CN100522811C - Preparation process of superfine zeolite powder - Google Patents
Preparation process of superfine zeolite powder Download PDFInfo
- Publication number
- CN100522811C CN100522811C CNB03111069XA CN03111069A CN100522811C CN 100522811 C CN100522811 C CN 100522811C CN B03111069X A CNB03111069X A CN B03111069XA CN 03111069 A CN03111069 A CN 03111069A CN 100522811 C CN100522811 C CN 100522811C
- Authority
- CN
- China
- Prior art keywords
- zeolite
- ultra
- soliquid
- fine
- urea
- 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.)
- Expired - Fee Related
Links
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000010457 zeolite Substances 0.000 title claims abstract description 152
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 146
- 239000000843 powder Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 90
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000004202 carbamide Substances 0.000 claims abstract description 47
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 6
- 125000004429 atom Chemical group 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000011164 primary particle Substances 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000012452 mother liquor Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000000725 suspension Substances 0.000 abstract description 26
- 239000007788 liquid Substances 0.000 abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000000084 colloidal system Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 2
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract 1
- 229960004279 formaldehyde Drugs 0.000 description 22
- 235000019256 formaldehyde Nutrition 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 16
- 230000008025 crystallization Effects 0.000 description 16
- 239000000499 gel Substances 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 238000004062 sedimentation Methods 0.000 description 15
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 14
- 238000010538 cationic polymerization reaction Methods 0.000 description 12
- 238000005119 centrifugation Methods 0.000 description 12
- 238000011027 product recovery Methods 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 238000010907 mechanical stirring Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000000703 high-speed centrifugation Methods 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 241000237502 Ostreidae Species 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 235000020636 oyster Nutrition 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000008098 formaldehyde solution Substances 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 229910004339 Ti-Si Inorganic materials 0.000 description 3
- 229910010978 Ti—Si Inorganic materials 0.000 description 3
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- -1 14 (1994) 557 Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005360 mashing Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 101000809257 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 4 Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 102100038463 Ubiquitin carboxyl-terminal hydrolase 4 Human genes 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 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 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The present invention belongs to the technology field of preparing oil refining and petrochemical catalyst and relates to the preparation process of superfine zeolite powder from the superfine zeolite particle-mother liquid colloid suspension formed through hydrothermal process. Technologically, the present invention features that the said suspension is mixed with formaldehyde and urea in certain proportion to obtain mixture solution of pH 2-5; the mixture solution is let stand at 30-80 deg.c for 0.5-24 hr before the solid matter is collected through filtering; and the solid matter is washed, dried and roasted to obtain the superfine zeolite powder. The superfine zeolite powder has regular pore canal system, is silicate (aluminosilicate) crystal containing hetero metal atoms and has primary particle size below 100 nm.
Description
Technical field
The invention belongs to oil refining and petrochemical catalyst preparing technical field, relate generally to the method that from the synthetic formed ultrafine zeolite particle of hydro-thermal-mother liquor soliquid, prepares superfine zeolite powder.Said ultrafine zeolite is the crystal type silicate with regular pore canal system, silico-aluminate and crystal type silicon (aluminium) hydrochlorate that contains the metal heteroatom outside the sial atom, their primary particle granularity is below 500 nanometers, especially below 100 nanometers.
Background technology
The silicate of crystal type, silico-aluminate and crystal type silicon (aluminium) hydrochlorate that contains the metal heteroatom beyond the sial atom are the important Zeolite molecular sieve catalysis materials of a class, are used as catalyzer or support of the catalyst widely.According to big quantity research in recent years, if when hydro-thermal is synthetic, can make the grain fineness number of above-mentioned zeolite reach ultra-fine level, promptly the grain fineness number of zeolite is reduced to below 500 nanometers, especially be reduced to below 100 nanometers, then can improve it significantly as activity of such catalysts and anti-inactivation stability.Ultrafine zeolite also may be used to make densification and the successive mineral membrane, thereby is used for chemical sensor manufacturing and membrane catalytic reactor manufacturing.Following patent documentation and open source literature are illustrated this: WO93/17788, Appl.Catal.23 (1986) 69, Appl.Catal.35 (1987) 299, Appl.Catal.55 (1989) 65, Appl.Catal.A92 (1992) 113, J.Catal.141 (1993) 548, Zeolites14 (1994) 643, Adv.Mater.9 (1997) 585, J.Catal.179 (1998) 537, Micropor.Mesopor.Mater.21 (1998) 213, J.Memb.Sci.159 (1999) 263, Micropor.Mesopor.Mater.38 (2000) 25.Therefore, ultrafine zeolite has exploitation to be worth as novel material very much.
Yet, because the ultrafine zeolite particle can form stable soliquid with its hydro-thermal synthesis mother liquid, so at present can only be with high speed centrifugation partition method and/or freeze-drying obtain superfine zeolite powder repeatedly.Following patent documentation and open source literature are illustrated this: EP 0 435 625 A2 (1990), USP 6 258 991, Zeolites 14 (1994) 557, Stud.Surf.Sci.Catal.Part A, 105 (1997) 341, Micropor.Mesopor.Mater.25 (1998) 59-74, Micropor.Mesopor.Mater.43 (2001) 51-59, Micropor.Mesopor.Mater.50 (2001) 121-128, Mater.Sci.Eng.C19 (2002) 111-114, Micropor.Mesopor.Mater.55 (2002) 171-179.Since repeatedly high speed centrifugation separate and/or the freeze-drying method power consumption, consuming time, efficient is low and need Special Equipment, is unfavorable for large-scale production, therefore, the separation and recovery method of existing ultrafine zeolite has restricted the development and use of ultrafine zeolite material.
Summary of the invention
The purpose of this invention is to provide a kind of novel method that from the soliquid that contains the ultrafine zeolite particle, prepares superfine zeolite powder.
The technical scheme that realizes the object of the invention is to cause by the urea formadehyde cationic polymerization in soliquid to realize: at first, regulate the pH value and the temperature of soliquid.Secondly, make the soliquid that contains the ultrafine zeolite particle, be mixed in proportion, leave standstill with formaldehyde and urea, cationic polymerization takes place in formaldehyde and urea under suitable pH value and temperature.Then, collect solid substance, solid substance is washed with filtration method.At last, the dry and resulting solid substance of roasting, thus obtain superfine zeolite powder.
Technical scheme of the present invention is specifically carried out as follows:
The first step: the pH value and the temperature of regulating the ultrafine zeolite soliquid.
Wherein, the said ultrafine zeolite of the present invention refers to have the crystal type silicate of regular pore canal system, silico-aluminate and crystal type silicon (aluminium) hydrochlorate that contains the metal heteroatom outside the sial atom, their primary particle granularity is below 500 nanometers, especially below 100 nanometers.
About the hydrothermal synthesis method of above-mentioned ultrafine zeolite, in many patent documentations and open source literature, illustrate.Such as the method for being mentioned in following patent documentation and the open source literature: the hydrothermal synthesis method that relates to ultra-fine faujusite (Y zeolite) sees EP 0 435 625 A2, and USP4 372 931, and USP 3 516 786, Zeolites, 14 (1994) 110; Relate to ultra-fine five-membered ring type zeolite and (comprise ZSM-5, ZSM-11, Silicalite-1) hydrothermal synthesis method sees Zeolites 14 (1994) 643, Mater.Res.Soc.Symp.Proc.371 (1995) 21, Micropor.Mesopor.Mater.22 (1998) 9, Zeolites 18 (1997) 97, Micropor.Mater.5 (1996) 381, Aangew.Chem.Int.Ed.Engl.34 (1995) 73, Chem.Mater 5 (1993) 452, Micropor.Mesopor.Mater.25 (1998) 434, J.Phys.Chem.B101 (1997) 10094, Chem.Mater.7 (1995) 920, J.Catal.145,243-245 (1994), Micropor.Mesopor.Mater.39 (2000) 393, Inorg.Chem.39 (2000) 2279, DanishPatent PR 173,486, Chem.Comm.673 (1999), Mater.Sci.Eng.C 19 (2002) 111-114, Micropor.Mesopor.Mater.50 (2001) 121-128, Zeolites, 14 (1994) 557, Colloid Interface Sci., 170 (1995) 449, Micropor.Mesopor.Mater.43 (2001) 51-59, Micropor.Mesopor.Mater.31 (1999) 141, Micropor.Mesopor.Mater.31 (1999) 141; Relate to ultra-fine beta zeolite water process for thermosynthesizing and see J.Phys.Chem.B 103 (1999) 4972., Stud.Surf.Sci.Catal.105 (1997) 341, Zeolites11 (1991) 202, Zeolites11 (1991) 792; Relate to ultra-fine zeolite L hydrothermal synthesis method and see USP 6,258,991, relate to ultra-fine offretite hydrothermal synthesis method and see USP 6,258,991; Relate to ultra-fine Ti-Si zeolite (TS-1) hydrothermal synthesis method and see USP 4,410,501, or the like.Therefore, any slip-stick artist who is familiar with this area can synthesize the said ultrafine zeolite of the present invention-mother liquor soliquid according to the method hydro-thermal that document discloses.Wherein, for the zeolite structured and affirmation zeolite grain size,, adopt X-ray polycrystal powder diffraction approach and scanning (transmission) electron microscope method to carry out respectively according to the common way in this field.
Make the ultrafine zeolite soliquid have suitable pH value and temperature is the prerequisite of formaldehyde and urea generation cationic polymerization.According to the present invention, the soliquid of ultrafine zeolite is 2～5 in the pH value, temperature is to leave standstill under 30～80 ℃ 0.5～24 hour, can make the formaldehyde and the urea that are dissolved in wherein that cationic polymerization takes place fully, cause ultrafine zeolite particle aggregation, sedimentation, thereby the water in the hydro-thermal synthesis mother liquid is discharged from soliquid.
The influence of the cationic polymerization of pH value PARA FORMALDEHYDE PRILLS(91,95) and urea is, when pH value≤2, polymerization rate is fast, but polymer particle size is little, is unfavorable for causing the reunion of ultrafine zeolite particle.On the other hand, when pH value 〉=5, polymer particle size is big, but polymerization rate is too slow, also is unfavorable for causing the reunion of ultrafine zeolite particle.
The influence of the cationic polymerization of temperature PARA FORMALDEHYDE PRILLS(91,95) and urea is that when temperature was hanged down, polymerization rate was slow, was difficult to cause the reunion of ultrafine zeolite particle.On the other hand, when temperature was too high, polymerization rate was too fast, and polymkeric substance self adhesion is to the initiation variation of ultrafine zeolite particle aggregation.
According to the present invention, regulate ultrafine zeolite soliquid pH value and can use sulfuric acid, hydrochloric acid and nitric acid, the vitriol oil, concentrated hydrochloric acid and the concentrated nitric acid of preferred industrial goods.Hydro-thermal synthetic ultrafine zeolite soliquid is strong basicity, and pH value is generally 11～14.Regulate the pH value with dense inorganic acid and help reducing the waste liquid volume.The process that adds concentrated acid adjusting pH value in the soliquid of ultrafine zeolite will be carried out under mechanical stirring.
The synthetic of ultrafine zeolite generally carries out under 〉=100 ℃ hydrothermal temperature.Therefore, in order to satisfy the temperature condition that formaldehyde and urea carry out cationic polymerization, can be easily the colloidal suspension liquid temp be dropped in 30～80 ℃ the optimum range by means of cooling naturally.
Second step: formaldehyde and urea are dissolved in the soliquid of ultrafine zeolite particle in proportion, cause cationic polymerization.
According to big quantity research, needn't dilute from the synthetic ultrafine zeolite soliquid that obtains of hydro-thermal, can be directly used in and collect the ultrafine zeolite particle.In the soliquid that contains the ultrafine zeolite particle, the minimum add-on of urea is 2.0 grams per liters, and the suitable proportion of formaldehyde and urea is 0.8～1.5.Wherein, it is 36% industrial formol solution that the formaldehyde raw material can adopt concentration, and the urea raw material can adopt granular industrial urea.Formaldehyde and urea add under mechanical stirring in the suspension, and churned mechanically effect is to promote that urea dissolves fully, and suspension is mixed.In case urea dissolves fully, suspension mixes, and promptly stops to stir, and makes the formaldehyde and the urea that are dissolved in the mixed solution carry out cationic polymerization in the process of leaving standstill, and causes the ultrafine zeolite particle aggregation simultaneously.Preferred plan is, colloidal suspension liquid temp at ultrafine zeolite reaches 30～80 ℃, the pH value reaches under 2～5 the condition, if at first under mechanical stirring, add urea granules, and continue to stir 5 minutes, and then add formaldehyde solution, continue to stir 5 minutes, can guarantee that urea dissolves fully, suspension mixes.After stopping mechanical stirring, mixed solution left standstill 0.5～24 hour in said temperature and pH value scope, can make the formaldehyde and the urea that are dissolved in wherein that cationic polymerization takes place fully, and caused ultrafine zeolite particle aggregation, sedimentation.
The 3rd step: collect the solid substance that contains the ultrafine zeolite particle with filtration method.
After the processing of second step, formed stable soliquid is broken between ultrafine zeolite particle and its synthesis mother liquid, and polymkeric substance one synsedimentary of ultrafine zeolite particle and urea formadehyde is separated out from the hydro-thermal synthesis mother liquid.The solid substance of separating out can be finished with common filtration method with separating of clear liquid.When filtering, use deionized water repetitive scrubbing solid substance, up to checking the pH value of washing lotion to reach till 6～7 with wide pH value value test paper.
The 4th step: dry, roasting solid substance is with the pure superfine zeolite powder of the attitude that obtains reuniting.
Exsiccant optimal temperature scope is 100-200 ℃, and dry atmosphere is air atmosphere, gets time of drying 3-24 hour.The optimal temperature scope of roasting is 300-600 ℃, and calcination atmosphere is an air atmosphere, and roasting time was got 3-24 hour.Wherein, the purpose of roasting is the urea formadehyde polymkeric substance that removes with ultrafine zeolite particle cosedimentation, and occupies the organic formwork agent in the ultrafine zeolite duct.According to the present invention, said roasting preferable procedure intensification roasting mode.Temperature-programmed calcination helps preventing that the violent burning of large amount of organic from causing temperature control, destroys the ultrafine zeolite crystalline structure.As a special case, said drying is carried out under 110 ℃, and dry atmosphere is air, and be 3 hours time of drying; Said temperature-programmed calcination carries out in retort furnace, air atmosphere, and heating mode is: rise to 300 ℃ from room temperature with the temperature rise rate of 1 ℃/min, 300 ℃ of following constant temperature 1 hour; Be warming up to 400 ℃ with same temperature rise rate again, 400 ℃ of following constant temperature 1 hour; Be warming up to 500 ℃ with same temperature rise rate again, 500 ℃ of following constant temperature 1 hour; Be warming up to 550 ℃ with same temperature rise rate again, 550 ℃ of following constant temperature 12 hours.
Advantage of the present invention and effect are, by in the soliquid of ultrafine zeolite, adding a small amount of formaldehyde and urea, cationic polymerization by means of formaldehyde and urea causes ultrafine zeolite particle aggregation, sedimentation, and further by means of general operation such as filtration, drying and roasting, the pure superfine zeolite powder of the attitude that obtains reuniting.The inventive method save energy is saved time, and the efficient height does not need specific installation, and is raw materials used cheap and easy to get, can reach fully the ultrafine zeolite particle and reclaim, and is applicable to the large-scale production of ultrafine zeolite.
Embodiment
Below be described in detail specific embodiments of the invention.
Embodiment 1: preparation ultra-fine ZSM-5 zeolite powder (comparative example) from the soliquid of ultra-fine ZSM-5 zeolite
With Tai-Ace S 150 (Al
2(SO
4)
318H
2O), water glass (Na
2O%wt.=8.87, SiO
2%wt.=26.88, H
2O%wt.=64.25), 98% vitriol oil (H
2SO
4), sodium-chlor (NaCl), n-Butyl Amine 99 (n-Bu-NH
2) and deionized water be raw material (all being industrial goods), according to mol ratio be: 1.0Al
2O
3: 31.2SiO
2: 2.0Na
2O:833.3H
2O:12.2n-Bu-NH
2: 18.0NaCl prepares about 400 milliliters silica-alumina gel, gel through 1.0 hours intense mechanical beat glue handle after (300rpm), be sealed to 500 milliliters and have and carry out two stage variable temperature crystallizations in the churned mechanically stainless steel crystallizing kettle.Two stage variable temperature crystallizations refer to: the crystallization initial stage, with the temperature rise rate of 1 ℃/min gel is heated to 100 ℃, and 100 ℃ aging 24 hours down.Then, gel further is heated to 170 ℃ with the temperature rise rate of 1 ℃/min, and 170 ℃ of following crystallization 42 hours.In two stage variable temperature crystallization processes, keeping mechanical stirring speed is 100rpm.After crystallization finishes, stop mechanical stirring and begin the nature cooling.So, obtain the soliquid of ultra-fine ZSM-5 zeolite.
Treat that the colloidal suspension liquid temp of above-mentioned ultra-fine ZSM-5 zeolite reduces to about 40 ℃, open the stainless steel synthesis reactor, the soliquid that will contain ultra-fine ZSM-5 zeolite is poured in 500 ml beakers, and the wherein sedimentation situation of suspended substance is observed in static placement.As a result, through after 30 days standing sedimentations, beaker bottom has only the small amount of precipitate thing, and most ultra-fine ZSM-5 zeolite particles still exist with stable oyster white soliquid form with its synthesis mother liquid.Get 10 milliliters of this suspension with the high speed centrifugation test tube, attempt centrifugation.At last, after centrifuge speed reached 10000rpm, centrifugation time reached 10min, just forced ultra-fine ZSM-5 zeolite particles to settle down from mother liquor fully.
Embodiment 2: the ultra-fine ZSM-5 zeolite powder of preparation from the soliquid of ultra-fine ZSM-5 zeolite
Repeat embodiment 1, but when the soliquid of resulting ultra-fine ZSM-5 zeolite is cooled to 50 ℃ in synthesis reactor after, open synthesis reactor, wherein contained thing (about 400 milliliters) is transferred in a band insulation and the churned mechanically plastic tank.Under the mechanical stirring speed of 100rpm, in suspension, drip 98% vitriol oil, until with the wide pH value detection paper to the pH value reach about 2.0.Then according to total liquid measure (about 400 milliliters), according to urea 8 grams per liters, formaldehyde and urea mol ratio are 1.2, under agitation in suspension, add 3.2 gram urea, the formaldehyde solution that in suspension, adds 5.44 milliliter 36% after 5 minutes again, continue to stir 5 minutes, stop then stirring, left standstill after plastic tank is added a cover 2 hours.Leave standstill in the process, the temperature that contains the ultrafine zeolite soliquid of formaldehyde and urea remains on 40 ℃.Leave standstill and finish, can be observed originally stable soliquid layering, the upper strata is a clear liquid, and lower floor is for having the hydrophobic shape throw out of consolidating.With B and common suction filtration paper, 400 mmhg can be easily under with interior vacuum tightness with said solid shape throw out suction filtration and with deionized water wash to pH value 6～7.Then, the filter cake that will contain ultra-fine ZSM-5 zeolite 110 ℃ dry 3 hours down, in retort furnace, carry out temperature-programmed calcination at last, heating mode is: rise to 300 ℃ from room temperature with the temperature rise rate of 1 ℃/min, 300 ℃ of following constant temperature 1 hour; Be warming up to 400 ℃ with same temperature rise rate again, 400 ℃ of following constant temperature 1 hour; Be warming up to 500 ℃ with same temperature rise rate again, 500 ℃ of following constant temperature 1 hour; Be warming up to 550 ℃ with same temperature rise rate again, 550 ℃ of following constant temperature 12 hours.So far, obtain the ultra-fine ZSM-5 zeolite powder that exists with the coacervate form, actual product weight 41.95 grams (theoretical product weight is 42.11 grams), product recovery rate is greater than 99%.Learn with tem study, about 0.5～0.7 micron of the coacervate size of ultra-fine ZSM-5 zeolite, after this ultra-fine ZSM-5 zeolite aggregate powder of AI/Yt disperseed with ultrasonic oscillation in the mixed solvent of alcohol-water, use tem study again, coacervate disperses again as a result, can be observed the about 20-50 nanometer of primary particle size that constitutes ultra-fine ZSM-5 zeolite coacervate.
Embodiment 3: the ultra-fine ZSM-5 zeolite powder of preparation from the soliquid of ultra-fine ZSM-5 zeolite
Repeat embodiment 2, when still in suspension, dripping 98% vitriol oil, make the pH value of suspension reach 3.0,4.0,5.0 successively.The ultra-fine ZSM-5 zeolite powder actual weight that exists with the coacervate form that then obtains at last is followed successively by 42.04 grams, 41.17 grams and 38.35 grams (theoretical product weight is 42.11 grams), product recovery rate is followed successively by〉99%, ≈ 98% and ≈ 91%.
Embodiment 4: the ultra-fine ZSM-5 zeolite powder of preparation from the soliquid of ultra-fine ZSM-5 zeolite
Repeat embodiment 2, still, the ultrafine zeolite soliquid that contains formaldehyde and urea is in 2 hours standing and reacting process, and its temperature remains on 75 ℃ successively, 60 ℃ and 35 ℃.The ultra-fine ZSM-5 zeolite powder actual weight that exists with the coacervate form that then obtains at last is followed successively by 38.50 grams, 38.94 grams and 40.71 grams (theoretical product weight is 42.11 grams), and product recovery rate is followed successively by ≈ 91%, ≈ 92% and ≈ 97%.
Embodiment 5: the ultra-fine ZSM-5 zeolite powder of preparation from the soliquid of ultra-fine ZSM-5 zeolite
Repeat embodiment 2, but be 6 grams per liters, 4 grams per liters, 2 grams per liters according to urea concentration successively, formaldehyde and urea mol ratio are 1.2, add urea and formaldehyde solution in the soliquid of ultra-fine ZSM-5 zeolite.The ultra-fine ZSM-5 zeolite powder actual weight that exists with the coacervate form that then obtains at last is followed successively by 39.05 grams, 34.56 grams and 28.60 grams (theoretical product weight is 42.11 grams), and product recovery rate is followed successively by ≈ 93%, ≈ 82% and ≈ 68%.Wherein, when the urea concentration in the soliquid of ultra-fine ZSM-5 zeolite is low to moderate 2 grams per liters, Gu the sedimentary filtration velocity of shape obviously slows down.
Embodiment 6: the ultra-fine ZSM-5 zeolite powder of preparation from the soliquid of ultra-fine ZSM-5 zeolite
Repeat embodiment 2, but be 0.9,1.1,1.3 and 1.5 in the soliquid of ultra-fine ZSM-5 zeolite, to add formaldehyde solution according to formaldehyde and urea mol ratio successively.Wherein, to maintain 8 grams per liters constant for the concentration of urea in suspension.The ultra-fine ZSM-5 zeolite powder actual weight that exists with the coacervate form that then obtains at last is followed successively by 39.44 grams, 41.09 grams, 40.65 grams and 36.32 (theoretical product weight is 42.11 grams), product recovery rate is followed successively by ≈ 94%, ≈ 98%, and ≈ 97%, and ≈ 86%.
Embodiment 7: the ultra-fine ZSM-5 zeolite powder of preparation from the soliquid of ultra-fine ZSM-5 zeolite
Repeating embodiment 2, is 4 grams per liters according to urea concentration still, and formaldehyde and urea mol ratio are 1.2, adds urea and formaldehyde solution in the soliquid of ultra-fine ZSM-5 zeolite.And the time that will contain the ultrafine zeolite soliquid standing and reacting of formaldehyde and urea extended to 8 hours successively from 2 hours, 16 hours and 24 hours.The ultra-fine ZSM-5 zeolite powder actual weight that exists with the coacervate form that then obtains at last is followed successively by 37.00 grams, 38.79 grams and 39.00 (theoretical product weight is 42.11 grams), and product recovery rate is followed successively by ≈ 88%, and ≈ 92%, and ≈ 93%.
Embodiment 8: on the amplification scale, and the ultra-fine ZSM-5 zeolite powder of preparation from the soliquid of ultra-fine ZSM-5 zeolite
Repeat embodiment 2, but the synthetic scale of the hydro-thermal of ultra-fine ZSM-5 zeolite soliquid expands 2000 liters to.After synthesis reactor is cooled to 50 ℃, with mashing pump the soliquid of ultra-fine ZSM-5 zeolite being transferred to one has in the churned mechanically glass cylinder of steel, finish operations such as adjusting of pH value and urea formadehyde cationic polymerization in the glass cylinder of steel, always being mixed liquid measure is 2035 liters.Wherein, the time of containing the ultrafine zeolite soliquid standing and reacting of formaldehyde and urea changes 20 hours into.At last, stratified mixed solution is transported on the track type vacuum filter with mashing pump and filters, washs.Filter, when washing is shared 4 hours.Then, the filter cake that will contain ultra-fine ZSM-5 zeolite is following dry 12 hours in 150～200 ℃ in the electrothermic type air dry oven, carry out temperature-programmed calcination at last in box retort furnace, heating mode is: rise to 300 ℃ from room temperature with the temperature rise rate of 1 ℃/min, 300 ℃ of following constant temperature 3 hours; Be warming up to 450 ℃ with same temperature rise rate again, 450 ℃ of following constant temperature 2 hours; Be warming up to 550 ℃ with same temperature rise rate again, 550 ℃ of following constant temperature 10 hours.Obtain 218 kilograms of ultra-fine ZSM-5 zeolite powders that exist with the coacervate form (theoretical product weight is 210.55 kilograms) altogether, product recovery rate is greater than 99%.The part that the actual product weight that obtains is higher than theoretical yield is the contribution of remaining organism in the zeolite cavity, crystal water and balance sodium ion etc.
Embodiment 9: preparation ultra-fine beta zeolite powder (comparative example) from the soliquid of ultra-fine beta zeolite
With alumina dry glue (water content 30%wt.), silicon sol (SiO
2% wt.=30, H
2O% wt.=70), tetraethylammonium bromide (TEABr), sodium hydroxide (96%wt.), strong aqua (25-28% wt.NH
3) and deionized water be raw material (all being industrial goods), according to mol ratio be: 1.0Al
2O
3: 27.4SiO
2: 1.9Na
2O:519.6H
2O:7.4TEABr:19.2NH
3Prepare about 400 milliliters silica-alumina gel, gel through 1.0 hours intense mechanical beat glue handle after (300rpm), be sealed to 500 milliliters and have and carry out two stage variable temperature crystallizations in the churned mechanically stainless steel crystallizing kettle.Two stage variable temperature crystallizations refer to: the crystallization initial stage, with the temperature rise rate of 1 ℃/min gel is heated to 100 ℃, and 100 ℃ aging 24 hours down.Then, gel further is heated to 140 ℃ with the temperature rise rate of 1 ℃/min, and 140 ℃ of following crystallization 96 hours.In two stage variable temperature crystallization processes, keeping mechanical stirring speed is 400rpm.After crystallization finishes, stop mechanical stirring and begin the nature cooling.So, obtain the soliquid of ultra-fine beta zeolite.
Treat that the colloidal suspension liquid temp of above-mentioned ultra-fine beta zeolite reduces to about 40 ℃, open the stainless steel synthesis reactor, the soliquid that will contain the ultra-fine beta zeolite is poured in 500 ml beakers, and the wherein sedimentation situation of suspended substance is observed in static placement.As a result, through after 10 days standing sedimentations, beaker bottom has only the small amount of precipitate thing, and most ultra-fine beta zeolite particles still exist with stable oyster white soliquid form with its synthesis mother liquid.Get 10 milliliters of this suspension with the high speed centrifugation test tube, attempt centrifugation.At last, after centrifuge speed reached 15000rpm, centrifugation time reached 10min, just forced the ultra-fine beta zeolite particles to settle down from mother liquor fully.Tem study shows that institute's synthetic ultra-fine beta zeolite particles size is between the 20-30 nanometer.
Embodiment 10: preparation ultra-fine beta zeolite powder from the soliquid of ultra-fine beta zeolite
Repeat embodiment 9, but the soliquid of institute's synthetic ultra-fine beta zeolite carries out separating treatment according to embodiment 2.The ultra-fine beta zeolite powder actual weight that exists with the coacervate form that then obtains at last is 72.5 grams (theoretical product weight is 73 grams), product recovery rate〉99%.
Embodiment 11: preparation ultra-fine ZSM-11 zeolite powder (comparative example) from the soliquid of ultra-fine ZSM-11 zeolite
With tetraethoxy (SiO
2Content is no less than 28%wt., and density is 0.929-0.936), TBAH (40%wt.TBAOH) and deionized water are raw material, are 1.0SiO according to mol ratio
2: 0.15 (TBA)
2O:12.0H
2O:4.0EtOH prepares about 400 milliliters of gels.Wherein, EtOH represents ethanol, is produced by teos hydrolysis.At first above-mentioned gel was at room temperature worn out 100 hours, be sealed in then in 500 milliliters of stainless steel crystallizing kettles and descended static crystallization 72 hours, obtain the soliquid of ultra-fine ZSM-11 zeolite at 100 ℃.
Treat that the colloidal suspension liquid temp of above-mentioned ultra-fine ZSM-11 zeolite reduces to about 40 ℃, open the stainless steel synthesis reactor, the soliquid that will contain ultra-fine ZSM-11 zeolite is poured in 500 ml beakers, and the wherein sedimentation situation of suspended substance is observed in static placement.As a result, through after 10 days standing sedimentations, beaker bottom has only the small amount of precipitate thing, and most ultra-fine ZSM-11 zeolite particles still exist with stable oyster white soliquid form with its synthesis mother liquid.Get 10 milliliters of this suspension with the high speed centrifugation test tube, attempt centrifugation.At last, after centrifuge speed reached 8000rpm, centrifugation time reached 10min, just forced ultra-fine ZSM-11 zeolite particles to settle down from mother liquor fully.Learn that with tem study the ultra-fine ZSM-11 zeolite particles of institute's synthetic size is about 100 nanometers.
Embodiment 12: the ultra-fine ZSM-11 zeolite powder of preparation from the soliquid of ultra-fine ZSM-11 zeolite
Repeat embodiment 11, but the soliquid of the ultra-fine ZSM-11 zeolite of institute's synthetic carries out separating treatment according to embodiment 2.The ultra-fine ZSM-11 zeolite powder actual weight that exists with the coacervate form that then obtains at last is 59.3 grams (theoretical product weight is 60 grams), product recovery rate ≈ 99%.
Embodiment 13: preparation ultra-fine offretite powder (comparative example) from the soliquid of ultra-fine offretite (offretite)
With alumina dry glue (water content 30%wt.), silicon sol (SiO
2% wt.=30, H
2O%wt.=70), Tetramethylammonium hydroxide (50% wt.TMAOH), sodium hydroxide (96% wt.NaOH), potassium hydroxide (82% wt.KOH) and deionized water are raw material, are 1.0Al according to mol ratio
2O
3: 9.8SiO
2: 136H
2O:0.12Na
2O:0.5K
2O:4.0 (TMA)
2O prepares about 400 milliliters of gels.Then, this gel seal is had in the churned mechanically stainless steel crystallizing kettle in 500 milliliters, stirred crystallization 170 hours down, obtain the soliquid of ultra-fine offretite at 100 ℃.
Treat that the colloidal suspension liquid temp of above-mentioned ultra-fine offretite reduces to about 40 ℃, open the stainless steel synthesis reactor, the soliquid that will contain ultra-fine offretite is poured in 500 ml beakers, and the wherein sedimentation situation of suspended substance is observed in static placement.As a result, through after 10 days standing sedimentations, beaker bottom has only a certain amount of throw out, and most of ultra-fine offretite particle still exists with stable oyster white soliquid form with its synthesis mother liquid.Get 10 milliliters of this suspension with the high speed centrifugation test tube, attempt centrifugation.At last, after centrifuge speed reached 10000rpm, centrifugation time reached 10min, just forced ultra-fine offretite particle to settle down from mother liquor fully.Learn that with tem study the ultra-fine offretite size of particles of institute's synthetic is between the 30-200 nanometer.
Embodiment 14: the ultra-fine offretite powder of preparation from the soliquid of ultra-fine offretite (offretite)
Repeat embodiment 13, but the soliquid of the ultra-fine offretite of institute's synthetic carries out separating treatment according to embodiment 2.The ultra-fine offretite powder actual weight that exists with the coacervate form that then obtains at last is 108.5 grams (theoretical product weight is 110 grams), product recovery rate ≈ 99%.
Embodiment 15: preparation ultra-fine faujusite (Y zeolite) powder (comparative example) from the soliquid of faujusite (Y zeolite)
With alumina dry glue (water content 30% wt.), water glass (Na
2O% wt.=8.87, SiO
2%wt.=26.88, H
2O% wt.=64.25),, sodium hydroxide (96% wt.NaOH) and deionized water are raw material, are 1.0Al according to mol ratio
2O
3: 16SiO
2: 336H
2O:16.8Na
2O prepares about 400 milliliters of gels.With this gel with high shearing mixing emulsor (Shanghai prestige space) emulsification 1 hour under 5000rpm.Then, this gel was at room temperature worn out 12 hours, finally sealed is in 500 milliliters of stainless steel crystallizing kettles, and static crystallization is 8 hours under 100 ℃, obtains the soliquid of ultra-fine Y zeolite.
Treat that the colloidal suspension liquid temp of above-mentioned ultra-fine Y zeolite reduces to about 40 ℃, open the stainless steel synthesis reactor, the soliquid that will contain ultra-fine Y zeolite is poured in 500 ml beakers, and the wherein sedimentation situation of suspended substance is observed in static placement.As a result, through after 10 days standing sedimentations, beaker bottom has only the small amount of precipitate thing, and most ultra-fine Y zeolite particles still exist with stable oyster white soliquid form with its synthesis mother liquid.Get 10 milliliters of this suspension with the high speed centrifugation test tube, attempt centrifugation.At last, after centrifuge speed reached 10000rpm, centrifugation time reached 10min, just forced ultra-fine Y zeolite particle to settle down from mother liquor fully.Learn that with tem study the ultra-fine Y zeolite size of particles of institute's synthetic is between the 20-50 nanometer..
Embodiment 16: preparation ultra-fine faujusite (Y zeolite) powder from the soliquid of ultra-fine faujusite (Y zeolite)
Repeat embodiment 15, but the soliquid of the ultra-fine Y zeolite of institute's synthetic carries out separating treatment according to embodiment 2.The ultra-fine Y zeolite powder actual weight that exists with the coacervate form that then obtains at last is 18.0 grams (theoretical product weight is 17.6 grams), and product recovery rate is greater than 99%.It partly is the contribution of balance sodium ion and crystal water that product weight exceeds theoretical yield.
Embodiment 17: preparation ultra-fine Ti-Si zeolite (TS-1) powder (comparative example) from the soliquid of ultra-fine titanium heteroatoms silicon zeolite (TS-1)
With tetraethoxy (SiO
2Content is no less than 28%wt., and density is 0.929-0.936), tetraethyl titanate, TPAOH solution (25%wt.TPAOH) and deionized water are raw material, are 1.0TiO according to mol ratio
2: 32SiO
2: 505H
2O:7.5 (TPA)
2O prepares about 160 milliliters of mixed solutions.With this mixed solution at room temperature mechanical stirring under agitation be warmed up to 80 ℃ after 1 hour, steam the ethanol that estersil and the hydrolysis of titanium ester produce.The evaporation latter temperature is brought up to 90 ℃, steams whole ethanol 4.5 hours consuming time.Then, the gained gel is diluted to 400 milliliters, and is sealed in 500 milliliters and has in the churned mechanically stainless steel crystallizing kettle, stirred crystallization 240 hours down, obtain the soliquid of ultra-fine TS-1 at 170 ℃.
Treat that the colloidal suspension liquid temp of above-mentioned ultra-fine TS-1 reduces to about 40 ℃, open the stainless steel synthesis reactor, the soliquid that will contain ultra-fine TS-1 is poured in 500 ml beakers, and the wherein sedimentation situation of suspended substance is observed in static placement.As a result, through after 10 days standing sedimentations, beaker bottom has only a certain amount of throw out, but most of ultra-fine TS-1 particle still exists with stable oyster white soliquid form with its synthesis mother liquid.Get 10 milliliters of this suspension with the high speed centrifugation test tube, attempt centrifugation.At last, after centrifuge speed reached 6000rpm, centrifugation time reached 10min, just forced ultra-fine TS-1 particle to settle down from mother liquor fully.Learn that with tem study the ultra-fine TS-1 size of particles of institute's synthetic is about 100 nanometers.
Embodiment 18: preparation ultra-fine Ti-Si zeolite (TS-1) powder from the soliquid of ultra-fine titaniferous heteroatoms silicon zeolite (TS-1)
Repeat embodiment 17, but the soliquid of the ultra-fine TS-1 of institute's synthetic carries out separating treatment according to embodiment 2.The ultra-fine TS-1 powder actual weight that exists with the coacervate form that then obtains at last is 35.25 grams (theoretical product weight is 35.38 grams), and product recovery rate is greater than 99%.
Claims (1)
1. method for preparing superfine zeolite powder, be with after the synthetic formed ultrafine zeolite particle of hydro-thermal-the mother liquor soliquid is regulated pH value and temperature, be mixed in proportion with formaldehyde and urea, leave standstill, collect solid substance with filtration method then, solid substance is washed, obtain superfine zeolite powder after drying and the roasting, it is characterized in that;
A) ultrafine zeolite refers to have the crystal type silicate and the silico-aluminate of regular pore canal system and crystal type silicate and the silico-aluminate that contains the metal heteroatom outside the sial atom, and their primary particle granularity is below 500 nanometers;
B) in the soliquid that contains the ultrafine zeolite particle, the minimum add-on of urea is 2.0 grams per liters, and the mol ratio of formaldehyde and urea is 0.8～1.5;
C) making the ultrafine zeolite soliquid that contains formaldehyde and urea is 2～5 in the pH value, and temperature is to leave standstill under 30～80 ℃ 0.5～24 hour;
D) after the ultrafine zeolite soliquid that contains formaldehyde and urea left standstill, formed mixed solution was collected solid substance with filtration method;
E) to wash the pH value be 6～7 to the solid substance that filtration is obtained with deionized water, then with its 100～200 ℃ dry 3～24 hours down, again 300～600 ℃ of following roastings 3～24 hours, obtain pure superfine zeolite powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03111069XA CN100522811C (en) | 2003-02-25 | 2003-02-25 | Preparation process of superfine zeolite powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03111069XA CN100522811C (en) | 2003-02-25 | 2003-02-25 | Preparation process of superfine zeolite powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1436726A CN1436726A (en) | 2003-08-20 |
| CN100522811C true CN100522811C (en) | 2009-08-05 |
Family
ID=27634109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB03111069XA Expired - Fee Related CN100522811C (en) | 2003-02-25 | 2003-02-25 | Preparation process of superfine zeolite powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100522811C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299986C (en) * | 2004-12-02 | 2007-02-14 | 复旦大学 | Organic and inorganic carbon hybridized silicon zeolite solid acid cellular material and its prepn |
| EP1779855A1 (en) * | 2005-10-28 | 2007-05-02 | Abdula Kurkayev | Nanoparticles of a heterocrystal mineral for use as a medicament and method of producing the same |
| CN106032278B (en) * | 2015-03-18 | 2018-09-28 | 中国石油大学(华东) | A kind of preparation method of the silica zeolite Silicalite-1 of high hydrogen bond silicone hydroxyl content |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| US6258991B1 (en) * | 1995-07-10 | 2001-07-10 | Exxonmobil Chemical Patents Inc. | Zeolites and processes for their manufacture |
-
2003
- 2003-02-25 CN CNB03111069XA patent/CN100522811C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| US6258991B1 (en) * | 1995-07-10 | 2001-07-10 | Exxonmobil Chemical Patents Inc. | Zeolites and processes for their manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1436726A (en) | 2003-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102502687B (en) | Method for greenly synthesizing Ti-Si molecular sieve | |
| KR100542959B1 (en) | Titanium silicalite-1 containing granules, preparation methods thereof, suspension catalysts containing them and methods for using them in various chemical reactions | |
| US5919430A (en) | Preparation of crystalline microporous and mesoporous metal silicates, products produced thereby and use thereof | |
| CN104556111B (en) | A kind of Titanium Sieve Molecular Sieve and its synthetic method | |
| CN101134575B (en) | Method for preparing TS-1 molecular sieve | |
| CN107530693A (en) | Renovation process for the titanium zeolite catalysts of epoxidation of propylene | |
| CN102190312A (en) | Method for recycling molecular sieve mother solution | |
| CN107188194B (en) | A method of preparing high catalytic activity Ti-MWW molecular sieve | |
| CN102942192A (en) | Preparation method for high-dispersion nanometer zeolite molecular sieve | |
| CN102249258A (en) | Method for synthesizing heteroatom Sn-beta zeolite | |
| US5474754A (en) | Preparation of an aluminosilicotitanate isomorphous with zeolite beta | |
| CN106044793A (en) | Method for synthesis of nanometer ZSM-5 molecular sieve from mother liquor flocculate | |
| CN102674389B (en) | Preparation method of titanium-containing nano-mordenite molecular sieve | |
| CN107792863A (en) | Catalyzing hydrogen peroxide oxidation reaction HTS TS 1 synthetic method | |
| CN102309980B (en) | Steam modifying method of titanium-silicon molecular sieve | |
| CN108793181A (en) | A kind of Titanium Sieve Molecular Sieve and preparation and application | |
| CN105776244B (en) | A method of TS-1 molecular sieves are synthesized by aerosol processing/spray drying process assisted Solid-state | |
| CN100522811C (en) | Preparation process of superfine zeolite powder | |
| CN100553774C (en) | The preparation method of nano molecular sieve/sieve and silica-sesquioxide compound catalyze material | |
| CN104692409B (en) | A kind of method of synthesis of titanium silicon molecular sieve | |
| CN100360405C (en) | LTA and FAU molecular screen nanocrystalline preparation method | |
| CN100369812C (en) | Preparation method of inorganic laminated column molecular sieve type titanium lithium containing soapstone | |
| US6896859B2 (en) | Method for the production of a titanium-containing zeolite | |
| CN102583426A (en) | Method for adjusting pH value with oligosaccharide during synthesizing titanium silicalite molecular sieve (TS-1) | |
| CN102311128A (en) | Method for treating titanium-silicon molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| CI01 | Correction of invention patent gazette |
Correction item: deemed to have been withdrawn Correct: delete False: Wrong announcement Number: 14 Volume: 22 |
|
| ERR | Gazette correction |
Free format text: CORRECT: DEEMED WITHDRAWAL; FROM: WRONG PUBLICATION TO: DELETION |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: LEADING GROUP OF DALIAN UNIVERSITY OF TECHNOLOGY C Free format text: FORMER OWNER: DALIAN UNIVERSITY OF SCIENCE AND TECHNOLOGY Effective date: 20101111 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 116024 NO.2, LINGGONG ROAD, GANJINGZI DISTRICT, DALIAN CITY, LIAONING PROVINCE TO: 116023 ROOM 312, TOWER B, KEJI BUILDING, NO.80, RUANJIANYUAN ROAD, NEW AND HIGH TECHNOLOGY PARK, DALIAN CITY, LIAONING PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20101111 Address after: 312, room 116023, building B, building 80, software garden road, Dalian hi tech park, Liaoning Patentee after: Dalian University of Technology Leading Group Limited Address before: 116024 Liaoning, Dalian, Ganjingzi Ling Road, No. 2 Patentee before: Dalian University of Technology |
|
| ASS | Succession or assignment of patent right |
Owner name: DALIAN UNIVERSITY OF TECHNOLOGY QIWANGDA CHEMICAL Free format text: FORMER OWNER: DALIAN UNIVERSITY OF SCIENCE AND TECHNOLOGY Effective date: 20110111 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 116024 NO. 2, LINGGONG ROAD, GANJINGZI DISTRICT, DALIAN CITY, LIAONING PROVINCE TO: 116023 ROOM 312, TOWER B, KEJI BUILDING, NO. 80, RUANJIANYUAN ROAD, HIGH-TECH. PARK, DALIAN CITY, LIAONING PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20110111 Address after: 312, room 116023, building B, building 80, software garden road, Dalian hi tech park, Liaoning Patentee after: Dalian Ligong Qiwangda Chemical Technology Co., Ltd. Address before: 116024 Liaoning, Dalian, Ganjingzi Ling Road, No. 2 Patentee before: Dalian University of Technology |
|
| ASS | Succession or assignment of patent right |
Owner name: DALIAN UNIVERSITY OF SCIENCE AND TECHNOLOGY Free format text: FORMER OWNER: DALIAN UNIVERSITY OF TECHNOLOGY QIWANGDA PETROCHEMICAL TECHNOLOGY CO., LTD. Effective date: 20110325 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 116023 ROOM 312, TOWER B, SCI-TECH BUILDING, NO. 80, RUANJIANYUAN ROAD, HIGH-TECH. ZONE, DALIAN CITY, LIAONING PROVINCE TO: 116024 NO. 2, LINGGONG ROAD, HIGH-TECH. ZONE, DALIAN CITY, LIAONING PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20110325 Address after: 116024 Dalian high tech park, Liaoning Ling Road, No. 2 Patentee after: Dalian University of Technology Address before: 312, room 116023, building B, building 80, software garden road, Dalian hi tech park, Liaoning Patentee before: Dalian Ligong Qiwangda Chemical Technology Co., Ltd. |
|
| ASS | Succession or assignment of patent right |
Owner name: DALIAN UNIVERSITY OF TECHNOLOGY INDUSTRIAL INVESTM Free format text: FORMER OWNER: DALIAN UNIVERSITY OF SCIENCE AND TECHNOLOGY Effective date: 20110426 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 116024 NO. 2, LINGGONG ROAD, HIGH-TECH. PARK, DALIAN CITY, LIAONING PROVINCE TO: 116023 NO. 2, LINGGONG ROAD, GANJINGZI DISTRICT, DALIAN CITY, LIAONING PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20110426 Address after: 116023 Liaoning, Dalian, Ganjingzi Ling Road, No. 2 Patentee after: Dalian University of Technology Industry Investment Company Limited Address before: 116024 Dalian high tech park, Liaoning Ling Road, No. 2 Patentee before: Dalian University of Technology |
|
| ASS | Succession or assignment of patent right |
Owner name: DALIAN UNIVERSITY OF TECHNOLOGY LEADING GROUP CO., Free format text: FORMER OWNER: DALIAN UNIVERSITY OF TECHNOLOGY INDUSTRY INVESTMENT CO., LTD. Effective date: 20110805 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20110805 Address after: 116023 Liaoning, Dalian, Ganjingzi Ling Road, No. 2 Patentee after: Dalian union leader group Co., Ltd. Address before: 116023 Liaoning, Dalian, Ganjingzi Ling Road, No. 2 Patentee before: Dalian University of Technology Industry Investment Company Limited |
|
| ASS | Succession or assignment of patent right |
Owner name: DLUT QIWANGDA CHEMICAL TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: DLUT LINGXIAN GROUP CO., LTD. Effective date: 20110923 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 116023 DALIAN, LIAONING PROVINCE TO: 116024 DALIAN, LIAONING PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20110923 Address after: 410, room 116024, building B, building 80, software garden road, Dalian hi tech park, Liaoning Patentee after: Dalian Ligong Qiwangda Chemical Technology Co., Ltd. Address before: 116023 Liaoning, Dalian, Ganjingzi Ling Road, No. 2 Patentee before: Dalian union leader group Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090805 Termination date: 20200225 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |