CN115178074B - Catalytic extraction sludge amino acid carbon capturing functional fertilizer release column and preparation method and using method thereof - Google Patents
Catalytic extraction sludge amino acid carbon capturing functional fertilizer release column and preparation method and using method thereof Download PDFInfo
- Publication number
- CN115178074B CN115178074B CN202210808800.0A CN202210808800A CN115178074B CN 115178074 B CN115178074 B CN 115178074B CN 202210808800 A CN202210808800 A CN 202210808800A CN 115178074 B CN115178074 B CN 115178074B
- Authority
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- China
- Prior art keywords
- resin
- aluminum
- magnesium
- amino acid
- column
- Prior art date
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- 150000001413 amino acids Chemical class 0.000 title claims abstract description 111
- 239000010802 sludge Substances 0.000 title claims abstract description 84
- 239000003337 fertilizer Substances 0.000 title claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 22
- 238000000605 extraction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 224
- 229920005989 resin Polymers 0.000 claims abstract description 224
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 154
- 239000004005 microsphere Substances 0.000 claims abstract description 95
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 89
- 238000001179 sorption measurement Methods 0.000 claims abstract description 89
- 239000002131 composite material Substances 0.000 claims abstract description 81
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 78
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 78
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000945 filler Substances 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 126
- -1 aluminum ion Chemical class 0.000 claims description 71
- 239000000243 solution Substances 0.000 claims description 63
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 60
- 239000011777 magnesium Substances 0.000 claims description 56
- 229910052749 magnesium Inorganic materials 0.000 claims description 56
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 55
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 51
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims description 29
- GSWGDDYIUCWADU-UHFFFAOYSA-N aluminum magnesium oxygen(2-) Chemical compound [O--].[Mg++].[Al+3] GSWGDDYIUCWADU-UHFFFAOYSA-N 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 25
- 229920006395 saturated elastomer Polymers 0.000 claims description 25
- 238000007789 sealing Methods 0.000 claims description 25
- 229910052719 titanium Inorganic materials 0.000 claims description 24
- 239000010936 titanium Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 239000006228 supernatant Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 14
- 238000010926 purge Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- 238000003958 fumigation Methods 0.000 claims description 10
- 238000007664 blowing Methods 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003546 flue gas Substances 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 239000003729 cation exchange resin Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229920000180 alkyd Polymers 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 150000003609 titanium compounds Chemical class 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000003621 irrigation water Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 238000004364 calculation method Methods 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000012271 agricultural production Methods 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 235000001014 amino acid Nutrition 0.000 description 89
- 238000005516 engineering process Methods 0.000 description 7
- 235000018102 proteins Nutrition 0.000 description 7
- 102000004169 proteins and genes Human genes 0.000 description 7
- 108090000623 proteins and genes Proteins 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000035425 carbon utilization Effects 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 238000007696 Kjeldahl method Methods 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 230000004720 fertilization Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/06—Treatment of sludge; Devices therefor by oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- 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
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
-
- 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C11/00—Other nitrogenous fertilisers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D7/00—Fertilisers producing carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Fertilizers (AREA)
Abstract
A release column for capturing functional fertilizer by catalyzing and extracting sludge amino acid and a preparation method and a use method thereof belong to the technical fields of ecological environment and agriculture. The catalytic extraction sludge amino acid carbon trapping functional fertilizer releasing column comprises a column tube, catalytic adsorption trapping filler filled in the column tube, and filter plates and corresponding connectors arranged at two ends of the column tube. The catalytic adsorption trapping filler is resin aluminum magnesium titanate composite porous microspheres with functions of catalyzing ozone oxidation to break sludge and adsorbing enriched amino acids, and absorbs and traps carbon dioxide, so that when water is introduced, the adsorbed enriched amino acids and the trapped carbon dioxide can be eluted, and the functional fertilizer is obtained by releasing and dissolving the adsorbed enriched amino acids and the trapped carbon dioxide in the water. When the water purifying device is used, the release column is connected into the water pipeline, and carbon dioxide and amino acid in the release column are uniformly eluted and released through water flow, so that the water purifying device is used for agricultural production. The process can realize sludge treatment such as sludge cracking, amino acid enrichment and recovery, carbon dioxide trapping, fertilizer utilization of sludge amino acid and carbon dioxide in one step, is simple and stable, has low energy consumption and no secondary pollution, and is easy to realize industrial production.
Description
Technical Field
The invention belongs to the technical fields of ecological environment and agriculture, and particularly relates to a carbon capturing functional fertilizer release column for catalyzing and extracting sludge amino acid, a preparation method and a use method thereof.
Background
The disposal of the sludge is a recognized problem in the field of water treatment, the sludge contains rich nutritional ingredients such as protein, the protein is broken, and the extraction of amino acids in the sludge becomes a research hot spot. At present, the extraction of amino acid in sludge mainly adopts physical (such as ultrasonic and heating), chemical (such as ozone oxidation, alkali hydrolysis, acid hydrolysis and catalytic oxidation) or biological (such as protease hydrolysis) methods to crack sludge protein, release amino acid, and then the separation and recovery (Tian Ganpei, etc., a method for extracting mixed amino acid by mild hydrolysis of dehydrated sludge, 201910858842.3; su Ruijing, enzymatic hydrolysis of residual sludge to prepare protein-amino acid and mechanism research thereof, doctor's theory of east China university paper, 2013; li Na, influence rules and mechanism research of different pretreatment methods on the types and contents of amino acid in sludge dehydration, science and technology's theory of China paper, 2021; jie, etc., and the research progress of protein recovery technology based on sludge cracking, applied chemical industry, 2021,50 (2): 438-443). The technologies are carried out by steps of decomposition and separation, and the technology is complex.
With the emission of greenhouse gases, carbon peak reaching and carbon neutralization targets are proposed, and the recycling of carbon dioxide is one of important ways for achieving the double-carbon targets. At present, the recovery of carbon dioxide in flue gas by using a carbon capture agent is the most convenient and effective method for realizing carbon utilization. Amino acids can absorb and trap carbon dioxide (Yang Ji, mao Songbai, etc.), a class of alpha-amino acid salt type absorbents for trapping carbon dioxide-application number: 202010898314.3), and amino acids are a very excellent functional fertilizer. Among the carbon dioxide utilization, agricultural utilization is an optimal carbon utilization method, and there has been disclosed a technology for preparing a functional fertilizer for agricultural production by absorbing carbon dioxide with amino acids (Su, etc., an amino acid waste liquid preparation carbon dioxide scavenger usable for fertilizer, 202111299684.6). However, this technique requires the addition of an absorption enhancer, a solvent enhancer, organic ammonia, and other additives to the amino acid solution. Meanwhile, the liquid fertilizer is inconvenient to store and transport and use, carbon dioxide is easy to escape, and the fertilization is troublesome.
Although the ammonia-containing acid solution can be obtained after the residual sludge is cracked, the concentration of the amino acid in the solution is very low, the requirement of absorbing carbon dioxide cannot be met, and the solution must be concentrated, so that the energy consumption is high, the process is complex, and the application cannot be realized.
Sludge treatment and comprehensive utilization, carbon dioxide trapping and utilization, and development and utilization of agricultural functional fertilizers are all urgently needed a new technology and device with convenience and high performance.
Disclosure of Invention
The invention provides a process and a convenient device for synchronously cracking and extracting amino acid from sludge, capturing carbon dioxide and producing carbon dioxide amino acid functional fertilizer for agricultural production. When the water purifying device is used, the release column is connected into the water pipeline, and carbon dioxide and amino acid in the release column are uniformly eluted and released through water flow, so that the water purifying device is used for agricultural production.
The invention relates to a release column for a catalytic extraction of sludge amino acid carbon trapping functional fertilizer, which comprises a column tube, catalytic adsorption trapping filler filled in the column tube, and filter plates and corresponding connectors arranged at two ends of the column tube.
The catalytic adsorption trapping filler is resin aluminum magnesium titanate composite porous microspheres with functions of catalyzing ozone to oxidize and crack sludge and adsorbing and enriching amino acids, and absorbs and traps carbon dioxide, so that when water is introduced, the adsorption and enrichment amino acids and the trapped carbon dioxide can be eluted, and the adsorption and enrichment amino acids and the trapped carbon dioxide are released and dissolved in the water to obtain the functional fertilizer.
The preparation method of the catalytic extraction sludge amino acid carbon capturing functional fertilizer release column specifically comprises the following steps:
step 1: carrying out impurity removal and activation pretreatment on macroporous cation exchange resin to obtain pretreated resin;
testing the pretreated resin to obtain saturated adsorption capacity of magnesium ions and aluminum ions, and calculating average saturated adsorption capacity;
preparing a magnesium source and an aluminum source, wherein the quantity of the magnesium source and the aluminum source is 30-50% of the average saturated adsorption capacity of the total quantity of magnesium ions and aluminum ions adsorbed on the pretreated resin during adsorption, and the mole number of the magnesium ions adsorbed is as follows: the mole number of the aluminum ions is (5-1): 1;
step 2: preparing an aluminum source into an aluminum ion aqueous solution; immersing the pretreated resin in an aluminum ion aqueous solution, carrying out adsorption reaction, measuring the content of aluminum ions in supernatant, and calculating the amount of the aluminum ions adsorbed on the pretreated resin; when the amount of the aluminum ions adsorbed on the pretreated resin reaches the adsorption-planned amount, carrying out solid-liquid separation, carrying out moisture-preserving aging on the resin for 24-48 hours, and then purging the resin with hot air at 80-100 ℃ to remove the surface moisture, thereby obtaining the resin for adsorbing the aluminum ions;
then introducing mixed steam released by heating and boiling the ammonia water solution, sealing and fumigating for 2-3h, and then introducing hot air at 80-100 ℃ to purge excess ammonia gas, thus obtaining the load aluminum resin;
step 3: preparing a prepared magnesium source into a magnesium ion aqueous solution, immersing the supported aluminum resin in the magnesium ion aqueous solution, carrying out adsorption reaction, measuring the content of magnesium ions in supernatant fluid, and calculating the amount of magnesium ions adsorbed on the supported aluminum resin;
when the amount of magnesium ions adsorbed on the supported aluminum resin reaches the intended adsorption amount, separating, and blowing the aqueous solution on the supported aluminum resin by hot air at 80-100 ℃ to obtain the resin for adsorbing aluminum and magnesium;
then, the absolute ethyl alcohol steam at 80-100 ℃ is used for closed circulation and fumigation modification for 60-120min, and excessive moisture and ethanol on the surface of the resin absorbing aluminum and magnesium are purged and removed, so that the aluminum-magnesium loaded resin is obtained;
step 4: weighing a titanium compound with the molar ratio of titanium being 1:1, dissolving and diluting the titanium compound into a titanium solution with the concentration of 1-3mol/L by using an alkyd mixed solution of absolute ethyl alcohol and concentrated hydrochloric acid, dropwise adding the titanium solution into the aluminum-magnesium-loaded resin under the stirring condition of continuously 30-60 r/min, continuously stirring for 30-60min after dropwise adding, hermetically preserving heat and aging for 8-24h at 60-78 ℃, soaking and washing by using absolute ethyl alcohol, and removing hydrochloric acid to obtain resin-loaded aluminum-magnesium titanate precursor microspheres;
step 5: placing the resin-loaded magnesium aluminum titanate precursor microspheres in a tubular reactor, continuously introducing air heated to 40-60 ℃, heating the hot air to 100-110 ℃ at a heating rate of 1-2 ℃/min after 10-20min, introducing saturated steam at the same temperature, sealing, preserving heat, reacting for 24-48h, naturally cooling to room temperature, and washing with water until no foam exists, thus obtaining the resin-magnesium aluminum titanate composite porous microspheres;
step 6: taking fresh sludge, adjusting the water content of the sludge to 96.5% -99%, sieving with a 50-mesh sieve, and removing particles to obtain the sludge;
according to the mass ratio, the resin alumina magnesium titanate composite porous microsphere: mixing resin alumina magnesium titanate composite porous microspheres with sludge in a ratio of 1-5:1, placing the mixture into a reactor, introducing ozone, and stirring the mixture for reaction for 20-40min to obtain feed liquid; wherein, according to the mass ratio, ozone: resin alumina magnesium titanate composite porous microsphere=0.01-0.06: 1, a step of;
separating and recycling resin aluminum magnesium titanate composite porous microspheres from the feed liquid by using a filter screen to obtain amino acid resin aluminum magnesium titanate composite porous microspheres, wherein the broken sludge can be directly dehydrated;
step 7: the amino acid resin aluminum magnesium titanate composite porous microsphere is filled into a column tube, filter plates are additionally arranged at two ends of the column tube to prepare the amino acid resin aluminum magnesium titanate composite porous microsphere carbon capturing column, flue gas after dust removal and purification is introduced to capture carbon dioxide, after adsorption saturation, the amino acid resin aluminum magnesium titanate composite porous microsphere carbon capturing column capturing carbon dioxide is taken down, and two ends of the amino acid resin aluminum magnesium titanate composite porous microsphere carbon capturing column are sealed by connectors, namely the amino acid carbon capturing functional fertilizer releasing column for catalyzing and extracting sludge is obtained.
Further, the macroporous cation exchange resin is preferably macroporous strong acid styrene cation exchange resin.
In the step 1, the aluminum source is one or more of an aluminum simple substance, an aluminum oxide or an aluminum salt, and the magnesium source is one or more of a magnesium simple substance, a magnesium oxide or a magnesium salt;
in the step 2, the calculation method for calculating the amount of the aluminum ions adsorbed on the pretreated resin comprises the following steps: adsorption amount = [ (initial concentration of aluminum ion-concentration of aluminum ion in adsorption supernatant) ×solution volume ]/mass of resin after pretreatment.
In the step 2, when preparing the aluminum ion aqueous solution, the volume of the solution is preferably just immersed in the pretreated resin.
In the step 2, the ammonia solution is preferably 8-15% ammonia solution.
In the step 3, the amount of magnesium ions adsorbed on the supported aluminum resin is calculated, and the calculation method comprises the following steps: adsorption amount = [ (initial concentration of magnesium ion-concentration of magnesium ion in adsorption supernatant) ×solution volume ]/mass of resin after pretreatment.
In the step 3, when preparing the magnesium ion aqueous solution, the solution volume is preferably just immersed in the supported aluminum resin.
In the step 4, the titanium compound is preferably one of titanium tetrachloride and tetra-n-butyl titanate.
In the step 4, absolute ethyl alcohol is used according to the volume ratio: concentrated hydrochloric acid= (4-2): 1.
In the step 4, the dropping speed of the titanium solution is 1-12mL/min.
The invention relates to a method for using a catalytic extraction sludge amino acid carbon capturing functional fertilizer release column, which comprises the following steps:
the carbon capturing functional fertilizer release column for catalyzing and extracting the sludge amino acid is connected into a crop irrigation water spraying pipeline, and amino acid and carbon dioxide in the column can be released into a field along with irrigation water or sprayed on the leaf surfaces of crops to nourish the crops; after the release of the amino acid and the carbon dioxide, the amino acid resin magnesium aluminum oxide titanate composite porous microsphere with the carbon dioxide trapped in the column is converted into the resin magnesium aluminum oxide titanate composite porous microsphere, and after the resin magnesium aluminum oxide titanate composite porous microsphere is taken out, the resin magnesium aluminum oxide titanate composite porous microsphere is returned to the step 6 of the preparation method, the amino acid resin magnesium aluminum oxide titanate composite porous microsphere is obtained again after catalytic extraction and adsorption enrichment of the amino acid, and the carbon dioxide is trapped in the column and is reused.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the ion exchange and adsorption capacity of the resin are utilized, the aluminum ions, the magnesium ions and the titanium ions are adsorbed on the resin, aluminum hydroxide is generated by the aluminum ions adsorbed on the resin through stepwise gas phase mild hydrolysis, the aluminum hydroxide is converted into aluminum oxide, the magnesium adsorption post-treatment is to remove a large amount of moisture in a pore canal, the rapid hydrolysis of titanium during the titanium adsorption is avoided, ventilation fumigation is carried out after the titanium adsorption, gas phase thermal hydrolysis is carried out, the magnesium ions and the titanium ions generate nano magnesium titanate, and meanwhile, part of functional groups of the resin are released again, so that the resin aluminum oxide magnesium titanate composite porous microsphere is obtained, and the resin aluminum oxide magnesium titanate composite porous microsphere maintains the excellent characteristics of the porous structure, adsorption capacity, mechanical strength, toughness and the like of the resin by controlling the adsorption capacity and the proportion of aluminum, magnesium and titanium;
2. the method has the advantages that the method comprises the steps of synchronously catalyzing ozone to oxidize and crack sludge and adsorbing and enriching amino acid in the cracked sludge, preparing an adsorption material adsorbing the amino acid, then utilizing the trapping capacity of the adsorption material and the amino acid to carbon dioxide to trap carbon dioxide, and then using the carbon dioxide as a functional fertilizer, wherein the technical process is simple, and the preparation of the functional fertilizer realizes the fertilizer utilization of the amino acid in the sludge and the carbon dioxide in the flue gas;
3. the problems of weak carbon dioxide adsorption capacity and low trapping amount of pure amino acid are solved by compounding resin aluminum magnesium titanate;
4. the method is stored and transported in a column form and used, so that the loss of the amino acid carbon dioxide fertilizer is reduced;
5. the process disclosed by the invention realizes sludge treatment such as sludge cracking, amino acid enrichment and recovery, carbon dioxide trapping, fertilizer utilization of sludge amino acid and carbon dioxide in one step, is simple and stable, has low energy consumption and no secondary pollution, and is easy to realize industrial production.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a release column for catalyzing and extracting sludge amino acid carbon capture functional fertilizer.
Detailed Description
The present invention will be described in further detail with reference to examples.
According to analysis, the types and proportions of amino acids obtained by catalytically decomposing sludge are consistent with those reported in literature (Pan Qian, a method for extracting protein from excess sludge is preferable, and research on a sludge breakage mechanism is performed in the university of Kunming university of Shuoshi, 2021, li Na, and research on the rules and mechanisms of influence of different pretreatment methods on the types and contents of amino acids in sludge dewatering, the university of Chinese science and technology of Shuoshi, 2019), so that the total amount of amino acids is measured by adopting a Kjeldahl nitrogen method according to the embodiment of the invention for convenience and referring to the literature method.
The resin used in the embodiment of the invention is D001 macroporous strong acid styrene cation exchange resin.
In the embodiment of the invention, the D001 macroporous strong acid styrene cation exchange resin is subjected to impurity removal and activation pretreatment according to a conventional method, namely: firstly, using saturated saline water, taking the amount of the saturated saline water to be about twice the volume of the resin to be treated, soaking the resin in the saline solution for 20 hours, then completely discharging the saline water, and rinsing and cleaning the resin with clean water to ensure that the discharged water is not yellow; then using 4% NaOH solution, soaking for 2 hours, and washing the resin until the discharged water is nearly neutral; finally, 5% HCl solution with the same amount is used for soaking for 6 hours, acid liquor is discharged, and the pretreated resin is obtained by drifting with clear water to be neutral for standby.
In the following examples, the process flow chart of the preparation method of the carbon capturing functional fertilizer release column for catalyzing and extracting sludge amino acid is shown in fig. 1.
Example 1
Preparation of catalytic extraction sludge amino acid carbon capturing functional fertilizer release column 1
Step 1, taking resin pretreated by a conventional method, testing the saturated adsorption capacities of the resin on magnesium and aluminum ions to be 4.22mmol/g and 4.08mmol/g respectively, calculating the average saturated adsorption capacity of the resin for adsorbing the magnesium and aluminum ions to be 4.15mmol/g, wherein 40% of the saturated adsorption capacity is 1.66mmol/g, and when the molar ratio of the magnesium ions to the aluminum ions is controlled to be 3:1, the amount of the adsorbed magnesium ions is 1.245mmol/g, and the amount of the adsorbed aluminum ions is 0.415mmol/g;
step 2, weighing 691.4g (Al) of the aluminum ions according to the required amount calculated in the step 1 2 (SO 4 ) 3 ·18H 2 O is dissolved in 5L of water to prepare an aqueous solution of aluminum ions, 5000g of pretreated resin is immersed in the solution, the solution is stirred for adsorption reaction, the content of the aluminum ions in the solution is measured, and the formula is utilized: adsorption amount = [ (initial concentration of aluminum ion-concentration of aluminum ion in adsorption supernatant liquid) ×solution volume]The mass of the pretreated resin, and the amount of aluminum ions adsorbed on the pretreated resin can be calculated and appropriately added (Al) 2 (SO 4 ) 3 ·18H 2 O, when the required concentration of aluminum ions adsorbed on the pretreated resin reaches 0.415mmol/g, separating and recovering the pretreated resin, sealing, keeping moisture, aging for 32 hours, purging with hot air at 90 ℃ to remove residual redundant moisture, introducing mixed steam released by heating and boiling ammonia water solution with the concentration of 12%, sealing and fumigating for 2 hours, and introducing hot air at 100 ℃ to purge redundant ammonia gas to obtain the loaded aluminum resin 1;
step 3, weighing 1534.3g of MgSO 4 ·7H 2 O is dissolved in 5L of water to prepare magnesium ion water solution, the supported aluminum resin 1 obtained in the step 2 is immersed in the magnesium ion water solution, stirred and adsorbed for reaction, and MgSO is properly added 4 ·7H 2 O, determining the content of magnesium ions in the solution by using the formula: adsorption amount = [ (initial concentration of magnesium ion-concentration of magnesium ion in adsorption supernatant) ×solution volume]The mass of the pretreated resin, the amount of magnesium ions adsorbed on the loaded aluminum resin is calculated, when the adsorption amount reaches 1.245mmol/g, the loaded aluminum resin with adsorbed magnesium is separated and recovered, and hot air at 90 ℃ is usedPurging and adsorbing the aqueous solution on the magnesium-loaded aluminum resin, then carrying out airtight circulation flow fumigation modification by using absolute ethyl alcohol steam at 90 ℃ for 90min, and purging and removing redundant water and ethanol to obtain the aluminum-loaded magnesium resin 1;
step 4, weighing 1180.8g of titanium tetrachloride, preparing an alkyd mixed solution with the volume ratio of absolute ethyl alcohol to concentrated hydrochloric acid of 3:1 into a titanium solution with the volume ratio of 2mol/L, dropwise adding the titanium solution onto the aluminum magnesium resin 1 with the dropwise adding speed of 6mL/min under the condition of continuous stirring at 50rpm, continuously stirring for 50min after dropwise adding, hermetically preserving the heat at 70 ℃ for soaking and aging for 16h, soaking and washing with absolute ethyl alcohol, and removing hydrochloric acid to obtain the magnesium aluminum titanate precursor microsphere 1 loaded with the resin;
step 5, placing the resin-loaded magnesium aluminum titanate precursor microsphere 1 in a tubular reactor, continuously introducing hot air heated to 50 ℃, heating the hot air to 105 ℃ at a heating rate of 1.5 ℃/min after 10min, introducing 105 ℃ saturated steam, sealing, preserving heat, reacting for 36h, naturally cooling to room temperature, and washing with water until no foam exists, thus obtaining the resin-alumina magnesium titanate composite porous microsphere 1;
step 6, taking fresh sludge, adjusting the water content of the sludge to 96.5%, sieving the sludge with a 50-mesh sieve, removing particles, adding the resin aluminum magnesium titanate composite porous microspheres 1 prepared in the step 5, which is 3.5% of the mass of the sludge, into a reactor, introducing ozone, adjusting the ozone concentration to enable the ozone amount to be 0.03g/g of the resin aluminum magnesium titanate composite porous microspheres 1, and stirring and reacting for 30min to obtain a feed liquid 1;
separating the feed liquid 1 by using a 50-mesh filter screen to obtain resin aluminum oxide magnesium titanate composite porous microspheres 1, and obtaining amino acid resin aluminum oxide magnesium titanate composite porous microspheres 1; the sludge is directly dewatered.
And 7, loading the amino acid resin magnesium aluminum titanate composite porous microspheres 1 into an organic glass column tube with the effective inner diameter of 100mm and the effective length of 500mm, mounting filter plates and connectors at two ends to prepare the amino acid resin magnesium aluminum titanate composite porous microsphere carbon trapping column 1, introducing flue gas with the carbon dioxide content of 20% after dust removal and purification, absorbing carbon dioxide, monitoring the concentration of carbon dioxide at an outlet of the column, replacing the column when the concentration of carbon dioxide at the outlet is increased to 5%, removing the carbon dioxide adsorbed on the column to prepare the amino acid resin magnesium aluminum titanate composite porous microsphere carbon trapping column 1, and sealing the two ends by sealing heads to obtain the amino acid carbon trapping functional fertilizer releasing column 1 for catalyzing and extracting sludge.
Example 2
Preparation of catalytic extraction amino acid carbon capturing functional fertilizer release resin column 2
Step 1, taking resin pretreated by a conventional method, testing the saturated adsorption capacities of the resin on magnesium and aluminum ions to be 4.22mmol/g and 4.08mmol/g respectively, calculating the average saturated adsorption capacity of the resin for adsorbing the magnesium and aluminum ions to be 4.15mmol/g, wherein the average saturated adsorption capacity of the resin for adsorbing the magnesium and aluminum ions is 1.66mmol/g, and when the molar ratio of the magnesium to the aluminum is controlled to be 5:1, the amount of the magnesium ions to be adsorbed is 1.383mmol/g, and the amount of the aluminum ions to be adsorbed is 0.277mmol/g;
step 2, weighing 461.5g (Al) of the aluminum ions according to the required amount calculated in the step 1 2 (SO 4 ) 3 ·18H 2 O is dissolved in 5L of water to prepare an aqueous solution of aluminum ions, 5000g of pretreated resin is immersed in the solution, the solution is stirred for adsorption reaction, the content of the aluminum ions in the solution is measured, and the formula is utilized: adsorption amount = [ (initial concentration of aluminum ion-concentration of aluminum ion in adsorption supernatant liquid) ×solution volume]The mass of the pretreated resin, and the amount of aluminum ions adsorbed on the pretreated resin can be calculated and appropriately added (Al) 2 (SO 4 ) 3 ·18H 2 O, when the required concentration of aluminum ions adsorbed on the pretreated resin reaches 0.277mmol/g, separating and recovering the pretreated resin, sealing, keeping moisture, aging for 24 hours, purging with hot air at 80 ℃ to remove residual redundant moisture, introducing mixed steam released by heating and boiling 8% ammonia water solution, sealing and fumigating for 2 hours, and introducing hot air at 100 ℃ to purge redundant ammonia gas to obtain the supported aluminum resin 2;
step 3, weighing 1704.3g of MgSO 4 ·7H 2 O is dissolved in 5L of water to prepare magnesium ion water solution, the supported aluminum resin 2 obtained in the step 2 is immersed in the magnesium ion water solution, stirred and adsorbed for reaction, and MgSO is properly added 4 ·7H 2 O, determining the content of magnesium ions in the solution by using the formula: adsorption amount = [ (initial concentration of magnesium ion-adsorption supernatant)Concentration of magnesium ions in the solution) x volume of solution]Calculating the amount of magnesium ions adsorbed on the loaded aluminum resin, separating and recovering the loaded aluminum resin adsorbing magnesium when the adsorption amount reaches 1.383mmol/g, blowing hot air at 80 ℃ to adsorb aqueous solution on the loaded aluminum resin adsorbing magnesium, then carrying out airtight circulation flow fumigation modification for 60min by using absolute ethanol steam at 80 ℃, and blowing to remove redundant water and ethanol to obtain the loaded aluminum-magnesium resin 2;
step 4, weighing 2353.3g of tetra-n-butyl titanate, preparing 3mol/L titanium solution by using an alkyd mixed solution of absolute ethyl alcohol and concentrated hydrochloric acid with the volume ratio of 2:1, dropwise adding the titanium solution onto the aluminum magnesium resin 2 with the dropwise adding speed of 1ml/min under the condition of continuous stirring at 60rpm, continuously stirring for 60min after dropwise adding, hermetically preserving the heat at 78 ℃ for soaking and aging for 20h, soaking and washing by using the absolute ethyl alcohol, and removing hydrochloric acid to obtain the resin-loaded aluminum magnesium titanate precursor microsphere 2;
step 5, placing the resin-loaded magnesium aluminum titanate precursor microsphere 2 in a tubular reactor, continuously introducing hot air heated to 50 ℃, heating the hot air to 105 ℃ at a heating rate of 1.5 ℃/min after 15min, introducing 105 ℃ saturated steam, sealing, preserving heat, reacting for 36h, naturally cooling to room temperature, and washing with water until no foam exists, thus obtaining the resin-alumina magnesium titanate composite porous microsphere 2;
step 6, taking fresh sludge, adjusting the water content of the sludge to 97.3%, sieving the sludge with a 50-mesh sieve, removing particles, adding the resin aluminum magnesium titanate composite porous microspheres 2 prepared in the step 5, which is 5% of the mass of the sludge, placing the resin aluminum magnesium titanate composite porous microspheres 2 in a reactor, introducing ozone, adjusting the ozone concentration to enable the ozone amount to be 0.06g/g of the resin aluminum magnesium titanate composite porous microspheres 2, and stirring and reacting for 40min to obtain a feed liquid 2;
separating the feed liquid 2 by using a 50-mesh filter screen to obtain resin aluminum oxide magnesium titanate composite porous microspheres 2, and obtaining amino acid resin aluminum oxide magnesium titanate composite porous microspheres 2; the sludge is directly dewatered.
And 7, filling the amino acid resin magnesium aluminum titanate composite porous microspheres 2 into an organic glass column tube with the effective inner diameter of 100mm and the effective length of 500mm, mounting filter plates and connectors at two ends to prepare the amino acid resin magnesium aluminum titanate composite porous microsphere carbon trapping column 2, introducing flue gas with the carbon dioxide content of 20% after dust removal and purification, absorbing carbon dioxide, monitoring the concentration of carbon dioxide at an outlet of the column, replacing the column when the concentration of carbon dioxide at the outlet is increased to 5%, removing the carbon dioxide adsorbed on the column to prepare the amino acid resin magnesium aluminum titanate composite porous microsphere carbon trapping column 2, and sealing the two ends by sealing heads to obtain the amino acid carbon trapping functional fertilizer releasing column 2 for catalyzing and extracting sludge.
Example 3
Preparation of catalytic extraction amino acid carbon capturing functional fertilizer release resin column 3
Step 1, taking resin pretreated by a conventional method, testing the saturated adsorption capacities of the resin on magnesium and aluminum ions to be 4.22mmol/g and 4.08mmol/g respectively, calculating the average saturated adsorption capacity of the resin for adsorbing the magnesium and aluminum ions to be 4.15mmol/g, wherein 50% of the adsorption capacity is 2.075mmol/g, and when the molar ratio of the magnesium to the aluminum is controlled to be 1:1, the amount of the adsorbed magnesium ions is 1.0375mmol/g, and the amount of the adsorbed aluminum ions is 1.0375mmol/g;
step 2, according to the required amount of aluminum ions calculated in the step 1, 1728.6g (Al) is weighed 2 (SO 4 ) 3 ·18H 2 O is dissolved in 5L of water to prepare an aqueous solution of aluminum ions, 5000g of pretreated resin is immersed in the solution, the solution is stirred for adsorption reaction, the content of the aluminum ions in the solution is measured, and the formula is utilized: adsorption amount = [ (initial concentration of aluminum ion-concentration of aluminum ion in adsorption supernatant liquid) ×solution volume]The mass of the pretreated resin, and the amount of aluminum ions adsorbed on the pretreated resin can be calculated and appropriately added (Al) 2 (SO 4 ) 3 ·18H 2 O, when the required 1.0375mmol/g of aluminum ions adsorbed on the pretreated resin is reached, separating and recovering the pretreated resin, sealing, keeping moisture and aging for 48 hours, then purging with hot air at 100 ℃, removing residual redundant moisture, introducing mixed steam released by heating and boiling 15% ammonia water solution, sealing and fumigating for 3 hours, and introducing hot air at 100 ℃ to purge redundant ammonia gas to obtain the supported aluminum resin 3;
step 3, weighing 493.9g of MgCl 2 Dissolving in 5L water to obtain magnesium ion water solutionImmersing the supported aluminum resin 3 obtained in the step 2, stirring and adsorbing the supported aluminum resin, and properly supplementing MgCl 2 Determining the magnesium ion content in the solution by using the formula: adsorption amount = [ (initial concentration of magnesium ion-concentration of magnesium ion in adsorption supernatant) ×solution volume]Calculating the amount of magnesium ions adsorbed on the loaded aluminum resin, separating and recovering the loaded aluminum resin adsorbing magnesium when the adsorption amount reaches 1.0375mmol/g, blowing hot air at 100 ℃ to adsorb aqueous solution on the loaded aluminum resin adsorbing magnesium, then carrying out airtight circulation flow fumigation modification for 120min by using absolute ethanol vapor at 100 ℃, and blowing to remove redundant water and ethanol to obtain the loaded aluminum-magnesium resin 3;
step 4, weighing 984.0g of titanium tetrachloride, preparing 3mol/L titanium solution by using an alkyd mixed solution of absolute ethyl alcohol and concentrated hydrochloric acid in a volume ratio of 4:1, dropwise adding the titanium solution onto the aluminum magnesium resin 3 with a dropwise adding speed of 1ml/min under a continuous stirring condition of 60rpm, continuously stirring for 60min after dropwise adding, hermetically preserving the heat, soaking and aging for 24 hours at 60 ℃, soaking and washing by using absolute ethyl alcohol, and removing hydrochloric acid to obtain the magnesium aluminum titanate precursor microsphere 3 loaded on the resin;
step 5, placing the resin-loaded magnesium aluminum titanate precursor microspheres 3 in a tubular reactor, continuously introducing hot air heated to 60 ℃, heating the hot air to 110 ℃ at a heating rate of 2 ℃/min after 20min, introducing 110 ℃ saturated steam, sealing, preserving heat, reacting for 48h, naturally cooling to room temperature, and washing with water until no foam exists, thus obtaining resin-alumina magnesium titanate composite porous microspheres 3;
step 6, taking fresh sludge, adjusting the water content of the sludge to 98%, sieving the sludge with a 50-mesh sieve, removing particles, adding the resin aluminum oxide magnesium titanate composite porous microspheres 3 prepared in the step 5, which is 10% of the mass of the sludge, placing the resin aluminum oxide magnesium titanate composite porous microspheres 3 in a reactor, introducing ozone, adjusting the ozone concentration to enable the ozone amount to be 0.01g/g of the resin aluminum oxide magnesium titanate composite porous microspheres 3, and stirring and reacting for 20min to obtain a feed liquid 3;
separating the feed liquid 3 by using a 50-mesh filter screen to obtain resin aluminum oxide magnesium titanate composite porous microspheres 3, and obtaining amino acid resin aluminum oxide magnesium titanate composite porous microspheres 3; the sludge is directly dewatered.
And 7, filling the amino acid resin magnesium aluminum titanate composite porous microspheres 3 into an organic glass column tube with the effective inner diameter of 100mm and the effective length of 500mm, mounting filter plates and connectors at two ends to prepare the amino acid resin magnesium aluminum titanate composite porous microsphere carbon trapping column 3, introducing flue gas with the carbon dioxide content of 20% after dust removal and purification, absorbing carbon dioxide, monitoring the concentration of carbon dioxide at an outlet of the column, replacing the column when the concentration of carbon dioxide at the outlet is increased to 5%, taking down the carbon dioxide adsorbed on the column to prepare the amino acid resin magnesium aluminum titanate composite porous microsphere carbon trapping column 3, and sealing the two ends by using sealing heads to obtain the amino acid carbon trapping functional fertilizer releasing column 3 for catalyzing and extracting sludge.
Example 4
Preparation of catalytic extraction amino acid carbon capturing functional fertilizer release resin column 4
Step 1, taking resin pretreated by a conventional method, testing the saturated adsorption capacities of the resin on magnesium and aluminum ions to be 4.22mmol/g and 4.08mmol/g respectively, calculating the average saturated adsorption capacity of the resin for adsorbing the magnesium and aluminum ions to be 4.15mmol/g, wherein 30% of the saturated adsorption capacity is 1.245mmol/g, and when the molar ratio of the magnesium ions to the aluminum ions is controlled to be 3:1, the amount of the adsorbed magnesium ions is 0.93375mmol/g, and the amount of the adsorbed aluminum ions is 0.31125mmol/g;
step 2, weighing 207.5g of AlCl according to the required amount of the aluminum ions calculated in the step 1 3 Dissolving in 5L of water to prepare an aqueous solution of aluminum ions, immersing 5000g of pretreated resin in the solution, stirring for adsorption reaction, measuring the content of the aluminum ions in the solution, and using the formula: adsorption amount = [ (initial concentration of aluminum ion-concentration of aluminum ion in adsorption supernatant liquid) ×solution volume]The mass of the pretreated resin is calculated, and the AlCl can be properly supplemented 3 When the required 0.31125mmol/g of aluminum ions adsorbed on the pretreated resin is reached, separating and recovering the pretreated resin, sealing, keeping moisture, aging for 24 hours, purging with hot air at 80 ℃ to remove residual redundant moisture, introducing mixed steam released by heating and boiling 8% ammonia water solution, sealing and fumigating for 2 hours, and introducing hot air at 100 ℃ to purge redundant ammonia gas to obtain the supported aluminum resin 4;
step 3, weighing 188.2g of MgO, dissolving with dilute hydrochloric acid, diluting with water to prepare 5L of magnesium ion solution, immersing the supported aluminum resin 4 obtained in the step 2, stirring for adsorption reaction, and appropriately supplementing MgCl 2 Determining the magnesium ion content in the solution by using the formula: adsorption amount = [ (initial concentration of magnesium ion-concentration of magnesium ion in adsorption supernatant) ×solution volume]Calculating the amount of magnesium ions adsorbed on the loaded aluminum resin, separating and recovering the loaded aluminum resin adsorbing magnesium when the adsorption amount reaches 0.93375mmol/g, blowing hot air at 80 ℃ to adsorb aqueous solution on the loaded aluminum resin adsorbing magnesium, then carrying out airtight circulation flow fumigation modification for 60min by using absolute ethanol vapor at 80 ℃, and blowing to remove redundant water and ethanol to obtain the loaded aluminum-magnesium resin 4;
step 4, weighing 1588.87g of tetra-n-butyl titanate, preparing 1mol/L titanium solution by using an alkyd mixed solution of absolute ethyl alcohol and concentrated hydrochloric acid in a volume ratio of 3:1, dropwise adding the titanium solution onto the aluminum magnesium resin 4 with a dropwise acceleration of 12ml/min under a continuous stirring condition of 30rpm, continuously stirring for 30min after dropwise adding, hermetically preserving the heat at 65 ℃ for soaking and aging for 8 hours, soaking and washing by using the absolute ethyl alcohol, and removing hydrochloric acid to obtain the resin-loaded aluminum magnesium titanate precursor microsphere 4;
step 5, placing the resin-loaded magnesium aluminum titanate precursor microspheres 4 in a tubular reactor, continuously introducing hot air heated to 40 ℃, heating the hot air to 100 ℃ at a heating rate of 1 ℃/min after 10min, introducing 100 ℃ saturated steam, sealing, preserving heat, reacting for 24 hours, naturally cooling to room temperature, and washing with water until no foam exists, thus obtaining the resin-alumina magnesium aluminum titanate composite porous microspheres 4;
step 6, taking fresh sludge, adjusting the water content of the sludge to 99%, sieving the sludge with a 50-mesh sieve, removing particles, adding the resin aluminum oxide magnesium titanate composite porous microspheres 4 prepared in the step 5, which is 3% of the mass of the sludge, placing the resin aluminum oxide magnesium titanate composite porous microspheres 4 in a reactor, introducing ozone, adjusting the ozone concentration to enable the ozone amount to be 0.03g/g of the resin aluminum oxide magnesium titanate composite porous microspheres 4, and stirring and reacting for 25min to obtain a feed liquid 4;
separating the feed liquid 4 by using a 50-mesh filter screen to obtain resin aluminum oxide magnesium titanate composite porous microspheres 4, and obtaining amino acid resin aluminum oxide magnesium titanate composite porous microspheres 4; the sludge is directly dewatered.
And 7, filling the amino acid resin magnesium aluminum titanate composite porous microspheres 4 into an organic glass column tube with the effective inner diameter of 100mm and the effective length of 500mm, mounting filter plates and connectors at two ends to prepare the amino acid resin magnesium aluminum titanate composite porous microsphere carbon trapping column 4, introducing flue gas with the carbon dioxide content of 20% after dust removal and purification, absorbing carbon dioxide, monitoring the concentration of carbon dioxide at an outlet of the column, replacing the column when the concentration of carbon dioxide at the outlet is increased to 5%, taking down the carbon dioxide adsorbed on the column to prepare the amino acid resin magnesium aluminum titanate composite porous microsphere carbon trapping column 4, and sealing the two ends by using sealing heads to obtain the amino acid carbon trapping functional fertilizer releasing column 4 for catalyzing and extracting sludge.
Example 5
Performance of resin alumina magnesium titanate composite porous microsphere
According to the steps 1-4, 6 and 7, treating sludge by using resin alumina magnesium titanate composite porous microspheres, absorbing carbon dioxide, and measuring the total amount of total protein of the sludge by adopting a Kjeldahl method to represent the total amount of amino acids; the change of the content of the amino acid before and after extraction in the sludge is compared with the original resin and ozone oxidation. The amount of amino acid and the amount of carbon dioxide adsorbed on the resin were measured, and the results are shown in tables 1 and 2.
Table 1 changes in protein content of sludge after treatment with the Supported catalyst adsorption resin in examples
Table 2 adsorption properties of materials for carbon dioxide
The result shows that the adsorption quantity of the original resin to the amino acid and the carbon dioxide is very low, and the adsorption quantity of the resin to the amino acid and the carbon dioxide is obviously increased after the catalytic adsorbent is loaded, and the adsorption quantity of the resin to the carbon dioxide is positively related to the quantity of the amino acid.
Example 6 use and regeneration of a resin column for the catalytic extraction of amino acid carbon Capture functional Fertilizer Release
The catalytic extraction sludge amino acid carbon capturing functional fertilizer release column 1-4 obtained in the embodiment 1-4 is connected with a water way by a water pump or a water tap, water flows through the column, and then is sprayed on the leaf surfaces of crops (especially crops in vegetable greenhouse), in sunny weather, carbon dioxide in water is released into the air under illumination, photosynthesis is supplied to crops, and nutrient substances such as amino acid are absorbed and utilized by the crops by the leaf surfaces or dripped into the root parts of the crops; the amount of amino acids and carbon dioxide released from the column into the water can be regulated by adjusting the speed of the water flow.
After the release of the amino acid and the carbon dioxide in the column is finished, the amino acid resin aluminum magnesium titanate composite porous microsphere in the column is changed into a resin aluminum magnesium titanate composite porous microsphere, the resin aluminum magnesium titanate composite porous microsphere in the column is taken out, the step 6 is returned, the amino acid is catalytically extracted again, the amino acid is converted into the amino acid resin aluminum magnesium titanate composite porous microsphere, and the carbon dioxide is adsorbed by the column for repeated use.
Comparative example 1
The difference from example 1 is that: and 2, after adsorbing aluminum, the ammonia water mixed steam gas-phase fumigation process is not performed, so that the resin aluminum oxide magnesium titanate composite porous microspheres cannot be obtained, aluminum ions are released during use, and the resin has no extraction capacity on sludge amino acid and has very low carbon dioxide absorption capacity.
Comparative example 2
The difference with example 1 is that after the magnesium is adsorbed in step 3, no fumigation modification process is performed by using absolute ethanol steam, when titanium solution is dripped, titanium is directly and rapidly hydrolyzed to generate white titanium oxide on the resin, magnesium ions are released when the resin is used, the extraction amount of amino acid in sludge is very low, and the absorption amount of carbon dioxide is also very low.
Comparative example 3
The difference is that in step 5, air heated to 100 ℃ is continuously introduced, after 30min, the temperature of the hot air is raised to 150 ℃ at a heating rate of 10 ℃/min, saturated steam at the same temperature is introduced, closed heat preservation is carried out for 48 hours, most of the particles of the resin are broken, white powder is separated out, the titanium oxide is analyzed, magnesium ions are dissolved in resin-impregnated water, and the failure of generating resin-alumina-magnesium titanate composite porous microspheres is indicated;
meanwhile, researches on changing the ventilation temperature, the heating speed and the mode of introducing steam are carried out, when the heating speed is too high and the temperature is too high, the resin balls are broken and cannot be used later when the temperature exceeds the limit value of the invention; when the temperature rising speed or temperature is lower than the limit value of the invention, the synthetic resin composite microsphere has titanium dioxide phase, and the resin aluminum oxide magnesium titanate composite porous microsphere can not be obtained, and has no functions of catalyzing and decomposing sludge, adsorbing and enriching protein and absorbing carbon dioxide, and releasing amino acid and carbon dioxide.
Claims (9)
1. The preparation method of the functional fertilizer release column is characterized by comprising the following steps of:
carrying out impurity removal and activation pretreatment on macroporous cation exchange resin, and then carrying out aluminum ion adsorption to obtain resin for adsorbing aluminum ions;
then heating and boiling mixed steam released by the ammonia water solution, fumigating for 2-3h, and purging excessive ammonia gas by hot air to obtain the loaded aluminum resin;
then carrying out magnesium ion adsorption and titanium ion adsorption to obtain resin-loaded aluminum oxide magnesium titanate precursor microspheres, wherein after the magnesium ion adsorption, absolute ethyl alcohol vapor at 80-100 ℃ is adopted for airtight circulation flow fumigation modification for 1-2h;
placing the resin-loaded magnesium aluminum titanate precursor microspheres in a tubular reactor, continuously introducing hot air heated to 40-60 ℃, balancing for 10-20min, heating the hot air to 100-110 ℃ at a heating rate of 1-2 ℃/min, introducing saturated steam, sealing, preserving heat, reacting for 24-48h, naturally cooling to room temperature, washing with water until no foam exists, and blowing out water by air to obtain resin-loaded magnesium aluminum titanate composite porous microspheres;
the resin aluminum oxide magnesium titanate composite porous microspheres are used for catalyzing, extracting and adsorbing amino acid in the enriched sludge, and then the amino acid is filled into a column to capture carbon dioxide, so that a functional fertilizer release column is obtained;
the functional fertilizer release column comprises a column tube, catalytic adsorption trapping filler filled in the column tube, filter plates arranged at two ends of the column tube and corresponding connectors;
the catalytic adsorption trapping filler is resin aluminum magnesium titanate composite porous microspheres with functions of catalyzing ozone to oxidize and crack sludge and adsorbing and enriching amino acids, absorbs and trapping carbon dioxide, and can realize that the adsorbed and enriched amino acids and the trapped carbon dioxide can be eluted and released and dissolved in water when water is introduced to obtain the functional fertilizer.
2. The method for preparing a functional fertilizer release column according to claim 1, characterized in that the method for preparing a functional fertilizer release column specifically comprises the following steps:
step 1: carrying out impurity removal and activation pretreatment on macroporous cation exchange resin to obtain pretreated resin;
testing the pretreated resin to obtain saturated adsorption capacity of magnesium ions and aluminum ions, and calculating average saturated adsorption capacity;
preparing a magnesium source and an aluminum source, wherein the quantity of the magnesium source and the aluminum source is 30-50% of the average saturated adsorption capacity of the total quantity of magnesium ions and aluminum ions adsorbed on the pretreated resin during adsorption, and the mole number of the magnesium ions adsorbed is as follows: the mole number of the aluminum ions is (5-1): 1;
step 2: preparing an aluminum source into an aluminum ion aqueous solution; immersing the pretreated resin in an aluminum ion aqueous solution, carrying out adsorption reaction, measuring the content of aluminum ions in supernatant, and calculating the amount of the aluminum ions adsorbed on the pretreated resin; when the amount of the aluminum ions adsorbed on the pretreated resin reaches the adsorption-planned amount, carrying out solid-liquid separation, carrying out moisture-preserving aging on the resin for 24-48 hours, and then purging the resin with hot air at 80-100 ℃ to remove the surface moisture, thereby obtaining the resin for adsorbing the aluminum ions;
then introducing mixed steam released by heating and boiling the ammonia water solution, sealing and fumigating for 2-3h, and then introducing hot air at 80-100 ℃ to purge excess ammonia gas, thus obtaining the load aluminum resin;
step 3: preparing a prepared magnesium source into a magnesium ion aqueous solution, immersing the supported aluminum resin in the magnesium ion aqueous solution, carrying out adsorption reaction, measuring the content of magnesium ions in supernatant fluid, and calculating the amount of magnesium ions adsorbed on the supported aluminum resin;
when the amount of magnesium ions adsorbed on the supported aluminum resin reaches the intended adsorption amount, separating, and blowing the aqueous solution on the supported aluminum resin by hot air at 80-100 ℃ to obtain the resin for adsorbing aluminum and magnesium;
then, the absolute ethyl alcohol steam at 80-100 ℃ is used for closed circulation and fumigation modification for 60-120min, and excessive moisture and ethanol on the surface of the resin absorbing aluminum and magnesium are purged and removed, so that the aluminum-magnesium loaded resin is obtained;
step 4: weighing a titanium compound with the molar ratio of titanium being 1:1, dissolving and diluting the titanium compound into a titanium solution with the concentration of 1-3mol/L by using an alkyd mixed solution of absolute ethyl alcohol and concentrated hydrochloric acid, dropwise adding the titanium solution into the aluminum-magnesium-loaded resin under the stirring condition of continuously 30-60 r/min, continuously stirring for 30-60min after dropwise adding, hermetically preserving heat and aging for 8-24h at 60-78 ℃, soaking and washing by using absolute ethyl alcohol, and removing hydrochloric acid to obtain resin-loaded aluminum-magnesium titanate precursor microspheres;
step 5: placing the resin-loaded magnesium aluminum titanate precursor microspheres in a tubular reactor, continuously introducing air heated to 40-60 ℃, heating the hot air to 100-110 ℃ at a heating rate of 1-2 ℃/min after 10-20min, introducing saturated steam at the same temperature, sealing, preserving heat, reacting for 24-48h, naturally cooling to room temperature, and washing with water until no foam exists, thus obtaining the resin-magnesium aluminum titanate composite porous microspheres;
step 6: taking fresh sludge, adjusting the water content of the sludge to 96.5% -99%, sieving with a 50-mesh sieve, and removing particles to obtain the sludge;
according to the mass ratio, the resin alumina magnesium titanate composite porous microsphere: mixing resin alumina magnesium titanate composite porous microspheres with sludge in a ratio of 1-5:1, placing the mixture into a reactor, introducing ozone, and stirring the mixture for reaction for 20-40min to obtain feed liquid; wherein, according to the mass ratio, ozone: resin alumina magnesium titanate composite porous microsphere=0.01-0.06: 1, a step of;
separating and recycling resin aluminum magnesium titanate composite porous microspheres from the feed liquid by using a filter screen to obtain amino acid resin aluminum magnesium titanate composite porous microspheres, and directly dehydrating the cracked sludge;
step 7: the amino acid resin aluminum magnesium titanate composite porous microsphere is filled into a column tube, filter plates are additionally arranged at two ends of the column tube to prepare the amino acid resin aluminum magnesium titanate composite porous microsphere carbon trapping column, flue gas after dust removal and purification is introduced to trap carbon dioxide, after adsorption saturation, the amino acid resin aluminum magnesium titanate composite porous microsphere carbon trapping column trapping carbon dioxide is taken down, and two ends of the amino acid resin aluminum magnesium titanate composite porous microsphere carbon trapping column are sealed by connectors, so that the functional fertilizer releasing column is obtained.
3. The method for preparing a functional fertilizer release column according to claim 2, wherein in the step 1, the aluminum source is one or more of an aluminum simple substance, an aluminum oxide or an aluminum salt, and the magnesium source is one or more of a magnesium simple substance, a magnesium oxide or a magnesium salt.
4. The method for preparing a functional fertilizer release column according to claim 2, wherein the calculation method for calculating the amount of aluminum ions adsorbed on the pretreated resin is: adsorption amount = [ (initial concentration of aluminum ions-concentration of aluminum ions in adsorption supernatant) ×solution volume ]/mass of pretreated resin;
the amount of magnesium ions adsorbed on the supported aluminum resin was calculated by: adsorption amount = [ (initial concentration of magnesium ion-concentration of magnesium ion in adsorption supernatant) ×solution volume ]/mass of resin after pretreatment.
5. The method for preparing a functional fertilizer release column according to claim 2, wherein in the step 2, the ammonia solution is 8-15% ammonia solution.
6. The method for preparing a functional fertilizer release column according to claim 2, wherein in the step 4, one of titanium tetrachloride and tetra-n-butyl titanate is a titanium compound.
7. The method for preparing a functional fertilizer release column according to claim 2, wherein in the step 4, absolute ethyl alcohol is used according to the volume ratio: concentrated hydrochloric acid= (4-2): 1.
8. The method for preparing a functional fertilizer release column according to claim 2, wherein in the step 4, the titanium solution is dropped at a rate of 1-12mL/min.
9. The method for using the functional fertilizer release column according to claim 1, wherein the functional fertilizer release column is connected into a crop irrigation water spray pipeline, and amino acid and carbon dioxide in the column can be released into the field along with irrigation water or sprayed on the leaf surfaces of crops to nourish the crops; after the release of the amino acid and the carbon dioxide, the amino acid resin magnesium aluminum titanate composite porous microsphere with the carbon dioxide trapped in the column is converted into the resin magnesium aluminum titanate composite porous microsphere, and after the amino acid resin magnesium aluminum titanate composite porous microsphere is taken out, the preparation method returns to the step 6 of the preparation method of claim 2, the amino acid resin magnesium aluminum titanate composite porous microsphere is obtained again through catalytic extraction and adsorption of the enriched amino acid, and the carbon dioxide is trapped in the column and is reused.
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