CN106348309A - Titanium silicon molecular sieve and preparation method thereof - Google Patents
Titanium silicon molecular sieve and preparation method thereof Download PDFInfo
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- CN106348309A CN106348309A CN201510421742.6A CN201510421742A CN106348309A CN 106348309 A CN106348309 A CN 106348309A CN 201510421742 A CN201510421742 A CN 201510421742A CN 106348309 A CN106348309 A CN 106348309A
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Abstract
The invention relates to a titanium silicon molecular sieve and a preparation method of the titanium silicon molecular sieve and mainly aims at solving the problems of low activity and poor diffusivity of the titanium silicon molecular sieve synthesized by the existing method. The laminar titanium silicon molecular sieve is prepared by controlling the proportion of a synthetic solution and controlling the nucleation and growing process of the molecular sieve, and the above problems are well solved. The molecular sieve can be used for industrial production of purification and separation of shale gas.
Description
Technical field
The present invention relates to a kind of HTS and preparation method thereof.
Background technology
Zeolite molecular sieve is the crystalline microporous material that a class has framing structure, there is the pore passage structure of specific dimensions, shape, larger specific surface and stronger adjustable Acidity, it is widely used in the process of petroleum refining and processing, the such as catalytic reaction such as catalytic cracking, alkane isomerization, catalytic reforming and toluene disproportionation.
With the development of petrochemical industry, round the yield how improving purpose product, suppress the problems such as side reaction, selectivity of raising reaction, people have carried out increasing research.In general, improving molecular sieve during the course of the reaction optionally simultaneously, often cause the significantly decline of molecular sieve activity.Therefore, in order to improve the selecting property performance of molecular sieve molecular sieve, reduce the loss of activity of molecular sieve, researcher has carried out numerous studies to the modification of zeolite molecular sieve simultaneously.The method of modifying generally adopting includes: high-temperature vapor is processed, organic acid dealuminzation, chemical modification, outer surface organosilicon passivation etc., bury in oblivion the acidic site of molecular sieve outer surface, so that molecular sieve has selectivity of product, however, the shortcoming of this method to be preparation process various, industrial operation repeatability is poor, carry out processing modified raising molecular sieve optionally simultaneously in molecular sieve outer surface, also tend to blocking portion aperture or duct, so that catalysis activity significantly declines.
HTS is a kind of catalysis material with good catalytic selective oxidation activity.Aoxidize in the reaction such as carbonyl compound processed in benzene oxidatoin phenol, oxidation of phenol preparing benzenediol, oxidation of alkanes ketone and alcohol, ammoxidation of cyclohexanone preparing cyclohexanone oxime, olefin oxidation epoxide, alcohol, HTS has excellent catalysis activity and selectivity as molecular sieve.
United States Patent (USP) us4410501 reports with tetraethyl orthosilicate as silicon source, and butyl titanate is titanium source, and TPAOH synthesizes ts-1 HTS for template, because tetraethyl orthosilicate and butyl titanate cost of material are expensive,.The method synthesizes ts-1 HTS high cost；In addition the method operating process is complicated, and the response time is up to 30 days, and the non-body phase anatase generating containing tetraethyl titanate hydrolytic polymerization.
Document journal of catalysis 130,440-446 (1991) and document applied catalysis, the synthesis of ts-2 HTS is described in 58 (1990), with tetraethyl orthosilicate as silicon source, ts-2 HTS is synthesized for template with TBAH.Due to tetraethyl orthosilicate and TBAH cost of material all costly, limit HTS application further industrially.
Industrial shale gas containing methane and nitrogen, coal bed gas, oven gas etc., due to the methane that contains and nitrogen molecule diameter closely, and polarity is weaker, all close to inertia, bad adsorbing separation, hinder the purification application of above-mentioned gas.
Report HTS at present, major part is spherical or cube pattern, the invention discloses a kind of flake HTS, the diffuser efficiency of the gas greatly improving.At present the titanium silicon crystal of report is all the crystal structure such as spherical, bar-shaped, belongs to orthorhombic system, this crystal structure due in germ nucleus surface distance longer, when gas absorption spreads, because the stroke that gas passes through is longer, be not easy to the diffusion of product.And the flat crystal synthesizing, then can avoid this problem, there is preferable diffusion, show excellent absorption property in terms of separation of methane and nitrogen.
Content of the invention
One of problem to be solved by this invention is the problem that HTS activity is low, diffusion is poor of prior art synthesis.The invention provides a kind of new lamellar HTS, there is preferable diffusion, and higher catalysis activity.
The two of technology to be solved by this invention are the preparation methoies of the HTS providing a kind of one of new solution technical problem.
For one of solving the above problems, the technical solution used in the present invention is as follows: a kind of HTS, and, the thickness of lamellar is 10～2000 nanometers under scanning electron microscope in the form of sheets, and the aperture of HTS is 0.30 ~ 0.6 nanometer.
In technique scheme, preferred technical scheme is that the length of lamellar HTS crystal grain is 100 ~ 5000 nanometers, and width is 50 ~ 4000 nanometers, and thickness is 10～1000 nanometers, and the aperture of HTS is 0.35 ~ 0.55 nanometer.
In technique scheme, preferred technical scheme is that HTS is one of ets-4, ets-10, ts-1, ts-2.
In technique scheme, preferred technical scheme is, in terms of HTS percentage by weight, Ti content is 0.1 ~ 20wt%.
In technique scheme, preferred technical scheme is, in terms of HTS percentage by weight, Ti content is 0.5 ~ 15wt%.
In technique scheme, preferred technical scheme is, in terms of HTS percentage by weight, Ti content is 5 ~ 10wt%, and the aperture of HTS is 0.35 ~ 0.40 nanometer.
For solve the above problems two, the technical solution used in the present invention is as follows: the preparation method of described HTS, and, to make solution by certain proportioning, the mol ratio of wherein solution is: sio for silicon source, titanium source, template m and distilled water2: (0.0001～0.5) tio2: (0.01～2) m: (20～200) h2O, under 80～200 DEG C of crystallization temperatures, hydrothermal crystallizing 5～200 hours, obtain described HTS；Wherein, silicon source is tetraethyl orthosilicate, Ludox, aerosil, white carbon, at least one in sodium silicate, and titanium source is tetraethyl titanate, at least one in butyl titanate, tetramethoxy titanate ester, titanium dioxide, titanous chloride., titanium tetrachloride, crystal redstone, titanium sulfate, Titanium Nitrate；Template is pressed for tetraethyl hydroxide, at least one in tetraethylammonium bromide, 4-propyl bromide, 4-propyl bromide, hexadecane and trimethylammonium bromide, triethylamine, n-butylamine, ethylenediamine or ethamine.
In technique scheme, preferred technical scheme is that the preparation method of HTS is it is characterised in that the mol ratio of solution is according to claim 1: sio2: (0.01～0.2) tio2: (0.01～1) m: (40～100) h2O, also contains sodium ion in synthetic solvent, in terms of the molal quantity of silicon oxide in synthetic solvent, na/si mol ratio is 0.1 ~ 2.
In technique scheme, preferred technical scheme is, also containing at least one anion surfactant in carboxylate, sulfonate, carbonate, bicarbonate, phosphate, hydrophosphate or citrate in synthetic solvent；In terms of silicon oxide percentage by weight, its consumption is 0.1～20%.
In technique scheme, preferably technical scheme is, at least one in ammonium oxalate, ammonium acetate, sodium alkyl benzene sulfonate, ammonium hydrogen carbonate, ammonium hydrogen phosphate, disodium hydrogen phosphate, ammonium citrate for the anion surfactant, in terms of silicon oxide percentage by weight, its consumption is 0.5～5%.
The present invention is suitable for the proportioning of HTS growth, controls the silica alumina ratio being suitable for growth and crystallization temperature due to adjusting, under hydrothermal conditions, control the HTS crystal seed inducing in mixed sols, and control the temperature and time that crystal grain is grown up, generate HTS.It is also added into anion surfactant in synthetic solvent, have adjusted the surface energy of titanium silicon wafer core, make it along the surface energy reduction of maximum (001) crystal face of crystal face density, the speed of growth slows down, crystal is easy to the direction growth along (100) crystal face and (010) crystal face, define laminated structure, for separation of nitrogen in shale gas, coal bed gas, oven gas and methane it is shown that good separating effect.
Brief description
Fig. 1 is the scanning electron microscope collection of illustrative plates of the molecular sieve synthesized by embodiment 1；
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
Take 540 grams of tetraethyl orthosilicates to be dissolved in 1500 grams of deionized waters to stir the lower sodium hydroxide solution 90ml adding 3mol/l to uniform.Again 108.8 grams of tetraethyl titanates are added to add in previous solu after dissolving in 900 ml deionized water and be stirred until homogeneous.Carry out conventional hydrothermal to synthesize 40 hours at 180 DEG C.Product carries out ammonium in the 10wt% ammonium nitrate solution of 1000ml at 90 DEG C through filtration washing and exchanges 2 hours.Product carries out an ammonium after being dried 2 hours at filtration, washing, 130 DEG C again and exchanges.Through filtering, washing, be dried 3 hours at 130 DEG C after at 550 DEG C roasting 5 hours, the molecular sieve of present invention offer is provided.Molecular sieve xrd collection of illustrative plates shows containing HTS ets-4 thing phase.As shown in figure 1, showing that sieve particle is lamellar, thickness is 0.1 microns to stereoscan photograph, Atomic Absorption Spectrometry, and Ti content is 5wt%, and it is 0.37nm that nitrogen adsorption desorption measures molecular sieve bore diameter.Prepared molecular sieve tabletting, break into pieces, sieve after, take the granule of 20～40 mesh to put in adsorption tower, then by the shale gas that are 2% containing nitrogen volumetric concentration, in adsorption column outlet gas, nitrogen volumetric concentration is 0.01%.
[embodiment 2]
Take 500 grams of tetraethyl orthosilicates to be dissolved in 1500 grams of deionized waters to stir the lower sodium hydroxide solution 90ml adding 1mol/l to uniform.Again 28.0 grams of tetraethyl titanates are added to add in previous solu after dissolving in 900 ml deionized water and be stirred until homogeneous, add 100 gram of four third class ammonium hydroxide and 20 grams of cetyl trimethylammonium bromide.Carry out conventional hydrothermal to synthesize 80 hours at 180 DEG C.Product carries out ammonium in the 10wt% ammonium nitrate solution of 1000ml at 90 DEG C through filtration washing and exchanges 2 hours.Product carries out an ammonium after being dried 2 hours at filtration, washing, 130 DEG C again and exchanges.Through filtering, washing, be dried 3 hours at 130 DEG C after at 550 DEG C roasting 5 hours, the molecular sieve of present invention offer is provided.Molecular sieve xrd collection of illustrative plates shows containing HTS ts-1 thing phase.Stereoscan photograph shows, sieve particle is lamellar, and thickness is 0.01 microns, and Ti content is 2.8wt%, and it is 0.55nm that nitrogen adsorption desorption measures molecular sieve bore diameter.Prepared molecular sieve tabletting, break into pieces, sieve after, take the granule of 20～40 mesh to put in adsorption tower, then by the shale gas that are 2% containing nitrogen volumetric concentration, in adsorption column outlet gas, nitrogen volumetric concentration is 0.05%.
[embodiment 3]
Take the lower sodium hydroxide solution 90ml adding 1mol/l of stirring in 600 grams of Ludox and 1000 grams of deionized waters to uniform.Again 28.0 grams of butyl titanates are added to add in previous solu after dissolving in 900 ml deionized water and be stirred until homogeneous.Carry out conventional hydrothermal to synthesize 40 hours at 160 DEG C.Product carries out ammonium in the 10wt% ammonium nitrate solution of 1000ml at 90 DEG C through filtration washing and exchanges 2 hours.Product carries out an ammonium after being dried 2 hours at filtration, washing, 130 DEG C again and exchanges.Through filtering, washing, be dried 3 hours at 130 DEG C after at 550 DEG C roasting 5 hours, the molecular sieve of present invention offer is provided.Molecular sieve xrd collection of illustrative plates shows, containing HTS ets-10 thing phase.Stereoscan photograph shows, sieve particle is lamellar, and thickness is 0.1 microns, and it is 0.9nm that nitrogen adsorption desorption measures molecular sieve bore diameter.Prepared molecular sieve tabletting, break into pieces, sieve after, take the granule of 20～40 mesh to put in adsorption tower, then by the oven gas that is 2% containing nitrogen volumetric concentration, in adsorption column outlet gas, nitrogen volumetric concentration is 0.2%.
[embodiment 4]
Take the lower sodium hydroxide solution 90ml adding 1mol/l of stirring in 500 grams of Ludox and 1500 grams of deionized waters to uniform.Again 28.0 grams of tetramethoxy titanate esters are added to add in previous solu after dissolving in 900 ml deionized water and be stirred until homogeneous, add 100 gram of four second class ammonium hydroxide and 10 grams of cetyl trimethylammonium bromide.Carry out conventional hydrothermal to synthesize 40 hours at 160 DEG C.Product carries out ammonium in the 10wt% ammonium nitrate solution of 1000ml at 90 DEG C through filtration washing and exchanges 2 hours.Product carries out an ammonium after being dried 2 hours at filtration, washing, 130 DEG C again and exchanges.Through filtering, washing, be dried 3 hours at 130 DEG C after at 550 DEG C roasting 5 hours, the molecular sieve of present invention offer is provided.Molecular sieve xrd collection of illustrative plates shows, containing HTS ts-2 thing phase.Stereoscan photograph shows, sieve particle is lamellar, and thickness is 0.05 microns.Prepared molecular sieve tabletting, break into pieces, sieve after, take the granule of 20～40 mesh to put in adsorption tower, by the coal bed gas being 12% containing nitrogen volumetric concentration, in adsorption column outlet gas, nitrogen volumetric concentration is 0.5%.
[embodiment 5]
Take the lower sodium hydroxide solution 90ml adding 1mol/l of stirring in 500 grams of Ludox and 1500 grams of deionized waters to uniform.Again by 28.0 grams of titanium tetrachlorides, add and be stirred until homogeneous in addition previous solu after dissolving in 900 ml deionized water, add 100 grams of triethylamines and 20 grams of ammonium hydrogen carbonate, carry out conventional hydrothermal at 160 DEG C and synthesize 40 hours.Product carries out ammonium in the 10wt% ammonium nitrate solution of 1000ml at 90 DEG C through filtration washing and exchanges 2 hours.Product carries out an ammonium after being dried 2 hours at filtration, washing, 130 DEG C again and exchanges.Through filtering, washing, be dried 3 hours at 130 DEG C after at 550 DEG C roasting 5 hours, the molecular sieve of present invention offer is provided.Molecular sieve xrd collection of illustrative plates shows containing HTS ets-4 thing phase.Stereoscan photograph shows, sieve particle is lamellar, and thickness is 0.02 microns, and it is 0.38nm that nitrogen adsorption desorption measures molecular sieve bore diameter.Prepared molecular sieve tabletting, break into pieces, sieve after, take the granule of 20～40 mesh to put in adsorption tower, by the coal bed gas being 10% containing nitrogen volumetric concentration, in adsorption column outlet gas, nitrogen volumetric concentration is 0.02%.
[embodiment 6]
Take the lower sodium hydroxide solution 90ml adding 1mol/l of stirring in 500 grams of Ludox and 1500 grams of deionized waters to uniform.Again by 28.0 grams of titanium tetrachlorides, add and be stirred until homogeneous in addition previous solu after dissolving in 900 ml deionized water, then plus 20 grams of ammonium oxalate.Carry out conventional hydrothermal to synthesize 40 hours at 160 DEG C.Product carries out ammonium in the 10wt% ammonium nitrate solution of 1000ml at 90 DEG C through filtration washing and exchanges 2 hours.Product carries out an ammonium after being dried 2 hours at filtration, washing, 130 DEG C again and exchanges.Through filtering, washing, be dried 3 hours at 130 DEG C after at 550 DEG C roasting 5 hours, the molecular sieve of present invention offer is provided.Molecular sieve xrd collection of illustrative plates shows containing HTS ets-4 thing phase.Stereoscan photograph shows, sieve particle is lamellar, and thickness is 0.02 microns, and it is 0.36nm that nitrogen adsorption desorption measures molecular sieve bore diameter.Prepared molecular sieve tabletting, break into pieces, sieve after, take the granule of 20～40 mesh to put in adsorption tower, by the coal bed gas being 12% containing volume percent methane, in adsorption column outlet gas, volume percent methane is 0.02%.
[embodiment 7]
Take the lower sodium hydroxide solution 90ml adding 1mol/l of stirring in 500 grams of Ludox and 1500 grams of deionized waters to uniform.Again by 28.0 grams of titanium tetrachlorides, add and be stirred until homogeneous in addition previous solu after dissolving in 900 ml deionized water.Carry out conventional hydrothermal to synthesize 40 hours at 160 DEG C.Product carries out ammonium in the 10wt% ammonium nitrate solution of 1000ml at 90 DEG C through filtration washing and exchanges 2 hours.Product carries out an ammonium after being dried 2 hours at filtration, washing, 130 DEG C again and exchanges.Through filtering, washing, be dried 3 hours at 130 DEG C after at 550 DEG C roasting 5 hours, the molecular sieve of present invention offer is provided.Molecular sieve xrd collection of illustrative plates shows containing HTS ets-4 thing phase.Stereoscan photograph shows, sieve particle is lamellar, and thickness is 0.02 microns,.Prepared molecular sieve tabletting, break into pieces, sieve after, take the granule of 20～40 mesh to put in adsorption tower, by the coal bed gas being 20% containing volume percent methane, in adsorption column outlet gas, methane nitrogen volumetric concentration is 0.5%.
Claims (10)
1. a kind of HTS, the thickness of lamellar is 10～2000 nanometers under scanning electron microscope in the form of sheets, and the aperture of HTS is 0.30 ~ 0.6 nanometer.
2. it is characterised in that the length of lamellar HTS crystal grain is 100 ~ 5000 nanometers, width is 50 ~ 4000 nanometers to HTS according to claim 1, and thickness is 10～1000 nanometers, and the aperture of HTS is 0.35 ~ 0.55 nanometer.
3. HTS according to claim 1 is it is characterised in that HTS is one of ets-4, ets-10, ts-1, ts-2.
4. HTS according to claim 1 is it is characterised in that in terms of HTS percentage by weight, Ti content is 0.1 ~ 20wt%.
5. HTS according to claim 4 is it is characterised in that in terms of HTS percentage by weight, Ti content is 0.5 ~ 15wt%.
6. it is characterised in that in terms of HTS percentage by weight, Ti content is 5 ~ 10wt%, the aperture of HTS is 0.35 ~ 0.40 nanometer to HTS according to claim 4.
7. the preparation method of the HTS described in claim 1, to make solution by certain proportioning, the mol ratio of wherein solution is: sio for silicon source, titanium source, template m and distilled water2: (0.0001～0.5) tio2: (0～2) m: (20～200) h2O, under 80～200 DEG C of crystallization temperatures, hydrothermal crystallizing 5～200 hours, obtain described HTS；Wherein, silicon source is tetraethyl orthosilicate, Ludox, aerosil, white carbon, at least one in sodium silicate, and titanium source is tetraethyl titanate, at least one in butyl titanate, tetramethoxy titanate ester, titanium dioxide, titanous chloride., titanium tetrachloride, crystal redstone, titanium sulfate, Titanium Nitrate；Template is pressed for tetraethyl hydroxide, at least one in tetraethylammonium bromide, 4-propyl bromide, 4-propyl bromide, hexadecane and trimethylammonium bromide, triethylamine, n-butylamine, ethylenediamine or ethamine.
8. according to claim 1 the preparation method of HTS it is characterised in that the mol ratio of solution is: sio2: (0.01～0.2) tio2: (0.01～1) m: (40～100) h2O, also contains sodium ion in synthetic solvent, in terms of the molal quantity of silicon oxide in synthetic solvent, na/si mol ratio is 0.1 ~ 2.
9. according to claim 1 the preparation method of HTS it is characterised in that also containing at least one anion surfactant in carboxylate, sulfonate, carbonate, bicarbonate, phosphate, hydrophosphate or citrate in synthetic solvent；In terms of silicon oxide percentage by weight, its consumption is 0.1～20%.
10. the preparation method of HTS according to claim 9, it is characterized in that at least one in ammonium oxalate, ammonium acetate, sodium alkyl benzene sulfonate, ammonium hydrogen carbonate, ammonium hydrogen phosphate, disodium hydrogen phosphate ammonium citrate for the anion surfactant, in terms of silicon oxide percentage by weight, its consumption is 0.5～5%.
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Cited By (8)
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| CN107262148A (en) * | 2017-06-28 | 2017-10-20 | 中触媒新材料股份有限公司 | A kind of strip crystallite titanium-silicon molecular sieve and its synthetic method and application |
| CN110498778A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method that epoxidation of cyclohexene prepares 7-oxa-bicyclo[4.1.0 |
| CN110577228A (en) * | 2019-09-18 | 2019-12-17 | 常州工学院 | Hierarchical pore ETS-10 zeolite molecular sieve with specific molecular recognition function and synthesis method |
| CN111468182A (en) * | 2020-04-28 | 2020-07-31 | 大连理工大学 | Synthesis method of hollow titanium silicalite TS-1 |
| CN111470517A (en) * | 2020-04-28 | 2020-07-31 | 大连理工大学 | Large-particle titanium silicalite molecular sieve with excellent diffusivity performance and preparation method thereof |
| CN114920262A (en) * | 2022-05-17 | 2022-08-19 | 北京科技大学 | Method for preparing anatase-free TS-1 molecular sieve by using aromatic carboxylic acid as regulator |
| CN116081635A (en) * | 2023-01-09 | 2023-05-09 | 中国石油大学(北京) | Lamellar TS-1 molecular sieve and preparation method and application thereof |
| CN117003255A (en) * | 2022-04-27 | 2023-11-07 | 中国石油天然气股份有限公司 | Tungsten-containing TS-1 molecular sieve and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107262148A (en) * | 2017-06-28 | 2017-10-20 | 中触媒新材料股份有限公司 | A kind of strip crystallite titanium-silicon molecular sieve and its synthetic method and application |
| CN107262148B (en) * | 2017-06-28 | 2020-02-18 | 中触媒新材料股份有限公司 | Strip-shaped crystal grain titanium-silicon molecular sieve and synthesis method and application thereof |
| CN110498778A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method that epoxidation of cyclohexene prepares 7-oxa-bicyclo[4.1.0 |
| CN110577228A (en) * | 2019-09-18 | 2019-12-17 | 常州工学院 | Hierarchical pore ETS-10 zeolite molecular sieve with specific molecular recognition function and synthesis method |
| CN111468182A (en) * | 2020-04-28 | 2020-07-31 | 大连理工大学 | Synthesis method of hollow titanium silicalite TS-1 |
| CN111470517A (en) * | 2020-04-28 | 2020-07-31 | 大连理工大学 | Large-particle titanium silicalite molecular sieve with excellent diffusivity performance and preparation method thereof |
| CN111470517B (en) * | 2020-04-28 | 2022-08-30 | 大连理工大学 | Large-particle titanium silicalite molecular sieve with excellent diffusivity performance and preparation method thereof |
| CN111468182B (en) * | 2020-04-28 | 2023-04-25 | 大连理工大学 | Synthesis method of hollow titanium-silicon molecular sieve TS-1 |
| CN117003255A (en) * | 2022-04-27 | 2023-11-07 | 中国石油天然气股份有限公司 | Tungsten-containing TS-1 molecular sieve and preparation method and application thereof |
| CN114920262A (en) * | 2022-05-17 | 2022-08-19 | 北京科技大学 | Method for preparing anatase-free TS-1 molecular sieve by using aromatic carboxylic acid as regulator |
| CN114920262B (en) * | 2022-05-17 | 2023-08-11 | 北京科技大学 | Method for preparing anatase-free TS-1 molecular sieve by taking aromatic carboxylic acid as regulator |
| CN116081635A (en) * | 2023-01-09 | 2023-05-09 | 中国石油大学(北京) | Lamellar TS-1 molecular sieve and preparation method and application thereof |
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