CN102836741A - SAPO-34 (Silicoaluminophosphate-34) molecular sieve catalyst and application thereof to preparation of low-carbon olefin from methanol - Google Patents
SAPO-34 (Silicoaluminophosphate-34) molecular sieve catalyst and application thereof to preparation of low-carbon olefin from methanol Download PDFInfo
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Abstract
The invention belongs to the technical field of molecular sieve, and particularly relates to an SAPO-34 (Silicoaluminophosphate-34) molecular sieve catalyst and application thereof to preparation of low-carbon olefin from methanol. The spherical SAPO-34 molecular sieve agglomerated by nanoparticles is synthesized by modulating reaction initial gel concentration, and the size range is within a range of 0.5 micron to 10 microns. Tetraethylammonium hydroxide is used as a template and is mixed with an aluminum source, a silicon source and a phosphorus source; the gel concentration is controlled by adding a specific amount of solvent; and the catalyst is quickly prepared by the conventional hydrothermal or microwave heating mode. The spherical SAPO-34 molecular sieve provided by the invention has the characteristics of quickness in production, low cost in gel synthesis raw materials, low reaction energy consumption, high molecular sieve yield and the like. The characteristic of microspheres agglomerated by the nanoparticles enables long life of catalytic application of the nanoparticles, the characteristic of a catalytic effect of the molecular sieve in catalytic reaction can be obviously improved, and meanwhile, the molecular sieve catalyst also has the advantage of easiness in separation and extraction after synthesis of a micron scale catalyst.
Description
Technical field
The invention belongs to the sieve technology field, be specifically related to a kind of SAPO-34 molecular sieve catalyst and the application in preparing light olefins from methanol thereof.
Background technology
1984, U.S. combinating carbide company (UCC) developed silicon and has replaced aluminum phosphate series S-APO molecular sieve (USP4440871).This molecular sieve analog is a crystalline silico-alumino-phosphate, and its three-dimensional framework structure is by PO
2 +, AlO
2 -And SiO
2Tetrahedron constitutes.Wherein SAPO-34 type of being chabazite structure has elliposoidal cage and three-dimensional open-framework that the oxygen octatomic ring constitutes, and the aperture is 0.38nm * 0.38nm.The suitable pore passage structure of SAPO-34 molecular sieve and acid, bigger specific area, absorption property and heat endurance and hydrothermal stability make it in preparing low carbon olefinic hydrocarbon with methanol (MTO) reaction, demonstrate excellent catalytic performance and receive much concern preferably.
The SAPO-34 molecular sieve generally adopts hydrothermal synthesis method, is solvent with water, in airtight autoclave, carries out.Synthetic component comprises aluminium source, phosphorus source, silicon source, template and solvent.What can be elected to be the aluminium source has aluminium isopropoxide, boehmite, an activated alumina, and there are Ludox, active silica, ethyl orthosilicate in the silicon source, and the phosphoric acid of mass fraction 85% is often adopted in the phosphorus source.Template commonly used has diethylamine, triethylamine, morpholine, tetraethyl ammonium hydroxide, piperidines, different third ammonium etc. and one or more the mixture in them.Synthesis step is generally following:
(1) according to a certain percentage, a definite sequence mixes, and prepares the crystallization mixture silicon source, aluminium source, phosphorus source, template and water;
(2) the crystallization mixture is enclosed in the autoclave, at room temperature aging a period of time.
(3) autoclave is heated to 150～230 ℃, thermostatic crystallization reaction under self-generated pressure is treated after crystallization fully solid product to be filtered or centrifugation, and is spent deionised water to neutral, obtains the SAPO-34 molecular screen primary powder after the oven dry.
The small crystal grain molecular sieve of Nano grade is in the advantage that himself is arranged aspect the diffusion absorption, so its performance on commercial Application of synthesizing small-grain SAPO-34 molecular sieve raising has very important meaning.
WO2003/048042 has reported with ethyl orthosilicate and has obtained small grain size SAPO-34 molecular sieve as the mixture of silicon source, TEAOH or TEAOH and DPA as the method for template.It should be noted that though WO2003/048042 mentions that doing the silicon source with positive tetraethyl orthosilicate obtains small grain size SAPO-34, its mentioned part small grain size SAPO-34 does not provide scanning electron microscope sem photo proof its crystal size.
Except hydrothermal synthesis method, SAPO-34 also can synthesize through dried glue transformation approach (DGC), microwave heating method.People (Mater.Chem.Phys.123 (2010) 507) such as Hirota in 2010 with TEAOH be template to have synthesized the crystal average dimension through dried glue transformation approach be the SAPO-34 molecular sieve of 75 nanometers, but this method obtains molecular sieve crystal yardstick and the not enough homogeneous of pattern.People such as the Jhung of Korea S (Microporous Mesoporous Mater.64 (2003) 33) have studied the synthetic SAPO-34 of microwave heating method, find that heating using microwave makes the SAPO-34 of CHA structure change SAPO～5 of the brilliant AFI of generation structure easily.
People (Top.Catal.19 (2010) 1304) such as Lin synthesized the SAPO-34 molecular sieve of crystal size average out to 150 nanometers and the SAPO-34 molecular sieve of corresponding pattern through the synthetic mode of heating using microwave in 2010.Mentioned the preparation of nano particle size SAPO-34 molecular sieve and corresponding pattern SAPO-34 molecular sieve though should note Top.Catal.19 (2010) 1304, the used gel raw material of institute's production method that provides is more expensive, the processing generated time is longer and the molecular sieve productive rate is lower.
W001/36328 describes a kind of method; Method through add organic solvent and from surfactant to the initial species of crystallization is produced 0.5～30 micron diameter SAPO-34 molecular sieve of crystallization spherical particles in the same way, and the purposes of said solvent is to make the silicon source be dissolved in said moisture synthetic mixture.
Summary of the invention
The object of the present invention is to provide a kind of SAPO-34 molecular sieve catalyst and the application in preparing light olefins from methanol thereof.
The SAPO-34 molecular sieve catalyst is by SPAO-34 nano particle (50～150nm) self aggregation spheroidings; The advantage that this catalyst not only has the SAPO-34 nanoparticle catalyst (promptly can reduce and eliminate the restriction of diffusion mass transfer; Reduce the generation of secondary response, thereby prolong life of catalyst), be more conducive to the advantage of separating after synthetic but also have the micron particles catalyst with reactant liquor; Avoided the step of centrifugal extraction nanocatalyst like this, made building-up process energy-conservation more economically.
SAPO-34 molecular sieve catalyst grain morphology provided by the invention is clear, and rough surface is 0.5～10 micron ball-type for average mean crystal size.The present invention can obtain the SAPO-34 molecular sieve of pattern homogeneous with the method for control gel strength through adding specified quantitative solvent; Need not to use other special organic solvents and surfactant that nanocrystal is assembled and spheroiding SAPO-34; Compare with Top.Catal.19 (2010) 1304 with WO2003/048042; This method has used gel raw material more economic (solvent-oil ratio is few), processing generated time simple (through microwave heating method or traditional hydro-thermal heating), the preparation crystallization initial thing time is short, the molecular sieve productive rate is higher, the characteristics that catalytic life is longer.
SAPO-34 molecular sieve catalyst of the present invention; It is that the employing tetraethyl ammonium hydroxide is the organic ammonium template; In synthesized gel rubber, add simultaneously the specified quantitative solvent, be applicable to the component of producing SAPO-34 described in the normally known in the art or document of the component of its used synthetic mixture.
SAPO-34 molecular sieve catalyst of the present invention, it is prepared by following steps:
A) silicon source, aluminium source, organic ammonium template and solvent are stirred after, under 20～60 ℃, self-generated pressure condition, handle and obtained mixture in 0.5～36 hour;
B) the phosphorus source is joined in the said mixture, stir process is 0.5～12 hour under self-generated pressure, obtains SAPO-34 molecular sieve initial gel mixture;
C) initial gel mixture is packed in the agitated reactor, be heated to crystallization temperature, under self-generating pressure, carry out thermostatic crystallization; After treating that crystallization is fully, standing separation goes out solid product, solid matter with deionized water is repeatedly washed to neutrality, then under 20～80 ℃ of temperature in air drying, obtain the SAPO-34 molecular screen primary powder;
D) organic ammonium template contained in the former powder is removed in the roasting in air of SAPO-34 molecular screen primary powder, obtained the SAPO-34 molecular sieve catalyst.
Described solvent is a water;
Said silicon source is positive silicic acid tetraalkyl ester or Ludox;
Said aluminium source is a kind of in boehmite, boehmite, activated alumina, the aluminium isopropoxide;
Said phosphorus source is a phosphoric acid solution;
Said organic ammonium template is a tetraethyl ammonium hydroxide;
The mole proportioning of each component oxide, tetraethyl ammonium hydroxide and solvent is in the initial gel mixture: TEAOH:SiO
2: P
2O
5: Al
2O
3: H
2O=3.0～4.5:0.5～1.0:1.5～2.5:1:50～300;
Further, the mole proportioning of each component oxide, tetraethyl ammonium hydroxide and solvent is TEAOH:SiO in the initial gel mixture
2: P
2O
5: Al
2O
3: H
2O=3.5～4.5:0.5～1.0:1.8～2.2:1:80～250.
Crystallization temperature in the step c) is 160～230 ℃;
Mode of heating in the step c) is heating using microwave, and the time of thermostatic crystallization is 0.5～4 hour, and microwave power is 200 watts～1000 watts;
Mode of heating in the step c) is the hydro-thermal heating, and the time of thermostatic crystallization is 12～120 hours;
Sintering temperature in the step d) is 400～600 ℃, and roasting time is 3～10 hours;
Described SAPO-34 molecular sieve can be used as seed in producing molecular sieve, can be used for inoculating the molecular sieve that forms same structure type or different types of structure.
Said SAPO-34 molecular sieve is particularly useful for the various hydrocarbon conversions, separation and absorption.They can use separately or mix use with other molecular sieve, can load unsupported particle form or with the form of load layer for example the form of film (for example WO94/25151) use.The hydrocarbon conversion comprises the isomerization of hydro carbons, oligomeric, aromatisation, hydrofinishing, cracking and hydrocracking.Other conversion comprises the conversion of alcohol and conversion, the especially methanol-to-olefins, particularly low-carbon alkene of the reaction of alkene and oxygenatedchemicals system hydrocarbon.The SAPO-34 molecular sieve of producing through the inventive method is particularly useful for this conversion.Catalytic reaction condition is 300～500 ℃, and the methyl alcohol air speed is 2～15h
-1
Description of drawings
Fig. 1: the XRD spectra of the embodiment of the invention 1～6 preparation product;
Fig. 2: the SEM photo of the embodiment of the invention 1～6 preparation product.
The specific embodiment
Embodiment 1:
With positive tetraethyl orthosilicate, aluminium isopropoxide, water, tetraethyl ammonium hydroxide mix stir the back 20 ℃, handle down at self-generated pressure (closed container) and to obtain mixture in 36 hours; Phosphoric acid is joined in the said mixture, and stir process is 12 hours under self-generated pressure, obtains SAPO-34 molecular sieve initial gel mixture; In the reaction system in the initial gel mixture mole proportioning of each component oxide, tetraethyl ammonium hydroxide and solvent be 3.5TEAOH:0.5SiO
2: 1.8P
2O
5: Al
2O
3: 150H
2O; Initial gel mixture is packed in the microwave reaction kettle, airtightly under 1000 watts of power be heated to 160 ℃, under self-generated pressure, carried out thermostatic crystallization 0.5 hour.Then; Solid product is through standing separation; Spend deionised water to neutral, at room temperature behind air drying, obtain the SAPO-34 molecular screen primary powder; Former powder promptly obtains SAPO-34 molecular sieve catalyst (numbering SP34-1) after 550 ℃ of roastings were removed the organic ammonium template in 6 hours, the productive rate 51% of product (is that benchmark calculates gained with the aluminium in input and the output).
The XRD spectra of former powder sample is shown in Fig. 1 (a), and the SEM photo is shown in Fig. 2 (a).Show that what obtain is all homogeneous comparatively of SAPO-34 molecular sieve and size and pattern, the ball-type rough surface of SP34-1 sample, minimum dimension is about 0.5 micron.
Embodiment 2:
With positive tetraethyl orthosilicate, aluminium oxide, water, tetraethyl ammonium hydroxide mix stir the back 20 ℃, processing obtained mixture in 36 hours under self-generated pressure; Phosphoric acid is joined in the said mixture, and stir process is 12 hours under self-generated pressure, obtains SAPO-34 molecular sieve initial gel mixture; In the reaction system in the initial gel mixture mole proportioning of each component oxide, tetraethyl ammonium hydroxide and solvent be 3.5TEAOH:0.5SiO
2: 1.8P
2O
5: Al
2O
3: 150H
2O; The initial gel mixture that obtains is packed in the teflon-lined stainless steel autoclave, and static state is placed on (hydro-thermal heating) in 160 ℃ of baking ovens, under self-generated pressure, carries out thermostatic crystallization 120 hours.Then, solid product spends deionised water neutrality through standing separation; Behind air drying; Obtain the SAPO-34 molecular screen primary powder, former powder promptly obtains SAPO-34 molecular sieve catalyst (numbering SP34-2) after 550 ℃ of roastings were removed template in 6 hours, and the productive rate of product is 53% (is that benchmark calculates gained with the aluminium in input and the output); The XRD spectra of former powder sample is shown in Fig. 1 (b), and the SEM photo is shown in Fig. 2 (b).Can see that the SP34-2 sample is that nanoparticle aggregate forms.From then on example can be found out, with the also available SAPO-34 molecular sieve of traditional water by the use of thermal means, and crystalline size is 3 microns, and it is bigger to obtain crystal than microwave heating method.
Embodiment 3:
With positive tetraethyl orthosilicate, aluminium isopropoxide, water, tetraethyl ammonium hydroxide mix stir the back 20 ℃, processing obtained mixture in 36 hours under self-generated pressure; Phosphoric acid is joined in the said mixture, and stir process is 12 hours under self-generated pressure, obtains SAPO-34 molecular sieve initial gel mixture; In the reaction system in the initial gel mixture mole proportioning of each component oxide, tetraethyl ammonium hydroxide and solvent be 3.5TEAOH:0.5SiO
2: 1.8P
2O
5: Al
2O
3: 60H
2O; Initial gel mixture is packed in the microwave reaction kettle, airtightly under 200 watts of power be heated to 180 ℃, under self-generated pressure, carried out thermostatic crystallization 1 hour.Then; Solid product is through centrifugation; Spend deionised water neutrality, at room temperature behind air drying, obtain the SAPO-34 molecular screen primary powder; Former powder promptly obtains SAPO-34 molecular sieve catalyst (numbering SP34-3) after 550 ℃ of roastings were removed the organic ammonium template in 6 hours, the productive rate of product is 45% (is that benchmark calculates gained with the aluminium in input and the output).
The XRD spectra of former powder sample is shown in Fig. 1 (c), and the SEM photo is shown in Fig. 2 (c).Can prove that obtaining is all homogeneous comparatively of the shaggy volume median diameter cubic type SAPO-34 molecular sieve that is 70 nanometers and size and pattern.
Embodiment 4:
With Ludox, aluminium isopropoxide, water, tetraethyl ammonium hydroxide mix stir the back 20 ℃, processing obtained mixture in 36 hours under self-generated pressure; Phosphoric acid is joined in the said mixture, and stir process is 12 hours under self-generated pressure, obtains SAPO-34 molecular sieve initial gel mixture; In the reaction system in the initial gel mixture mole proportioning of each component oxide, tetraethyl ammonium hydroxide and solvent be 4.0TEAOH:0.7SiO
2: 2.2P
2O
5: Al
2O
3: 60H
2O; Initial gel mixture is packed in the microwave reaction kettle, airtightly under 200 watts of power be heated to 180 ℃, under self-generated pressure, carried out thermostatic crystallization 4 hours.Then; Solid product is through centrifugation; Spend deionised water neutrality; At room temperature behind air drying, obtain the SAPO-34 molecular screen primary powder, former powder promptly obtains SAPO-34 molecular sieve catalyst (numbering SP34-4) product after 550 ℃ of roastings were removed the organic ammonium template in 6 hours productive rate is 47% (is that benchmark calculates gained with the aluminium in input and the output).
The XRD spectra of former powder sample is shown in Fig. 1 (d), and the SEM photo is shown in Fig. 2 (d).Can prove that the volume that obtains is that the median diameter is the SAPO-34 molecular sieve of the sheet or the sheet state of aggregation of 200 nanometers.
Embodiment 5:
With positive tetraethyl orthosilicate, boehmite, water, tetraethyl ammonium hydroxide mix stir the back 60 ℃, processing obtained mixture in 0.5 hour under self-generated pressure; Phosphoric acid is joined in the said mixture, and stir process is 0.5 hour under self-generated pressure, obtains SAPO-34 molecular sieve initial gel mixture; In the reaction system in the initial gel mixture mole proportioning of each component oxide, tetraethyl ammonium hydroxide and solvent be 4.5TEAOH:SiO
2: 2.1P
2O
5: Al
2O
3: 8H
2O; The initial gel mixture that obtains is packed in the microwave reaction kettle, airtightly under 200 watts of power be heated to 230 ℃, under self-generated pressure, carried out thermostatic crystallization 4 hours.Then; Solid product is through standing separation; Spend deionised water neutrality; Behind air drying, obtain the SAPO-34 molecular screen primary powder, former powder promptly obtains ball-type molecular sieve catalyst (numbering SP34-5) product after 400 ℃ of roastings were removed template in 10 hours productive rate is 52% (is that benchmark calculates gained with the aluminium in input and the output).
The XRD spectra of former powder sample can prove that what obtain is the SAPO-34 molecular sieve shown in Fig. 1 (e).The SEM photo is shown in Fig. 2 (e).Can see, be that the aluminium source can obtain volume median diameter maximum and is about 4 microns with the boehmite under microwave condition, assembled the SAPO-34 molecular sieve catalyst that forms by nano particle.
Embodiment 6:
With tetraethyl orthosilicate, boehmite, water, tetraethyl ammonium hydroxide mix stir the back 40 ℃, processing obtained mixture in 12 hours under self-generated pressure; Phosphoric acid is joined in the said mixture, and stir process is 6 hours under self-generated pressure, obtains SAPO-34 molecular sieve initial gel mixture; In the reaction system in the initial gel mixture mole proportioning of each component oxide, tetraethyl ammonium hydroxide and solvent be 4.5TEAOH:SiO
2: 2.1P
2O
5: Al
2O
3: 250H
2O; The initial gel mixture that obtains is packed in the teflon-lined stainless steel autoclave, and static state is placed on (hydro-thermal heating) in 230 ℃ of baking ovens, under self-generated pressure, carries out thermostatic crystallization 12 hours.Then; Solid product is through standing separation; Spend deionised water neutrality; Behind air drying, obtain the SAPO-34 molecular screen primary powder, former powder promptly obtains SAPO-34 molecular sieve catalyst (numbering SP34-6) product of ball-type after 600 ℃ of roastings were removed template in 3 hours productive rate is 56% (is that benchmark calculates gained with the aluminium in input and the output).
The XRD spectra of former powder sample can prove that what obtain is the SAPO-34 molecular sieve shown in Fig. 1 (f).The SEM photo is shown in Fig. 2 (f).Can see with the boehmite being that the aluminium source can obtain volume median diameter and is about 10 microns under microwave condition, assemble the SAPO-34 molecular sieve catalyst that forms by nano particle.The crystalline size scope of the crystal that obtains with traditional hydro-thermal heating is bigger.
Embodiment 7:
The sample that embodiment 1 is obtained carries out compressing tablet, is crushed to 40～60 orders.Take by weighing the 1.0g sample fixed bed reactors of packing into, carry out MTO and estimate.Logical nitrogen activation is 1 hour under 550 ℃, is cooled to 500 ℃ then.Methyl alcohol is carried by nitrogen, and nitrogen flow rate is 40ml/min, methyl alcohol weight space velocity 2.0h
-1Product is analyzed by online gas-chromatography (Agilent7890).The result sees table 1.
Embodiment 8:
The sample that embodiment 1 is obtained carries out compressing tablet, is crushed to 40～60 orders.Take by weighing the 1.0g sample fixed bed reactors of packing into, carry out MTO and estimate.Logical nitrogen activation is 1 hour under 550 ℃, is cooled to 300 ℃ then.Methyl alcohol is carried by nitrogen, and nitrogen flow rate is 40ml/m in, methyl alcohol weight space velocity 2.0h
-1Product is analyzed by online gas-chromatography (Agilent7890).The result sees table 1.
Embodiment 9:
The sample that embodiment 1 is obtained carries out compressing tablet, is crushed to 40～60 orders.Take by weighing the 1.0g sample fixed bed reactors of packing into, carry out MTO and estimate.Logical nitrogen activation is 1 hour under 550 ℃, is cooled to 450 ℃ then.Methyl alcohol is carried by nitrogen, and nitrogen flow rate is 40ml/min, methyl alcohol weight space velocity 15.0h
-1Product is analyzed by online gas-chromatography (Agilent7890).The result sees table 1.
Embodiment 10:
With embodiment 1 and embodiment 2, the sample that embodiment 3 obtains carries out compressing tablet, is crushed to 40～60 orders.Take by weighing the 1.0g sample fixed bed reactors of packing into, carry out MTO and estimate.Logical nitrogen activation is 1 hour under 550 ℃, is cooled to 400 ℃ then.Methyl alcohol is carried by nitrogen, and nitrogen flow rate is 40ml/min, methyl alcohol weight space velocity 2.0h
-1Product is analyzed by online gas-chromatography (Agilent7890).The result sees table 1.
Can find out that from table 1 though the selectivity of low-carbon alkene is similar, catalytic life even ratio nano level other small grain size SAPO-34 molecular sieve (about 70nm) of the SAPO-34 molecular sieve that nanoparticle aggregate forms in hydrocarbon conversion reactions is taller.This ball shape catalyst of explaining that SAPO-34 nanoparticle aggregate according to the invention forms has even to be superior to the stability of independent SAPO-34 nanoparticle catalyst strong, the characteristics that catalytic life is high.And because catalyst according to the invention need not centrifugal process in separation process; Make it energy-conservation more economically in building-up process; Therefore SAPO-34 molecular sieve catalyst according to the invention can improve its catalytic applications performance greatly, can be widely used in methyl alcohol and produce the olefines conversion reaction.
Table 1: sample methanol conversion system olefine reaction result
*The highest (ethene+propylene) selectivity during 100% methanol conversion
Claims (8)
1. SAPO-34 molecular sieve catalyst, it is prepared by following steps:
A) silicon source, aluminium source, organic ammonium template and solvent are stirred after, under 20～60 ℃, self-generated pressure condition, handle and obtained mixture in 0.5～36 hour;
B) the phosphorus source is joined in the said mixture, stir process is 0.5～12 hour under self-generated pressure, obtains SAPO-34 molecular sieve initial gel mixture;
C) initial gel mixture is packed in the agitated reactor, be heated to crystallization temperature, under self-generating pressure, carry out thermostatic crystallization; After treating that crystallization is fully, standing separation goes out solid product, solid matter with deionized water is repeatedly washed to neutrality, then under 20～80 ℃ of temperature in air drying, obtain the SAPO-34 molecular screen primary powder;
D) organic ammonium template contained in the former powder is removed in the roasting in air of SAPO-34 molecular screen primary powder, obtained the SAPO-34 molecular sieve catalyst, be the ball-type of 0.5～10 micron of average mean crystal size.
2. a kind of SAPO-34 molecular sieve catalyst as claimed in claim 1 is characterized in that: the solvent described in the step a) is a water; Described silicon source is positive silicic acid tetraalkyl ester or Ludox; Said aluminium source is a kind of in boehmite, boehmite, activated alumina or the aluminium isopropoxide; Said phosphorus source is a phosphoric acid solution; Said organic ammonium template is a tetraethyl ammonium hydroxide.
3. a kind of SAPO-34 molecular sieve catalyst as claimed in claim 1 is characterized in that: the mole proportioning of each component oxide, tetraethyl ammonium hydroxide and solvent is in the initial gel mixture described in the step b): TEAOH:SiO
2: P
2O
5: Al
2O
3: H
2O=3.0～4.5:0.5～1.0:1.5～2.5:1:50～300.
4. a kind of SAPO-34 molecular sieve catalyst as claimed in claim 3 is characterized in that: the mole proportioning of each component oxide, tetraethyl ammonium hydroxide and solvent is in the initial gel mixture: TEAOH:SiO
2: P
2O
5: Al
2O
3: H
2O=3.5～4.5:0.5～1.0:1.8～2.2:1:80～250.
5. a kind of SAPO-34 molecular sieve catalyst as claimed in claim 1 is characterized in that: the crystallization temperature in the step c) is 160～230 ℃; Mode of heating is heating using microwave, and the time of thermostatic crystallization is 0.5～4 hour, and microwave power is 200 watts～1000 watts.
6. a kind of SAPO-34 molecular sieve catalyst as claimed in claim 1 is characterized in that: the crystallization temperature in the step c) is 160～230 ℃; Mode of heating is the hydro-thermal heating, and the time of thermostatic crystallization is 12～120 hours.
7. a kind of SAPO-34 molecular sieve catalyst as claimed in claim 1 is characterized in that: the sintering temperature in the step d) is 400～600 ℃, and roasting time is 3～10 hours.
8. any one described SAPO-34 molecular sieve catalyst application in preparing light olefins from methanol of claim 1～7.
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| CN103936027A (en) * | 2014-04-04 | 2014-07-23 | 南京工业大学 | SAPO (silicoaluminophosphate)-34 zeolite material assembled by nanosheets and having controllable flower shape, as well as preparation method thereof |
| CN104549478A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing MgO modified SAPO-34 molecular sieve |
| CN105983345A (en) * | 2015-02-03 | 2016-10-05 | 中国科学院上海高等研究院 | Method for separating gas-liquid/liquid mixtures through pervaporation and vapor permeation by SAPO-34 molecular sieve membrane prepared by xerogel method |
| CN107824215A (en) * | 2017-09-22 | 2018-03-23 | 中国华能集团公司 | A kind of recoverying and utilizing method of the nitrogenous organic formwork agent of methanol-to-olefin catalyst |
| CN108658094A (en) * | 2018-06-01 | 2018-10-16 | 南开大学 | A method of preparing SAPO-34 with the hydrothermal solution of silicon source and phosphoric acid silicon source |
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| CN104549478A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing MgO modified SAPO-34 molecular sieve |
| CN104549478B (en) * | 2013-10-28 | 2017-02-08 | 中国石油化工股份有限公司 | Method for preparing MgO modified SAPO-34 molecular sieve |
| CN103936027B (en) * | 2014-04-04 | 2015-12-30 | 南京工业大学 | Controlled SAPO-34 zeolitic material of colored shape of nanometer sheet assembling and preparation method thereof |
| CN103936027A (en) * | 2014-04-04 | 2014-07-23 | 南京工业大学 | SAPO (silicoaluminophosphate)-34 zeolite material assembled by nanosheets and having controllable flower shape, as well as preparation method thereof |
| CN105983345B (en) * | 2015-02-03 | 2021-03-19 | 中国科学院上海高等研究院 | Method for separating gas-liquid/liquid mixture by pervaporation and vapor permeation of SAPO-34 molecular sieve membrane prepared by xerogel method |
| CN105983345A (en) * | 2015-02-03 | 2016-10-05 | 中国科学院上海高等研究院 | Method for separating gas-liquid/liquid mixtures through pervaporation and vapor permeation by SAPO-34 molecular sieve membrane prepared by xerogel method |
| CN107824215A (en) * | 2017-09-22 | 2018-03-23 | 中国华能集团公司 | A kind of recoverying and utilizing method of the nitrogenous organic formwork agent of methanol-to-olefin catalyst |
| CN108658094A (en) * | 2018-06-01 | 2018-10-16 | 南开大学 | A method of preparing SAPO-34 with the hydrothermal solution of silicon source and phosphoric acid silicon source |
| CN110092390A (en) * | 2019-04-17 | 2019-08-06 | 汕头大学 | The loose porous spherical shape SAPO-34 molecular sieve of one kind and its preparation and application |
| CN110092390B (en) * | 2019-04-17 | 2022-03-22 | 汕头大学 | Loose porous spherical SAPO-34 molecular sieve and preparation and application thereof |
| CN114477228A (en) * | 2020-11-12 | 2022-05-13 | 国家能源投资集团有限责任公司 | SAPO-34 molecular sieve, and preparation method and application thereof |
| CN114031092A (en) * | 2021-12-16 | 2022-02-11 | 中节能万润股份有限公司 | Preparation method of SAPO-20 molecular sieve |
| CN114890435A (en) * | 2022-06-22 | 2022-08-12 | 中国石油大学(华东) | Hollow-structure SAPO-34 molecular sieve prepared by MTO waste catalyst and preparation method and application thereof |
| CN114890435B (en) * | 2022-06-22 | 2023-08-25 | 中国石油大学(华东) | Hollow-structure SAPO-34 molecular sieve prepared by MTO spent catalyst, and preparation method and application thereof |
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