CN105819460B - A kind of Hydrogen layer column saponite and its preparation method and application - Google Patents
A kind of Hydrogen layer column saponite and its preparation method and application Download PDFInfo
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- CN105819460B CN105819460B CN201510004015.XA CN201510004015A CN105819460B CN 105819460 B CN105819460 B CN 105819460B CN 201510004015 A CN201510004015 A CN 201510004015A CN 105819460 B CN105819460 B CN 105819460B
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- 229910000275 saponite Inorganic materials 0.000 title claims abstract description 165
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 55
- 239000001257 hydrogen Substances 0.000 title claims abstract description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 73
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 36
- 239000007853 buffer solution Substances 0.000 claims abstract description 25
- 230000002378 acidificating effect Effects 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 63
- 229910052782 aluminium Inorganic materials 0.000 claims description 63
- 239000004411 aluminium Substances 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052733 gallium Inorganic materials 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000003495 polar organic solvent Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 7
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- FYKDNWHPKQOZOT-UHFFFAOYSA-M sodium;dihydrogen phosphate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].OP(O)([O-])=O.OC(=O)CC(O)(C(O)=O)CC(O)=O FYKDNWHPKQOZOT-UHFFFAOYSA-M 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- BUCIWTBCUUHRHZ-UHFFFAOYSA-K potassium;disodium;dihydrogen phosphate;hydrogen phosphate Chemical compound [Na+].[Na+].[K+].OP(O)([O-])=O.OP([O-])([O-])=O BUCIWTBCUUHRHZ-UHFFFAOYSA-K 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000011175 product filtration Methods 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 18
- 238000007171 acid catalysis Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000000470 constituent Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 36
- 238000005119 centrifugation Methods 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 21
- 238000005342 ion exchange Methods 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 239000006228 supernatant Substances 0.000 description 9
- 239000004971 Cross linker Substances 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000005360 mashing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000009938 salting Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XPFJYKARVSSRHE-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].[Na+].OC(=O)CC(O)(C(O)=O)CC(O)=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XPFJYKARVSSRHE-UHFFFAOYSA-K 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical class O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- CBMPTFJVXNIWHP-UHFFFAOYSA-L disodium;hydrogen phosphate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].OP([O-])([O-])=O.OC(=O)CC(O)(C(O)=O)CC(O)=O CBMPTFJVXNIWHP-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical class O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 239000007981 phosphate-citrate buffer Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Abstract
The present invention provides a kind of Hydrogen layer column saponite, total specific surface area of the Hydrogen layer column saponite is 350m2/ g or more, total pore volume 0.35cm3/ g or more.The present invention provides a kind of method preparing Hydrogen layer column saponite of the present invention, this method includes：Sodium form saponite raw material is carried out first with acidic buffer solution to contact；It is pillared that progress is contacted with pillaring agent second after first contact；It is dried, roasts after second contact.The present invention provides application of the Hydrogen layer column saponite of the present invention in acid catalysis field.The total large specific surface area of Hydrogen layer column saponite of the present invention, total pore volume are big.And preparation method according to the invention, Hydrogen layer column saponite can be directly made by needing not move through ammonium exchange, and Hydrogen layer column saponite obtained can be directly used as catalyst or acidity of catalyst constituent element.
Description
Technical field
The present invention relates to a kind of Hydrogen layer column saponite and a kind of preparation sides of Hydrogen layer column saponite of the present invention
The application of method and Hydrogen layer column saponite of the present invention in acid catalysis field.
Background technology
Layer column saponite is a kind of molecular sieve analog poromerics, has two-dimentional gallery pore passage structure and suitable acid centre,
Its thermal stability is high, and has the catalysis such as isomerization, cracking and alkylation and react the required acid sites B, in acid catalysis
Field has obtained extensive research.
Zhao imitate flood et al. in (《Synthesis, characterization and the n-decane hydro-isomerization catalytic performance of layer column saponite》, institution of higher education
Learn journal, the 32nd phase, in March, 2011) a kind of method that hydro-thermal prepares layer column saponite is reported, this method includes by silicon source, aluminium
Crystallization generates saponite under hydrothermal conditions for source and magnesium source, then by the saponite of preparation through steps such as washing, drying, the exchanges of pillared and ammonium
Suddenly, it is prepared for a layer column saponite.There is layer column saponite prepared by this method preferable catalysis to live in terms of n-decane hysomer
Property, but need by the drying of multistep, roasting, grinding distribution step, step is relatively complicated.
Document (《The preparation and representation of the layer artificial hydrothermal synthesis saponite of column》, Chinese Journal of Inorganic Chemistry, the 8th phase, in August, 2004)
Also a layer hydrothermal preparing process for column saponite is reported, is that layer is former using having the artificial hydrothermal synthesis saponite of ideal saponite structure
Material, specifically includes hydrothermal crystallizing, washing, drying, pillared and etc., and saponite need by complicated drying, roasting, grinding and
Aluminium column saponite material could be made in the step of redisperse, and step is relatively complicated, need to take measures to simplify preparation process.
Document (《Review of Researches on Pillaring Species》, mineral rock geochemistry notification, the 4th phase of volume 21, in October, 2002) and report
Road prepares the pillaring agent type of laminated clay column, is referred to organic pillaring agent, inorganic pillaring agent, inorganic/organic composite pillaring agent,
Refer to that nonionic surfactant polyvinyl alcohol/Al makees crosslinking agent is pillared simultaneously.Wherein, polymerization hydroxy metal is introduced
Cation seperation column agent, and the construction of aluminium column is described in detail.When pointing out that aluminium column is pillared, metal polymerization cation
Structure is influenced especially big, Al by pH13 7+Hydrolysis, which can occur, causes aluminium ion type to change, when 1.5<OH-/Al3+(mol/
mol)<When 2.3, Al13 7+As leading ion.As pH is increased, Al13 7+Charge number is continuously decreased by+7, and structure changes,
The aluminium column saponite that macropore appearance can not be prepared, do not refer in document it is any can be with improved measure.
In current layer column saponite preparation method, preparation process is more, and preparation method is also all more complicated, and operates and want
Refinement is thin, such as aluminium column exchange process by pH influenced apparent, aluminium column exchange not enough thoroughly, drying process be easy to happen reunion,
Be required among preparation process being dried or roast simultaneously and etc., the performance of product is not only affected, but also because dry
Intermediate after step is required for being ground when carrying out next preparation process, to ensure the requirement compared with high dispersive, no
Only complex steps, and increase manufacturing cost and affect the performance of product, limit its application development.
Invention content
The purpose of the present invention is to provide a kind of total large specific surface area, total pore volume is big and the simple Hydrogen layer of preparation method
Column saponite and its preparation method and application.
To realize foregoing purpose, in a first aspect, the present invention provides a kind of Hydrogen layer column saponite, the Hydrogen layer column saponite
Total specific surface area is 350m2/ g or more, total pore volume 0.35cm3/ g or more.
Second aspect, the present invention provides a kind of method preparing Hydrogen layer column saponite of the present invention, this method packets
It includes：Sodium form saponite raw material is carried out first with acidic buffer solution to contact；It is contacted with pillaring agent second after first contact and carries out column
Support；It is dried, roasts after second contact.
The third aspect, the present invention provides application of the Hydrogen layer column saponite of the present invention in acid catalysis field.
The total large specific surface area of Hydrogen layer column saponite of the present invention, total pore volume are big.
And preparation method according to the invention, Hydrogen layer column saponite can be directly made by needing not move through ammonium exchange, be made
Hydrogen layer column saponite can be directly used as catalyst or acidity of catalyst constituent element.
The method of the present invention simultaneously can directly use saponite wet cake to carry out the first contact and the second contact process, save
The processes such as drying, grinding and redisperse, so that preparation process is significantly simplified.
In a preferred embodiment of the invention, layer column saponite is rinsed using polar organic solvent, solves a layer column saponite
The problem of being easy to reunite when dry, final Hydrogen layer column saponite obtained have large specific surface area and Kong Rong.
To sum up, method of the invention enormously simplifies a layer preparation process for column saponite, and it is very good that industry amplification is played
Directive function.
Specific implementation mode
As previously mentioned, the present invention provides a kind of Hydrogen layer column saponite, total specific surface area of the Hydrogen layer column saponite is
350m2/ g or more, total pore volume 0.35cm3/ g or more.
Total specific surface area of Hydrogen layer column saponite according to the present invention, the preferably described Hydrogen layer column saponite is 350-380m2/
G, total pore volume 0.36-0.38cm3/g。
The micropore specific area of Hydrogen layer column saponite according to the present invention, the preferably described Hydrogen layer column saponite is 230m2/g
More than, more preferably 230-250m2/g。
The micropore pore volume of Hydrogen layer column saponite according to the present invention, the preferably described Hydrogen layer column saponite is 0.1cm3/ g with
On, more preferably 0.1-0.15cm3/g。
Hydrogen layer column saponite according to the present invention, total specific surface area S of Hydrogen layer column saponitetotal, micropore specific area
Smicro, total pore volume VtotalWith micropore pore volume VmicroIt is measured with the method for nitrogen adsorption-desorption.
Hydrogen layer column saponite according to the present invention, the preferably described Hydrogen layer column saponite are Hydrogen aluminium column saponite, Hydrogen molybdenum column
Saponite, Hydrogen zirconium column saponite, Hydrogen silicon column saponite, Hydrogen titanium column saponite, Hydrogen iron prop saponite, Hydrogen chromium column saponite and Hydrogen gallium
It is one or more in column saponite.
The present invention provides a kind of method preparing Hydrogen layer column saponite of the present invention, this method includes：By sodium form
Saponite raw material carries out first with acidic buffer solution and contacts；It is pillared that progress is contacted with pillaring agent second after first contact；Second connects
It is dried, roasts after touch.
With the method for the invention it is preferred to which the pH value of acidic buffer solution is 2-6, preferably 3.5-5, more preferably 4-
4.5.It is possible thereby to further increase the specific surface area and pore volume of Hydrogen layer column saponite.
With the method for the invention it is preferred to which the condition of the first contact includes：Temperature is 20-80 DEG C, preferably 40-60 DEG C.
It is possible thereby to further increase the specific surface area and pore volume of Hydrogen layer column saponite.
With the method for the invention it is preferred to which the weight ratio of acidic buffer solution and the sodium form saponite raw material in terms of dry weight is
(10-20):1.It is possible thereby to further increase the specific surface area and pore volume of Hydrogen layer column saponite.
With the method for the invention it is preferred to which the condition of the first contact includes：Time is 0.5-10h, preferably 0.5-2h.
According to the method for the present invention, the acidic buffer solution is the mixed solution of weak acid and salt of weak acid composition and/or more
The mixed solution of the acid salt of first weak acid and the secondary salt composition of Multiple Weak Acid, the preferably described weak acid are citric acid and/or second
Acid, salt of weak acid are one or more in sodium citrate, sodium acetate and sodium dihydrogen phosphate；The more preferable acidic buffer solution is
Citric acid-sodium citrate, acetic acid-sodium acetate, sodium dihydrogen phosphate-citric acid, one kind in disodium hydrogen phosphate-potassium dihydrogen phosphate or
It is a variety of, further preferably citric acid-sodium citrate, acetic acid-sodium acetate and one kind or more in sodium dihydrogen phosphate-citric acid
Kind.
According to the method for the present invention, the sodium form saponite raw material is commercially available and can also be prepared, the present invention couple
This is without particular/special requirement, and for the present invention, the sodium form saponite raw material is that artificial Saponite pillared clay and/or natural steatite are exchanged by sodium
It obtains.
With the method for the invention it is preferred to which moisture is 75-90 weight % in the sodium form saponite raw material.
With the method for the invention it is preferred to which the sodium form saponite raw material is prepared as follows：A, according to x/2Na2O:
(8.0-x)SiO2:(x/2)Al2O3:6.0(M1)A(O)B:(400-1000)H2The raw material proportioning of O is by sodium source, silicon source, silicon source, M1
Source and water mixing, obtain Primogel；Wherein, 0.2≤x≤2, M1 are II A races metallic element, VIII race's metallic element and II B races
It is one or more in metallic element；
B, by after the Primogel hydrothermal crystallizing of gained in step a, the crystallization product filtration washing that will be obtained obtains sodium form
Saponite filter cake is as the sodium form saponite raw material.
According to the method for the present invention, (M1)AOBIn A and the numerical value of B determined according to the valence state of M1, numerical value both preferably
It is selected finally to make (M1)AOBFor the steady oxide of M1, such as when M1 is Mg, A and B are 1.
According to the method for the present invention, optional wider range of the type of the sodium source, sodium source commonly used in the art can be with
For the present invention, for the present invention, the preferably described sodium source is at least one in sodium hydroxide, sodium bicarbonate and sodium carbonate
Kind.
According to the method for the present invention, optional wider range of the type of the silicon source, silicon source commonly used in the art can be with
For the present invention, for the present invention, the preferably described silicon source is sodium metasilicate and/or sodium metasilicate.
According to the method for the present invention, optional wider range of the type of source of aluminium, silicon source commonly used in the art can be with
For the present invention, for the present invention, preferably source of aluminium be in aluminum sulfate, aluminum nitrate, aluminium chloride and sodium metaaluminate extremely
Few one kind.
According to the method for the present invention, optional wider range of the type in the sources M1, for the present invention, the preferably described sources M1
For selected from M1 the sulfate of chlorate, M1, the nitrate of M1, the hydroxide of M1 and M1 oxide in one kind or more
Kind.
With the method for the invention it is preferred to which the M1 is one or more in Mg, Ni and Fe.
With the method for the invention it is preferred to which in step b, the condition of the hydrothermal crystallizing includes：Temperature is 250-350 DEG C,
Preferably 275-300 DEG C.
With the method for the invention it is preferred to which in step b, the condition of the hydrothermal crystallizing includes：Time is 24-48 hours.
With the method for the invention it is preferred in step b, the pH value of the gel is 9-14, preferably 10-13.
With the method for the invention it is preferred to which the condition of second contact includes：In pillaring agent for column element and sodium form
The amount ratio of saponite is 1-10mmol/g, preferably 2-6mmol/g.
With the method for the invention it is preferred to which the condition of second contact includes：Temperature is 40-100 DEG C, preferably 60-
80℃。
With the method for the invention it is preferred to which the condition of second contact includes：Time is 1-5 hours, preferably 0.5-
1.5h。
According to the method for the present invention, optional wider range of the type of the pillaring agent, pillaring agent kind commonly used in the art
Class is used equally for the present invention, and for the present invention, the preferably described pillaring agent is aluminium pillaring agent, molybdenum pillaring agent, zirconium pillaring agent, silicon column
It is one or more in agent, pillaring solution, iron prop agent, chromium pillaring agent and gallium pillaring agent.
A kind of embodiment according to the present invention, when the pillaring agent is aluminium pillaring agent, the preferably described aluminium pillaring agent is
Al13 7+The aqueous solution of polymerizing cationically, a concentration of 0.14-0.17mol/L of Al in more preferable aluminium pillaring agent.
According to the method for the present invention, the aluminium pillaring agent, which is commercially available, can also synthesize to obtain, when the aluminium column
When agent is that synthesis obtains, the preparation process of the preferably described aluminium pillaring agent includes：By the sodium hydroxide solution of 0.1-2mol/L with
The aluminum salt solution of 0.1-2mol/L mixes, and then at 40-100 DEG C, preferably 60-80 DEG C, stirs 2-24 hours, preferably 8-12h；
Wherein, the pH for controlling obtained aluminium pillaring agent is 4.1-4.4, OH-/Al3+=2.0-2.5, preferably 2.2-2.4.
According to the method for the present invention, when the pillaring agent is gallium pillaring agent, gallium is a concentration of preferably in gallium pillaring agent
0.05-0.1mol/L, gallium pillaring agent can also synthesize to obtain according to the prior art, and this is not described in detail here.
According to the method for the present invention, the step of dry and roasting and condition are without particular/special requirement, according to conventional steps and condition
Progress, such as dry condition includes：Temperature is 60-150 DEG C, preferably 110-130 DEG C；Time is 4-12h, preferably
6-8h；The condition of roasting includes：Temperature be 400-650 DEG C, preferably 500-550 DEG C, time 2-3h.
With the method for the invention it is preferred to the material after the first contact is filtered (as centrifuged), washing, washing obtains
Saponite carry out again it is described second contact.
With the method for the invention it is preferred to the material after the second contact is filtered (as centrifuged), washing, washing obtains
Saponite be dried, roast again.
With the method for the invention it is preferred to which the material after the second contact is filtered, is washed, and washs and use water and pole
Property organic solvent carry out alternately washing.
According to the method for the present invention, the type of the polar organic solvent may be, for example, the alcohol of C1-C10 without particular/special requirement,
Preferably ethyl alcohol.Wherein, it may be hydrous ethanol that ethyl alcohol, which can be absolute ethyl alcohol,.
According to the method for the present invention, when being filtered using centrifugal method, the condition preferably centrifuged includes：Rotating speed is not low
In 4000rpm, centrifugation time 20-60min, preferably 30-40min.
A preferred embodiment of the invention without drying, is ground by filtration step after the preferably first contact
Grind dispersion steps；It is filtered, washed after second contact and before dry, filtration step is without ammonium exchange step.
A kind of more preferable embodiment according to the present invention, by filtration step after the preferably first contact, without drying,
Grinding distribution step；After second contact and before dry by filtering, water replace with polar organic solvent washing, filtration step without
Cross ammonium exchange step, wherein terminate washing step after polar organic solvent washing.
The present invention provides application of the Hydrogen layer column saponite of the present invention in acid catalysis field.
The feature that the invention is further illustrated by the following examples, but these embodiments can not limit the present invention.
In each embodiment and comparative example, total specific surface area S of Hydrogen layer column saponite product obtainedtotal, micropore compare table
Area Smicro, total pore volume VtotalWith micropore pore volume VmicroIt is measured with the method for nitrogen adsorption-desorption, and passes through BET and t-
Plod analysis methods are calculated, and specific method can refer to《The Pore Characterization of porous material and its analysis》, periodical：Material
Leader, reign title and reel number：The 7th phase of volume 23 in 2009.Constituent content Na2O、MgO、SiO2And Al2O3Method X-ray fluorescence spectra
Analytic approach (XRF) measures, and specific method can refer to《Synthesis containing magnesium smelting and characterization》, periodical：Mining industry research and development, year
The volume phase：The 3rd phase of volume 26 in 2006.
Saponite raw material preparation example 1
It takes 99.5g non-hydrate sodium metasilicates, 4.8g sodium hydroxides, 82.68g sodium carbonate to be dissolved in 500g water and lye is made, so
After take 60.9g magnesium chloride hexahydrates, 12.1g Aluminum Chloride Hexahydrates, which are dissolved in 50g water, is made salting liquid, by salting liquid under the conditions of 60 DEG C
It is slowly dropped into and obtains the Primogel (pH 10.58) that Saponite pillared clay layer charge is 1.0 in above-mentioned lye, then proceed to aging
30min is packed into 1L autoclaves, in 300 DEG C of crystallization 48h.Obtained product is centrifuged with deionized water, is washed in
Property, it obtains magnesium smelting wet cake, is denoted as Na-MgSP (moisture is 80 weight %).
Saponite raw material preparation example 2
It takes 99.5g non-hydrate sodium metasilicates, 4.8g sodium hydroxides, 82.68g sodium carbonate to be dissolved in 500g water and lye is made, so
After take 12.1g Aluminum Chloride Hexahydrates, six water nickel chlorides of 72.7g, which are dissolved in 50g water, is made salting liquid, by salting liquid under the conditions of 60 DEG C
It is slowly dropped into and obtains the Primogel (pH 12.10) that Saponite pillared clay layer charge is 1.0 in above-mentioned lye, then proceed to aging
30min is packed into 1L autoclaves, in 300 DEG C of crystallization 48h.Obtained product is centrifuged with deionized water, is washed in
Property, it obtains pimelite wet cake, is denoted as Na-NiSP (moisture is 80 weight %).
Pillaring agent preparation example 1
In the state of heating stirring, 1M sodium hydroxide solutions are added dropwise into 0.4M liquor alumini chloridis, finally so that OH-/
Al3+=2.3, heating temperature is 80 DEG C, ageing time 12h.The poly- state aluminum solutions of height with keggin structures are made, are denoted as
Al13 7+(a concentration of 0.149mol/L of Al).
Pillaring agent preparation example 2
In the state of heating stirring, 0.5M sodium hydroxide solutions are added dropwise into 0.1M chlorination Gallium solutions, finally so that pH
=4.0, heating temperature is 50 DEG C, ageing time 2h.The poly- state Gallium solution of height with keggin structures is made, is denoted as Ga13 7+
(a concentration of 0.071mol/L of Ga).
Embodiment 1
(pH 4.0) acidic buffer solution in the buffer solution of citric acid-sodium citrate is added in saponite raw material Na-MgSP
Weight ratio with the sodium form saponite raw material in terms of dry weight is 10:1, in 40 DEG C of heating stirring 0.5h, then it is centrifuged, from
Scheming rotating speed 4500rpm, centrifugation time 30min obtain acid treated saponite wet cake；Saponite wet cake is dispersed into aluminum crosslinker
Al13 7+In (aluminium/saponite (in terms of dry weight)=2mmol/g), carry out ion exchange 1h in 80 DEG C of heating stirrings, then centrifuged
Separation, centrifuge speed 4500rpm, centrifugation time 30min outwell supernatant and are washed with water, rear addition water stirring to pulp,
Centrifuge, be eventually adding ethyl alcohol, stirring to pulp, centrifugation, obtain it is pillared after aluminium column saponite wet cake.Aluminium column saponite is wet
Cake dry 6h at 120 DEG C, roasts 2h in 550 DEG C in Muffle furnace, obtains Hydrogen aluminium column saponite, be denoted as HA-MgSP-1, tie
Fruit is shown in Table 1.
Embodiment 2
Saponite raw material Na-MgSP is added in the buffer solution of acetic acid-sodium acetate (pH 4.2), acidic buffer solution with
The weight ratio of sodium form saponite raw material in terms of dry weight is 15:1, in 60 DEG C of heating stirring 1h, then it is centrifuged, centrifuge
Rotating speed is 4500rpm, and centrifugation time 30min obtains saponite wet cake；Saponite wet cake is dispersed into aluminum crosslinker Al13 7+In
(aluminium/saponite=4mmol/g) carries out ion exchange 2h in 80 DEG C of heating stirrings, is then centrifuged for detaching, centrifuge speed is
4500rpm, centrifugation time 30min, outwell supernatant be washed with water, stirring to pulp, centrifugation, be eventually adding ethyl alcohol, stir
Mix mashing, centrifuge, obtain it is pillared after aluminium column saponite wet cake.Aluminium column saponite wet cake is dried into 6h at 120 DEG C, in Muffle
2h is roasted in 550 DEG C in stove, Hydrogen aluminium column saponite is obtained, is denoted as HA-MgSP-2, the results are shown in Table 1.
Embodiment 3
Saponite raw material Na-MgSP is added in sodium dihydrogen phosphate-citric acid solution (pH 4.5), acidic buffer is molten
The weight ratio of liquid and the sodium form saponite raw material in terms of dry weight is 20:1, in 60 DEG C of heating stirring 1h, then it is centrifuged, from
Scheming rotating speed is 4500rpm, and centrifugation time 30min obtains saponite wet cake；Saponite wet cake is dispersed into aluminum crosslinker Al13 7+
In (aluminium/saponite=2mmol/g), carry out ion exchange 1h in 60 DEG C of heating stirrings, be then centrifuged for detaching, centrifuge speed is
4500rpm, centrifugation time 30min, outwell supernatant be washed with water, stirring to pulp, centrifugation, be eventually adding ethyl alcohol, stir
Mix mashing, centrifuge, obtain it is pillared after aluminium column saponite wet cake.Aluminium column saponite wet cake is dried into 8h at 110 DEG C, in Muffle
2h is roasted in 550 DEG C in stove, Hydrogen aluminium column saponite is obtained, is denoted as HA-MgSP-3, the results are shown in Table 1.
Embodiment 4
Saponite raw material Na-MgSP is added in disodium hydrogen phosphate-potassium dihydrogen phosphate buffer solution (pH 5.8), acidity is slow
The weight ratio for rushing solution and the sodium form saponite raw material in terms of dry weight is 15:1, in 60 DEG C of heating stirring 1h, then carry out centrifugation point
From centrifuge speed 4500rpm, centrifugation time 30min obtain saponite wet cake；Saponite wet cake is dispersed into aluminum crosslinker
Al13 7+In (aluminium/saponite=2mmol/g), carry out ion exchange 1.5h in 60 DEG C of heating stirrings, be then centrifuged for detaching, centrifuge
Rotating speed is 4500rpm, centrifugation time 30min, outwell supernatant be washed with water, stirring to pulp, centrifugation, be eventually adding second
Alcohol, stirring to pulp, centrifugation, obtain it is pillared after aluminium column saponite wet cake.Aluminium column saponite wet cake is dried into 6h at 120 DEG C,
2h is roasted in 550 DEG C in Muffle furnace, aluminium column saponite is obtained, is denoted as HA-MgSP-4, the results are shown in Table 1.
Embodiment 5
Saponite raw material Na-NiSP is added in the buffer solution of acetic acid-sodium acetate (pH 4.2), acidic buffer solution with
The weight ratio of sodium form saponite raw material in terms of dry weight is 15:1, in 60 DEG C of heating stirring 1h, then it is centrifuged, centrifuge
Rotating speed is 4500rpm, and centrifugation time 30min obtains saponite wet cake；Saponite wet cake is dispersed into aluminum crosslinker Al13 7+In
(aluminium/saponite=2mmol/g) carries out ion exchange 1.5h in 60 DEG C of heating stirrings, is then centrifuged for detaching, centrifuge speed is
4500rpm, centrifugation time 30min, outwell supernatant be washed with water, stirring to pulp, centrifugation, be eventually adding ethyl alcohol, stir
Mix mashing, centrifuge, obtain it is pillared after aluminium column saponite wet cake.Aluminium column saponite wet cake is dried into 6h at 120 DEG C, in Muffle
2h is roasted in 550 DEG C in stove, aluminium column saponite is obtained, is denoted as HA-NiSP-5, the results are shown in Table 2.
Embodiment 6
Saponite raw material Na-MgSP is added in the buffer solution of acetic acid-sodium acetate (pH 4.2), acidic buffer solution with
The weight ratio of sodium form saponite raw material in terms of dry weight is 15:1, in 60 DEG C of heating stirring 1h, then it is centrifuged, centrifuge
Rotating speed is 4500rpm, and centrifugation time 30min obtains saponite wet cake；Saponite wet cake is dispersed into gallium crosslinking agent Ga13 7+In
(gallium/saponite=2mmol/g) carries out ion exchange 1.5h in 60 DEG C of heating stirrings, is then centrifuged for detaching, centrifuge speed is
4500rpm, centrifugation time 30min, outwell supernatant be washed with water, stirring to pulp, centrifugation, be eventually adding ethyl alcohol, stir
Mix mashing, centrifuge, obtain it is pillared after gallium column saponite wet cake.Gallium column saponite wet cake is dried into 6h at 120 DEG C, in Muffle
2h is roasted in 550 DEG C in stove, gallium column saponite is obtained, is denoted as HG-MgSP-6, the results are shown in Table 2.
Embodiment 7
It is prepared according to the method for embodiment 2, it is specific as follows：
Saponite raw material Na-MgSP is added disodium hydrogen phosphate-citrate buffer solution (pH 6.4), acidic buffer solution with
The weight ratio of sodium form saponite raw material in terms of dry weight is 15:1, in 60 DEG C of heating stirring 1h, then it is centrifuged, centrifuge
Rotating speed is 4500rpm, and centrifugation time 30min obtains saponite wet cake；Saponite wet cake is dispersed into aluminum crosslinker Al13 7+In
(aluminium/saponite=4mmol/g) carries out ion exchange 2h in 80 DEG C of heating stirrings, is then centrifuged for detaching, centrifuge speed is
4500rpm, centrifugation time 30min, outwell supernatant be washed with water, stirring to pulp, centrifugation, be eventually adding ethyl alcohol, stir
Mix mashing, centrifuge, obtain it is pillared after aluminium column saponite wet cake.Aluminium column saponite wet cake is dried into 6h at 120 DEG C, in Muffle
2h is roasted in 550 DEG C in stove, Hydrogen aluminium column saponite is obtained, is denoted as HA-MgSP-7, the results are shown in Table 2.
Embodiment 8
It is prepared according to the method for embodiment 2, it is specific as follows：
Saponite raw material Na-MgSP is added in the buffer solution of acetic acid-sodium acetate (pH 4.2), acidic buffer solution with
The weight ratio of sodium form saponite raw material in terms of dry weight is 2:1, in 60 DEG C of heating stirring 1h, then it is centrifuged, centrifuge
Rotating speed is 4500rpm, and centrifugation time 30min obtains saponite wet cake；Saponite wet cake is dispersed into aluminum crosslinker Al13 7+In
(aluminium/saponite=4mmol/g) carries out ion exchange 2h in 80 DEG C of heating stirrings, is then centrifuged for detaching, centrifuge speed is
4500rpm, centrifugation time 30min, outwell supernatant be washed with water, stirring to pulp, centrifugation, be eventually adding ethyl alcohol, stir
Mix mashing, centrifuge, obtain it is pillared after aluminium column saponite wet cake.Aluminium column saponite wet cake is dried into 6h at 120 DEG C, in Muffle
2h is roasted in 550 DEG C in stove, Hydrogen aluminium column saponite is obtained, is denoted as HA-MgSP-8, the results are shown in Table 2.
Comparative example
Saponite raw material Na-MgSP is detected by being centrifuged repeatedly, wash to supernatant silver nitrate (2wt%) without Cl-, in
Dry 6h at 120 DEG C, is then ground into powdery using analysis grinder.Saponite is dispersed in water and is made a concentration of 2wt%'s
Then aluminum crosslinker Al is added in saponite slurries thereto13 7+(aluminium/saponite=4mmol/g), is heated to 80 DEG C, high-speed stirred
Under the conditions of ion exchange 2h, be then washed with deionized, the filter cake centrifuged, in 120 DEG C of dry 6h, 550 DEG C of roasting 2h,
Sodium form aluminium column saponite is made, 500ml 1M NH then are added in sodium form aluminium column saponite4In Cl aqueous solutions, 60 DEG C of heating stirring shapes
Ion exchange 1h under state is then centrifuged for, washs, and obtained product roasts 2h at 120 DEG C of dry 6h, 500 DEG C, and hydrogen is finally made
Type aluminium column saponite, is denoted as HA-MgSP-ref.
Table 1
Table 2
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, it can be combined by any suitable means.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (19)
1. total specific surface area of a kind of method preparing Hydrogen layer column saponite, the Hydrogen layer column saponite is 350m2/ g or more, total hole
Volume is 0.35cm3/ g or more, which is characterized in that this method includes：
Sodium form saponite raw material is carried out first with acidic buffer solution to contact；It is contacted with pillaring agent second after first contact and carries out column
Support；It is dried, roasts after second contact；
Wherein, by filtration step after the first contact, without drying, grinding distribution step；It is passed through after second contact and before dry
Filtering, water replace washing, filtration step with polar organic solvent without ammonium exchange step, wherein polar organic solvent is washed
Terminate washing step after washing.
2. according to the method described in claim 1, wherein, the pH value of acidic buffer solution is 2-6；The condition packet of first contact
It includes：The weight ratio of acidic buffer solution and the sodium form saponite raw material in terms of dry weight is (10-20):1；Temperature is 20-80 DEG C；Time
For 0.5-10h.
3. according to the method described in claim 2, wherein, the pH value of acidic buffer solution is 3.5-5.
4. according to the method described in claim 2, wherein, the pH value of acidic buffer solution is 4.0-4.5.
5. according to the method described in claim 2, wherein, the condition of the first contact includes：Temperature is 40-60 DEG C, and the time is
0.5-2h。
6. according to the method described in any one of claim 1-5, wherein the acidic buffer solution is weak acid and salt of weak acid
The mixed solution of the secondary salt of the mixed solution of composition and/or the acid salt of Multiple Weak Acid and Multiple Weak Acid composition.
7. according to the method described in any one of claim 1-5, wherein the acidic buffer solution is citric acid-lemon
It is one or more in sour sodium, acetic acid-sodium acetate, sodium dihydrogen phosphate-citric acid, disodium hydrogen phosphate-potassium dihydrogen phosphate.
8. according to the method described in any one of claim 1-5, wherein the sodium form saponite raw material is artificial Saponite pillared clay
And/or natural steatite exchanges to obtain by sodium.
9. according to the method described in any one of claim 1-5, wherein moisture is in the sodium form saponite raw material
75-90 weight %.
10. according to the method described in any one of claim 1-5, wherein the sodium form saponite raw material is made as follows
It is standby：
A, according to x/2Na2O:(8.0-x)SiO2:(x/2)Al2O3:6.0(M1)A(O)B:(400-1000)H2The raw material proportioning of O will
Sodium source, silicon source, silicon source, the sources M1 and water mixing, obtain Primogel；Wherein, 0.2≤x≤2, M1 are II A races metallic element, VIII
It is one or more in race's metallic element and II B races metallic element；
B, by after the Primogel hydrothermal crystallizing of gained in step a, the crystallization product filtration washing that will be obtained obtains sodium form saponite
Filter cake is as the sodium form saponite raw material.
11. according to the method described in claim 10, wherein,
The sodium source is selected from least one of sodium hydroxide, sodium bicarbonate and sodium carbonate；
The silicon source is sodium metasilicate and/or sodium metasilicate；
Source of aluminium is selected from least one of aluminum sulfate, aluminum nitrate, aluminium chloride and sodium metaaluminate；
The sources M1 are in the oxide of chlorate selected from M1, the sulfate of M1, the nitrate of M1, the hydroxide of M1 and M1
It is one or more；
The M1 is one or more in Mg, Ni and Fe.
12. according to the method described in claim 10, wherein, in step b, the condition of the hydrothermal crystallizing includes：Temperature is
250-350℃；Time is 24-48 hours；Gel pH value is 9-14.
13. according to the method for claim 12, wherein in step b, the condition of the hydrothermal crystallizing includes：Temperature is
275-300℃；Gel pH value is 10-13.
14. according to the method described in any one of claim 1-5, wherein the pillaring agent is aluminium pillaring agent, molybdenum column
It is one or more in agent, zirconium pillaring agent, silicon column agent, pillaring solution, iron prop agent, chromium pillaring agent and gallium pillaring agent.
15. according to the method described in any one of claim 1-5, wherein the pillaring agent is aluminium pillaring agent, aluminium pillaring agent
A concentration of 0.14-0.17mol/L of middle Al；The pillaring agent is gallium pillaring agent, a concentration of 0.05- of gallium in gallium pillaring agent
0.1mol/L。
16. according to the method described in any one of claim 1-5, wherein it is described second contact condition include：Pillaring agent
In the amount ratio for column element and sodium form saponite be 1-10mmol/g；Temperature is 40-100 DEG C；Time is 1-5 hours.
17. according to the method described in any one of claim 1-5, wherein it is described second contact condition include：Pillaring agent
In the amount ratio for column element and sodium form saponite be 2-6mmol/g；Temperature is 60-80 DEG C；Time is 0.5-1.5h.
18. according to the method described in any one of claim 1-5, wherein polar organic solvent is the alcohol of C1-C10.
19. according to the method described in any one of claim 1-5, wherein polar organic solvent is ethyl alcohol.
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