CN110227420A - A kind of preparation method of boehmite modified cation adsorbent - Google Patents
A kind of preparation method of boehmite modified cation adsorbent Download PDFInfo
- Publication number
- CN110227420A CN110227420A CN201910448796.XA CN201910448796A CN110227420A CN 110227420 A CN110227420 A CN 110227420A CN 201910448796 A CN201910448796 A CN 201910448796A CN 110227420 A CN110227420 A CN 110227420A
- Authority
- CN
- China
- Prior art keywords
- boehmite
- esterification
- monomer
- double bond
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001593 boehmite Inorganic materials 0.000 title claims abstract description 79
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 title claims abstract description 79
- 150000001768 cations Chemical class 0.000 title claims abstract description 31
- 239000003463 adsorbent Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000032050 esterification Effects 0.000 claims abstract description 37
- 238000005886 esterification reaction Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000007524 organic acids Chemical class 0.000 claims abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004005 microsphere Substances 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- -1 Kynoar Polymers 0.000 claims description 4
- 229940056319 ferrosoferric oxide Drugs 0.000 claims description 4
- 239000004088 foaming agent Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 229940113088 dimethylacetamide Drugs 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 2
- PSCXFXNEYIHJST-QPJJXVBHSA-N (e)-4-phenylbut-3-enoic acid Chemical compound OC(=O)C\C=C\C1=CC=CC=C1 PSCXFXNEYIHJST-QPJJXVBHSA-N 0.000 claims 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims 1
- 229940047670 sodium acrylate Drugs 0.000 claims 1
- PSCXFXNEYIHJST-UHFFFAOYSA-N trans-styrilacetic acid Natural products OC(=O)CC=CC1=CC=CC=C1 PSCXFXNEYIHJST-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000003093 cationic surfactant Substances 0.000 abstract description 3
- 230000000536 complexating effect Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 238000005406 washing Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QGZKDVFQNNGYKY-OUBTZVSYSA-N Ammonia-15N Chemical compound [15NH3] QGZKDVFQNNGYKY-OUBTZVSYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- QFCQSIFDBNDNBP-UHFFFAOYSA-N C1(=CC=CC=C1)C=CCC(=O)O.C(C)(=O)O Chemical compound C1(=CC=CC=C1)C=CCC(=O)O.C(C)(=O)O QFCQSIFDBNDNBP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 description 1
- 229940089960 chloroacetate Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 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
- 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
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
- C08F259/04—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
- C08F271/02—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00 on to polymers of monomers containing heterocyclic nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of preparation methods of boehmite modified cation adsorbent, belong to field of compound material.The preparation method includes first being esterified with organic acid containing double bonds to boehmite, obtain double bond containing esterification boehmite, then initiator is added in water, monomer (contains carboxyl, sulfonic monomer), the polymer microballoon of a small amount of crosslinking agent and esterification boehmite or the boehmite containing esterification, it is graft-polymerized under nitrogen protection to double bond containing esterification boehmite, obtain boehmite modified cation adsorbent, the adsorbent can pass through the metal cation in ion exchange or complexing quick adsorption water body, cationic surfactant or the dye of positive ion etc., with large amount of adsorption, the rate of adsorption is fast, the features such as being easily recycled with regeneration.
Description
Technical field
The invention belongs to field of compound material, and in particular to a kind of preparation method of boehmite modified cation adsorbent.
Background technique
Activated alumina is a kind of common adsorbent, and in order to improve its adsorption capacity, Du Wen etc. is modified using copper chloride
Aluminium oxide adsorbs demercuration ability to improve it;Also sodium hydroxide is used to go fluorine ability to alumina modified to improve;Also it adopts
With calcium, magnesium-modified aluminium oxide, to improve the removal ability to fluorine and humic acid;Also its using the modified raising of manganese removes fluorine
Removing solid capacity;Also it uses phosphotungstic acid for modifying agent, support type alumina adsorbant removing wax tailings is prepared for using infusion process
Middle nitride is also had and is introduced using coupling agent (silane coupling agent, titanate coupling agent, aluminate coupling agent) by etherification reaction
Then double bond is grafted and is modified to aluminium oxide.
Boehmite (γ-Al00H) contains a large amount of hydroxyl, itself has certain adsorption capacity, in recent years, Many researchers pair
The modification of boehmite has carried out a large amount of research, as Wu Xiu bravely prepares boehmite powder using esterification assisting alcohol-hydrothermal method: should
Application (application number: the 201220319265.4) water for generating esterification, for the hydrolysis of urea, and then in hydrothermal condition
Under, it reacts with aluminium salt, while obtaining esterification product, obtains that granularity is small and uniform boehmite powder;With this
Meanwhile the consumption of water, the balanced sequence of esterification can also be promoted, be conducive to shorten reaction time of esterification, a reaction week
In phase, organic esterified product and inorganic ultrafine powder can be obtained simultaneously, is conducive to the comprehensive utilization of energy, energy-saving effect is bright
It is aobvious;For another example by the activity and chloroacetate reaction of sulfydryl in 5- amido-1,3,4-thiadiazoles -2- mercaptan, prepare end group is beam space
The corrosion inhibiter of carboxylic acid group.Then corrosion inhibiter is bonded by esterification with the hydroxyl in boehmite, is grafted to boehmite
PH sensitivity release type inhibition antirust filler is made in surface.
In general, containing carboxyl, sulfonic polymer such as polyacrylic acid, polyphenyl sodium sulfonate to the dye of positive ion in water body,
Cation surface activating and metal ion have very strong adsorption capacity, but they are dissolved in water, cannot be very when using as adsorbent
Good recycling, and boehmite is weak to cation adsorbing capabilities, not soluble in water;By the method that is esterified, is grafted by two
Person is firmly combined together the shortcomings that both can overcoming, and plays its advantage, can prepare can recycle it is new and effective
Adsorbent.
Summary of the invention
A kind of boehmite modified cation absorption that the purpose of the present invention is design aiming at the problem that background technique proposes
The preparation method of agent, this method obtains boehmite and organic acid reaction containing double bond to be esterified boehmite containing double bond, then to containing double
The esterification boehmite of key is graft-polymerized, the boehmite modified cation adsorbent of preparation can be used for adsorbing in water sun from
Sub- dyestuff, cationic surfactant, Pb2+、Ni2+、Cr3+、Au3+、Cu2+、Cd2+, Hg2+,Ca2+,Mg2+, Fe3+, Ag+,Zn2+,
Al3+Equal cations.
Inventor passes through a large number of experiments and unremitting effort, is finally obtained following scheme:
A kind of preparation method of boehmite modified cation adsorbent, includes the following steps:
(1) boehmite be first added to the water or the water containing a certain amount of hydroquinone in or be added dimethylbenzene in carry out at dispersion
Reason, double bond containing organic acid is then added and carries out esterification, obtains double bond containing esterification boehmite, esterification condition
Are as follows: aqueous solution is stirred to react 10-72 hours or in dimethylbenzene, 138-145 DEG C, reflux 10-72 hours at 70-100 DEG C of temperature;
The molar ratio of the boehmite and the organic acid containing double bond is 1:1-1:4;
The double bond containing organic acid is acrylic acid, methacrylic acid, butene dioic acid, styrene sulfonic acid, trans--styrene
Any one of acetic acid (4- phenyl -3-butenoic acid);
Concentration of the boehmite in water or in the water containing a certain amount of hydroquinone or in dimethylbenzene is 1-8wt%;
(2) initiator, monomer, crosslinking agent and esterification boehmite are added in water, to containing double bond under nitrogen protection, stirring
Esterification boehmite be graft-polymerized, reaction temperature be 50-80 DEG C, reaction time 3-15 hour, then through centrifugation, mistake
Filter, washing are dried in vacuo to get boehmite modified cation adsorbent is arrived;
Monomer concentration is 2-10wt% in the aqueous solution, and initiator additive amount is the 0.5-2wt% of monomer;Crosslinking agent is used
Amount is the 0.5-3wt% of monomer, and the mass ratio for being esterified boehmite and monomer is 1:1-1:10.
The initiator includes any one of potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate;
The monomer is containing carboxyl, sulfonic monomer, is specifically acrylic acid, propylene containing carboxyl, sulfonic monomer
Sour sodium, methacrylic acid, Sodium methacrylate, sodium p styrene sulfonate, butene dioic acid it is any one or more;
The crosslinking agent that obtains is any one of ethylene glycol, diethylenetriamine.
Preferably, a kind of preparation method of boehmite modified cation adsorbent as described above, in the step (2)
Being esterified boehmite can also be the polymer magnetic micro-sphere of the boehmite containing esterification.
Preferably, a kind of preparation method of boehmite modified cation adsorbent as described above, described is vigorous containing esterification
The polymer magnetic micro-sphere of nurse stone the preparation method comprises the following steps: by polymer, ferroso-ferric oxide, double bond containing esterification boehmite, solvent,
Pore-foaming agent mixing, is prepared using immersion precipitation phase inversion process;
The polymer is any one of polyvinyl chloride, Kynoar, polysulfones;
The pore-foaming agent includes any one of polyethylene glycol and polyvinylpyrrolidone;
The solvent is dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, any in N-Methyl pyrrolidone
Kind.
The present invention is as follows using the principle of boehmite and the organic acid reaction containing double bond: contain great amount of hydroxy group on boehmite, with
Carboxyl in organic acid containing double bond reacts, and dehydration obtains double bond containing ester.
Compared with prior art, advantages of the present invention are as follows:
1, by the esterification of boehmite and the organic acid containing double bond, double bond containing active monomer is secured by covalent bond
Ground is incorporated on boehmite, and then can easily carry out subsequent graft modification, to overcome the profit of hydrophobic adsorbent
The problems such as wet problem or the water solubility of hydrophilic adsorbent.
2, boehmite modified adsorbent prepared by the present invention not only contains hydroxyl, also contains a large amount of carboxyl or sulfonic group,
Adsorbent soluble easily in water, is on the other hand fixed on boehmite not soluble in water by the adsorption capacity on the one hand improving boehmite
On, it can recycle very well.This boehmite modified adsorbent can be by ion exchange or complexing quick adsorption water body
Metal cation, cationic surfactant or the dye of positive ion etc., have that large amount of adsorption, the rate of adsorption are fast, are easily recycled
The features such as with regeneration.
3, the cation adsorbent prepared by the present invention can be used for adsorbing the dye of positive ion, cation surface activating in water
Agent, Pb2+、Ni2+、Cr3+、Au3+、Cu2+、Cd2+, Hg2+,Ca2+,Mg2+, Fe3+, Ag+,Zn2+,Al3+Cation.
Detailed description of the invention
Fig. 1 is the schematic diagram that boehmite is reacted with acrylic acid.
Specific embodiment
Below in conjunction with attached drawing, embodiments of the present invention is further illustrated, to make the purpose of the present invention, technical solution and excellent
Point is clearer, below technical solution in the present invention be clearly and completely described, it is clear that described embodiment is this
Invention a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art exist
Every other embodiment obtained under the premise of creative work is not made, shall fall within the protection scope of the present invention.
Embodiment 1
A kind of preparation method of boehmite modified cation adsorbent, this method comprises the following steps:
(1) 6.49g sodium hydroxide is added to the sodium hydroxide solution that 3.24M is made into 50 milliliters of water, then violent
Sodium hydroxide is added dropwise with 2.94 milliliters of speed per minute into the aluminum chloride aqueous solution that 30ml aluminium ion concentration is 1.78M under stirring
Solution is added dropwise completely for about 17 minutes, then ultrasound 3 hours at 25 DEG C, and precipitating filtering washing, finally baking 4 is small at 220 DEG C
When, obtain boehmite.
(2) it takes 50 grams of boehmites (0.83mol) to be added in 800 milliliters of distilled water to disperse, and is ultrasonically treated, 5 points
3 grams of hydroquinones are added after clock;Then it is slowly added to methacrylic acid (154g, 1.8mol) at room temperature, under 70 DEG C of stirrings
Carry out reaction in 20 hours, solid matter with deionized water washing, finally in a vacuum 50 DEG C drying 20 hours be to be esterified
Boehmite.
(3) with 10g polyvinyl chloride, 5g ferroso-ferric oxide, 10g esterification boehmite, 5g polyethylene glycol and 70g dimethylacetamide
Amine is added drop-wise to the polymer magnetic for obtaining the boehmite containing esterification for gel 24 hours in distilled water in 60 DEG C of stirrings, 12 hours wiring solution-formings
Property microballoon, drains to be put into ethyl alcohol and impregnate 1 hour, air drying.
(4) glycol water that acrylic acid and 0.05wt% containing 3wt% are prepared with 500 milliliters of aqueous solutions, leads to nitrogen
15 minutes, the polymer microballoon and 0.1g potassium peroxydisulfate of boehmite of the 15g containing esterification, then logical nitrogen 10 minutes are added, stir,
It reacts 4 hours at 70-75 DEG C, then washes, boehmite modified cation microsphere adsorbing agent, performance are dried to obtain at 50 DEG C
It is shown in Table 1.
Embodiment 2
A kind of preparation method of boehmite modified cation adsorbent, this method comprises the following steps:
(1) 10.2g sodium metaaluminate and 28.8g urea are dissolved in the deionized water of 1L, then pipette 30mL meta-aluminic acid
Sodium/urea mixed solution is placed in the hydrothermal reaction kettle of 50mL, carries out hydro-thermal reaction for 24 hours in 160 DEG C of baking oven, cooling, is washed
It washs filtration drying and obtains boehmite.
(2) it disperses 10.0g boehmite in 250mL dimethylbenzene, adds 48g acrylic acid, mixture 138- in dimethylbenzene
145 DEG C are flowed back 72 hours, and vacuum distillation removal toluene washs solid removal impurity with ether, and it is vigorous that white esterification is obtained after dry
Nurse stone powder.
(3) 20.6g sodium p styrene sulfonate and 0.2g diethylenetriamine and 5g is added to be esterified boehmite powder into the water of 500mL
End, leads to nitrogen 15 minutes, then plus 0.1g potassium peroxydisulfate and logical nitrogen, stirring, react 5 hours at 70-80 DEG C, then washing with
Ethanol washing is dried to obtain boehmite modified cation adsorbent at 80 DEG C.
Embodiment 3
A kind of preparation method of boehmite modified cation adsorbent, this method comprises the following steps:
(1) take 6.0g business boehmite, after adding 250mL water dispersion, then plus 11.6g butene dioic acid, agitating and heating is in diformazan
It flows back 24 hours for 138-145 DEG C in benzene, filtering, ethanol washing is dried to obtain esterification boehmite at 80 DEG C.
(2) with 12g Kynoar, 5g ferroso-ferric oxide, 5g esterification boehmite, 3g polyvinylpyrrolidone and 75g bis-
Then first sulfoxide is added drop-wise to gel 24 hours in distilled water in 60 DEG C of stirrings, 12 hours wiring solution-formings and obtains polymer microballoon, drip
Dry be put into ethyl alcohol is impregnated 1 hour, and air drying obtains esterification boehmite polymer microballoon.
(3) sodium p styrene sulfonate that acrylic acid and 3wt% containing 3wt% are prepared with 500 milliliters of aqueous solutions, adds 0.7g second
Glycol leads to nitrogen 15 minutes, and the polymer microballoon and 0.2g ammonium persulfate of 10g boehmite containing esterification, then logical nitrogen gas stirring is added,
It reacts 4 hours at 60-70 DEG C, then washes, boehmite modified cation microsphere adsorbing agent is dried to obtain at 80 DEG C.
The sample that we prepare embodiment 1 is determined the absorption property of its cation, is specifically shown in Table 1.
The absorption property of table 1, boehmite modified cation adsorbent
Claims (3)
1. a kind of preparation method of boehmite modified cation adsorbent, it is characterised in that: this method comprises the following steps:
(1) boehmite be first added to the water or the water containing a certain amount of hydroquinone in or be added dimethylbenzene in carry out decentralized processing, so
After double bond containing organic acid be added carry out esterification, obtain double bond containing esterification boehmite, esterification condition are as follows: temperature
At 70-100 DEG C aqueous solution be stirred to react 10-72 hours or in dimethylbenzene, 138-145 DEG C reflux 10-72 hours;
The molar ratio of the boehmite and the organic acid containing double bond is 1:1-1:4;
The double bond containing organic acid is acrylic acid, methacrylic acid, butene dioic acid, styrene sulfonic acid, trans--phenylethyl acetate
Any one of (4- phenyl -3-butenoic acid);
Concentration of the boehmite in water or in the water containing a certain amount of hydroquinone or in dimethylbenzene is 1-8wt%;
(2) initiator, monomer, crosslinking agent and esterification boehmite are added in water, obtains mixed aqueous solution, in nitrogen protection, stirs
Mix it is lower be graft-polymerized to double bond containing esterification boehmite, reaction temperature be 50-80 DEG C, reaction time 3-15 hour, so
Boehmite modified cation adsorbent is arrived by being centrifuged, being filtered, washed, be dried in vacuo afterwards;
Monomer concentration is 2-10wt% in the mixed aqueous solution, and initiator additive amount is the 0.5-2wt% of monomer;Dosage of crosslinking agent
For the 0.5-3wt% of monomer, the mass ratio for being esterified boehmite and monomer is 1:1-1:10;
The initiator is any one of potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate;
The monomer be containing carboxyl, sulfonic monomer, specifically containing carboxyl, sulfonic monomer be acrylic acid, sodium acrylate,
Methacrylic acid, Sodium methacrylate, sodium p styrene sulfonate, butene dioic acid are any one or more of;
The crosslinking agent is any one of ethylene glycol, diethylenetriamine.
2. a kind of preparation method of boehmite modified cation adsorbent as described in claim 1, it is characterised in that: the step
Suddenly the esterification boehmite in (2) can also be the polymer magnetic micro-sphere of the boehmite containing esterification.
3. a kind of preparation method of boehmite modified cation adsorbent as claimed in claim 2, it is characterised in that: it is described
The polymer magnetic micro-sphere of the boehmite containing esterification the preparation method comprises the following steps: by polymer, ferroso-ferric oxide, the vigorous nurse of double bond containing esterification
Stone, solvent, pore-foaming agent mixing, are prepared using immersion precipitation phase inversion process;
The polymer is any one of polyvinyl chloride, Kynoar, polysulfones;
The pore-foaming agent is any one of polyethylene glycol and polyvinylpyrrolidone;
The solvent is dimethylformamide, in dimethyl acetamide, dimethyl sulfoxide, N-Methyl pyrrolidone
It is any.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2018115311374 | 2018-12-13 | ||
CN201811531137 | 2018-12-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN110227420A true CN110227420A (en) | 2019-09-13 |
Family
ID=67858513
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910448796.XA Pending CN110227420A (en) | 2018-12-13 | 2019-05-27 | A kind of preparation method of boehmite modified cation adsorbent |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110227420A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112316910A (en) * | 2020-10-28 | 2021-02-05 | 东北大学 | Method for preparing adsorbent by graft modification of waste boric sludge sulfonic acid group |
CN112691637A (en) * | 2020-12-22 | 2021-04-23 | 广东电网有限责任公司电力科学研究院 | Adsorbent for transformer oil and preparation method thereof |
CN113735151A (en) * | 2021-09-24 | 2021-12-03 | 中铝郑州有色金属研究院有限公司 | Low-iron boehmite and preparation method and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090264280A1 (en) * | 2007-01-09 | 2009-10-22 | Nikolay Aleksandrovich BADULIN | Sorbent for removing heavy metal ions from water |
CN103613109A (en) * | 2013-12-06 | 2014-03-05 | 重庆理工大学 | Boehmite adsorbing material in 3D structure, preparation method and use thereof |
CN106362713A (en) * | 2016-11-02 | 2017-02-01 | 湖北工业大学 | Magnetic adsorbent containing sodium polystyrene sulfonate and preparation method |
CN107501483A (en) * | 2017-07-19 | 2017-12-22 | 成都理工大学 | A kind of preparation method of stalk/hectorite Compound Heavy Metals ion adsorbent |
-
2019
- 2019-05-27 CN CN201910448796.XA patent/CN110227420A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090264280A1 (en) * | 2007-01-09 | 2009-10-22 | Nikolay Aleksandrovich BADULIN | Sorbent for removing heavy metal ions from water |
CN103613109A (en) * | 2013-12-06 | 2014-03-05 | 重庆理工大学 | Boehmite adsorbing material in 3D structure, preparation method and use thereof |
CN106362713A (en) * | 2016-11-02 | 2017-02-01 | 湖北工业大学 | Magnetic adsorbent containing sodium polystyrene sulfonate and preparation method |
CN107501483A (en) * | 2017-07-19 | 2017-12-22 | 成都理工大学 | A kind of preparation method of stalk/hectorite Compound Heavy Metals ion adsorbent |
Non-Patent Citations (1)
Title |
---|
PARISA DARAEI ET AL.: "PAA grafting onto new acrylate-alumoxane/PES mixed matrix nano-enhanced membrane: Preparation, characterization and performance in dye removal", 《CHEMICAL ENGINEERING JOURNAL》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112316910A (en) * | 2020-10-28 | 2021-02-05 | 东北大学 | Method for preparing adsorbent by graft modification of waste boric sludge sulfonic acid group |
CN112691637A (en) * | 2020-12-22 | 2021-04-23 | 广东电网有限责任公司电力科学研究院 | Adsorbent for transformer oil and preparation method thereof |
CN113735151A (en) * | 2021-09-24 | 2021-12-03 | 中铝郑州有色金属研究院有限公司 | Low-iron boehmite and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110227420A (en) | A kind of preparation method of boehmite modified cation adsorbent | |
CN100562534C (en) | A kind of method of grafting polymer on inorganic material surface | |
CN100443508C (en) | Process for preparing functional high molecule composite micro ball with quick magnetic field responsiveness | |
CN102671641B (en) | Preparation and application for nanometer SiO2 strengthened calcium alginate-xanthan gum composite absorbent | |
CN102716722A (en) | Preparation method of graphene-based novel nano magnetic biological adsorbent | |
CN103159891B (en) | Magnetic amino-modified superhighly-crosslinked resin and preparation method thereof | |
CN105214629A (en) | A kind of biomass-based nano lanthanum oxide dephosphorization compound adsorbent and preparation method thereof | |
CN105131332B (en) | A kind of method of surface grafting polymerization thing modified carbon fiber | |
CN116835734B (en) | Desulfurization wastewater integrated efficient flocculation medicament and preparation method thereof | |
CN108047361B (en) | A kind of Properties of Magnetic Chelating Resins, preparation method and its application in combined pollution water body purification | |
CN109794080A (en) | It is a kind of can magnetic recovery composite diatomite demulsifying material preparation method and application | |
CN102161880A (en) | Preparation method of superparamagnetism easily-degradable oil stain absorption material and product obtained by method | |
CN104347192B (en) | A kind of method that simple adsorbing metal palladium ion prepares the conductive micro-balloons producing for anisotropic conductive film | |
CN110105486A (en) | A kind of electric conductivity aluminium based lithium-ion adsorption column material and preparation method thereof | |
CN106362703B (en) | Modified carragheen-chitosan polyelectrolyte microsphere and its preparation method and application | |
CN105037630A (en) | Hydrophilic polymer microsphere and simple preparing method thereof | |
JP5967435B2 (en) | Ferrocyanide composite vinyl polymer, preparation of the polymer, and cesium ion adsorbent containing the polymer | |
CN108034073B (en) | Intelligently-changed particles and preparation method thereof | |
CN110215911A (en) | A kind of preparation method of modified boehmite adsorbed film | |
CN102504283B (en) | Method for preparing lignosulfonate micro gel | |
CN104479076B (en) | A kind of hydrophilic luffa | |
CN108499535A (en) | A kind of preparation of beta-cyclodextrin-ferriferrous oxide nano magnetic bead | |
CN116809034A (en) | Preparation method of dephosphorizing agent based on rare earth modified gangue | |
CN106111085B (en) | A kind of material and preparation method thereof of the chitosan-based adsorbent of quick processing waste water from dyestuff | |
CN110215910A (en) | A kind of preparation method of boehmite modified adsorbent |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190913 |
|
RJ01 | Rejection of invention patent application after publication |