CN117534091A - Resource utilization method of salt-containing organic waste - Google Patents
Resource utilization method of salt-containing organic waste Download PDFInfo
- Publication number
- CN117534091A CN117534091A CN202311578835.0A CN202311578835A CN117534091A CN 117534091 A CN117534091 A CN 117534091A CN 202311578835 A CN202311578835 A CN 202311578835A CN 117534091 A CN117534091 A CN 117534091A
- Authority
- CN
- China
- Prior art keywords
- salt
- organic waste
- water
- content
- liquid
- 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
- 150000003839 salts Chemical class 0.000 title claims abstract description 215
- 239000010815 organic waste Substances 0.000 title claims abstract description 169
- 238000000034 method Methods 0.000 title claims abstract description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 160
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 82
- 239000007788 liquid Substances 0.000 claims abstract description 77
- 238000002425 crystallisation Methods 0.000 claims abstract description 32
- 230000008025 crystallization Effects 0.000 claims abstract description 32
- 238000004064 recycling Methods 0.000 claims abstract description 29
- 239000012452 mother liquor Substances 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 17
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 14
- 239000011630 iodine Substances 0.000 claims abstract description 14
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004821 distillation Methods 0.000 claims abstract description 13
- 239000002699 waste material Substances 0.000 claims abstract description 6
- 238000002309 gasification Methods 0.000 claims description 50
- 159000000000 sodium salts Chemical class 0.000 claims description 42
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000011259 mixed solution Substances 0.000 claims description 37
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 32
- 239000007791 liquid phase Substances 0.000 claims description 27
- 238000010791 quenching Methods 0.000 claims description 26
- 230000000171 quenching effect Effects 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 23
- 230000008018 melting Effects 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 23
- 239000011780 sodium chloride Substances 0.000 claims description 22
- 239000012267 brine Substances 0.000 claims description 18
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 239000011737 fluorine Substances 0.000 claims description 13
- 239000002893 slag Substances 0.000 claims description 13
- 239000010888 waste organic solvent Substances 0.000 claims description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000011833 salt mixture Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 235000019738 Limestone Nutrition 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- 239000002817 coal dust Substances 0.000 claims description 4
- 239000006028 limestone Substances 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000008346 aqueous phase Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000012530 fluid Substances 0.000 description 12
- -1 alicyclic hydrocarbon Chemical class 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000001103 potassium chloride Substances 0.000 description 5
- 235000011164 potassium chloride Nutrition 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- 150000008282 halocarbons Chemical class 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- JTXJZBMXQMTSQN-UHFFFAOYSA-N amino hydrogen carbonate Chemical compound NOC(O)=O JTXJZBMXQMTSQN-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- WZWSOGGTVQXXSN-UHFFFAOYSA-N cyclohexanone;toluene Chemical compound CC1=CC=CC=C1.O=C1CCCCC1 WZWSOGGTVQXXSN-UHFFFAOYSA-N 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 229940090181 propyl acetate Drugs 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
-
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Abstract
The invention belongs to the technical field of waste recycling, and particularly relates to a recycling method of organic waste containing salt. The invention adopts salt-containing organic waste and non-salt organic waste liquid as raw materials to prepare high-concentration inorganic salt mixed liquor, gasifies and chilled water quenches the high-concentration inorganic salt mixed liquor to enable organic matters to generate synthetic gas, and makes different chemical products to enable the synthetic gas to be efficiently utilized, and simultaneously enables inorganic salt to enter an aqueous phase, and then inorganic salt is recovered through reduced pressure distillation and crystallization separation; further, when the organic waste containing salt also contains bromine and/or iodine, the method further comprises the step of further extracting the halogen-containing mother liquor obtained after the crystallization separation to recover bromine simple substance and/or iodine simple substance. According to the invention, through the mutual combination of various technological processes, inorganic salt can be recovered while the synthesis gas is prepared, so that harmless treatment and high-value recycling of organic wastes containing salt are realized, and the comprehensive recycling treatment rate can reach more than 95%.
Description
Technical Field
The invention belongs to the technical field of waste recycling, and particularly relates to a recycling method of organic waste containing salt.
Background
In the industrial production process, a large amount of salt-containing organic waste is generated, and the generation links mainly comprise chemical processes such as chlorination, diazotization, acidification, nitration, oxidation, condensation and the like, and wastewater treatment processes such as neutralization, filtration, evaporation, crystallization and the like. Among them, the main kinds of inorganic salts in the organic waste containing salt are sodium salt, calcium salt, ammonia salt, potassium salt, etc., and the organic waste containing sodium salt and potassium salt is the largest.
The existing treatment modes of the salt-containing organic waste can be divided into two methods of harmless treatment and resource utilization, wherein the harmless treatment is mainly carried out by landfill; according to the specification that waste with the total content of water-soluble salts being more than or equal to 10% or the content of organic matters being more than or equal to 5% in GB 18598-2019 pollution control Standard for hazardous waste landfill, the organic waste containing salt should enter a rigid landfill. However, the entry of organic waste containing salt into a rigid landfill site has four drawbacks: (1) For the same-scale landfill, the investment of the rigid landfill is larger than that of the flexible landfill, and the occupied area is relatively large; (2) Most of the landfill sites in China are flexible landfill sites, the quantity of rigid landfill sites is small, and the landfill of organic wastes containing salt is limited; (3) The landfill cost of the organic waste containing salt is up to 4000 yuan/ton or more; (4) Organic pollutants in the organic waste containing salt can enter the environment along with percolate, so that the environment is polluted.
The salt-containing organic waste is recycled, so that the problems caused by harmless treatment can be avoided. At present, the resource utilization of the salt-containing organic waste is mostly carried out by adopting modes such as oxidation, cracking, melting and the like, firstly removing organic matters in the salt-containing organic waste, and then carrying out operations such as membrane separation, electrolysis, crystallization separation and the like on inorganic salt so as to realize the refining and purifying treatment of the salt-containing organic waste. However, this treatment method converts organic matter into greenhouse gas emission, does not effectively and reasonably utilize the organic waste containing salt in a resource manner, and cannot utilize the organic waste containing salt in an element level, so that chemical resources are wasted.
Disclosure of Invention
The invention aims to provide a resource utilization method of organic waste containing salt, which is used for treating the organic waste containing salt, so that synthesis gas and inorganic salt can be obtained at the same time, bromine and iodine can be recovered, and efficient recycling of the organic waste containing salt is realized.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for recycling organic wastes containing salt comprises the following steps:
(1) Mixing the organic waste containing salt with the non-salt organic waste liquid to obtain a high-concentration inorganic salt mixed solution; the concentration of inorganic salt in the high-concentration inorganic salt mixed solution is more than 90% of the saturated concentration of inorganic salt; the fluorine content of the high-concentration inorganic salt mixed solution is less than 5wt%, the silicon content is less than 3wt%, the aluminum content is less than 3wt%, the sulfur content is less than or equal to 2wt%, the magnesium content is less than 5wt%, the phosphorus content is 0.1-5 wt%, the calcium content is 1-10 wt%, and the heat value is not less than 10000J/g; the inorganic salt in the salt-containing organic waste comprises sodium salt and/or potassium salt;
the non-salt organic waste liquid comprises organic waste liquid and water; the water content of the non-salt organic waste liquid is 20-60wt% and the heat value is 10000-30000J/g;
(2) Gasifying and quenching the high-concentration inorganic salt mixed solution in sequence to obtain a gas-water mixture, first liquid-phase water and solid slag respectively;
(3) Carrying out gas-water separation on the gas-water mixture to respectively obtain synthesis gas and second liquid phase water;
(4) Mechanically filtering the first liquid-phase water and the second liquid-phase water to obtain a water body with high salt content and water quenching slag respectively; the total content of potassium salt and/or sodium salt in the high-salt-content water body is not less than 15wt%;
(5) And concentrating and crystallizing and separating the water body with high salt content in sequence to obtain sodium salt and/or potassium salt.
Preferably, the organic waste liquid is a waste organic solvent, and the waste organic solvent is a compound containing carbon and hydrogen;
the salt-containing organic waste is solid salt-containing organic waste or liquid salt-containing organic waste;
the mass ratio of water in the solid salt-containing organic waste to the non-salt organic waste liquid is 0.1-2:1;
the mass ratio of the organic waste liquid in the liquid saline organic waste to the organic non-saline waste liquid is 0.2-0.8:1.
Preferably, after the high-concentration inorganic salt mixed solution is obtained, the method further comprises the step of adding an additive into the high-concentration inorganic salt mixture; the additive is at least one of limestone, coal dust and activated carbon.
Preferably, the gasification temperature is based on the ash melting point of insoluble matters in the high-concentration inorganic salt mixed solution: when the ash melting point of the insoluble matters is higher than 1300 ℃, the gasification temperature is 1350-1400 ℃;
when the ash melting point of the insoluble matters is lower than 1100 ℃, the gasification temperature is 1050-1100 ℃;
when the ash melting point of the insoluble matters is between 1100 and 1250 ℃, the gasification temperature is 50 to 100 ℃ higher than the ash melting point of the insoluble matters;
the gasification pressure is 0-10 Mpa; the gasified gasifying agent is oxygen; the volume ratio of the oxygen to the high-concentration inorganic salt mixed solution in the gasification process is 300-600:1.
Preferably, the mass flow ratio of the chilling water used for chilling water quenching to the high-concentration inorganic salt mixed solution is 4-10:1.
Preferably, the concentration method is reduced pressure distillation; the temperature of the reduced pressure distillation is 25-140 ℃, and the pressure is-200 to-50 KPa.
Preferably, when the inorganic salts in the organic waste containing salt are sodium salt and potassium salt, the crystallization is separated into: crystallizing the concentrated solution at a first temperature reduction to obtain sodium salt, and crystallizing the concentrated solution at a second temperature reduction to obtain potassium salt; the final temperature of the first cooling crystallization is 60-100 ℃; the final temperature of the second cooling crystallization is 25-60 ℃;
when the inorganic salt in the salt-containing organic waste is sodium salt, the crystallization is separated into: cooling the concentrated solution to 60-100 ℃ for crystallization to obtain sodium salt;
when the inorganic salt in the salt-containing organic waste is a potassium salt, the crystallization is separated into: and cooling the concentrated solution to 25-60 ℃ for crystallization to obtain the potassium salt.
Preferably, the crystallization separation also obtains brine mother liquor; when the brine mother liquor contains bromide, the method further comprises the step of introducing chlorine into the brine mother liquor and then blowing out nitrogen to obtain bromine simple substance.
Preferably, when the brine mother liquor further contains iodide, the method further comprises mixing the mother liquor left after nitrogen is blown out with an extractant for extraction to obtain an iodine simple substance.
Preferably, when the total content of sodium salt and/or potassium salt in the filtrate obtained by mechanical filtration is lower than 15wt%, the filtrate is recycled as chilled water for chilled water quenching until the total content of sodium salt and/or potassium salt in the filtrate obtained by mechanical filtration is not lower than 15wt%;
condensed water generated by the reduced pressure distillation is used as chilling water for chilling water quenching in a circulating way.
The invention provides a resource utilization method of organic wastes containing salt. The resource utilization method provided by the invention realizes efficient element level utilization of the organic waste containing salt. The invention takes the salt-containing organic waste and the non-salt organic waste liquid as raw materials, all the technological processes are combined mutually to prepare the synthesis gas, and the inorganic salt is recovered, thereby realizing the harmless treatment and comprehensive high-efficiency high-value recycling of the salt-containing organic waste. The method has the following specific beneficial effects:
(1) Efficient utilization of organic matters in salt-containing organic waste
Compared with the traditional recycling process of the organic wastes containing salt, the method for treating the organic matters in the organic wastes containing salt is more efficient and reasonable: the invention combines the salt-containing organic waste and the non-salt organic waste liquid, so that the mixed materials of the salt-containing organic waste and the non-salt organic waste meet the gasification condition, the full utilization of organic matters in the salt-containing organic waste is realized through gasification, meanwhile, the organic matters are prevented from interfering the recovery of subsequent inorganic salts, and the synthesis gas generated by gasifying the organic matters can be directly used as a product or can be used as a raw material for producing other chemical products.
(2) Gasification chilling impurity removal
The high-concentration inorganic salt mixed solution realizes the recycling utilization of organic matters through gasification, and simultaneously realizes the melting or partial melting of inorganic salts, and then the refractory matters and harmful metal matters in the salt-containing organic waste are solidified through chilling water quenching to form solidified slag, so that the inorganic matters with toxic action in the salt-containing organic waste are removed, and the harmless treatment is realized. The invention can realize the vitrification rate of heavy metal >90 percent and acid dissolution rate <2 percent through gasification treatment, and various indexes meet the technical requirement of solid waste vitrification treatment products (GB/T41015-2021).
(3) Organic combination of inorganic salt extraction process
The invention provides convenience for the subsequent extraction of inorganic salt in each process flow: component adjustment is realized through mixing of the salt-containing organic waste and the non-salt organic waste liquid, and chemical components of the mixture are strictly controlled in the component adjustment stage, so that calcium and magnesium ions form phosphate precipitation in the gasification chilling process, and the interference of the calcium ions and the magnesium ions on the extraction of inorganic salts is avoided; the high-efficiency gasification utilization of the organic matters is realized in the gasification chilling process, and the interference of the organic matters on the subsequent process is avoided. In the extraction stage of the high-salt wastewater, the potassium salt and the sodium salt in the water body are firstly recycled, and then the obtained concentrated liquid is subjected to bromine and iodine extraction, so that the extraction efficiency is improved, and the comprehensive recycling treatment rate can reach more than 95%.
In summary, the recycling treatment method of the invention is used as an organic whole, each technological process is organically combined with the aim of efficient recycling, and finally the high-value recycling of the organic wastes containing salt is realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a method for recycling organic waste containing salt.
Detailed Description
The invention provides a resource utilization method of organic waste containing salt, which comprises the following steps:
(1) Mixing the organic waste containing salt with the non-salt organic waste liquid to obtain a high-concentration inorganic salt mixed solution; the concentration of inorganic salt in the high-concentration inorganic salt mixed solution is more than 90% of the saturated concentration of inorganic salt; the fluorine content of the high-concentration inorganic salt mixed solution is less than 5wt%, the silicon content is less than 3wt%, the aluminum content is less than 3wt%, the sulfur content is less than or equal to 2wt%, the magnesium content is less than 5wt%, the phosphorus content is 0.1-5 wt%, the calcium content is 1-10 wt%, and the heat value is not less than 10000J/g; the inorganic salt in the salt-containing organic waste comprises sodium salt and/or potassium salt;
the non-salt organic waste liquid comprises organic waste liquid and water; the water content of the non-salt organic waste liquid is 20-60wt% and the heat value is 10000-30000J/g;
(2) Gasifying and quenching the high-concentration inorganic salt mixed solution in sequence to obtain a gas-water mixture, first liquid-phase water and solid slag respectively;
(3) Carrying out gas-water separation on the gas-water mixture to respectively obtain synthesis gas and second liquid phase water;
(4) Mechanically filtering the first liquid-phase water and the second liquid-phase water to obtain a water body with high salt content and water quenching slag respectively; the total content of sodium salt and/or potassium salt in the water body with high salt content is not less than 15wt%;
(5) And concentrating and crystallizing and separating the water body with high salt content in sequence to obtain sodium salt and/or potassium salt.
The invention mixes the organic waste containing salt and the non-salt organic waste liquid to obtain the high-concentration inorganic salt mixed liquid. In the invention, the inorganic salt in the salt-containing organic waste comprises sodium salt and/or potassium salt; the sodium salt preferably comprises one or two of sodium chloride and sodium carbonate, and the potassium salt preferably comprises one or two of potassium chloride and potassium carbonate; in a specific embodiment of the present invention, the inorganic salt in the salt-containing organic waste may be only sodium salt and/or potassium salt, or may contain one or more of sodium sulfate, potassium sulfate, sodium iodide and sodium bromide in addition to the sodium salt and/or potassium salt.
In the present invention, the salt-containing organic waste is preferably solid salt-containing organic waste or liquid salt-containing organic waste; the solid content of the liquid saline organic waste is preferably 15-35 wt%, more preferably 20-30 wt%; the solid salt-containing organic waste is preferably waste salt generated by acid-base neutralization reaction in the industrial production process; the liquid saline organic waste is preferably saline wastewater generated in the industrial production process; in the invention, the liquid organic waste containing salt comprises inorganic salt and organic solvent, wherein the organic solvent preferably comprises one or more of aromatic hydrocarbon, aliphatic hydrocarbon, alicyclic hydrocarbon, halogenated hydrocarbon, alcohol, ether, ester, ketone and glycol derivative; the aromatic hydrocarbon preferably comprises one or more of benzene, toluene and xylene; the aliphatic hydrocarbon preferably comprises one or more of pentane, hexane and octane; the alicyclic hydrocarbon preferably comprises one or more of cyclohexane, cyclohexanone and toluene cyclohexanone; the halogenated hydrocarbon preferably comprises one or more of chlorobenzene, dichlorobenzene and dichloromethane; the alcohol preferably comprises one or more of methanol, ethanol and isopropanol; the ether preferably comprises one or both of diethyl ether and propylene oxide; the ester preferably comprises one or more of methyl acetate, ethyl acetate and propyl acetate; the ketone preferably comprises one or more of acetone, methyl butanone and methyl isobutyl ketone; the glycol derivative preferably includes one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether.
In the present invention, the salt-containing organic waste is preferably one, two or more salt-containing organic waste; that is, the organic waste containing salt may be treated alone or by mixing a plurality of organic waste containing salt.
In the present invention, the non-salt organic waste liquid is preferably a homogeneous system or a multiphase fluid; the non-salt organic waste liquid comprises organic waste liquid and water, the organic waste liquid is preferably a waste organic solvent, the waste organic solvent is preferably a compound containing hydrocarbon, and the waste organic solvent specifically comprises one or more of aromatic hydrocarbon, aliphatic hydrocarbon, alicyclic hydrocarbon, halogenated hydrocarbon, alcohol, ether, ester, ketone and glycol derivatives; the aromatic hydrocarbon preferably comprises one or more of benzene, toluene and xylene; the aliphatic hydrocarbon preferably comprises one or more of pentane, hexane and octane; the alicyclic hydrocarbon preferably comprises one or more of cyclohexane, cyclohexanone and toluene cyclohexanone; the halogenated hydrocarbon preferably comprises one or more of chlorobenzene, dichlorobenzene and dichloromethane; the alcohol preferably comprises one or more of methanol, ethanol and isopropanol; the ether preferably comprises one or both of diethyl ether and propylene oxide; the ester preferably comprises one or more of methyl acetate, ethyl acetate and propyl acetate; the ketone preferably comprises one or more of acetone, methyl butanone and methyl isobutyl ketone; the glycol derivative preferably comprises one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; the water content of the non-salt organic waste liquid is 20-60wt%, preferably 25-55wt%, more preferably 30-50wt%, and the heat value is 10000-30000J/g, preferably 15000-30000J/g, more preferably 20000-30000J/g. The moisture content of the non-salt organic waste liquid is the basis for ensuring that the salt-containing organic waste can be dissolved in the non-salt organic waste liquid, and the heat value requirement can meet the supply of a heat source in the subsequent gasification process.
In the present invention, the non-salt organic waste liquid is preferably one, two or more non-salt organic waste liquids; the non-salt organic waste liquid preferably comprises one or more of organic solvents generated in the processes of pharmacy, leather production, chemical synthesis and raw material cleaning. The non-salt organic waste liquid can be prepared from a single source or multiple sources.
In the invention, the mass ratio of water in the solid salt-containing organic waste to the non-salt organic waste liquid is preferably 0.1-2:1, more preferably 0.1-1:1, and even more preferably 0.5-1:1; the mass ratio of the organic waste liquid in the liquid salt-containing organic waste and the non-salt organic waste liquid is preferably 0.2-0.8:1, more preferably 0.3-0.7:1, and even more preferably 0.4-0.6:1. In the invention, the mixing process of the salt-containing organic waste and the non-salt organic waste liquid is based on the moisture content in the non-salt organic waste liquid, and the salt-containing organic waste is fully dissolved by mixing, so that the non-salt organic waste liquid is converted into salt-containing organic fluid.
In the present invention, the mixing of the salt-containing organic waste and the non-salt organic waste liquid is preferably: premixing part of the salt-containing organic waste and non-salt organic waste liquid, and then mixing the obtained salt-containing organic fluid with the rest of the salt-containing organic waste to obtain high-concentration inorganic salt mixed liquid; in the present invention, after premixing the part of the salt-containing organic waste and the non-salt organic waste liquid, the method preferably further comprises performing chemical analysis on the obtained salt-containing organic fluid; the chemical analysis preferably comprises: analyzing the saturated salt content and chemical components of the salt-containing organic fluid, and determining the adding amount of the subsequent salt-containing organic waste; the chemical components preferably include, but are not limited to, phosphorus content, fluorine content, silicon content, aluminum content, sulfur content, calcium content, and magnesium content. In the invention, the fluorine content of the salt-containing organic fluid is preferably less than 5wt%, the silicon content is less than 3wt%, the aluminum content is less than 3wt%, the sulfur content is less than or equal to 2wt%, the magnesium content is preferably less than 5wt%, the phosphorus content is preferably 0.1-5 wt%, and the calcium content is preferably 1-10 wt%. The method comprises the steps of mixing and dissolving the salt-containing organic waste and the non-salt organic waste liquid step by step, firstly preliminarily premixing to form salt-containing organic fluid, then supplementing the salt-containing organic waste to improve the inorganic salt concentration, and forming high-concentration inorganic salt mixed liquid, thereby improving the treatment capacity of single treatment of the salt-containing organic waste.
In the present invention, after the high-concentration inorganic salt mixed solution is obtained, it is preferable that an additive is further added to the high-concentration inorganic salt mixed solution; the additive is preferably at least one of limestone, coal dust and activated carbon; the limestone is used for removing impurities such as fluorine, silicon and the like, and the coal dust or the activated carbon can improve the heat value; the invention has no special requirement on the addition amount of the additive, and the additive is added according to the actual requirement, so that the content or the heat value of impurities such as fluorine, silicon and the like of the high-concentration inorganic salt mixed solution can meet the requirement. In the invention, the particle size of the pulverized coal is preferably 40-300 meshes, more preferably 100-200 meshes.
In the present invention, the concentration of the inorganic salt in the high-concentration inorganic salt mixture is 90% or more, preferably 95% or more, more preferably the saturated inorganic salt mixture; the high-concentration inorganic salt mixed solution has the fluorine content of less than 5wt%, the silicon content of less than 3wt%, the aluminum content of less than 3wt%, the sulfur content of less than or equal to 2wt%, the magnesium content of less than 5wt%, the phosphorus content of 0.1-5 wt%, the calcium content of 1-10 wt%, and the heat value of not less than 10000J/g. The invention controls the content of phosphorus in the range, so that phosphate radical can be generated in the gasification process of phosphorus, and further, the removal of calcium and magnesium plasma in the water body with high salt content is realized; the invention controls the fluorine content in the range, prevents the higher fluorine content from influencing the extraction process of the subsequent inorganic salt in the treatment process of the subsequent salt-containing organic waste, and simultaneously controls the calcium content in the range, and calcium ions in the high-concentration inorganic salt mixed solution generate calcium fluoride precipitation in the chilling water quenching process, thereby realizing the removal of fluorine ions; the invention controls the silicon and aluminum content in the above range, which can reduce the viscous state temperature in the water quenching slag melting process, thereby controlling the temperature of the gasification furnace; the invention controls the content of sulfur and magnesium in the range, can reduce the sulfate generated in the gasification process in a reasonable range, and is beneficial to improving the quality of the product salt.
After the high-concentration inorganic salt mixed solution is obtained, the high-concentration inorganic salt mixed solution is gasified and quenched by chilled water in sequence, and a gas-water mixture, first liquid-phase water (namely chilled water after use) and solid slag are respectively obtained. In the present invention, the gasification temperature is preferably based on the ash melting point of the insoluble matter in the high concentration inorganic salt mixture: when the ash melting point of the insoluble matters is higher than 1300 ℃, the gasification temperature is preferably 1350-1400 ℃, more preferably 1350-1380 ℃; when the ash melting point of the insoluble matters is lower than 1100 ℃, the gasification temperature is preferably 1050-1100 ℃, and more preferably 1070-1100 ℃; when the ash melting point of the insoluble matter is 1100-1250 ℃, the gasification temperature is preferably 50-100 ℃, more preferably 60-90 ℃, and even more preferably 70-80 ℃ higher than the ash melting point of the insoluble matter.
In the invention, the gasification pressure is preferably 0-10 MPa, more preferably 1-8 MPa, and even more preferably 2-6 MPa; the gasifying agent for gasification is preferably oxygen; the volume ratio (expressed as oxygen-material ratio) of the oxygen and the high-concentration inorganic salt mixed solution in the gasification process is preferably 300-600:1, more preferably 400-500:1, and even more preferably 450:1; the gasification equipment is preferably a gasifier. The invention generates synthesis gas by gasifying and pyrolyzing organic matters in organic wastes containing salt at high temperature, and the main components of the synthesis gas comprise CO and H 2 And CO 2 The method comprises the steps of carrying out a first treatment on the surface of the The volume fraction of CO in the synthesis gas is preferably more than or equal to 30%, H 2 The volume fraction of (2) is preferably not less than 30%.
In the invention, the heat value and ash melting point analysis and determination are preferably carried out on the high-concentration inorganic salt mixed solution before gasification; when the heat value of the high-concentration inorganic salt mixed solution is less than 10000J/g, preferably, non-salt organic waste liquid is added in the gasification process until the heat value meets the requirement; the additional non-salt organic waste liquid is preferably fed in a multi-channel manner. The ash melting point of the insoluble matters is determined by analyzing the ash melting point, and a reference basis is provided for temperature selection in the gasification process.
In the gasification process of the invention, the organic matter is converted into CO and CO 2 And H 2 The gas makes the gasification atmosphere present a strong reducing atmosphere, thereby leading the sulfate in the inorganic salt to generate H through reduction reaction 2 S, although part of the synthesis gas (CO, CO) 2 And H 2 ) But realizes the removal of most sulfate radicals and prevents the influence on the subsequent recycling process; and the inorganic matters in the high-concentration inorganic salt mixed solution form a molten state or a partial molten state; meanwhile, phosphate generated in the gasification process can remove calcium and magnesium ions, and the content of metal cations in the water body with high salt content is reduced.
In the invention, the mass flow ratio of the chilling water used for chilling water quenching to the high-concentration inorganic salt mixed solution is preferably 4-10:1, more preferably 5-9:1, and even more preferably 6-8:1. In the quenching process, molten or partial molten inorganic matters generated by gasification are contacted with the quenching water, water-soluble matters are transferred and converted into the quenching water, insoluble matters are converted into water quenching slag (solid slag), and the insoluble matters form a vitreous structure through water quenching treatment, so that the removal of insoluble inorganic salts in the salt-containing organic waste is realized. The invention adds the above-mentioned dosage of chilling water in the chilling water quenching process, can prevent crystallization salting out from happening.
After obtaining a gas-water mixture, first liquid-phase water and solid slag, the invention carries out gas-water separation on the gas-water mixture to respectively obtain synthesis gas and second liquid-phase water (namely, water phase obtained by gas-water separation). In the present invention, the apparatus for gas-water separation is preferably an industrial conventional column plate type gas-water separator.
In the present invention, the gas obtained after the gas-water separation is preferably scrubbed; the washing water is preferably fresh water or evaporated water generated by cooling when the water body with high salt content is subjected to reduced pressure distillation.
After the first liquid-phase water and the second liquid-phase water are obtained, the first liquid-phase water and the second liquid-phase water are mechanically filtered to obtain a water body with high salt content and water quenching fine slag respectively. In the present invention, the mechanical filtration is preferably a plate-frame filtration.
In the invention, the high-salt-content water body is an unsaturated high-salt-content water body, and the total content of potassium salt and sodium salt in the high-salt-content water body is not less than 15wt%, preferably 15-20 wt%; in the invention, when the total content of sodium salt and/or potassium salt in the filtrate obtained by mechanical filtration is lower than 15wt%, the filtrate is preferably recycled as chilled water for chilled water quenching until the total content of sodium salt and/or potassium salt in the filtrate obtained by mechanical filtration is not lower than 15wt%, and the filtrate is a water body with high salt content.
After the water body with high salt content is obtained, the water body with high salt content is concentrated, crystallized and separated in sequence to obtain sodium salt and/or potassium salt. In the present invention, the concentration method is preferably distillation under reduced pressure; the temperature of reduced pressure distillation is preferably 25-140 ℃, more preferably 50-80 ℃, and the pressure is preferably-200 to-50 KPa, more preferably-100 to-50 KPa; the reduced pressure distillation is preferably performed for a time period that the water content of the water body with high salt content is reduced to a precipitation point of sodium chloride. The method is characterized in that the water body with high salt content is distilled under reduced pressure to form saturated solution.
In the present invention, when the inorganic salts in the salt-containing organic waste are sodium and potassium salts, the crystallization separation is preferably: crystallizing the concentrated solution at a first temperature reduction to obtain sodium chloride, and crystallizing the concentrated solution at a second temperature reduction to obtain potassium chloride; the final temperature of the first cooling crystallization is preferably 60-100 ℃, more preferably 70-90 ℃, and further preferably 80 ℃; the final temperature of the second cooling crystallization is preferably 25-60 ℃, more preferably 35-60 ℃, and even more preferably 45-60 ℃. The invention uses the solubility difference of sodium salt and potassium salt at different temperatures to separate sodium salt and potassium salt in crystallization.
In the present invention, when the inorganic salt in the salt-containing organic waste is a sodium salt, the crystallization is separated into: and cooling the concentrated solution to 60-100 ℃ for crystallization to obtain sodium salt.
In the present invention, when the inorganic salt in the organic waste containing salt is a potassium salt, the crystallization is separated into: and cooling the concentrated solution to 25-60 ℃ for crystallization to obtain the potassium salt.
In the present invention, the sodium salt is preferably obtained by further comprising: and mixing the sodium salt, carbon dioxide and ammonia gas to perform double decomposition reaction to obtain ammonia chloride and sodium carbonate (alkali preparation method). The potassium salt obtained by the invention can be used for producing a downstream potassium salt product, and the sodium salt is used for preparing alkali, so that the resource utilization of the potassium salt and the sodium salt in the water body with high salt content is realized.
In the invention, the crystallization separation also obtains brine mother liquor; when the brine mother liquor contains bromide, the method further comprises the step of introducing chlorine into the brine mother liquor and then blowing out nitrogen to obtain bromine simple substance. In the invention, the mass ratio of the brine mother liquor to the chlorine is preferably 100:1-5, more preferably 100:2-4, and further preferably 100:3; the nitrogen gas is preferably blown out by a bubbling device.
In the invention, when the brine mother liquor also contains iodide, the method further comprises the step of mixing the residual mother liquor after nitrogen is blown out with an extractant for extraction to obtain an iodine simple substance. In the invention, the mass ratio of the mother liquor and the extractant remaining after nitrogen blowing is preferably 100:5-15, more preferably 100:8-12, and even more preferably 100:10; the extractant preferably comprises carbon tetrachloride.
In the present invention, the iodine-free mother liquor obtained after the extraction is preferably subjected to wastewater treatment. In the invention, brine mother liquor is obtained through crystallization and separation, bromine and iodine are further concentrated and enriched, and the brine mother liquor is subjected to brine bromine extraction by utilizing chlorine gas, so that bromine ions in the brine mother liquor are reduced into bromine simple substances, meanwhile, iodine ions are reduced into iodine simple substances, and then the iodine is extracted through extraction.
The invention realizes the high-efficiency utilization of the soluble inorganic salt in the salt-containing organic waste by organically combining the utilization mode of the water body with high salt content. According to the invention, firstly, sodium chloride and potassium chloride in the water body with high salt content are sequentially extracted, the sodium, potassium and chlorine contents in the water body are reduced, meanwhile, concentration of bromine and iodine in the water body is realized, and the concentrated brine mother liquor is sequentially extracted for the bromine and the iodine, so that high-efficiency extraction is realized.
The following describes the invention in detail with reference to examples for further illustration of the invention, but they should not be construed as limiting the scope of the invention.
Example 1
The solid salt-containing organic waste evaporated by the three-effect of the fertilizer plant is treated, and because a large amount of organic matters are contained in the water body of the evaporation mother liquor, the impurity salt generated by evaporation contains the organic matters, and the solid salt-containing organic waste is difficult to directly separate and purify. The main component of the solid organic waste containing salt is sodium chloride, and contains a certain amount of sodium sulfate, potassium sulfate, sodium iodide, sodium bromide and the like.
The non-salt organic waste liquid adopted in the treatment process of the embodiment is waste organic solvent generated by organically synthesizing vitamin C in pharmaceutical factories, the main components of the non-salt organic waste liquid are acetone, pyridine and the like, the water content of the non-salt organic waste liquid is 36wt%, the heat value of the non-salt organic waste liquid is 16587J/g, and the non-salt organic waste liquid meets the requirements and can be directly used.
First, solid salt-containing organic waste (the solid salt-containing organic waste accounts for 12wt% of the non-salt organic waste) is added into the non-salt organic waste liquid, and the solid salt-containing organic waste and the non-salt organic waste liquid are fully mixed to obtain salt-containing organic fluid, wherein the chemical compositions are shown in table 1.
TABLE 1 chemical composition of salt-containing organic fluids
| Composition of the components | Phosphorus content | Fluorine content | Calcium content | Magnesium content | Sulfur content | Silicon content | Aluminum content | Salt content |
| Proportion of | 4wt% | 2wt% | 2.5wt% | 3wt% | 2wt% | 2wt% | 2wt% | 11wt% |
The organic fluid containing salt meets the requirement of the preamble index; meanwhile, through measurement and analysis, the saturated salt content of the salt-containing organic fluid is 13.5wt%, the existing salt content of the salt-containing organic fluid is 11wt%, crystalline dirty salt with main components of sodium chloride and sodium carbonate is added to form a saturated solution, and a high-concentration inorganic salt mixed solution is obtained, and through detection, the heat value of the obtained high-concentration inorganic salt mixed solution is 15471J/g, and the ash melting point is 1121 ℃; because the heat value of the high-concentration inorganic salt mixed solution meets the gasification requirement, the gasification treatment is carried out by adopting independent feeding in the material gasification process.
In the gasification process, the temperature of the gasification furnace is controlled to be 1200 ℃, the pressure is controlled to be 3 MPa, the oxygen-material ratio is 550, the material treatment capacity is 10 tons/hour, and the chilling water is used for cooling the materialThe amount was 60 tons/hour; in the gasification process of the material, the volume fraction of each gas in the synthesis gas is H 2 38%, CO 40% and CO 2 22 percent; after gas-water separation, the synthesis gas is used for producing products such as ammonia water, ammonia bicarbonate and the like after gas washing.
Quenching water to obtain first liquid phase water (namely chilled water after use) and a gas-water mixture, separating the gas-water mixture by a gas-water separator to obtain second liquid phase water, mixing the first liquid phase water and the second liquid phase water, filtering to obtain a saline water body, wherein the salt content of the saline water body is 5wt% and is not satisfied with the extraction requirement, recycling the saline water body as chilled water, filtering the saline water body for 3 times to obtain clear liquid, entering a distillation device to remove part of water, controlling the temperature to be 100 ℃, cooling the water body when the water quantity of the water body is reduced to a potassium chloride precipitation point, and controlling the temperature of the water body to be 25 ℃, wherein the precipitated crystal is potassium chloride.
Sodium salt obtained by crystallization and separation is used for preparing sodium carbonate by a combined alkali method, mother liquor enters the next procedure to extract bromine, and the method specifically comprises the following steps: adding 10wt% of 30wt% hydrogen peroxide and 10wt% of concentrated hydrochloric acid into the mother solution, performing reaction treatment, performing stripping treatment on the water body by using a bubbling tower, absorbing the stripped gas by using a water body containing sulfur dioxide, enriching bromine, introducing 4% phosgene into the sulfur dioxide water body, extracting by using carbon tetrachloride, and extracting bromine after the step is finished.
The blown liquid is directly used for extracting and extracting iodine simple substance by carbon tetrachloride liquid. The iodine content of the residual iodine in the iodine-free mother liquor after the extraction is lower than 1wt%, the bromine content is lower than 1wt% and the total inorganic salt content is lower than 5wt%, and the iodine-free mother liquor is subjected to wastewater treatment.
Example 2
The main components of the liquid salt-containing organic waste produced by the hydrochloric acid production enterprises are sodium chloride, hydrochloric acid and water, and the liquid salt-containing organic waste has low heat value and high salt content. In the subsequent treatment process, the waste organic solvent with high heat value is utilized to improve the heat value of the waste organic solvent, so as to form slurry meeting the gasification requirement.
The waste organic solvent used in this example was waste organic solvent produced in leather production plant, its main component was DMF, its water content was 8% by weight, and its heat value was 18541J/g.
Both materials cannot be used independently, and the two materials are required to be mixed for use.
Through preliminary screening, liquid salt-containing organic waste and waste organic solvent are mixed according to the mass ratio of 2:3, the salt content of the obtained inorganic salt mixed solution is 10wt%, the salt is sodium chloride, the fluorine content of the mixed material is 0.1wt%, the silicon content is 0.3wt%, the aluminum content is 0.3wt%, the sulfur content is 0.2wt%, the magnesium content is 3wt%, the phosphorus content is 2wt%, the calcium content is 5wt%, the heat value is 19000J/g, and the ash melting point is 1140 ℃. And directly gasifying the obtained inorganic salt mixed solution.
In the gasification process, the temperature of the gasification furnace is controlled to be 1200 ℃, the pressure is 3 MPa, the oxygen-material ratio is 550, the material treatment capacity is 11 tons/hour, and the chilling water quantity is 60 tons/hour; the material generates synthesis gas in the gasification process, and the volume fraction of each component in the obtained synthesis gas is H 2 39%, CO 37% and CO 2 24 percent; after gas-water separation, the synthesis gas is used for producing products such as ammonia water, ammonia bicarbonate and the like after gas washing.
Quenching water to obtain first liquid phase water (namely chilled water after use) and a gas-water mixture, separating the gas-water mixture by a gas-water separator to obtain second liquid phase water, mixing the first liquid phase water with the second liquid phase water, filtering to obtain a salt-containing water body, wherein the salt content of the salt-containing water body is 6.5wt% and is not satisfied with the extraction requirement, the salt-containing water body is recycled as chilled water, the salt content of the salt-containing water body is 21wt% after 3 times of recycling, the high salt-containing water body is filtered by a plate frame to obtain clear liquid, the clear liquid enters a distillation device to remove part of water, the temperature is controlled to be 100 ℃, and the precipitated crystal is sodium chloride because the inorganic salt is only sodium chloride in the treatment process, and the subsequent process flow is not performed any more.
Comparative example 1
The solid salt-containing organic waste in example 1 was treated by incineration to remove organic matter from the solid salt-containing organic waste using conventional treatment methods, and the ash was landfill treated.
In example 1, the salt content of the solid salt-containing organic waste reaches more than 13.5wt%, the main component is chloride, a large amount of dioxin cancerogenic substances are generated in the incineration process, and the subsequent treatment and analysis of the gas are huge.
Comparative example 2
In order to test the influence of sulfur content on the extraction process, hazardous waste materials with higher sulfur content are added into the high-salt-content mixed solution in the embodiment 2, so that the sulfur content is more than 2%, and extraction is carried out according to the method in the embodiment 2, and as a result, the chilled water contains a large amount of sulfate radicals in the process of recycling the saline water, although the reaction in the gasification process is not obviously influenced, the sulfate radicals in the process of separating inorganic salts can reduce the purity of crystalline salts, and the extraction of sodium salts and potassium salts cannot be fully carried out.
According to the embodiment, the resource utilization method provided by the invention uses the organic waste containing salt and the organic waste liquid containing no salt as raw materials, all the technological processes are combined mutually, the prepared synthesis gas can be used for producing chemical products, inorganic salt is recovered, and efficient element level utilization of the organic waste containing salt is realized.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (10)
1. A method for recycling organic wastes containing salt comprises the following steps:
(1) Mixing the organic waste containing salt with the non-salt organic waste liquid to obtain a high-concentration inorganic salt mixed solution; the concentration of inorganic salt in the high-concentration inorganic salt mixed solution is more than 90% of the saturated concentration of inorganic salt; the fluorine content of the high-concentration inorganic salt mixed solution is less than 5wt%, the silicon content is less than 3wt%, the aluminum content is less than 3wt%, the sulfur content is less than or equal to 2wt%, the magnesium content is less than 5wt%, the phosphorus content is 0.1-5 wt%, the calcium content is 1-10 wt%, and the heat value is not less than 10000J/g; the inorganic salt in the salt-containing organic waste comprises sodium salt and/or potassium salt;
the non-salt organic waste liquid comprises organic waste liquid and water; the water content of the non-salt organic waste liquid is 20-60wt% and the heat value is 10000-30000J/g;
(2) Gasifying and quenching the high-concentration inorganic salt mixed solution in sequence to obtain a gas-water mixture, first liquid-phase water and solid slag respectively;
(3) Carrying out gas-water separation on the gas-water mixture to respectively obtain synthesis gas and second liquid phase water;
(4) Mechanically filtering the first liquid-phase water and the second liquid-phase water to obtain a water body with high salt content and water quenching slag respectively; the total content of potassium salt and/or sodium salt in the high-salt-content water body is not less than 15wt%;
(5) And concentrating and crystallizing and separating the water body with high salt content in sequence to obtain sodium salt and/or potassium salt.
2. The recycling method according to claim 1, wherein the organic waste liquid is a waste organic solvent, and the waste organic solvent is a hydrocarbon-containing compound;
the salt-containing organic waste is solid salt-containing organic waste or liquid salt-containing organic waste;
the mass ratio of water in the solid salt-containing organic waste to the non-salt organic waste liquid is 0.1-2:1;
the mass ratio of the organic waste liquid in the liquid saline organic waste to the organic non-saline waste liquid is 0.2-0.8:1.
3. The recycling method according to claim 1 or 2, characterized in that after obtaining a high-concentration inorganic salt mixture, further comprising adding an additive to the high-concentration inorganic salt mixture; the additive is at least one of limestone, coal dust and activated carbon.
4. The recycling method according to claim 1, wherein the gasification temperature is based on the ash melting point of insoluble substances in the high-concentration inorganic salt mixture: when the ash melting point of the insoluble matters is higher than 1300 ℃, the gasification temperature is 1350-1400 ℃;
when the ash melting point of the insoluble matters is lower than 1100 ℃, the gasification temperature is 1050-1100 ℃;
when the ash melting point of the insoluble matters is between 1100 and 1250 ℃, the gasification temperature is 50 to 100 ℃ higher than the ash melting point of the insoluble matters;
the gasification pressure is 0-10 Mpa; the gasified gasifying agent is oxygen; the volume ratio of the oxygen to the high-concentration inorganic salt mixed solution in the gasification process is 300-600:1.
5. The recycling method according to claim 1, wherein the mass flow ratio of the chilled water used for the chilled water quenching to the high-concentration inorganic salt mixed solution is 4-10:1.
6. The recycling method according to claim 1, wherein the concentration method is reduced pressure distillation; the temperature of the reduced pressure distillation is 25-140 ℃, and the pressure is-200 to-50 KPa.
7. The recycling method according to claim 1, wherein when the inorganic salts in the organic waste containing salt are sodium salt and potassium salt, the crystallization is separated into: crystallizing the concentrated solution at a first temperature reduction to obtain sodium salt, and crystallizing the concentrated solution at a second temperature reduction to obtain potassium salt; the final temperature of the first cooling crystallization is 60-100 ℃; the final temperature of the second cooling crystallization is 25-60 ℃;
when the inorganic salt in the salt-containing organic waste is sodium salt, the crystallization is separated into: cooling the concentrated solution to 60-100 ℃ for crystallization to obtain sodium salt;
when the inorganic salt in the salt-containing organic waste is a potassium salt, the crystallization is separated into: and cooling the concentrated solution to 25-60 ℃ for crystallization to obtain the potassium salt.
8. The method of claim 7, wherein the crystallization separation further yields a brine mother liquor; when the brine mother liquor contains bromide, the method further comprises the step of introducing chlorine into the brine mother liquor and then blowing out nitrogen to obtain bromine simple substance.
9. The recycling method according to claim 8, wherein when the brine mother liquor further contains iodide, the method further comprises mixing the mother liquor remaining after nitrogen is blown out with an extractant to extract, thereby obtaining elemental iodine.
10. The recycling method according to claim 1, wherein when the total content of sodium salt and/or potassium salt in the filtrate obtained by mechanical filtration is lower than 15wt%, the filtrate is recycled as chilled water for chilled water quenching until the total content of sodium salt and/or potassium salt in the filtrate obtained by mechanical filtration is not lower than 15wt%;
condensed water generated by the reduced pressure distillation is used as chilling water for chilling water quenching in a circulating way.
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