CN108236939A - A kind of alumina support of containing mesopore/macropore and preparation method thereof - Google Patents
A kind of alumina support of containing mesopore/macropore and preparation method thereof Download PDFInfo
- Publication number
- CN108236939A CN108236939A CN201611228490.6A CN201611228490A CN108236939A CN 108236939 A CN108236939 A CN 108236939A CN 201611228490 A CN201611228490 A CN 201611228490A CN 108236939 A CN108236939 A CN 108236939A
- Authority
- CN
- China
- Prior art keywords
- macropore
- agent
- alumina support
- acid
- mesopore
- 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.)
- Granted
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 80
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 45
- 229920000126 latex Polymers 0.000 claims abstract description 40
- 239000004816 latex Substances 0.000 claims abstract description 39
- 239000011148 porous material Substances 0.000 claims abstract description 33
- 238000009826 distribution Methods 0.000 claims abstract description 26
- 230000002902 bimodal effect Effects 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- -1 propylene nitrile Chemical class 0.000 claims description 22
- 239000003995 emulsifying agent Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 19
- 229910001593 boehmite Inorganic materials 0.000 claims description 17
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 17
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- 230000003750 conditioning effect Effects 0.000 claims description 16
- 150000007522 mineralic acids Chemical class 0.000 claims description 15
- 150000007524 organic acids Chemical class 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 10
- 238000004945 emulsification Methods 0.000 claims description 9
- 239000011812 mixed powder Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 150000004665 fatty acids Chemical group 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- 239000000344 soap Substances 0.000 claims description 8
- 239000002738 chelating agent Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims description 2
- 230000001404 mediated effect Effects 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 150000004053 quinones Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 18
- 238000007792 addition Methods 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 16
- 241000219782 Sesbania Species 0.000 description 14
- 238000000465 moulding Methods 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 8
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229920002379 silicone rubber Polymers 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 241000219793 Trifolium Species 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000004966 Carbon aerogel Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 description 4
- 235000011151 potassium sulphates Nutrition 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000011805 ball Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035800 maturation Effects 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical class OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910018512 Al—OH Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QDADQGMWHGQPDW-UHFFFAOYSA-N OS(O)=O.OCl(=O)=O Chemical compound OS(O)=O.OCl(=O)=O QDADQGMWHGQPDW-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920013820 alkyl cellulose Polymers 0.000 description 1
- HNCFMHGQOBPUCW-UHFFFAOYSA-G aluminum silicon(4+) heptahydroxide Chemical compound [Si+4].[OH-].[Al+3].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] HNCFMHGQOBPUCW-UHFFFAOYSA-G 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
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Abstract
The present invention relates to a kind of alumina supports of containing mesopore/macropore, 10~200nm of pore-size distribution, 0.8~2.2ml/g of total pore volume, aperture is in bimodal distribution, the mesoporous Kong Rong of wherein 10~50nm accounts for the 10%~50% of total pore volume, the macropore hole of 50~200nm, which holds, accounts for the 50%~90% of total pore volume, and carrier uses acrylonitrile-butadiene rubber latex as expanding agent.The characteristics of alumina support of containing mesopore/macropore is adjusted with pore size, and mesopore/macropore ratio can be controlled effectively.The invention further relates to a kind of preparation methods of the alumina support of containing mesopore/macropore.
Description
Technical field
It is particularly a kind of with containing pole the present invention relates to a kind of alumina support of containing mesopore/macropore and preparation method thereof
Property acrylonitrile-butadiene rubber latex as expanding agent, synthesis with mesopore/macropore bimodal pore distribution and mesopore/macropore pore-size distribution it is adjustable
The alumina support and preparation method that section, mesopore/macropore ratio can be controlled effectively.
Background technology
The branch of catalytic science and process as important chemical is to improve reaction transformation efficiency and purpose product
Selectivity, the economy for improving reaction process, the important means for reducing reaction severity.Catalyst is the core skill of catalytic process
Art, the exploitation of effective catalyst are always the common pursuit of researcher.Loaded catalyst has technology maturation, producer
The advantages that method is simple, reliable in quality is always the first choice of catalyst exploitation.Important composition portion of the carrier as loaded catalyst
Point, in addition to improving active component utilization rate and improving active component dispersion performance, also carried for the diffusion process of reactants and products
For channel, in recent years, macropore carrier material is widely used in improving the performance of catalyst because can effectively improve mass transfer rate due to.
Aluminium oxide as traditional catalyst carrier material, have technology maturation, pore structure is adjusted, use cost is low,
The characteristics of being easily worked molding is widely used for the preparation of various catalyst.According to differential responses to pore structure and surface acidity
Requirement, form miscellaneous process for making alumina and product, such as：It is acted on for improving aluminium oxide with active metal
The composite aluminas product such as titaniferous, zirconium；For improving the alumina products such as the fluorine-containing of Surface Acidity of Alumina Support, chlorine；With
And the alumina products such as high heap ratio, low heap ratio, high-specific surface area, high-purity.The pore passage structure of aluminium oxide from particle or
The accumulation gap of intergranular, the gama-alumina aperture of conventional method synthesis is generally less than 15nm, so researchers have carried out largely
Macroporous structure aluminium oxide Study of synthesis method.
Alumina supporting material containing macroporous structure in order to obtain, researchers are by using expanding agent, hydro-thermal process etc.
Method obtains the aluminium oxide of macroporous structure.The pertinent literature of expanding agent method synthesis macroporous aluminium oxide material is more, according to expanding agent
Type is different, can be divided into：Two methods of hard expanding agent and soft expanding agent.Hard expanding agent method using activated carbon as representative can be with
Preferable macroporous aluminium oxide is obtained, US19820384626 discloses a kind of carbon black as expanding agent, can obtain pore-size distribution and exist
The macroporous aluminium oxide of 15~300nm, but since the particle diameter distribution of carbon black is inhomogenous, it is more difficult to prepare pore-size distribution concentration
Macroporous aluminium oxide.CN201410347665.X discloses a kind of macropore appearance, the preparation method of high-strength alumina, poly- by adding in
The expanding agents such as acrylamide, polyvinyl alcohol, alkylcellulose, sesbania powder, starch are obtained containing eurypyloue alumina support,
The dosage of expanding agent accounts for the 10%~30% of aluminium oxide, but specific pore diameter range is not disclosed.Although hard expanding agent method can obtain
To preferable macropore alumina supporter, but the dosage of its expanding agent causes processing cost to greatly improve, greatly more preferably greater than 20%
The decomposition of amount expanding agent does not meet the demand for development of low-carbon environment-friendly yet.CN201010509425.7 discloses a kind of hydro-thermal and reaming
The method of the common reaming of agent to prepare the alumina support containing macroporous structure, is acted on, expanding agent by the complementary reaming of hydro-thermal
Dosage can be reduced to 3%~10%, but hydro-thermal is assisted to cause the raising of energy consumption.CN200310103035.X is disclosed
A kind of preparation method of macroporous aluminium oxide carries out reaming, by adding using polyvinyl alcohol, poly- propyl alcohol, the soft expanding agent of polyethylene glycol
Enter 1% polyethylene glycol, Kong Rong of the aperture more than 100nm accounts for the 26.2% of total pore volume.Soft expanding agent has that dosage is low, reaming effect
The advantages of fruit is good, but the solubility property of the soft expanding agent of the alcohols of higher molecular weight in water is poor, it is caused to be used to expand super large
Porous aluminum oxide is restricted.CN201410148773.4 discloses a kind of preparation method of aluminum oxide porous microballoon, including following
Step：1) surfactant is dissolved in deionized water, stirred, as water phase；2) by chelating agent, alumina precursor with it is just pungent
Alcohol mixes, stirring, as oil phase；3) Span80 and pore-foaming agent, stirring are added in oil phase；It 4) will be clear obtained by step 3)
Oil phase, which is poured into water phase, continues stirring and emulsifying；5) step 4) gains are filtered by vacuum, it is dry after gained Washing of Filter Cake, obtain oxygen
Change aluminium porous microsphere.The microballoon has internal closing macroporous structure, and Microsphere Size is 1~100 μm, the invention using pore-foaming agent with
Sol-gel process in lotion obtains the metal porous microballoon with internal closing macroporous structure.It is prepared using phase separation principle
Porous microsphere.Inside closing aperture is 50nm~5 μm.Pore-foaming agent is polyvinylpyrrolidone, polyacrylamide or polyacrylic acid.
The invention has used a large amount of surfactant, chelating agent, pore-foaming agent, and it is more to prepare raw material, and synthesis technology is complicated.
CN201310748661.8 discloses a kind of preparation method of aluminium oxide/carbon aerogel composite material, will in closed container
Water-soluble saccharides compound and water soluble polymer are dissolved in water, then add in aluminium salt or aluminium hydroxide, are reacted at 140~300 DEG C,
Calcining obtains aluminium oxide/carbon aerogel composite material under 300~1500 DEG C of inert atmospheres after drying.The invention uses one pot
Aluminium oxide/carbon aerogel composite material of method preparation low-density, high porosity, there is the present invention raw material to be easy to get, preparation process letter
The advantages that single, at low cost, aluminium oxide/carbon aerogel composite material of gained is light, porosity is high, available for catalyst carrier,
Gas sensor, solid electrolytic diaphragm, molten steel oxygen measuring probe material etc..CN201310499233.6 discloses a kind of alumina support
Preparation method, including following content：Alkaline precipitating agent aqueous solution is sunk with the progress neutralization reaction of acid aluminium salt aqueous solution first
Shallow lake slurries；Then water-soluble resin is added in into sediment slurry and burin-in process is carried out to it using microwave heating；Last aging
Rear mixed material is filtered, final alumina support is made in washing, dry, molding.Alumina support tool prepared by this method
There are larger aperture and the pore size distribution concentrated, the particularly hole of 10~20nm to account for total pore volume ratio big, reach 60%~80%, fit
In the carrier as heavy-oil hydrogenation catalyst.CN201310258011.5 is related to a kind of tooth spherical alumina support, tooth spherical shape oxygen
Change aluminium hydrotreating catalyst and preparation method thereof, including following components：Peptizing agent, 0.5~4 parts by weight；Lubricant, 0.2~2
Parts by weight；Dispersant, 0.2~3 parts by weight；Expanding agent, 0.3~4 parts by weight；Aluminium hydroxide, 100 parts by weight.Expanding agent is poly-
One kind or mixture in vinyl alcohol, Sodium Polyacrylate, starch derivatives or carbon black.The invention is added to anion surface active
Agent, specific surface area increases 246m while various auxiliary component additive amounts are reduced2/g.Tooth spherical shape oxidation described in the invention
Alumina supporter, since the wherein various auxiliary agents such as groups such as peptizing agent, expanding agent, dispersant, anion surfactant are greatly lowered
The content divided, has not only saved cost, has also had many advantages, such as large specific surface area, high mechanical strength.CN201110170283.0 is public
A kind of three-dimensional ordered macroporous alumina and preparation method thereof is opened.The three-dimensional ordered macroporous alumina, diameter macropores for 50~
1000nm, grain diameter are 1~50mm, and mechanical strength is 80~280g/mm.This method includes the following steps：Gather to monodisperse
Adding carbohydrate compound and the concentrated sulfuric acid in object microballoon lotion are closed, polymer-modified microballoon glue crystal template is obtained, is subsequently filled oxidation
Aluminum sol, then through aging and roasting, obtain three-dimensional ordered macroporous alumina.This method can increase substantially aluminium oxide precursor
Adhesion amount enhances the mechanical strength of material, and it is subtle powder that when removing template is removed in high-temperature roasting, large pore material is not easily broken,
Higher integrity degree can still be kept.CN201110116418.5 provides a kind of mesoporous sphere aluminium oxide and using expanding agent
It is oriented to the method for preparing the mesoporous sphere aluminium oxide.Using oil-drop method, add during Aluminum sol is prepared into Aluminum sol
Enter the expanding agent with guide function, Aluminum sol is in molding and ageing process, due to depositing for the expanding agent with guide function
Make to produce a large amount of meso-hole structure in alumina balls.Expanding agent be organic monomer or linear polymer, organic monomer third
One kind in olefin(e) acid, ammonium acrylate, acrylamide, allyl alcohol, linear polymer are polyvinyl alcohol, poly amic acid, polypropylene
One kind in amide, POLYPROPYLENE GLYCOL.The mesoporous sphere alumina ratio surface is 150~300m2/ g, 0.1~5mm of particle diameter,
Pore volume is 0.7~1.5ml/g, and the hole that bore dia is 2~40nm is more than 97%, and heap density is 0.30~0.80g/cm3, crushing
Intensity is 70~250N/.The mesoporous sphere alumina pore diameter that the invention is prepared using expanding agent compares concentration, the Mesoporous Spheres
Shape aluminium oxide can be used for being used as catalyst or catalyst carrier in petrochemical industry and fine chemistry industry.
Aluminium hydroxide is added in rubber or alumina ratio is more typical, for example, CN201110360481.3 provides one kind
The preparation method of aluminum hydroxide-silicon rubber composite material, it is characterized in that：It is carrier by filler, silicon rubber of aluminium hydroxide, straight
Compound heat-conducting silicon rubber is prepared in galvanic electricity off field.The blending ratio of aluminium hydroxide and silicon rubber is 0：100~40：60.
The composite heat-conducting silicon rubber prepared under the conditions of applying direct current electric field, can improve effective thermal conductivity 30%.CN97112353.5 is disclosed
A kind of diene rubber composition of aluminium oxide as reinforcing filler and tire and tire tread comprising the composition.With at least
It is based on a kind of diene elastomer, including the aluminium oxide and the rubber composition of coupling agent as reinforcing filler, the oxidation
Aluminium has：BET specific surface area is 30~400m2/ g, average particle size are less than or equal to 500nm, a high proportion of Al-OH surfaces reaction
Active function groups and polymolecularity, the amount of coupling agent is every square metre of aluminium oxide 10-7~10-5Mol, the composition are particularly suitable for
Manufacture tire.CN200510113501.1 is related to the silicone rubber compound for high voltage insulator.More precisely, it is related to addition
Or the silicone rubber compound of peroxide crosslinking, the composition contain aluminium hydroxide as filler, used aluminium hydroxide is
The aluminium hydroxide of unprocessed mistake.
CN102311134A discloses a kind of spherical integral macroporous alumina, and specific surface area is 100~350m2/g, hole
Hold for 0.5~1.5ml/g, macropore average pore diameter is 0.05~1.0 μm, and preparation method is also disclosed in invention, in a constant temperature
Polymer microballoon, alumina sol and coagulant are uniformly mixed under degree, are subsequently dispersed in oil phase, is heated to certain temperature,
Make alumina sol gelling balling-up, the molding gel micro-ball of sub-department from oil phase, polymer microballoon are micro- for polystyrene later
Ball, poly (methyl methacrylate) micro-sphere, polyacrylic acid ester microsphere etc., but it is prepared as the macroporous aluminium oxide of Unimodal Distribution, aperture
There is big advantage in solid catalysis reaction in the alumina support of bimodal distribution：Macropore is conducive to reactant molecule and work
Property center come into full contact with, or the deposition of impurity accommodates the memory space for providing bigger, while is the fast of product molecule
Speed diffusion provides facility with abjection, and aperture portion then provides specific surface area and the reacting environment of bigger, is also beneficial to improve
The dispersion degree of supported active metals.
Macroporous aluminium oxide has been successfully applied to multiple catalyst systems, to the activity, selectivity and stability of catalyst
Aspect has different degrees of improvement result.Although hard expanding agent can obtain preferable macroporous structure, in adjustment aperture
There are certain deficiency in terms of size, the solubility of the soft expanding agent of polyvinyl alcohol in water is influenced by the degree of polymerization, leads to it
It is also subject to certain restrictions in preparation for super large porous aluminum oxide.
Invention content
For macroporous aluminium oxide in the extensive use of catalytic field, butadiene-acrylonitrile of the present invention use containing polarized
Copolymer rubber (nitrile rubber) lotion synthesizes the alumina support of containing mesopore/macropore as expanding agent.Nitrile rubber is due to pole
Property itrile group exist, therefore have higher stability to nonpolarity or the solvent of low pole, be more suited to mesopore/macropore carrying alumina
There is mesopore/macropore pore size to be adjusted for the expanding agent of body, the mesopore/macropore alumina support of preparation, mesopore/macropore ratio
The characteristics of can effectively controlling.The alumina support of containing mesopore/macropore can be used for petrochemical industry and field of fine chemical.This hair
It is bright it is described it is mesoporous be hole of the aperture between 2 to 50 nanometers, macropore is the hole that aperture is more than 50 nanometers.
A kind of alumina support containing macropore, 10~200nm of pore-size distribution, aperture is in bimodal distribution, wherein 10~50nm
Mesoporous Kong Rong account for the 10%~50% of total pore volume, the macropore hole of 50~200nm, which holds, accounts for the 50%~90% of total pore volume, preferably greatly
Hole pore-size distribution is 80~180nm, and macropore hole, which holds, accounts for the 60%~80% of total pore volume；Mesoporous pore size be 20~50nm, total pore volume
0.8~2.2ml/g, preferably preferably 0.8~1.2ml/g or 1.8~2.2ml/g, 260~290m of specific surface area2/ g, carrier use
Particle size range be the acrylonitrile-butadiene rubber latex of 10~200nm as expanding agent, the particle size of synthetic emulsion is controllable, stability is good,
Alumina support is more prone to meso/macroporous structure, and mesopore/macropore pore-size distribution can when therefore being used as expanding agent
It adjusts, pore-size distribution is in 10~200nm ranges.
The alumina support of containing mesopore/macropore of the present invention, aperture can by change the molecular weight of expanding agent, grain size and
Addition is adjusted.Pore-size distribution can change between 10~200nm, as macropore diameter is distributed as 80~180nm, macropore
Kong Rong accounts for the 60%~80% of total pore volume；Mesoporous pore size is 20~50nm.It is preferred that macropore diameter is distributed as 80~100nm or 100
~130nm or 150~180nm, mesoporous pore size are distributed as 20~30nm.
The present invention also provides a kind of preparation methods of containing mesopore/macropore alumina supporter, include the following steps：
First, acrylonitrile-butadiene rubber latex of the grain size in 10~200nm is prepared, and organic acid or inorganic acid are added thereto, is had
The addition of machine acid or inorganic acid is 0.2wt%~3.4wt% of acrylonitrile-butadiene rubber latex, then by boehmite powder and field
The mixed-powder of cyanines powder is added in kneader and is uniformly mixed, then will be added in containing the acrylonitrile-butadiene rubber latex of organic acid or inorganic acid
It is mediated into mixed-powder uniformly, the addition of the acrylonitrile-butadiene rubber latex containing organic acid or inorganic acid is mixed-powder
0.1wt%~45wt%, preferably 0.5wt%~30wt%, more preferable 5wt%~20.0wt%, by extrusion-molding-drying-
Roasting, obtains the alumina support of containing mesopore/macropore.
The acrylonitrile-butadiene rubber latex is prepared using emulsion polymerisation process, is included the following steps：
It will be first by polymer grade divinylic monomer, polymerization-grade propylene nitrile monomer, deionized water, emulsifier, electrolyte and auxiliary
Auxiliary agent adds in paradigmatic system, using two kinds of polymer grade divinylic monomer, polymerization-grade propylene nitrile monomer monomer gross mass as 100 parts
Meter, wherein polymer grade butadiene dosage are 50~80 parts, preferably 58~75 parts；Deionized water dosage is 100~300 parts；Emulsification
Agent dosage is 0.2~10 part；Electrolyte dosage is 0.1~2 part；Auxiliary addition agent dosage is 0.01~0.2 part；
Under agitation, material is made to mix 20~40min of pre-emulsification into emulsion, adds in and causes after being cooled to 5~8 DEG C
Agent and conditioning agent are counted using two kinds of polymer grade butadiene, polymerization-grade propylene nitrile monomer gross mass as 100 parts, and initiator amount is
0.005~0.5 part；Conditioning agent dosage is 0.1~2 part；
Control 5~8 DEG C, 0.1~0.5MPa of pressure, 10~12h of reaction time of temperature, grade butadiene to be polymerized, polymer grade
Two kinds of monomer conversions of acrylonitrile add in terminator when reaching 70%~85% and terminate polymerisation, obtain acrylonitrile-butadiene rubber latex.
The grain size of the acrylonitrile-butadiene rubber latex of synthesis is between 10~200nm, and grain size is mainly by the type of emulsifier, emulsifier
Dosage and conditioning agent dosage control.In general, select the emulsifying effectiveness of emulsifier better in building-up process, emulsifier is used
Amount is more, and conditioning agent dosage is more, and the grain size of the acrylonitrile-butadiene rubber latex of synthesis is smaller.
Emulsifier of the present invention is selected from anionic initiator (fatty acid soaps, long chain alkyl sulphonates, chain alkyl sulphur
Hydrochlorate etc., preferred fatty acid soap, long chain alkyl sulphonates), amphoteric emulsifier (carboxylic acids, sulfuric acid ester, sulphonic acids, preferably sulphur
Acids), among macromolecule emulsifier (such as carboxymethyl cellulose, p styrene sulfonic acid salt, preferably p styrene sulfonic acid salt)
It is one or more of.Electrolyte is selected from one or more of potassium chloride, sodium chloride, niter cake, sodium fluoride, preferably potassium chloride.
Auxiliary addition agent is selected from pH adjusting agent (KOH, Na2CO3Deng preferably Na2CO3), chelating agent (ethylenediamine tetra-acetic acid and its metal salt,
One or more of it is preferred that iron edta sodium salt (EDTA)), the initiator may be selected from inorganic peroxide (mistake
Potassium sulfate, Ammonium Persulfate 98.5 etc., preferably potassium peroxydisulfate), oxidation-reduction system (persulfate-mercaptan, chlorate-bisulfite
Salt, organic peroxide-ferrous salt, Persulphate-Bisulphite etc., preferably organic peroxide-ferrous salt etc.), azo
One or more of class initiator (azodiisobutyronitrile).Conditioning agent is also referred to as chain-transferring agent, selected from containing sulphur, nitrogen, phosphorus or
One or both of one or more of compound of organic unsaturated bond, preferably mercaptan, thiuram-disulfide.The end
Only agent may be selected from one or more of hydroquinone type, quinones, sulfur-containing compound.
The addition of acrylonitrile-butadiene rubber latex containing organic acid or inorganic acid is 0.1wt%~45wt% of mixed-powder,
It is preferred that the addition of 0.5wt%~30wt%, more preferable 5wt%~20.0wt%, organic acid or inorganic acid is nitrile rubber breast
0.2wt%~3.4wt% of liquid, the acid used are common various organic acids or inorganic acid in the art, and organic acid is selected from vinegar
Acid or citric acid；Inorganic acid is selected from nitric acid or hydrochloric acid.The source of the boehmite powder and property do not limit, can
Think the product of the technique productions such as carbonizatin method, nitrate method, sulfuric acid process, ammonium method.It is adapted to different range specific surface area, Kong Rong, hole
The boehmite of diameter.
It mediates or extrusion technique is that the expanding agent containing organic acid or inorganic acid being configured is added to boehmite powder
End and sesbania powder mixed-powder in be uniformly mixed, later extrusion, molding, by 80~200 DEG C dry 2~8 hours, 550~
700 DEG C roast 4~6 hours, finally obtain the alumina support of containing mesopore/macropore.
The acrylonitrile-butadiene rubber latex of synthesis can make the grain size of acrylonitrile-butadiene rubber latex by the type and dosage for controlling emulsifier
It is adjusted in 10~200nm, while the dosage of initiator and conditioning agent can be controlled to make its molecular weight from thousand grades to 100,000 grade
It is adjustable, so can additions control aluminium oxide different according to acrylonitrile-butadiene rubber latex grain size and acrylonitrile-butadiene rubber latex it is mesoporous/
Macropore diameter size and ratio.
Description of the drawings
Fig. 1 is the graph of pore diameter distribution of embodiment 1.
Specific embodiment
The present invention is described in further detail by the following examples, but these embodiments are not considered as the limit to the present invention
System.
Prepare primary raw material source used in catalyst：Source chemicals used in the present invention are commercial product.
Embodiment 1
70 parts of (mass ratio) polymer grade divinylic monomers of addition in 10L polymeric kettles, 30 parts of polymerization-grade propylene nitrile monomers,
250 parts of deionized waters, 4.5 parts of emulsifier neopelexes and 4.5 parts of emulsifier fatty acid soaps, 1.5 parts of electrolyte
KCl, 0.12 part of chelating agent iron edta sodium salt (EDTA), pre-emulsification 30min are added in after temperature is cooled to 5 DEG C and are drawn
0.4 part of initiator cumyl peroxide-ferrous sulfate of agent is sent out, 1.5 parts of conditioning agent tert-dodecyl mercaptans react at 5 DEG C
12h, control initial reaction pressure are 0.1MPa, and monomer conversion control adds in hydroquinone type terminator at 80%, obtains
Grain size is the acrylonitrile-butadiene rubber latex of 15nm.
The deionized water of 260mL is measured in beaker, 15.0g acetic acid is added in deionized water and is uniformly mixed, and is placed in 80
DEG C water-bath in.It weighs 15.0g acrylonitrile-butadiene rubber latex and is added in prepared deionized water acid solution, stir evenly,
Obtain the acid solution containing expanding agent.300g boehmite powder and 15.0g sesbania powders are weighed, and is uniformly mixed in kneader,
The acid solution of acrylonitrile-butadiene rubber latex is added in boehmite and sesbania powder, is clover shape by kneading-extruded moulding.
6 hours dry at 150 DEG C, 600 DEG C roast 5 hours, obtain the alumina support A-1 of containing mesopore/macropore.Containing mesopore/macropore
Alumina support specific surface area is shown in Table 1 with pore-size distribution.
Embodiment 2
75 parts of (mass ratio) polymer grade divinylic monomers of addition in 10L polymeric kettles, 25 parts of polymerization-grade propylene nitrile monomers,
250 parts of deionized waters, 5.0 parts of emulsifier fatty acid soaps, 1.5 parts of electrolyte KCl, 0.05 part of pH adjusting agent Na2CO3, pre-emulsification
30min, 0.12 part of initiator potassium sulfate of addition after temperature is cooled to 5 DEG C, 1.0 parts of conditioning agent thiuram-disulfides, at 5 DEG C
10h is reacted, control initial reaction pressure is 0.2MPa, and two kinds of monomer conversion controls add in thiol terminations agent at 70%, obtain
To the acrylonitrile-butadiene rubber latex that grain size is 80nm.
The deionized water of 250mL is measured in beaker, a concentration of 68% nitric acid of 18.0g is added in deionized water and mixes
It is even, it is placed in 80 DEG C of water-bath.It weighs 30.0g acrylonitrile-butadiene rubber latex and is added to prepared deionized water salpeter solution
In, it stirs evenly, obtains the acid solution containing expanding agent.300g boehmite powder and 15.0g sesbania powders are weighed, and in kneader
In be uniformly mixed, the acid solution of acrylonitrile-butadiene rubber latex is added in boehmite and sesbania powder, is by kneading-extruded moulding
Clover shape.8 hours dry at 120 DEG C, 650 DEG C roast 4 hours, obtain the alumina support A-2 of containing mesopore/macropore.Contain
The alumina support specific surface area of mesopore/macropore is shown in Table 1 with pore-size distribution.
Embodiment 3
65 parts of (mass ratio) polymer grade divinylic monomers of addition in 10L polymeric kettles, 35 parts of polymerization-grade propylene nitrile monomers,
150 parts of deionized waters, 2.5 parts of emulsifier anhydrosorbitol esters, 0.8 part of electrolyte NaCl, 0.10 part of pH value adjustment agent KOH, in advance
40min is emulsified, 0.05 part of initiator azodiisobutyronitrile, 0.8 part of 12 carbon of conditioning agent uncle are added in after temperature is cooled to 12 DEG C
Mercaptan reacts 11h at 7 DEG C, and control initial reaction pressure is 0.2MPa, and it is whole that monomer conversion control adds in mercaptan at 70%
Only agent obtains the acrylonitrile-butadiene rubber latex that grain size is 100nm.
The deionized water of 260mL is measured in beaker, 12.0g acetic acid is added in deionized water and is uniformly mixed, and is placed in 80
DEG C water-bath in.It weighs 60.0g acrylonitrile-butadiene rubber latex and is added in prepared deionized water acid solution, stir evenly,
Obtain the acid solution containing expanding agent.300g boehmite powder and 15.0g sesbania powders are weighed, and is uniformly mixed in kneader,
The acid solution of acrylonitrile-butadiene rubber latex is added in boehmite and sesbania powder, is clover shape by kneading-extruded moulding.
8 hours dry at 130 DEG C, 700 DEG C roast 4 hours, obtain the alumina support A-3 of containing mesopore/macropore.Containing mesopore/macropore
Alumina support specific surface area is shown in Table 1 with pore-size distribution.
Embodiment 4
70 parts of (mass ratio) polymer grade divinylic monomers of addition in 10L polymeric kettles, 30 parts of polymerization-grade propylene nitrile monomers,
200 parts of deionized waters, 1.8 parts of emulsifier fatty acid soaps, 0.5 part of electrolyte KCl, 0.06 part of pH adjusting agent Na2CO3, pre-emulsification
30min, 0.12 part of initiator potassium sulfate of addition after temperature is cooled to 5 DEG C, 0.3 part of conditioning agent tert-dodecyl mercaptan, at 5 DEG C
10h is reacted, control initial reaction pressure is 0.3MPa, and two kinds of monomer conversion controls add in thiol terminations agent at 70%, obtain
To the acrylonitrile-butadiene rubber latex that grain size is 150nm.
The deionized water of 250mL is measured in beaker, a concentration of 68% nitric acid of 19.0g is added in deionized water and mixes
It is even, it is placed in 80 DEG C of water-bath.It weighs 45.0g acrylonitrile-butadiene rubber latex and is added to prepared deionized water salpeter solution
In, it stirs evenly, obtains the acid solution containing expanding agent.300g boehmite powder and 15.0g sesbania powders are weighed, and in kneader
In be uniformly mixed, the acid solution of acrylonitrile-butadiene rubber latex is added in boehmite and sesbania powder, is by kneading-extruded moulding
Clover shape.8 hours dry at 120 DEG C, 650 DEG C roast 4 hours, obtain the alumina support A-4 of containing mesopore/macropore.Contain
The alumina support specific surface area of mesopore/macropore is shown in Table 1 with pore-size distribution.
Embodiment 5
58 parts of (mass ratio) polymer grade divinylic monomers of addition in 10L polymeric kettles, 42 parts of polymerization-grade propylene nitrile monomers,
300 parts of deionized waters, 1.2 parts of emulsifier fatty acid soaps, 1.5 parts of electrolyte NaCl, 0.07 part of pH adjusting agent Na2CO3, 0.11
Part chelating agent iron edta sodium salt (EDTA), pre-emulsification 20min add in initiator 0.03 after temperature is cooled to 7 DEG C
Part cumyl peroxide-ferrous sulfate, 0.5 part of conditioning agent tert-dodecyl mercaptan react 11h at 5 DEG C, control initial reaction
Pressure is 0.35MPa, and monomer conversion control adds in thiol terminations agent at 70%, obtains the nitrile rubber that grain size is 180nm
Lotion.
The deionized water of 250mL is measured in beaker, a concentration of 68% nitric acid of 17.0g is added in deionized water and mixes
It is even, it is placed in 80 DEG C of water-bath.It weighs 16.0g acrylonitrile-butadiene rubber latex and is added in prepared deionized water acid solution,
It stirs evenly, obtains the acid solution containing expanding agent.300g boehmite powder and 15.0g sesbania powders are weighed, and in kneader
It is uniformly mixed, the acid solution of acrylonitrile-butadiene rubber latex is added in boehmite and sesbania powder, be three by kneading-extruded moulding
Clover shape shape.8 hours dry at 130 DEG C, 600 DEG C roast 6 hours, obtain the alumina support A-5 of containing mesopore/macropore.Containing Jie
The alumina support specific surface area of hole/macropore is shown in Table 1 with pore-size distribution.
Embodiment 6
75 parts of (mass ratio) polymer grade divinylic monomers of addition in 10L polymeric kettles, 25 parts of polymerization-grade propylene nitrile monomers,
300 parts of deionized waters, 0.8 part of emulsifier fatty acid soaps, 1.5 parts of electrolyte KCl, 0.05 part of pH adjusting agent Na2CO3, pre-emulsification
30min adds in 0.10 part of initiator potassium sulfate, 0.10 part of conditioning agent tert-dodecyl mercaptan, at 5 DEG C after temperature is cooled to 5 DEG C
Lower reaction 10h, control initial reaction pressure are 0.25MPa, and two kinds of monomer conversion controls add in thiol terminations agent at 70%,
Obtain the acrylonitrile-butadiene rubber latex that grain size is 200nm.
The deionized water of 250mL is measured in beaker, a concentration of 68% nitric acid of 12.0g is added in deionized water and mixes
It is even, it is placed in 80 DEG C of water-bath.It weighs 42.0g acrylonitrile-butadiene rubber latex and is added to prepared deionized water salpeter solution
In, it stirs evenly, obtains the acid solution containing expanding agent.300g boehmite powder and 15.0g sesbania powders are weighed, and in kneader
In be uniformly mixed, the acid solution of acrylonitrile-butadiene rubber latex is added in boehmite and sesbania powder, is by kneading-extruded moulding
Clover shape.8 hours dry at 120 DEG C, 650 DEG C roast 4 hours, obtain the alumina support A-6 of containing mesopore/macropore.Contain
The alumina support specific surface area of mesopore/macropore is shown in Table 1 with pore-size distribution.
The alumina support specific surface area and pore-size distribution of 1 containing mesopore of table/macropore
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
It should all belong to the scope of protection of the present invention.
Claims (10)
1. a kind of alumina support of containing mesopore/macropore, which is characterized in that 10~200nm of pore-size distribution, total pore volume 0.8~
2.2ml/g, 260~290m of specific surface area2/ g, aperture is in bimodal distribution, wherein the mesoporous Kong Rong of 10~50nm accounts for total pore volume
The macropore hole of 10%~50%, 50~200nm, which hold, accounts for the 50%~90% of total pore volume, and carrier uses acrylonitrile-butadiene rubber latex as expansion
Hole agent.
2. the alumina support of containing mesopore/macropore according to claim 1, which is characterized in that macropore diameter is distributed as 80
~180nm, macropore hole, which holds, accounts for the 60%~80% of total pore volume；Mesoporous pore size is 20~50nm.
3. the alumina support of containing mesopore/macropore according to claim 1, which is characterized in that macropore diameter is distributed as 80
~100nm, 100~130nm or 150~180nm, mesoporous pore size are distributed as 20~30nm.
4. the alumina support of containing mesopore/macropore according to claim 1, which is characterized in that total pore volume for 0.8~
1.2ml/g or 1.8~2.2ml/g.
5. a kind of preparation method of the alumina support of Claims 1 to 4 any one of them containing mesopore/macropore, feature exist
In including the following steps：
First, it prepares grain size and adds in it as expanding agent, and by organic acid or inorganic acid in the acrylonitrile-butadiene rubber latex of 10~200nm
In, the addition of organic acid or inorganic acid is 0.2wt%~3.4wt% of acrylonitrile-butadiene rubber latex, then by boehmite powder
The mixed-powder of end and sesbania powder is added in kneader and is uniformly mixed, then the nitrile rubber containing organic acid or inorganic acid is newborn
Liquid, which is added in mixed-powder, to be mediated uniformly, and the addition of the acrylonitrile-butadiene rubber latex containing organic acid or inorganic acid is mixed-powder
0.1wt%~45wt%, by extrusion-molding-drying-roasting, obtain the alumina support containing meso/macroporous structure.
6. the preparation method of the alumina support of containing mesopore/macropore according to claim 5, which is characterized in that described organic
Acid is acetic acid or citric acid；The inorganic acid is nitric acid or hydrochloric acid.
7. the preparation method of the alumina support of containing mesopore/macropore according to claim 5, which is characterized in that the butyronitrile
Rubber latex is prepared using emulsion polymerisation process, is included the following steps：
First by polymer grade divinylic monomer, polymerization-grade propylene nitrile monomer, deionized water, emulsifier, electrolyte and auxiliary addition agent
Paradigmatic system is added in, is counted using two kinds of polymer grade butadiene, polymerization-grade propylene nitrile monomer gross mass as 100 parts, wherein polymer grade fourth
Diene amount is 50~80 parts, preferably 58~75 parts；Deionized water dosage is 100~300 parts；Emulsifier is 0.2~10
Part；Electrolyte dosage is 0.1~2 part；Auxiliary addition agent dosage is 0.01~0.2 part；
Under agitation, material is made to mix 20~40min of pre-emulsification into emulsion, added in after being cooled to 5~8 DEG C initiator and
Conditioning agent is counted, initiator amount using two kinds of polymer grade divinylic monomer, polymerization-grade propylene nitrile monomer monomer gross mass as 100 parts
It is 0.005~0.5 part；Conditioning agent dosage is 0.1~2 part；
Control 5~8 DEG C, 0.1~0.5MPa of pressure, 10~12h of reaction time of temperature, grade butadiene to be polymerized, polymerization-grade propylene
Two kinds of monomer conversions of nitrile add in terminator when reaching 70%~85% and terminate polymerisation, obtain acrylonitrile-butadiene rubber latex.
8. the preparation method of the alumina support of containing mesopore/macropore according to claim 5, which is characterized in that described to contain
The addition of the acrylonitrile-butadiene rubber latex of organic acid or inorganic acid is 0.5wt%~30wt% of mixed-powder.
9. the carrying alumina preparation of containing mesopore/macropore according to claim 7, which is characterized in that the emulsifier
One or more of selected from anionic initiator, amphoteric emulsifier or macromolecule emulsifier；Electrolyte be selected from potassium chloride,
One or more of sodium chloride, niter cake or sodium fluoride；Auxiliary addition agent is selected from one among pH adjusting agent or chelating agent
Kind or two kinds, the one kind or several of the initiator in inorganic peroxide, oxidation-reduction system or azo-initiator
Kind；The conditioning agent is selected from one or more of compound containing sulphur, nitrogen, phosphorus or organic unsaturated bond, the terminator
One or more selected from hydroquinone type, quinones or sulfur-containing compound.
10. the preparation method of the alumina support of containing mesopore/macropore according to claim 9, which is characterized in that the emulsification
Agent is fatty acid soaps, and electrolyte is potassium chloride, and chelating agent is ethylenediamine tetra-acetic acid or the metal salt of ethylenediamine tetra-acetic acid, pH value tune
It is KOH, NaOH or Na to save agent2CO3One or more of, initiator is potassium peroxydisulfate, and conditioning agent is blue for mercaptan or curing autumn
One or both of nurse, terminator are mercaptan.
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| CN110665547A (en) * | 2019-10-12 | 2020-01-10 | 西安凯立新材料股份有限公司 | Hierarchical pore silicon-aluminum composite carrier and preparation method and application thereof |
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| CN101337186A (en) * | 2008-08-27 | 2009-01-07 | 云南大学 | Preparation method of meso-porous alumina and catalytic synthesis of alpha-tetralone |
| CN103706408A (en) * | 2013-12-18 | 2014-04-09 | 宁波金远东工业科技有限公司 | Protective agent of coal tar hydrogenation catalyst and preparation method of protective agent |
| CN105983443A (en) * | 2015-01-27 | 2016-10-05 | 中国石油天然气股份有限公司 | Double-peak-pore-structured aluminum oxide supporter and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337186A (en) * | 2008-08-27 | 2009-01-07 | 云南大学 | Preparation method of meso-porous alumina and catalytic synthesis of alpha-tetralone |
| CN103706408A (en) * | 2013-12-18 | 2014-04-09 | 宁波金远东工业科技有限公司 | Protective agent of coal tar hydrogenation catalyst and preparation method of protective agent |
| CN105983443A (en) * | 2015-01-27 | 2016-10-05 | 中国石油天然气股份有限公司 | Double-peak-pore-structured aluminum oxide supporter and preparation method thereof |
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| CN110665547A (en) * | 2019-10-12 | 2020-01-10 | 西安凯立新材料股份有限公司 | Hierarchical pore silicon-aluminum composite carrier and preparation method and application thereof |
| CN110665547B (en) * | 2019-10-12 | 2022-08-19 | 西安凯立新材料股份有限公司 | Hierarchical pore silicon-aluminum composite carrier and preparation method and application thereof |
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