washing the solution to obtain a filter cake with the solid content of 25%.
(b) To 30m 3 The reactor is charged by 5.5m 3 And (3) starting stirring and heating the pre-melted phenol solution, wherein the stirring speed is 80r/min, and the heat preservation temperature is 49 ℃. Adding 6.2m of phenol and sodium hydroxide into the reaction kettle according to the molar ratio of 1:1.03 3 Of 15% strength by weight sodium hydroxide solution, feed rate being 15m 3 And h, after the reaction is finished, keeping the temperature for reaction for 30 min. Then, mixing the mixture in a molar ratio of formaldehyde to phenol of 1: 1.5 preparation of 8.7m 3 37% formaldehyde solution and heated to 60 ℃. In the course of one-time reaction, 5.22m of catalyst was added 3 With the flow rate set at 4.0m, based on 60% of the total formaldehyde solution 3 And h, keeping the temperature for reaction for 30min after the reaction is finished. Then, the temperature of the reaction kettle and the rest of the formaldehyde solution are both increased to 89 ℃, the rest of 40 percent formaldehyde solution is added, and the flow rate is set to be 4.0m 3 And h, after the reaction is finished, keeping the temperature for reaction for 30min, and sampling to detect that the viscosity of the water-soluble phenolic resin product is 182 mPa.s. Cooling to room temperature after the product is qualified, packaging and warehousing.
(c) And (3) starting high-speed pulping, setting the low-speed stirring rotation speed to be 80r/min and the high-speed stirring rotation speed to be 1200r/min, slowly adding 0.99 ton of the filter cake obtained in the step (a) into the high-speed pulping machine, slowly adding 10 kg of sodium metaaluminate, detecting the viscosity to be 72mPa.s, transferring the mixture into a feeding tank of a centrifugal atomizing tower, and carrying out heat preservation and stirring at 80 ℃. Starting the centrifugal atomizing tower, setting the rotating speed at 18000r/min, and throwing 7m 3 Then introducing carbon dioxide until the pressure in the tower is 0.20MPa, after the carbon dioxide is stabilized, starting a feeding pump of an atomizing tower, and setting the flow rate to be 3.0m 3 And h, simultaneously transferring the atomized slurry into a plate and frame filter for dehydration. After the feeding is finished, the squeezing pressure of the plate and frame filter press is set to be 1.5MPa, the squeezing treatment time is 20min, and the solid content of the calcium carbonate filter cake is 46%.
(d) And (c) starting high-speed pulping, setting the low-speed stirring speed to be 80r/min and the high-speed stirring speed to be 1900r/min, and slowly adding 0.94 ton of filter cake in the step (c) into the high-speed pulping machine. Then, 30 kg of sodium metaaluminate, 20 kg of water-based polyamide wax, 6 kg of isothiazolinone bactericide and 4 kg of modified silicone polyether defoamer were slowly and sequentially added, and mixed at a high speed for 60 min. Conveying the calcium carbonate mixed slurry into a ball mill through a screw pump, wherein the ball-material ratio is 2.4:1, starting a circulating pump and a stirring motor, stirring the ball mill at the rotating speed of 35r/min, and ball-milling until the average particle size of calcium carbonate in the system is 4.8 mu m; and then conveying the materials subjected to ball milling treatment to a horizontal sand mill through a pneumatic diaphragm pump, wherein the rotational speed of the sand mill is 2500r/min, circularly grinding for 35min until the particle size of calcium carbonate in the system is 1.49 mu m, and finally obtaining the aqueous calcium carbonate suspension.
Experimental example 1
In order to illustrate the difference between the water-soluble phenolic resin and the aqueous calcium carbonate suspension of different examples and comparative examples, the physicochemical properties of the water-soluble phenolic resin and the aqueous calcium carbonate suspension of each example and comparative example were tested, and the test results are shown in tables 1 and 2.
TABLE 1 test results of water-soluble phenol resins of different examples and comparative example 1
Remarking: the gel time test method comprises the following steps: the time required for the water-soluble phenolic resin to change from a liquid state to a solid gel at a constant temperature of 100 ℃.
TABLE 2 test results of aqueous calcium carbonate suspensions of different examples and comparative example 2
Remarking: the method for testing the suspension stability comprises the following steps: 100ml of the suspension are placed in a 150ml measuring cylinder and placed at a temperature of 25 ℃ and a relative humidity of 50%.
From the test results, the water-soluble phenolic resin and the water-based calcium carbonate suspension prepared by the invention are equivalent to the product performance sold in the market at present, and the water-based calcium carbonate suspension has the advantages of low viscosity, high solid content, excellent suspension performance and the like.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A method for producing water-soluble phenolic resin and co-producing aqueous calcium carbonate suspension by using white carbon black wastewater is characterized by comprising the following steps:
step 1: firstly, concentrating raw white carbon black wastewater, then transferring the raw white carbon black wastewater into a causticization reaction tank, stirring and heating the raw white carbon black wastewater, and gradually adding a calcium hydroxide suspension until no substance is precipitated, namely, after the reaction is finished, dehydrating the raw white carbon black wastewater by using a plate and frame filter press to obtain a filtrate and a washed filter cake;
step 2: adding a phenol solution into a reaction kettle, stirring and heating, then carrying out heat preservation reaction for 30min after the reaction of the filtrate obtained in the step 1 is finished, then adding a formaldehyde solution with the concentration of 37%, carrying out heat preservation reaction for 30min after the reaction is finished, carrying out heat preservation reaction for 30min after the secondary temperature rise, carrying out heat preservation reaction for 30min again, adding the rest formaldehyde solution with the concentration of 37%, continuing the heat preservation reaction for 30min after the reaction is finished, cooling to room temperature through circulating cooling water after the viscosity is detected to be qualified, and adding a dispersing agent, an anti-settling agent, a preservative and a defoaming agent into the mixture to obtain a finished product of the aqueous calcium carbonate suspension;
and step 3: processing the filter cake in the step 1 into slurry through high-speed pulping, adding a dispersing agent to control the viscosity of the slurry, then putting the slurry into a centrifugal atomizing tower for atomization, after the atomization reaction, conveying the atomized slurry into a plate-and-frame type filter press, and performing filter pressing again to obtain a filter cake;
and 4, step 4: and (3) processing the filter cake in the step (3) into slurry by a high-speed beater, sequentially adding a surfactant, a viscosity reducer, an anti-settling agent, a preservative and a defoaming agent, mixing at a high speed for 30min, processing the calcium carbonate with a ball mill until the particle size D97 is (10-20) um, processing the calcium carbonate with a sand mill until the particle size D97 is (0.5-3) um, packaging and warehousing.
2. The method for producing the water-soluble phenolic resin and the aqueous calcium carbonate suspension by using the white carbon black wastewater as claimed in claim 1, is characterized in that: the conductivity of the raw white carbon black wastewater in the step 1 is less than or equal to 6 multiplied by 10 4 us/cm, the conductivity of the concentrated white carbon black raw wastewater is more than or equal to 10 5 us/cm; and the stirring speed of the causticization reaction tank in the step 1 is 20-100r/min, and the causticization reaction temperature is 40-80 ℃; the solid content of the calcium hydroxide suspension in the step 1 is 20-40%, and the feeding speed is 5-25m 3 /h。
3. The method for producing the water-soluble phenolic resin and the aqueous calcium carbonate suspension by using the white carbon black wastewater as claimed in claim 1, is characterized in that: the molar ratio of phenol to sodium hydroxide in the step 2 is (1-1.05): 1, the reaction temperature of phenol and sodium hydroxide is 43-50 ℃, the stirring frequency is 20-100r/min, and the feeding flow rate of the sodium hydroxide solution is 1-10m 3 H; in the step 2, formaldehyde solution with the concentration of 37 percent is added for the first time50-80% of liquid and 0.5-5m of feeding flow 3 H; and the secondary heating temperature is 80-95 ℃; the molar ratio of formaldehyde to phenol in the step 2 is (1-5): 1; and the viscosity of the qualified product in the step 2 is (100-200) mPa.s.
4. The method for producing the water-soluble phenolic resin and the aqueous calcium carbonate suspension by using the white carbon black wastewater as claimed in claim 1, is characterized in that: the low-speed running rotating speed of the high-speed beater in the step 3 is (10-100) r/min, and the high-speed running rotating speed is (1000-2000) r/min; in step 3, the temperature in the centrifugal atomization tower is 30-100 ℃, and the pressure in the tower is 0.1-0.5 MPa; the running rotating speed of the atomizer of the centrifugal atomizing tower in the step 3 is (1000- 3 H; and in the step 3, the squeezing pressure of the plate and frame filter press is (0.5-2.0) MPa, and the squeezing time is (5-60) min.
5. The method for producing the water-soluble phenolic resin and the aqueous calcium carbonate suspension by using the white carbon black wastewater as claimed in claim 1, is characterized in that: in the step 3, a dispersing agent accounting for 1-5% of the weight of the slurry is added, and the dispersing agent is any one of sodium dodecyl benzene sulfonate, sodium polyacrylate, fatty alcohol-polyoxyethylene ether sodium sulfate, fatty alcohol-polyoxyethylene ether ammonium sulfate, a dispersing agent NNO, a dispersing agent MF, alkyl polyether, fatty alcohol-polyoxyethylene ether, an alkyl naphthalene sulfonate formaldehyde condensate, polyvinylpyrrolidone and sodium metaaluminate.
6. The method for producing the water-soluble phenolic resin and the aqueous calcium carbonate suspension by using the white carbon black wastewater as claimed in claim 1, is characterized in that: the low-speed operation rotating speed of the high-speed beater in the step 4 is (10-100) r/min, and the high-speed operation rotating speed is (1000-; and in the step 4, the rotation speed of the ball mill is 50-100r/min, the ball milling time is 10-60min, and the ball material ratio is (1-2.5): 1.
7. The method for producing the water-soluble phenolic resin and the aqueous calcium carbonate suspension by using the white carbon black wastewater as claimed in claim 1, is characterized in that: the aqueous calcium carbonate suspension in the step 2 comprises the following components in percentage by weight: 90-98 parts of calcium carbonate slurry, 0.3-2.7 parts of dispersing agent, 0.5-4.0 parts of anti-settling agent, 0.1-0.3 part of preservative and 0.2-0.5 part of defoaming agent.
8. The method for producing the water-soluble phenolic resin and the aqueous calcium carbonate suspension by using the white carbon black wastewater as claimed in claim 7, is characterized in that: the dispersing agent in the step 2 is any one of sodium dodecyl sulfate, linear alkyl benzene sulfonate, fatty alcohol-polyoxyethylene ether sodium sulfate, methylene dinaphthalene sodium sulfonate, polyvinylpyrrolidone, sodium tripolyphosphate, ammonium metaphosphate, alkyl sodium naphthalene sulfonate formaldehyde condensate, fatty alcohol-polyoxyethylene ether ammonium sulfate, stearic acid monoglyceride, polyvinyl alcohol, heavy alkylbenzene sulfonate, nonylphenol polyoxyethylene ether, alkyl sulfonate, fatty alcohol-polyoxyethylene ether, sodium polyacrylate, ammonium polyacrylate, sodium metaaluminate and sodium pyrophosphate; and the anti-settling agent in the step 2 is any one of magnesium aluminum silicate, lithium magnesium silicate, sodium carboxymethylcellulose, xanthan gum, guar gum, water-based polyacrylamide, organic bentonite, fumed silica, water-based polyurea and associated polyurethane; the preservative in the step 2 is any one of isothiazolinone, benzimidazole, piperazine triazine, sorbic acid, dimethyl fumarate, trichloroisocyanuric acid and sodium diacetate; and the defoaming agent in the step 2 is any one of organic silicon, mineral oil, non-silicon, polyether and modified silicon polyether.
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| CN116040671A (en) * | 2022-12-28 | 2023-05-02 | 广西华纳新材料股份有限公司 | Preparation method of flaky calcium carbonate |
| CN116040671B (en) * | 2022-12-28 | 2024-05-03 | 广西华纳新材料股份有限公司 | Preparation method of flaky calcium carbonate |
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