CN104495868A - Preparation method of large-particle-size titanium silicon molecular sieve - Google Patents
Preparation method of large-particle-size titanium silicon molecular sieve Download PDFInfo
- Publication number
- CN104495868A CN104495868A CN201410712996.9A CN201410712996A CN104495868A CN 104495868 A CN104495868 A CN 104495868A CN 201410712996 A CN201410712996 A CN 201410712996A CN 104495868 A CN104495868 A CN 104495868A
- Authority
- CN
- China
- Prior art keywords
- preparation
- mixed solution
- inorganic
- hts
- large stone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a preparation method of a large-particle-size titanium silicon molecular sieve, which comprises the following steps: adding an inorganic silicon source into an organic template water solution at 30-90 DEG C, sufficiently stirring for 0.2-2 hours, adding an inorganic titanium source, sufficiently stirring for 0.5-4 hours, uniformly mixing, adding an alkali source at one time, and carrying out hydrothermal crystallization on the mixed solution (composed of the following components in parts by mole: 1 part of SiO2 in the inorganic silicon source, 0.01-0.03 part of TiO2 in the inorganic titanium source, 0.02-0.2 part of organic template, 20-80 parts of alkali source and 30-70 parts of alkali source) at 120-200 DEG C for 2-10 days; and filtering, washing, drying and roasting to obtain the titanium silicon molecular sieve. The titanium silicon molecular sieve catalyst prepared by the method has uniform particle size, has the average particle size of greater than 10 micrometers, and is easy for separation and recovery after reaction. The method can enhance the reutilization rate, has the advantages of fewer synthesis steps, low cost and high product quality stability, and is simple to operate.
Description
Technical field
The present invention relates to a kind of preparation method of HTS, particularly relate to a kind of preparation method of Large stone HTS.
Background technology
Namely HTS is that transition metal titanium atom is incorporated in the framework of molecular sieve with certain topological framework, forms the porous crystalline material with catalytic oxidation activity.HTS may be used for the multiple organic oxidizing reaction of catalysis, such as alkene epoxidation, partial oxidation of alkanes, oxidation of alcohols, phenolic hydroxy group, cyclic ketones ammonia oxidation etc., and in reaction, free of contamination lower concentration hydrogen peroxide can be adopted as oxygenant, reaction preference is high, technique is comparatively simple, has unrivaled energy-conservation, the advantage such as economy and environment is friendly of conventional oxidation system, is considered to the Typical Representative of environmentally friendly catalyzer.
HTS is prepared by hydrothermal synthesis method usually, and grain size, between 0.1 ~ 5 micron, because crystal grain is less, is difficult to be separated with reaction medium, hinders the widespread use of HTS on industrial reaction device.Therefore, follow-up inventor is all devoted to the technology of preparing developing Large stone molecular sieve.
Method required HTS powder and the larger carrier of another kind of yardstick is carried out a compound in technology building-up process in position, is prepared into composite catalyst.Granules of catalyst can be become large by the method to a certain extent, but there is the problem of binding ability difference between molecular sieve and carrier, and active ingredient is easily separated with carrier.As patent US5736479 adopts the colloid mother liquor of classical approach preparation Ti-Si zeolite, then by gac or metal oxide as A1
2o
3, SiO
2, TiO
2, ZrO
2or Al
2o
3siO
2etc. adding in Hydrothermal Synthesis system, Ti-Si zeolite grows the Ti-Si catalyst obtaining loading type in the carrier.Granularity≤5 micron of independent TS-1, and the size range of loaded catalyst is generally at 8 ~ 30 microns.But, peptization phenomenon can be there is, thus affect the degree of crystallinity of HTS in follow-up crystallization process in this instability in the strong basicity environment of HTS preparation process of the metal oxide carrier of routine.Especially be applied in ammoxidation of cyclohexanone reaction process, under hydrogen peroxide and ammoniacal liquor existent condition, the skeleton of carrier own can dissolve, and causes coming off of HTS, can not play much good supporting role.
Patent CN1554483 describes and the powdered graphite of inertia is introduced HTS Hydrothermal Synthesis system, obtained composite Ti-Si catalyst, alkene epoxidation oximes for alicyclic ketone and arene hydroxylation.But the specific surface of graphite is less, and the smooth and inertia of surface tissue, active ingredient TS-l is easy to come off.
Another method preparing Large stone Ti-Si catalyst is on the basis of the former powder of synthesis of titanium silicon molecular sieve, obtained by subsequent forming technology, as patent CN1911516A discloses a kind of preparation method of flake structure titanium silicon molecular sieve, by by HTS, extrusion aid, boric acid, non-acid SiO
2carrier and the rear extruded moulding of wetting agent mixing obtain, and because catalyzer crystalline form is homogeneous and laminar structural performance, catalyzer has good intensity and product diffusion, difficult drop-off, but because containing carrier S iO in catalyzer
2with other inactive ingredients, reduce the effective active component of every gram of catalyzer, the treatment capacity of unit catalyst is declined.
Patent CN102153104A discloses a kind of method of spray shaping HTS, after the HTS crystallization of Hydrothermal Synthesis, add substrate substance, tackiness agent, peptizing agent, expanding agent, through laggard row spray shaping of pulling an oar, by obtaining oarse-grained shaping HTS particle after roasting template.This process simplify operation steps, eliminate the operation such as separation, washing after HTS crystallization, but to be covered by other non-effective active ingredient due to catalyst activity component or active ingredient is diluted, there is the problem of catalyst activity deficiency equally.
Summary of the invention
The present invention is directed to the deficiencies in the prior art part, a kind of preparation method of Large stone HTS is provided, can solve by the HTS that the present invention is made the problem that small particle size HTS is industrially difficult to product separation and recovery preferably, improve the repeating utilization factor of catalyzer.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme:
A preparation method for Large stone HTS, is characterized in that comprising the steps:
1) first at the temperature of 30 ~ 90 DEG C, inorganic silicon source is joined in the organic formwork agent aqueous solution, form the first mixed solution, after reinforced, stir 0.2 ~ 2 hour with agitator, after the first mixed solution mixes, then add inorganic ti sources, form the second mixed solution, after reinforced, then stir 0.5 ~ 4 hour with agitator, disposablely after the second mixed solution mixes add alkali source, form the 3rd mixed solution, the SiO in the 3rd mixed solution in molar ratio in inorganic silicon source
2: the TiO in inorganic ti sources
2: organic formwork agent: alkali source: water=1:0.01 ~ 0.03:0.02 ~ 0.2:20 ~ 80:30 ~ 70;
2) then above-mentioned 3rd mixed solution is put into stainless steel sealed reactor, be 120 ~ 200 DEG C in temperature of reaction and carry out hydrothermal crystallizing 2 ~ 10 days, be precipitated thing after reaction terminates, throw out is filtered, and take out filter cake, be 8 ~ 9 with deionized water by filter cake washing to pH value;
3) then the filter cake after above-mentioned washing is carried out vacuum-drying at 120 DEG C of temperature, the reaction times is 10 ~ 16 hours;
4) last at 550 DEG C of temperature by dried filter cake roasting 4 ~ 12 hours, obtain titanium-silicon molecular screen material.
Preferably, the preparation temperature of the first mixed solution, the second mixed solution and the 3rd mixed solution is 40 ~ 60 DEG C.
Preferably, the SiO in inorganic silicon source
2: the TiO in inorganic ti sources
2: organic formwork agent: alkali source: water=1:0.015 ~ 0.025:0.08 ~ 0.15:40 ~ 60:40 ~ 55.
Preferably, step 2) in hydrothermal crystallization process, crystallization temperature and crystallization time are respectively 150 ~ 180 DEG C and 3 ~ 5 days.
Preferably, step 4) in the time of baking and banking up with earth be 6 ~ 10 hours.
Further, inorganic silicon source is selected from silica gel, silicon sol or White Carbon black.
Further, inorganic ti sources is TiC1
4, TiCl
3, TiOCl
2or Ti (SO
4)
2.
Further, organic formwork agent is TPAOH or 4-propyl bromide.
Further, alkali source is ammoniacal liquor or organic ammonium, and the general formula of organic ammonium is
fats compound, wherein R
3for the alkyl of 1-6 carbon atom, m=1-3, n=1 or 2, fat amine compound is the one in ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, quadrol, diethylamine, triethylamine, tripropyl amine or Tributylamine.
Further, step 3) in hydrothermal crystallization process static or dynamically under carry out.
The present invention, owing to have employed technique scheme, has following beneficial effect:
1, the present invention utilizes cheap inorganic ti sources and inorganic silicon source, and under a small amount of template exists, employing hydrothermal method can synthesize the Large stone HTS that median size is greater than more than 10 microns;
2, in building-up process without the need to adding the materials such as any carrier, tackiness agent or auxiliary agent, also do not need through post forming, synthesis step is few, and the catalyst crystal degree obtained is high, uniform crystal particles;
3, the present invention is simple to operate, good repetitiveness, with low cost, is easy to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is Fourier's infrared spectrum of titanium-silicon molecular screen material A in preparation method's embodiment 1 of a kind of Large stone HTS of the present invention;
Fig. 2 is the scanning electron microscope (SEM) photograph of titanium-silicon molecular screen material A in the embodiment of the present invention 1.
Embodiment
The preparation method of a kind of Large stone HTS of the present invention, comprises the steps:
1) first at the temperature of 30 ~ 90 DEG C, inorganic silicon source is joined in the organic formwork agent aqueous solution, form the first mixed solution, after reinforced, stir 0.2 ~ 2 hour with agitator, after the first mixed solution mixes, add inorganic ti sources again, form the second mixed solution, after reinforced, stir 0.5 ~ 4 hour with agitator again, disposablely after the second mixed solution mixes add alkali source, form the 3rd mixed solution, preferably the first mixed solution, the preparation temperature of the second mixed solution and the 3rd mixed solution is 40 ~ 60 DEG C, SiO in 3rd mixed solution in molar ratio in inorganic silicon source
2: the TiO in inorganic ti sources
2: organic formwork agent: alkali source: water=1:0.01 ~ 0.03:0.02 ~ 0.2:20 ~ 80:30 ~ 70, preferably, the SiO in inorganic silicon source
2: the TiO in inorganic ti sources
2: organic formwork agent: alkali source: water=1:0.015 ~ 0.025:0.08 ~ 0.15:40 ~ 60:40 ~ 55, inorganic silicon source is selected from silica gel, silicon sol or White Carbon black, and the impact of different silica sources on HTS is as shown in table 1, and inorganic ti sources is TiC1
4, TiCl
3, TiOCl
2or Ti (SO
4)
2, organic formwork agent is TPAOH or 4-propyl bromide, and alkali source is ammoniacal liquor or organic ammonium, and the general formula of organic ammonium is
fats compound, wherein R
3for the alkyl of 1-6 carbon atom, m=1-3, n=1 or 2, fat amine compound is the one in ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, quadrol, diethylamine, triethylamine, tripropyl amine or Tributylamine,
2) then above-mentioned 3rd mixed solution is put into stainless steel sealed reactor, be 120 ~ 200 DEG C in temperature of reaction and carry out hydrothermal crystallizing 2 ~ 10 days, preferably, in hydrothermal crystallization process, crystallization temperature and crystallization time are respectively 150 ~ 180 DEG C and 3 ~ 5 days, hydrothermal crystallization process static or dynamically under carry out, the impact of crystallization condition on HTS Crystallization Dynamics is as shown in table 2, thing is precipitated after reaction terminates, throw out is filtered, and take out filter cake, be 8 ~ 9 with deionized water by filter cake washing to pH value;
3) then the filter cake after above-mentioned washing is carried out vacuum-drying at 120 DEG C of temperature, the reaction times is 10 ~ 16 hours;
4) last at 550 DEG C of temperature by dried filter cake roasting 4 ~ 12 hours, preferably, the time of baking and banking up with earth is 6 ~ 10 hours, obtains titanium-silicon molecular screen material.
| Silicon source | Grain shape | Grain fineness number/μm | Yield/% |
| Silica gel | Olive shape | 1.2 | 80 |
| Silicon sol | Prismatic | 510 | 83 |
| White Carbon black | Soap shape | 1.5 | 79 |
| TEOS | Spherical | 0.2 | 75 |
Table 1 different silica sources is on the impact of HTS
Can find out, adopt the HTS grain fineness number difference of different silica sources synthesis comparatively large, the crystal grain that inorganic silicon source is synthesized than organosilicon source is large, therefore selects silicon sol.
Table 2 crystallization condition is on the impact of HTS Crystallization Dynamics
Embodiment 1
By 15.2g silicon sol (SiO
2content is 30%) slowly join in the TPAOH aqueous solution, stir 30 minutes at temperature 40 DEG C, make it to mix, slowly add Titanium Trichloride Solution, stir after 40 minutes, add ammoniacal liquor again, stir and within 60 minutes, obtain mixed solution, wherein silicon sol: titanous chloride: TPAOH: ammoniacal liquor: the mol ratio of water is 1:0.02:0.1:40:60.Above-mentioned mixed solution is put into stainless steel sealed reactor, be 170 DEG C in temperature of reaction and heat static crystallizations 4 days, obtain filter cake after filtering, then with deionized water by filter cake washing, the filter cake obtained is carried out vacuum-drying at 120 DEG C of temperature, finally 550 DEG C of roasting temperatures 6 hours, (volume mean diameter is 25.9 microns, particle diameter I d median (d to obtain titanium-silicon molecular screen material A
50) be 24.3 microns).As shown in Figure 1, scanning electron microscope (SEM) photograph as shown in Figure 2 for Fourier's infrared spectrum of A.From infrared spectrogram, at 960cm
-1there is strong absorption peak in place, is the feature of framework titania, illustrates that Ti atom enters framework of molecular sieve.Scanning electron microscope (SEM) photograph illustrates HTS regular crystal forms, homogeneous grain size, and high dispersing.
Embodiment 2
By 20.5g silicon sol (SiO
2content is 30%) slowly join in the TPAOH aqueous solution, stir 1 hour at temperature 80 DEG C, make it to mix, slowly add titanium sulfate aqueous solution, stir after 30 minutes, add ammoniacal liquor again, stir and within 40 minutes, obtain mixed solution, wherein silicon sol: titanium sulfate: TPAOH: ammoniacal liquor: the mol ratio of water is 1:0.015:0.08:50:50.Above-mentioned mixed solution is put into stainless steel sealed reactor, be 170 DEG C in temperature of reaction and heat static crystallizations 6 days, obtain filter cake after filtering, then with deionized water by filter cake washing, the filter cake obtained is carried out vacuum-drying at 120 DEG C of temperature, finally 550 DEG C of roasting temperatures 8 hours, (volume mean diameter is 21.5 microns, particle diameter I d median (d to obtain titanium-silicon molecular screen material B
50) be 18.4 microns).The FTIR spectrum of this sample is consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment sample A.
Embodiment 3
By 25.1g silicon sol (SiO
2content is 30%) slowly join in the TPAOH aqueous solution, stir 2 hours under temperature 70 C, make it to mix, slowly add Titanium Trichloride Solution, stir after 1 hour, add ammoniacal liquor again, stir and within 30 minutes, obtain mixed solution, wherein silicon sol: titanous chloride: TPAOH: ammoniacal liquor: the mol ratio of water is 1:0.024:0.15:30:60.Above-mentioned mixed solution is put into stainless steel sealed reactor, be 175 DEG C in temperature of reaction and heat dynamic crystallizations 5 days, obtain filter cake after filtering, then with deionized water by filter cake washing, the filter cake obtained is carried out vacuum-drying at 120 DEG C of temperature, finally 550 DEG C of roasting temperatures 6 hours, (volume mean diameter is 18.7 microns, particle diameter I d median (d to obtain titanium-silicon molecular screen material C
50) be 16.1 microns).The FTIR spectrum of this sample is consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment sample A.
Embodiment 4
By 12.4g silicon sol (SiO
2content is 30%) slowly join in the TPAOH aqueous solution, stir 1 hour under temperature 50 C, make it to mix, slowly add titanium sulfate aqueous solution, stir after 2 hours, add n-Butyl Amine 99 again, stir and within 40 minutes, obtain mixed solution, wherein silicon sol: titanium sulfate: TPAOH: n-Butyl Amine 99: the mol ratio of water is 1:0.028:0.2:25:40.Above-mentioned mixed solution is put into stainless steel sealed reactor, be 175 DEG C in temperature of reaction and heat static crystallizations 4 days, obtain filter cake after filtering, then with deionized water by filter cake washing, the filter cake obtained is carried out vacuum-drying at 120 DEG C of temperature, finally 550 DEG C of roasting temperatures 8 hours, (volume mean diameter is 20.5 microns, particle diameter I d median (d to obtain titanium-silicon molecular screen material D
50) be 18.9 microns).The FTIR spectrum of this sample is consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment sample A.
Embodiment 5
By 14.7g silicon sol (SiO
2content is 30%) slowly join in the 4-propyl bromide aqueous solution, stir 2 hours under temperature 60 C, make it to mix, slowly add titanium sulfate aqueous solution, stir after 3 hours, add ethamine again, stir and within 30 minutes, obtain mixed solution, wherein silicon sol: titanium sulfate: 4-propyl bromide: ethamine: the mol ratio of water is 1:0.023:0.05:70:60.Above-mentioned mixed solution is put into stainless steel sealed reactor, be 170 DEG C in temperature of reaction and heat static crystallizations 5 days, obtain filter cake after filtering, then with deionized water by filter cake washing, the filter cake obtained is carried out vacuum-drying at 120 DEG C of temperature, finally 550 DEG C of roasting temperatures 5 hours, (volume mean diameter is 13.6 microns, particle diameter I d median (d to obtain titanium-silicon molecular screen material E
50) be 12.2 microns).The FTIR spectrum of this sample is consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment sample A.
Embodiment 6
By 18.3g silicon sol (SiO
2content is 30%) slowly join in the 4-propyl bromide aqueous solution, stir 1 hour under temperature 70 C, make it to mix, slowly add Titanium Trichloride Solution, stir after 2 hours, add ethamine again, stir and obtain mixed solution after 1 hour, wherein silicon sol: titanous chloride: 4-propyl bromide: ethamine: the mol ratio of water is 1:0.014:0.13:30:50.Above-mentioned mixed solution is put into stainless steel sealed reactor, be 170 DEG C in temperature of reaction and heat dynamic crystallizations 6 days, obtain filter cake after filtering, then with deionized water by filter cake washing, the filter cake obtained is carried out vacuum-drying at 120 DEG C of temperature, finally 550 DEG C of roasting temperatures 6 hours, (volume mean diameter is 22.3 microns, particle diameter I d median (d to obtain titanium-silicon molecular screen material F
50) be 19.4 microns).The FTIR spectrum of this sample is consistent with the SPECTROSCOPIC CHARACTERIZATION of embodiment sample A.
These are only specific embodiments of the invention, but technical characteristic of the present invention is not limited thereto.Any based on the present invention, for realizing substantially identical technique effect, done ground simple change, equivalent replacement or modification etc., be all covered by among protection scope of the present invention.
Claims (10)
1. a preparation method for Large stone HTS, is characterized in that comprising the steps:
1) first at the temperature of 30 ~ 90 DEG C, inorganic silicon source is joined in the organic formwork agent aqueous solution, form the first mixed solution, after reinforced, stir 0.2 ~ 2 hour with agitator, after described first mixed solution mixes, add inorganic ti sources again, form the second mixed solution, after reinforced, then stir 0.5 ~ 4 hour with agitator, disposablely after described second mixed solution mixes add alkali source, form the 3rd mixed solution, the SiO in described 3rd mixed solution in molar ratio in inorganic silicon source
2: the TiO in inorganic ti sources
2: organic formwork agent: alkali source: water=1:0.01 ~ 0.03:0.02 ~ 0.2:20 ~ 80:30 ~ 70;
2) then above-mentioned 3rd mixed solution is put into stainless steel sealed reactor, be 120 ~ 200 DEG C in temperature of reaction and carry out hydrothermal crystallizing 2 ~ 10 days, thing is precipitated after reaction terminates, described throw out is filtered, and take out filter cake, be 8 ~ 9 with deionized water by described filter cake washing to pH value;
3) then the filter cake after above-mentioned washing is carried out vacuum-drying at 120 DEG C of temperature, the reaction times is 10 ~ 16 hours;
4) last at 550 DEG C of temperature by dried filter cake roasting 4 ~ 12 hours, obtain titanium-silicon molecular screen material.
2. the preparation method of a kind of Large stone HTS according to claim 1, is characterized in that: the preparation temperature of described first mixed solution, described second mixed solution and described 3rd mixed solution is 40 ~ 60 DEG C.
3. the preparation method of a kind of Large stone HTS according to claim 1, is characterized in that: the SiO in described inorganic silicon source
2: the TiO in inorganic ti sources
2: organic formwork agent: alkali source: water=1:0.015 ~ 0.025:0.08 ~ 0.15:40 ~ 60:40 ~ 55.
4. the preparation method of a kind of Large stone HTS according to claim 1, is characterized in that: step 2) described in hydrothermal crystallization process, crystallization temperature and crystallization time are respectively 150 ~ 180 DEG C and 3 ~ 5 days.
5. the preparation method of a kind of Large stone HTS according to claim 1, is characterized in that: step 4) described in the time of baking and banking up with earth be 6 ~ 10 hours.
6. the preparation method of a kind of Large stone HTS according to claim 3, is characterized in that: described inorganic silicon source is selected from silica gel, silicon sol or White Carbon black.
7. the preparation method of a kind of Large stone HTS according to claim 3, is characterized in that: described inorganic ti sources is TiC1
4, TiCl
3, TiOCl
2or Ti (SO
4)
2.
8. the preparation method of a kind of Large stone HTS according to claim 3, is characterized in that: described organic formwork agent is TPAOH or 4-propyl bromide.
9. the preparation method of a kind of Large stone HTS according to claim 3, it is characterized in that: described alkali source is ammoniacal liquor or organic ammonium, the general formula of organic ammonium is
fats compound, wherein R
3for the alkyl of 1-6 carbon atom, m=1-3, n=1 or 2, fat amine compound is the one in ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, quadrol, diethylamine, triethylamine, tripropyl amine or Tributylamine.
10. the preparation method of a kind of Large stone HTS according to claim 1, is characterized in that: step 3) described in hydrothermal crystallization process static or dynamically under carry out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410712996.9A CN104495868B (en) | 2014-11-28 | 2014-11-28 | A kind of preparation method of big particle diameter HTS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410712996.9A CN104495868B (en) | 2014-11-28 | 2014-11-28 | A kind of preparation method of big particle diameter HTS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104495868A true CN104495868A (en) | 2015-04-08 |
| CN104495868B CN104495868B (en) | 2017-12-22 |
Family
ID=52937349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410712996.9A Active CN104495868B (en) | 2014-11-28 | 2014-11-28 | A kind of preparation method of big particle diameter HTS |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104495868B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329909A (en) * | 2015-11-30 | 2016-02-17 | 湖北大学 | Method for synthesizing Ti-MWW molecular sieve hollow sphere with high external specific surface area |
| CN106348310A (en) * | 2016-08-17 | 2017-01-25 | 巨化集团技术中心 | Preparation method and application of titanium-silicalite-molecular-sieve polymer |
| CN106395847A (en) * | 2016-08-26 | 2017-02-15 | 巨化集团技术中心 | Preparation method of titanium-silicon molecular sieve polymer |
| CN108246362A (en) * | 2018-01-16 | 2018-07-06 | 阳泉煤业（集团）有限责任公司 | A kind of preparation method and applications of bulky grain TS-1 Titanium Sieve Molecular Sieve |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172616A (en) * | 2007-12-04 | 2008-05-07 | 南开大学 | Method of synthesizing micropore titanium silicon molecular sieve ETS-4 |
| CN101480622A (en) * | 2009-02-13 | 2009-07-15 | 中国天辰工程有限公司 | Method for preparing titanium-silicon molecular sieve catalyst of large particle diameter |
| CN101497450A (en) * | 2008-01-31 | 2009-08-05 | 中国石油化工股份有限公司 | Method for preparing titanium-containing mesoporous material |
| CN102989502A (en) * | 2012-11-26 | 2013-03-27 | 天津大学 | Preparation method of microspherical catalyst with titanium silicalite molecular sieve |
-
2014
- 2014-11-28 CN CN201410712996.9A patent/CN104495868B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172616A (en) * | 2007-12-04 | 2008-05-07 | 南开大学 | Method of synthesizing micropore titanium silicon molecular sieve ETS-4 |
| CN101497450A (en) * | 2008-01-31 | 2009-08-05 | 中国石油化工股份有限公司 | Method for preparing titanium-containing mesoporous material |
| CN101480622A (en) * | 2009-02-13 | 2009-07-15 | 中国天辰工程有限公司 | Method for preparing titanium-silicon molecular sieve catalyst of large particle diameter |
| CN102989502A (en) * | 2012-11-26 | 2013-03-27 | 天津大学 | Preparation method of microspherical catalyst with titanium silicalite molecular sieve |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329909A (en) * | 2015-11-30 | 2016-02-17 | 湖北大学 | Method for synthesizing Ti-MWW molecular sieve hollow sphere with high external specific surface area |
| CN106348310A (en) * | 2016-08-17 | 2017-01-25 | 巨化集团技术中心 | Preparation method and application of titanium-silicalite-molecular-sieve polymer |
| CN106395847A (en) * | 2016-08-26 | 2017-02-15 | 巨化集团技术中心 | Preparation method of titanium-silicon molecular sieve polymer |
| CN106395847B (en) * | 2016-08-26 | 2018-07-31 | 巨化集团技术中心 | A kind of polymeric preparation method of Titanium Sieve Molecular Sieve |
| CN108246362A (en) * | 2018-01-16 | 2018-07-06 | 阳泉煤业（集团）有限责任公司 | A kind of preparation method and applications of bulky grain TS-1 Titanium Sieve Molecular Sieve |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104495868B (en) | 2017-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104495867B (en) | The preparation method of big particle diameter HTS | |
| CN104150507B (en) | One one-step preparation method of ghost type ZSM-5 molecular sieve with small crystal grains | |
| CN106348310B (en) | A kind of polymeric preparation method and applications of Titanium Sieve Molecular Sieve | |
| CN104495868A (en) | Preparation method of large-particle-size titanium silicon molecular sieve | |
| CN103318911A (en) | Preparation method of beta zeolite with multilevel pore canals | |
| CN105776244B (en) | A method of TS-1 molecular sieves are synthesized by aerosol processing/spray drying process assisted Solid-state | |
| CN101530814A (en) | Nanosized gold catalyst used for preparing propylene oxide by direct propylene oxidation and preparation method thereof | |
| CN108525669A (en) | A kind of high degree of dispersion Silica Nanotube supported nickel catalyst and preparation method thereof | |
| CN108793181B (en) | Titanium-silicon molecular sieve, preparation and application thereof | |
| CN105800637A (en) | Alcohol-removal-free preparation method for rapidly-synthesized high-framework-titanium-content titanium silicalite molecular sieve | |
| CN108246362B (en) | A kind of preparation method and applications of bulky grain TS-1 Titanium Sieve Molecular Sieve | |
| CN104098110A (en) | Preparation method and application of B-Al-ZSM-5 zeolite with controllable particle diameter | |
| CN105903484A (en) | Nano-catalyst for preparing methyl formate by oxidizing methyl alcohol at one step and preparation method thereof | |
| CN109775714A (en) | A kind of MFI topology si molecular sieves and preparation method thereof containing trace rare-earth ion | |
| CN110756187A (en) | Gold-palladium/graphene catalyst growing on graphene surface in situ and preparation method thereof | |
| CN105253890A (en) | Method for synthesizing monodisperse SiO<2> micrometer-size particles through one-step method | |
| CN103285888B (en) | A kind of Catalysts and its preparation method preparing acrylic acid reaction for propylene oxidation step | |
| CN106082261A (en) | A kind of Ti MWW molecular sieve and preparation method thereof | |
| CN104310466A (en) | Hollow titanium dioxide microsphere based on gel sphere precursor and preparation method of hollow titanium dioxide microsphere | |
| CN108821304A (en) | High activity multi-stage porous Titanium Sieve Molecular Sieve and its preparation method and application | |
| CN108837827A (en) | A kind of bilayer core-shell structure platinum catalyst and its preparation method and application | |
| CN109678162A (en) | The method for preparing mesoporous silicon dioxide micro-sphere using alkali process recovered liquid | |
| CN102530982A (en) | Method for preparing titanium silicalite film by dynamic in-situ hydrothermal method | |
| US11434140B2 (en) | Hierarchical zeolites and preparation method therefor | |
| CN108176406A (en) | Size and the adjustable monokaryon bivalve Fe of shell thickness2O3@SiO2@MnO2And preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |