CN113117739B - Catalyst for treating wastewater and preparation method and application thereof - Google Patents
Catalyst for treating wastewater and preparation method and application thereof Download PDFInfo
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- CN113117739B CN113117739B CN202011612659.4A CN202011612659A CN113117739B CN 113117739 B CN113117739 B CN 113117739B CN 202011612659 A CN202011612659 A CN 202011612659A CN 113117739 B CN113117739 B CN 113117739B
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- treating wastewater
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 239000002351 wastewater Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- 239000000835 fiber Substances 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 38
- 239000011148 porous material Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- 238000004065 wastewater treatment Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 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 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 235000012241 calcium silicate Nutrition 0.000 claims description 4
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 229920002972 Acrylic fiber Polymers 0.000 claims description 2
- 238000005299 abrasion Methods 0.000 claims description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 claims description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 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 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 235000019794 sodium silicate Nutrition 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 235000019976 tricalcium silicate Nutrition 0.000 claims description 2
- 229910021534 tricalcium silicate Inorganic materials 0.000 claims description 2
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 description 13
- 238000009826 distribution Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 8
- 239000010865 sewage Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- BKHXUXAJEMYJPY-UHFFFAOYSA-N dichloro(dimethyl)silane;toluene Chemical compound C[Si](C)(Cl)Cl.CC1=CC=CC=C1 BKHXUXAJEMYJPY-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- UTXYQMBVYXGWOL-UHFFFAOYSA-N toluene trichloro(methyl)silane Chemical compound C[Si](Cl)(Cl)Cl.C1(=CC=CC=C1)C UTXYQMBVYXGWOL-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- -1 trimethylchlorosilane ethylbenzene Chemical compound 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7807—A-type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/643—
-
- B01J35/647—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention provides a catalyst for treating wastewater and a preparation method and application thereof, wherein the preparation method of the catalyst for treating wastewater comprises the steps of mixing inorganic silicon aluminum oxide, activated carbon, organic fiber chopped filaments, a binder and water in a contact manner, and performing molding and drying treatment to obtain a carrier B; and (3) treating the carrier B with an organic solvent and sodium hydroxide to obtain a composite carrier, then entering an active component to obtain a catalyst precursor, and finally contacting the catalyst precursor with an organosilane-containing solvent to obtain the catalyst after washing and drying. The catalyst prepared by the preparation method has the characteristics of good catalytic performance, strong wear resistance and high activity stability, and is beneficial to improving the removal rate of organic pollutants in wastewater.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a catalytic material for treating chemical wastewater and a preparation method thereof.
Background
A large amount of compound-rich sewage can be generated in the production process of chemical products, such as high-toxicity wastewater generated in the daily production process of pharmaceutical factories, agricultural factories, coal chemical enterprises and the like, and the wastewater is generally complex in chemical components, high in COD (chemical oxygen demand), good in salt content, strong in toxicity and poor in biochemistry.
At present, chemical wastewater is mostly treated by one or a combination of technologies of micro-electrolysis, chemical oxidation, flocculation, biochemistry and membrane technology, and in the technologies and the combination of technologies, the problems of sludge, secondary pollution, concentrated water and the like are generated, so that the treatment effect is not ideal. The catalytic oxidation method generates hydroxyl free radicals through catalysis, reacts with refractory organic pollutants in sewage, and thoroughly degrades pollutants into CO2 and H2O, thereby removing pollutants in the water. The common catalysts in the market such as ceramsite type and active carbon type have the characteristic of single pore distribution, and the narrow pore size distribution causes insufficient adsorption activity when complex organic components are treated, so that the catalytic activity of the catalyst is low. In order to further improve the removal of organic pollutants in the catalytic oxidation process, new catalytic materials with wide pore size distribution and high adsorption performance are developed, and effective enrichment of complex organic matters is improved, so that in-situ real-time catalytic degradation of the organic pollutants is realized on the surface of the catalyst, and the organic matters in the chemical wastewater are effectively removed.
CN201810389808.1 discloses a preparation method of an ozone-regenerable adsorbent, which takes one or two of molecular sieve and active carbon as adsorbent, adopts salt solution containing Mn, ce and La to load on the adsorbent, and calcines under the protection of nitrogen to obtain the ozone-regenerable adsorbent containing MnOx-CeOx-LaOx composite oxygen.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a catalyst for treating wastewater, and a preparation method and application thereof. The catalyst prepared by the preparation method has the characteristics of good catalytic performance, strong wear resistance and high activity stability, and is beneficial to improving the removal rate of organic pollutants in wastewater.
The first aspect of the invention provides a preparation method of a catalyst for treating wastewater, which comprises the following steps:
(1) Roasting inorganic silicon aluminum oxide to obtain a material A;
(2) The material A, the activated carbon, the organic fiber chopped filaments, the binder and the water are contacted, and after being uniformly mixed, the carrier B is obtained through further molding and drying treatment;
(3) The carrier B is contacted with an organic solvent, and organic fibers in the carrier B are removed by dissolution to obtain a carrier C;
(4) Adding the carrier C into a sodium hydroxide solution for treatment, washing to neutrality, and drying and roasting the solid material to obtain a composite carrier D;
(5) Introducing an active metal component into the composite carrier D, and then drying and roasting to obtain a catalyst precursor E;
(6) The catalyst precursor E is contacted with an organosilane-containing solvent for treatment, and then washed and dried to obtain the catalyst.
In the preparation method of the catalyst for treating wastewater, the inorganic silicon aluminum oxide in the step (1) is in a powder form, the weight content of silicon dioxide and aluminum oxide is higher than 80wt%, and the content of aluminum oxide is higher than 25wt%; the specific surface area of the inorganic silicon aluminum oxide is more than 50m 2 And/g, wherein the pore volume of the Kong Rongji pores with the pore diameter of 5.0-15.0 nm accounts for more than 80% of the total pore volume, and the average pore diameter is 1.7-35.0 nm.
In the preparation method of the catalyst for treating wastewater, the roasting treatment temperature in the step (1) is 500-1200 ℃, and the treatment time is 2-12 h.
In the preparation method of the catalyst for treating wastewater, the length of the organic fiber chopped filaments in the step (2) is 2-5 mm, and the diameter is 10-70 nm. The organic fiber is selected from one or more of polyester fiber, acrylic fiber and polyvinyl alcohol fiber, and can be dissolved by an organic solvent.
In the preparation method of the catalyst for treating wastewater, the binder in the step (2) is one or more of silicate inorganic binders and phosphate inorganic binders. Further preferably, the silicate-based inorganic binder may be one or more of aluminum silicate, sodium silicate, calcium silicate, dicalcium silicate and tricalcium silicate, preferably sodium silicate and aluminum silicate; the phosphate inorganic binder can be one or more of aluminum phosphate, aluminum dihydrogen phosphate, sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate, and is preferably aluminum dihydrogen phosphate and sodium tripolyphosphate.
In the preparation method of the catalyst for treating wastewater, the active carbon in the step (2) is powdery active carbon prepared from wood, coal and fruit shells serving as raw materials, and the specific surface area is 500-3000 m 2 And/g, the average pore diameter is 0.5-4.0 nm, and the pore volume of the pores with the pore diameter of Kong Rongji of 1.5-3.5 nm accounts for more than 90% of the total pore volume.
In the preparation method of the catalyst for treating wastewater, in the step (2), the inorganic silicon aluminum oxide, the activated carbon, the organic fiber chopped filaments and the binder are mixed according to the mass ratio of 10-40: 30-65: 5-15: 2 to 5.
In the preparation method of the catalyst for treating wastewater, the drying temperature in the step (2) is 50-150 ℃ and the time is 2-12 h.
In the preparation method of the catalyst for treating wastewater, the organic solvent in the step (3) is one or more of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), chloroform and acetone. The weight ratio of the organic solvent to the carrier B is 2-10.
In the preparation method of the catalyst for treating wastewater, the concentration of the sodium hydroxide solution in the step (4) is as follows: the Si molar ratio is 3-3.5, wherein the concentration of the NaOH solution is 7.5-10wt%.
In the preparation method of the catalyst for treating wastewater, the drying temperature in the step (4) is 50-90 ℃ and the drying time is 2-24 hours.
In the preparation method of the catalyst for treating wastewater, the roasting temperature in the step (4) is 300-1000 ℃, the roasting time is 2-10 h, and the roasting is performed under the condition of nitrogen or inert gas.
In the preparation method of the catalyst for treating wastewater according to the present invention, the method of introducing the active metal component into the composite carrier D in the step (5) is any conventional method existing in the art, such as impregnation method, kneading method, etc., preferably impregnation method. The active metal component loaded on the carrier by adopting an impregnation method is manufactured by adopting a conventional impregnation method, and a spray impregnation method, a saturation impregnation method or a supersaturation impregnation method can be adopted. The method for supporting the active metal component on the carrier is, for example, an impregnation method, which comprises preparing a solution of the active metal-containing compound and impregnating the carrier with the solution. The active metal is the combination of one or two of Cu and Mn and Ce. The compound containing active metal is a salt solution containing active metal, and can be one or more of sulfate, nitrate, acetate and chloride.
In the preparation method of the catalyst for treating wastewater, the organosilane-containing solvent in the step (6) is a mixed solution of organosilane and organic solvent, and the content of organosilane in the mixed solution is 2-20wt%; wherein the organosilane is one or more of trimethylchlorosilane, dimethyldichlorosilane and methyltrichlorosilane; the organic solvent is one or more of benzene, toluene, ethylbenzene and acetone.
In the preparation method of the catalyst for treating wastewater, the treatment condition in the step (6) is that a catalyst precursor E is placed in a container at 20-40 ℃ and is circularly treated by using a solvent containing organosilane, wherein the treatment time is 1-20 hours, preferably 1-8 hours. The dosage ratio of the catalyst precursor E to the organosilane-containing solvent is 0.1-1.
In the preparation method of the catalyst for treating wastewater, in the step (6), the washing is performed by ethanol, preferably more than 95wt% of ethanol, until no chloride ions exist, and the washing is performed and then the catalyst is dried at 50-100 ℃.
The invention also provides a catalyst for treating wastewater, which is prepared by the preparation method, wherein the active components of the catalyst are the combination of one or two of Cu and Mn and Ce; the carrier is a composite carrier consisting of active carbon, inorganic silicon aluminum oxide, a 4A molecular sieve and a binder; the content of the active metal Cu and/or Mn oxide is 1-15% and the content of Ce oxide is 1-15% based on the weight of the catalyst.
The catalyst for treating wastewater has the following properties: specific surface area of 200-1000 m 2 Per gram, the pore volume is 0.3-1.8 cm 3 /g, abrasion rate<3wt% and the side pressure strength is 100-250N/cm.
The catalyst for treating wastewater has regular geometric shape, preferably spherical shape and bar shape, particle diameter of 0.5-10 mm and particle length of 0.5-15 mm.
In the catalyst for treating wastewater, the composite carrier has a three-dimensional mutual through hole structure, wherein the three-dimensional mutual through hole structure is formed by removing organic fibers contained in a precursor of the composite carrier by chopping and shredding, wherein the total holes Rong Ji are 15% -45% of holes with the diameters of 0.1-1.5 nm, 20% -40% of holes with the diameters of 1.5-5 nm and 20% -50% of holes with the diameters of 5-50 nm.
In a third aspect, the present invention provides a wastewater treatment method comprising reacting wastewater and an oxidizing agent in a reactor in contact with the above-described catalyst for treating wastewater.
In the wastewater treatment method, the oxidant is one or more of air, oxygen, ozone and hydrogen peroxide. The amount of the oxidizing agent is one ten thousandth to one hundredth of the weight of the treated wastewater.
In the wastewater treatment method of the present invention, the contact reaction may be continuous or batch.
In the wastewater treatment method, when air or oxygen is used as an oxidant, the reaction temperature is 120-260 ℃, the reaction pressure is 0.3-9.0 MPa, the reaction time is 0.5-3.0 h, and the oxygen amount is 1-3 times of the theoretical material for completely oxidizing the organic matters in the wastewater. When ozone or peroxide is used as oxidant, the reaction is carried out at normal temperature and normal pressure, the ozone content is 10-100 mg/L, the peroxide usage amount is 1-3 times of the organic matter complete oxidation theoretical amount, and the reaction time is 0.5-3.0 h.
The method can treat chemical wastewater continuously or intermittently, effectively reduce COD and improve the biochemical value of the wastewater.
Compared with the prior art, the catalyst for treating wastewater, and the preparation method and application thereof provided by the invention have the following advantages:
1. the method is used for preparing the catalyst for treating the wastewater, the soluble chopped organic fiber is mixed with the carrier matrix before molding, and is further dissolved and removed by an organic solvent after molding and curing, so that a multi-level aperture through-hole structure can be generated, which is beneficial to the diffusion of reactants and products in the hole, and the mass transfer effect is improved; the inorganic silicon aluminum oxide with a macroporous structure in the precursor is subjected to hydro-thermal treatment by adopting a sodium hydroxide solution to carry out crystal transformation to generate a microporous structure 4A molecular sieve, wherein the aperture is 0.1-1.5 nm, so that the micropore content in the carrier is increased, and a higher surface area is provided, thereby improving the reaction rate; treatment with organosilane helps the resulting 4A molecular sieve to further increase hydrophobicity, thereby enhancing adsorption properties to organics.
2. The invention is used for preparing the catalyst for treating wastewater, and provides good structural support and rich pore structures after heat treatment by adopting inorganic silicon aluminum oxide and adhesive; the active carbon has rich surface area and adsorptivity, and provides good adsorptivity for the catalyst so as to provide catalytic active sites; the carrier surface layer is formed by transferring inorganic silicon aluminum oxide into a 4A molecular sieve to improve the rapid adsorption capacity of the material; the multistage aperture through-hole channel structure enhances the mass transfer effect of the carrier, and the increased hydrophobicity is beneficial to enhancing the adsorption of the material on organic matters in the sewage.
Detailed Description
The preparation method of the present invention will be further described with reference to specific examples, but the scope of the present invention is not limited to the examples.
In the embodiment and the comparative example of the invention, the pore volume, the specific surface area and the pore distribution are measured by adopting a low-temperature liquid nitrogen physical adsorption method. In the invention, the weight percent is the mass fraction. In the examples and comparative examples of the present invention, the relative crystallinity was obtained by an X-ray diffraction method (Xu Ruren, pang Wenqin, etc.. Molecular sieves and porous materials chemistry. Beijing: science Press. 2014).
The specific surface area of the commercial powdery coconut activated carbon used in the invention is 920m 2 Per gram, pore volume 1.0cm 3 Per gram, average pore radius of 1.1nm, iodine adsorption value of 700mg/g, particle diameter of 45 μm. The specific surface area of the inorganic oxide composite soil used in the invention is 105m 2 The mass ratio of the silica to the alumina was 3:2 and the particle diameter was 45. Mu.m.
Example 1
After a certain amount of inorganic silicon aluminum oxide is treated at 1100 ℃, the inorganic silicon aluminum oxide, active carbon, polyester fiber, 20% silica sol and a proper amount of water are fully mixed and then kneaded, extruded, dried at 100 ℃ for 6 hours, treated at 330 ℃ under nitrogen, circularly treated for 5 hours by using acetone with the amount which is 5 times that of the carrier at normal temperature, subjected to solid-liquid separation, organic solvent in solid particles is fully removed at 50 ℃, the obtained dry solid particles are added into sodium hydroxide solution, the sodium hydroxide solution is circularly treated for 5 hours, filtered, the obtained solid particles are washed to be neutral by using distilled water, dried at 100 ℃ for 6 hours, roasted at 600 ℃ for 5 hours under nitrogen, cooled to obtain carrier ZA, the solution containing active metal is used for quantitatively loading metal components, dried at 100 ℃ for 6 hours, roasted at 500 ℃ for 5 hours under nitrogen, the catalyst precursor is obtained, the catalyst precursor is soaked in trimethylchlorosilane ethylbenzene solution for 5 hours, the solution is circularly treated, filtered and dried in vacuum, and the catalyst A is obtained after the steps of treatment. The amounts of reagents used in the preparation are shown in Table 1, the pore distribution of the support is shown in Table 2, and the catalyst properties are shown in Table 3.
Example 2
After a certain amount of inorganic silicon aluminum oxide is treated at 700 ℃, the inorganic silicon aluminum oxide, active carbon, polyester fiber, 25% silica sol and a proper amount of water are fully mixed and then kneaded, extruded, dried at 110 ℃ for 5 hours, treated at 300 ℃ under nitrogen protection for 8 hours, the carrier is circularly treated for 5 hours by using DMF with the amount which is 4 times that of the carrier at normal temperature, solid-liquid separation is carried out, organic solvent in solid particles is fully removed at 60 ℃, the obtained dry solid particles are added into sodium hydroxide solution, the sodium hydroxide solution is circularly treated for 5 hours, filtration is carried out, the obtained solid particles are washed to be neutral by using distilled water, dried at 110 ℃ for 6 hours, roasted at 700 ℃ under nitrogen protection for 4 hours, the carrier ZB is obtained after cooling, the active metal-containing solution is quantitatively loaded with metal components, dried at 90 ℃ for 6 hours, roasted at 500 ℃ under nitrogen protection for 5 hours, the catalyst precursor is soaked in dimethyl dichlorosilane toluene solution for 5 hours, the solution is circularly treated, filtered, and dried in vacuum, and the catalyst B is obtained after vacuum drying. The amounts of reagents used in the preparation are shown in Table 1, the pore distribution of the support is shown in Table 2, and the catalyst properties are shown in Table 3.
Example 3
After a certain amount of inorganic silicon aluminum oxide is treated at 900 ℃, the inorganic silicon aluminum oxide, active carbon, polyvinyl alcohol fiber, 20% water glass and a proper amount of water are fully mixed and then kneaded, extruded, dried at 90 ℃ for 8 hours, treated at 315 ℃ for 8 hours under nitrogen protection, the carrier is circularly treated for 5 hours at normal temperature by using DMSO with the amount which is 4 times that of the carrier, solid-liquid separation is carried out, organic solvent in solid particles is fully removed at 80 ℃, the obtained dry solid particles are added into sodium hydroxide solution, the sodium hydroxide solution is circularly treated for 8 hours, filtration is carried out, the obtained solid particles are washed to be neutral by using distilled water, dried at 110 ℃ for 6 hours, roasted at 800 ℃ under nitrogen protection for 4 hours, the carrier ZC is obtained after cooling, the active metal-containing solution is quantitatively loaded with metal components, dried at 90 ℃ for 8 hours, roasted at 600 ℃ for 5 hours under nitrogen protection, the catalyst precursor is obtained after being soaked in methyl trichlorosilane toluene solution for 5 hours, the solution is circularly treated, filtered, and dried in vacuum, and the catalyst C is obtained after vacuum drying. The amounts of reagents used in the preparation are shown in Table 1, the pore distribution of the support is shown in Table 2, and the catalyst properties are shown in Table 3.
Example 4
According to the proportion of example 2, carrier ZD and catalyst D were obtained without adding polyester fibers during the preparation. The amounts of reagents used in the preparation are shown in Table 1, the pore distribution of the support is shown in Table 2, and the catalyst properties are shown in Table 3.
Comparative example 1
According to the active carbon: silicon-aluminum composite oxide: the carrier ZDA and catalyst DA were prepared in the same manner as in example 2, except that the ratio of the 4A molecular sieve was 30:35:35, alkali-soluble fiber was not added, alkali treatment was not performed, and silane treatment was not used. The support pore distribution is shown in Table 2 and the catalyst properties are shown in Table 3.
TABLE 1 amount of reagents used in preparation procedure
| Catalyst numbering | A | B | C | D | DA |
| Silicon-aluminum composite oxide g | 619 | 818 | 1030 | 818 | 839 |
| Organic fiber g | 38 | 130 | 348 | 0 | 0 |
| Activated carbon g | 69 | 329 | 1030 | 329 | 335 |
| Sodium hydroxide, g | 671 | 886 | 1116 | 886 | 0 |
| Silane amount, g | 43 | 143 | 387 | 143 | 0 |
TABLE 2 distribution of support pores
| Pore distribution | ZA | ZB | ZC | ZD | ZDA |
| 0~1.5nm | 39.29% | 31.53% | 22.65% | 34.95% | 36.27% |
| 1.5~5nm | 23.03% | 27.30% | 32.19% | 27.93% | 26.91% |
| 5~50nm | 37.69% | 41.17% | 45.16% | 37.12% | 36.82% |
TABLE 3 catalyst physico-chemical properties
| Catalyst numbering | A | B | C | D | DA |
| CeO 2 ，wt% | 5.27 | 2.36 | 6.53 | 2.30 | 2.31 |
| CuO，wt% | 10.66 | 4.34 | - | 4.39 | 4.38 |
| MnO 2 ，wt% | - | - | 12.81 | - | - |
| Specific surface area, m 2 /g | 168 | 331 | 372 | 316 | 339 |
| Pore volume, mL/g | 0.15 | 0.26 | 0.23 | 0.25 | 0.23 |
As can be seen from the physical and chemical properties of the carrier and the catalyst in tables 2 and 3, the pore distribution of the carrier migrates to the macropores after the organic fiber is added for treatment; the specific surface area of the catalyst is increased, and the physicochemical property of the catalyst is improved well.
The treatment method of the oily sewage comprises the following steps: the catalyst is filled in a fixed bed, the oily sewage is treated by a single-pass one-time ozone catalytic oxidation process at normal temperature and pressure, the COD of the oily sewage is 450mg/L, and the treatment condition airspeed is 0.67h -1 The ozone adding amount is 900mg/L. The results of the treatment after 100h and 1000h are shown in Table 4.
TABLE 4 ozone catalytic oxidation treatment results
| Catalyst | A | B | C | D | DA |
| COD of effluent after 100h, mg/L | 76 | 73 | 71 | 106 | 121 |
| COD of the effluent after 1000 hours, mg/L | 77 | 75 | 72 | 108 | 125 |
As can be seen from the treatment results in Table 4, the catalyst obtained after the treatment by adding the organic fiber has good treatment activity and stability in the treatment of oily sewage.
Claims (26)
1. The preparation method of the catalyst for treating wastewater comprises the following steps:
(1) Roasting inorganic silicon aluminum oxide to obtain a material A;
(2) The material A, the activated carbon, the organic fiber chopped filaments, the binder and the water are contacted, and after being uniformly mixed, the carrier B is obtained through further molding and drying treatment; the organic fiber is selected from one or more of polyester fiber, acrylic fiber and polyvinyl alcohol fiber, and can be dissolved by an organic solvent;
(3) The carrier B is contacted with an organic solvent, and organic fibers in the carrier B are removed by dissolution to obtain a carrier C;
(4) Adding the carrier C into a sodium hydroxide solution for treatment, washing to neutrality, and drying and roasting the solid material to obtain a composite carrier D;
(5) Introducing an active metal component into the composite carrier D, and then drying and roasting to obtain a catalyst precursor E;
(6) The catalyst precursor E is contacted with an organosilane-containing solvent for treatment, and then washed and dried to obtain the catalyst.
2. The method for preparing a catalyst for treating wastewater according to claim 1, wherein: the inorganic silica alumina in step (1) is in the form of a powder, the weight content of silica and alumina being greater than 80wt%, and wherein the alumina content is greater than 25wt%.
3. The method for preparing a catalyst for treating wastewater according to claim 1, wherein: the roasting treatment temperature in the step (1) is 500-1200 ℃ and the treatment time is 2-12 h.
4. The method for preparing a catalyst for treating wastewater according to claim 1, wherein: the length of the organic fiber chopped filaments in the step (2) is 2-5 mm, and the diameter is 10-70 nm.
5. The method for preparing a catalyst for treating wastewater according to claim 1, wherein: the binder in the step (2) is one or more of silicate inorganic binders and phosphate inorganic binders.
6. The method for preparing a catalyst for treating wastewater according to claim 5, wherein: the silicate inorganic binder is one or more of aluminum silicate, sodium silicate, calcium silicate, dicalcium silicate and tricalcium silicate; the phosphate inorganic binder is one or more of aluminum phosphate, aluminum dihydrogen phosphate, sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate.
7. The method for preparing a catalyst for treating wastewater according to claim 6, wherein: the silicate inorganic binder is sodium silicate and aluminum silicate; the phosphate inorganic binder is aluminum dihydrogen phosphate and sodium tripolyphosphate.
8. The method for preparing a catalyst for treating wastewater according to claim 1, wherein: in the step (2), the mass ratio of the inorganic silicon aluminum oxide, the activated carbon, the organic fiber chopped filaments and the binder is 10-40: 30-65: 5-15: 2 to 5.
9. The method for preparing a catalyst for treating wastewater according to claim 1, wherein: the drying temperature in the step (2) is 50-150 ℃ and the time is 2-12 h.
10. The method for preparing a catalyst for treating wastewater according to claim 1, wherein: the organic solvent in the step (3) is one or more of N, N-dimethylformamide, dimethyl sulfoxide, chloroform and acetone; the weight ratio of the organic solvent to the carrier B is 2-10.
11. The method for preparing a catalyst for treating wastewater according to claim 1, wherein: the concentration of the sodium hydroxide solution in step (4) is determined according to NaOH: the Si molar ratio is 3-3.5, wherein the concentration of the NaOH solution is 7.5-10wt%.
12. The method for preparing a catalyst for treating wastewater according to claim 1, wherein: the drying temperature in the step (4) is 50-90 ℃ and the drying time is 2-24 h.
13. The method for preparing a catalyst for treating wastewater according to claim 1, wherein: the roasting temperature in the step (4) is 300-1000 ℃ and the roasting time is 2-10 h, and the roasting is carried out under the condition of nitrogen or inert gas.
14. The method for preparing a catalyst for treating wastewater according to claim 1, wherein: the active metal in the step (5) is a combination of one or two of Cu and Mn and Ce.
15. The method for preparing a catalyst for treating wastewater according to claim 1, wherein: the organic silane-containing solvent in the step (6) is a mixed solution of organic silane and organic solvent, and the content of the organic silane in the mixed solution is 2-20wt%; wherein the organosilane is one or more of trimethylchlorosilane, dimethyldichlorosilane and methyltrichlorosilane; the organic solvent is one or more of benzene, toluene, ethylbenzene and acetone.
16. The method for preparing a catalyst for treating wastewater according to claim 1, wherein: the treatment condition in the step (6) is that the catalyst precursor E is placed in a container at the temperature of 20-40 ℃ and is circularly treated by using a solvent containing organosilane, and the treatment time is 1-20 h; the dosage ratio of the catalyst precursor E to the organosilane-containing solvent is 0.1-1.
17. The method for preparing a catalyst for treating wastewater according to claim 1, wherein: the treatment condition in the step (6) is that the catalyst precursor E is placed in a container at the temperature of 20-40 ℃ and is circularly treated by using a solvent containing organosilane, and the treatment time is 1-8 h; the dosage ratio of the catalyst precursor E to the organosilane-containing solvent is 0.1-1.
18. The method for preparing a catalyst for treating wastewater according to claim 1, wherein: the washing in the step (6) is ethanol washing until no chloridion exists.
19. The method for preparing a catalyst for treating wastewater according to claim 1, wherein: the washing in the step (6) is performed with 95wt% or more ethanol until no chloride ions are present.
20. A catalyst for treating wastewater obtained by the production method according to any one of claims 1 to 19, wherein the catalyst active component is a combination of Ce and one or both of Cu and Mn; the carrier is a composite carrier consisting of active carbon, inorganic silicon aluminum oxide, a 4A molecular sieve and a binder; the content of the active metal Cu and/or Mn oxide is 1-15% and the content of Ce oxide is 1-15% based on the weight of the catalyst.
21. The catalyst for treating wastewater according to claim 20, wherein: the properties of the catalyst are as follows: specific surface area of 200-1000 m 2 Per gram, the pore volume is 0.3-1.8 cm 3 /g, abrasion rate<3wt% and the side pressure strength is 100-250N/cm.
22. The catalyst for treating wastewater according to claim 20, wherein: the composite carrier has a three-dimensional mutual through hole structure, wherein the total holes Rong Ji are formed by removing organic fibers contained in a precursor of the composite carrier in a short cut manner, wherein the holes with the diameters of 0.1-1.5 nm account for 15% -45%, the holes with the diameters of 1.5-5 nm account for 20% -40%, and the holes with the diameters of 5-50 nm account for 20% -50%.
23. A method of treating wastewater by reacting the wastewater and an oxidant in a reactor in contact with a catalyst as claimed in any one of claims 20 to 22 for treating wastewater.
24. The wastewater treatment method according to claim 23, wherein: the oxidant is one or more of air, oxygen, ozone and hydrogen peroxide; the amount of the oxidizing agent is one ten thousandth to one hundredth of the weight of the treated wastewater.
25. The wastewater treatment method according to claim 24, wherein: when air or oxygen is used as an oxidant, the reaction temperature is 120-260 ℃, the reaction pressure is 0.3-9.0 MPa, the reaction time is 0.5-3.0 h, and the oxygen amount is 1-3 times of the theoretical material for completely oxidizing the organic matters in the wastewater.
26. The wastewater treatment method according to claim 24, wherein: when ozone or peroxide is used as oxidant, the reaction is carried out at normal temperature and normal pressure, the ozone content is 10-100 mg/L, the peroxide usage amount is 1-3 times of the organic matter complete oxidation theoretical amount, and the reaction time is 0.5-3.0 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5403809A (en) * | 1992-12-21 | 1995-04-04 | W. R. Grace & Co.-Conn. | Composite inorganic supports containing carbon for bioremediation |
| CN106975473A (en) * | 2017-05-27 | 2017-07-25 | 苏州思美特表面材料科技有限公司 | The supported materials catalyst of network structure |
| CN108786721A (en) * | 2017-05-02 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of composite adsorbing material and preparation method thereof |
| CN109718797A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
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| US8381738B2 (en) * | 2003-12-22 | 2013-02-26 | Philip Morris Usa Inc. | Composite materials and their use in smoking articles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5403809A (en) * | 1992-12-21 | 1995-04-04 | W. R. Grace & Co.-Conn. | Composite inorganic supports containing carbon for bioremediation |
| CN108786721A (en) * | 2017-05-02 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of composite adsorbing material and preparation method thereof |
| CN106975473A (en) * | 2017-05-27 | 2017-07-25 | 苏州思美特表面材料科技有限公司 | The supported materials catalyst of network structure |
| CN109718797A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
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Effective date of registration: 20231117 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |