CN109761243A - A kind of preparation of low silicon small grain SAPO-34 molecular sieve and application method - Google Patents
A kind of preparation of low silicon small grain SAPO-34 molecular sieve and application method Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of low silicon small grain SAPO-34 molecular sieve, comprising the following steps: silicon source, phosphorus source, silicon source, water and morpholine are mixed and stirred for uniformly, obtaining initial gel mixture by (a)；(b) SAPO-34 molecular sieve is processed into the crystal seed that granularity is 70-900nm；(c) crystal seed obtained by step (b) is added in initial gel mixture obtained by step (a), after mixing evenly, carries out aging process；(d) after aging, temperature is increased, reaction mixture crystallization at autogenous pressures；(e) after crystallization, solid crystallized product and mother liquor are centrifugated, is washed with deionized to neutrality, obtains SAPO-34 molecular screen primary powder after drying in an oven.Method and step of the invention is simple, strong operability, and low silicon small grain SAPO-34 molecular sieve obtained is a kind of high activity MTO catalyst.
Description
Technical field
The present invention relates to molecular sieve preparation fields, and in particular to a kind of using morpholine as the low silicon small grain SAPO- of template
The preparation of 34 molecular sieves and application method.
Background technique
Ethylene, propylene are the important foundation raw materials of chemical industry, and traditional processing technology is split mainly from naphtha catalysis
Solution.China's oil shortage of resources and rich coal resources, thus using coal as raw material, via the MTO technique of methanol-to-olefins be to replace
For the important technology of petroleum path production low-carbon alkene, the pressure that china natural resources are unevenly distributed can be effectively relieved.
SAPO-34 is the pinhole type molecular sieve with chabasie (CHA) structure, and skeleton is by SiO2、AlO2 -、PO2 +Three kinds
Tetrahedron element is connected with each other.The four-membered ring made of skeletal atom periodic arrangement, hexatomic ring and octatomic ring constitute ellipse
Spherical cage is connected with each other between cage and cage by hexagonal prism, forms the three-dimensional open-framework of about 0.38 nm of aperture.SAPO-34 points
Son is sieved since good hydrothermal stability is enriched and had to acid moderate, cellular structure, is in reaction for preparing light olefins from methanol
Reveal excellent catalytic performance.
SAPO-34 molecular sieve is that P atom or Al atom in aluminium phosphate molecular sieve is replaced to be formed by Si.Aluminum phosphate point
Sub- sieve skeleton frame is in electroneutral, after Si enters skeleton by substitution mode, needs proton due to generating net skeleton negative electrical charge
It is equipped with holding electroneutral, therefore contains Bronsted acid position.Silicone content and its coordination environment have weight to the acidity of SAPO-34 molecular sieve
It influences, when silicone content is lower in synthesized gel rubber, silicon mainly individually replaces P atom to enter skeleton formation Si (4Al) structure；And
When silicone content is higher, two Si atoms replace a pair of adjacent Al and P atom simultaneously, form Si (nAl) (n=0-3) structure.
It is generally acknowledged that the different corresponding acid strengths of silicon coordination structure has as follows sequentially: Si (1Al) > Si (2Al) > Si (3Al) >
Si(4Al)> Si(0Al)。
The Acidity (sour density, acid strength) of SAPO-34 molecular sieve has a major impact MTO reactivity worth, acid too strong
Or the sour excessively high rate that can accelerate catalyst carbon deposition inactivation of density, and acid too weak methanol may be prevented from converting completely.SAPO-
It can effectively improve the selectivity of low-carbon alkene in reactant, same time delay in 34 framework of molecular sieve rich in Si (4Al) coordination structure
The service life of long catalyst, it is therefore desirable to acid content and acid strength are adjusted, so that the silicon environment in SAPO-34 framework of molecular sieve is with Si
Based on (4Al).
Low silicon SAPO-34 has excellent MTO reactivity worth, but SAPO-18 or SAPO-5 stray crystal easily occurs, and synthesis is more
It is difficult.CN104326483A discloses a kind of preparation method of low silicon SAPO-5/SAPO-34 composite molecular screen, and such compound point
Son sieve greatly limits its application due to containing stray crystal.
CN104556142A has invented a kind of preparation method of low silicon SAPO-34 molecular sieve, and this method is first by silicon source, phosphorus
Source, silicon source and water are dried to obtain dry glue of the solid content greater than 60% after mixing, then dry glue is uniformly mixed with template,
Segmented crystallization prepares SAPO-34 molecular sieve, and this method is relatively complicated and is not easy industrial amplification.
The micropore canals of SAPO-34 molecular sieve make its low-carbon alkene selection with higher in methanol to olefins reaction
Property, but limitation also is generated to the diffusion mass transfer of reactant or product, so as to cause quick carbon distribution inactivation.Reducing crystallite dimension can
It effectively shortens diffusion path, the mass transfer rate of reactant, intermediate and product is improved, to extend catalytic life.
CN102275948A has invented a kind of synthetic method of fine grain SAPO-34 molecular sieve, and this method is first by silicon source, silicon source, organic
Pretreatment a period of time at high temperature under high pressure after amine, the mixing of part water, then it is in situ be added phosphorus source and remaining water, this method is to setting
It is standby that high, more difficult operation is required to implement.CN102464338 prepares fine grain SAPO-34, method by the way that crystallization director and HF is added
Also relatively complicated.
Morpholine is a kind of template of synthesis SAPO-34 molecular sieve cheap and easy to get, the research of R. Vomscheid et al.
Show under identical silicon input amount, morpholine will form more Si (4Al) structure (J. Phys. than tetraethyl ammonium hydroxide
Chem. 1994,98,9614-9618), but the product grains of morpholine synthesis are larger (9-12 μm), and under the conditions of low silicon not
It is easy to get to pure phase SAPO-34, these limit morpholine in the application in methanol-to-olefins field.It is therefore desirable to develop better conjunction
At method, to obtain the SAPO-34 molecular sieve of low silicon small grain.
Summary of the invention
In order to overcome the shortcomings in the prior art, the present invention is old by carrying out at a lower temperature by template of morpholine
Change and Crystallizing treatment synthesizing low silicon SAPO-34 molecular sieve, and reduce crystallite dimension by the way that crystal seed is added, provide a kind of high activity
The low silicon small grain SAPO-34 molecular sieve preparation method as MTO catalyst.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme:
A kind of preparation method of low silicon small grain SAPO-34 molecular sieve, comprising the following steps: (a) is by silicon source, phosphorus source, silicon source, water
It is mixed and stirred for uniformly, obtaining initial gel mixture with morpholine；(b) SAPO-34 molecular sieve is processed into granularity is 70-
The crystal seed of 900nm；(c) crystal seed obtained by step (b) is added in initial gel mixture obtained by step (a), after mixing evenly,
Carry out aging process；(d) after aging, temperature is increased, reaction mixture crystallization at autogenous pressures；(e) crystallization terminates
Afterwards, solid crystallized product and mother liquor are centrifugated, are washed with deionized to neutrality, obtain SAPO- after drying in an oven
34 molecular screen primary powders.
Preferably, silicon source described in step (a) is aluminium oxide, in boehmite, aluminum soluble salt, aluminium isopropoxide
The mixture of one or any of several；Phosphorus source is one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate or any several mixing
Object；Silicon source is one of silica solution, ethyl orthosilicate, white carbon black or any several mixture.
Preferably, in the initial gel mixture that silicon source, phosphorus source, silicon source, water and morpholine are formed, the molar ratio of each component
For Al2O3: P2O5: SiO2: Mor:H2O=1:0.5 ~ 1.5:0.1 ~ 0.6:1 ~ 4:30 ~ 100.
Preferably, being Mechanical Crushing, acid corrosion or caustic corrosion to the processing method of SAPO-34 molecular sieve in step (b)
One or more of processing.
It is Mechanical Crushing to the processing method of SAPO-34 molecular sieve in step (b) as further preferred.
Preferably, the temperature of aging process is 100 ~ 150 in step (c)oC, time are 8 ~ 36 hours.
As further preferred, the aging temperature of mixture is 120 ~ 140oC, ageing time are 12 ~ 24 hours.
Preferably, crystal seed and the mass ratio of initial gel mixture are 0.1 ~ 10:100 in step (c).It is walked by changing
The adjustable crystallite dimension of the additional amount of crystal seed, the granularity of low silicon small grain SAPO-34 molecular sieve obtained with crystal seed dosage
Increase and reduces.The composition for being used to prepare the SAPO-34 molecular sieve of crystal seed is any, can be using SAPO- commercial or from synthesis
34。
As further preferred, the mass ratio of crystal seed and initial gel mixture is 0.5 ~ 8:100.
Preferably, crystal seed and initial gel mixture are placed in the stainless steel with teflon lined in step (c)
In reaction kettle, reaction kettle sealing, which is placed in rotary oven, carries out aging process.
Preferably, the temperature of crystallization is 150 ~ 210 in step (d)oC, time are 1 ~ 3 day.
As further preferred, the crystallization temperature of mixture is 170 ~ 190oC, reaction time are 1 ~ 2 day.
Preferably, the temperature of baking oven is 90 ~ 140 when dry in step (e)oC, drying time are 2 ~ 8 hours.
With the application method for the low silicon small grain SAPO-34 molecular sieve that above-mentioned preparation method obtains, by SAPO-34 molecular sieve
After original powder roasting, the catalyst as preparing low carbon olefinic hydrocarbon with methanol.
Preferably, the temperature of roasting is 500 ~ 650 DEG C, calcining time is 4 ~ 24 hours.
The beneficial effects of the present invention are:
The present invention provides a kind of method for preparing low silicon SAPO-34 molecular sieve as template using inexpensive morpholine, this method steps
It is rapid simple, strong operability, be easy to industrial amplification.Low silicon SAPO-34 has excellent MTO reactivity worth, but SAPO- easily occurs
18 or SAPO-5 stray crystal, synthesis are more difficult.The present invention using morpholine as template, by carry out at a lower temperature aging and
Crystallizing treatment synthesis is rich in the low silicon SAPO-34 molecular sieve of Si (4Al) structure, and reduces crystallite dimension, system by the way that crystal seed is added
The low silicon small grain SAPO-34 molecular sieve obtained has good catalytic activity in MTO reaction.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of embodiment 1,2 and comparative example 2,3；
Fig. 2 is the Electronic Speculum result figure of embodiment 1；
Fig. 3 is the Electronic Speculum result figure of comparative example 3.
Specific embodiment
Present invention will be further described below with reference to the accompanying drawings and specific embodiments:
SAPO-34 molecular sieve is taken, the crystal seed that granularity is 70-900nm, crystalline substance used in subsequent embodiment and comparative example are processed into
Kind walks crystal seed obtained thus.The composition for being used to prepare the SAPO-34 molecular sieve of crystal seed is any, can be using commercial or conjunction certainly
At SAPO-34.To the processing method of SAPO-34 molecular sieve be one of Mechanical Crushing, acid corrosion or caustic corrosion processing or
It is several.
Embodiment 1
80g deionized water, 16.6g boehmite, 26.8g phosphoric acid, 4.8g silica solution, the stirring of 24g morpholine are added into beaker
It obtains initial gel mixture, is added crystal seed, the mass ratio of crystal seed and initial gel mixture is 8:100, is turned after mixing evenly
It moves in stainless steel cauldron, 140 oC agings 18 hours, 160oC crystallization 60 hours.It is cooling after crystallization, by solid knot
Brilliant product and mother liquor are centrifugated, and are washed with deionized to neutrality, obtain SAPO-34 after 2 hours dry in 140 DEG C of baking ovens
Molecular screen primary powder roasts 24 hours at 500 DEG C and obtains SAPO-34 molecular sieve.Its X-ray diffraction result is as shown in Figure 1, Electronic Speculum knot
Evaluation results are shown in Table 1 as shown in Fig. 2, carrying out methanol-to-olefins experiment with it for fruit.
Embodiment 2
50g deionized water, 10.5g aluminium oxide, 29.2g phosphoric acid, 3.9g silica solution, 26.3g morpholine are added into beaker to stir
To initial gel mixture, it is added crystal seed, the mass ratio of crystal seed and initial gel mixture is 0.1:100, is thoroughly mixed
It is transferred in stainless steel cauldron after uniformly, 145oC aging 18 hours, 210oC crystallization 24 hours.It is cooling after crystallization, it will
Solid crystallized product and mother liquor are centrifugated, and are washed with deionized to neutrality, 4 hours dry in 120 DEG C of baking ovens, then
It is roasted 16 hours at 550 DEG C and obtains white solid powder, through XRD characterization, which is SAPO-34 molecular sieve, such as Fig. 1 institute
Show.It is 9.2 μm with the particle size average that Malvern laser particle analyzer measures sample, the evaluation of methanol-to-olefins experiment is carried out with it
It the results are shown in Table 1.
Embodiment 3
77g deionized water, 10g aluminium oxide, 28g phosphoric acid, 2.13g ethyl orthosilicate, 21.8g morpholine are added into beaker to stir
To initial gel mixture, it is added crystal seed, the mass ratio of crystal seed and initial gel mixture is 3:100, is thoroughly mixed
It is transferred in stainless steel cauldron after even, 135oC aging 20 hours, 150oC crystallization 72 hours.It is cooling after crystallization, it will consolidate
Body crystallized product and mother liquor are centrifugated, and are washed with deionized to neutrality, are obtained after 8 hours dry in 90 DEG C of baking ovens
SAPO-34 molecular screen primary powder roasts 4 hours at 650 DEG C and obtains SAPO-34 molecular sieve.Sample is measured with Malvern laser particle analyzer
The particle size average of product is 4.4 μm, and carrying out methanol-to-olefins experiment with it, evaluation results are shown in Table 1.
Embodiment 4
94g deionized water, 14g boehmite, 26.4g diammonium hydrogen phosphate, 1.7g white carbon black, 26.5g are added into beaker
Quinoline stirs to get initial gel mixture, is added crystal seed, and the mass ratio of crystal seed and initial gel mixture is 4:100, sufficiently stirs
It mixes and is transferred in stainless steel cauldron after mixing, 150 oC agings 8 hours, 190oC crystallization 24 hours.After crystallization,
It is cooling, solid crystallized product and mother liquor are centrifugated, are washed with deionized to neutrality, it is 6 hours dry in 100 DEG C of baking ovens
After obtain SAPO-34 molecular screen primary powder, 600oIt is roasted 10 hours under C and obtains SAPO-34 molecular sieve.With Malvern laser particle analyzer
The particle size average for measuring sample is 3.9 μm, and carrying out methanol-to-olefins experiment with it, evaluation results are shown in Table 1.
Embodiment 5
72g deionized water, 40.8g aluminium isopropoxide, 13.26g phosphoric acid, 6.3g silica solution, the stirring of 9.25g morpholine are added into beaker
It obtains initial gel mixture, is added crystal seed, the mass ratio of crystal seed and initial gel mixture is 5:100, is thoroughly mixed
It is transferred in stainless steel cauldron after uniformly, 100 oC agings 36 hours, 200oC crystallization 28 hours.It is cooling after crystallization,
Solid crystallized product and mother liquor are centrifugated, are washed with deionized to neutrality, is obtained after 5 hours dry in 110 DEG C of baking ovens
To SAPO-34 molecular screen primary powder, 630oIt is roasted 8 hours under C and obtains SAPO-34 molecular sieve.It is measured with Malvern laser particle analyzer
The particle size average of sample is 3.2 μm, and carrying out methanol-to-olefins experiment with it, evaluation results are shown in Table 1.
Embodiment 6
Into beaker be added 95g deionized water, 12.8g boehmite, 17.6g ammonium dihydrogen phosphate, 3.5g ethyl orthosilicate,
25.8g morpholine stirs to get initial gel mixture, is added crystal seed, and the mass ratio of crystal seed and initial gel mixture is 10:
100, it is transferred in stainless steel cauldron after being thoroughly mixed uniformly, 110oC aging 32 hours, 185 oC crystallization 32 hours.
It is cooling after crystallization, solid crystallized product and mother liquor are centrifugated, are washed with deionized to neutrality, in 130 DEG C of baking ovens
Middle drying obtains SAPO-34 molecular screen primary powder after 3 hours, and 580oIt is roasted 12 hours under C and obtains SAPO-34 molecular sieve.Use Ma Er
The particle size average that literary laser particle analyzer measures sample is 200nm, is shown in Table with its evaluation result for carrying out methanol-to-olefins experiment
1。
Embodiment 7
145g deionized water, 29.1g aluminum sulfate, 29.32g ammonium dihydrogen phosphate, 11.36g silica solution, 34.5g are added into beaker
Morpholine stirs to get initial gel mixture, is added crystal seed, and the mass ratio of crystal seed and initial gel mixture is 7:100, sufficiently
It is transferred in stainless steel cauldron after being uniformly mixed, 125oC aging 24 hours, 170oC crystallization 48 hours.Crystallization terminates
Afterwards, cooling, solid crystallized product and mother liquor are centrifugated, are washed with deionized to neutrality, dry 7 is small in 95 DEG C of baking ovens
When after obtain SAPO-34 molecular screen primary powder, 520oIt is roasted 20 hours under C and obtains SAPO-34 molecular sieve.With Malvern laser particle size
The particle size average that instrument measures sample is 1.9 μm, and carrying out methanol-to-olefins experiment with it, evaluation results are shown in Table 1.
Embodiment 8
88g deionized water, 29.1g aluminum sulfate, 20.7g phosphoric acid, 3.2g ethyl orthosilicate, 21.5g morpholine are added into beaker to stir
It mixes to obtain initial gel mixture, is added crystal seed, the mass ratio of crystal seed and initial gel mixture is 6:100, is sufficiently stirred mixed
It is transferred in stainless steel cauldron after closing uniformly, 120 oC agings 28 hours, 175oC crystallization 40 hours.It is cold after crystallization
But, solid crystallized product and mother liquor are centrifugated, are washed with deionized to neutrality, after 4 hours dry in 125 DEG C of baking ovens
Obtain SAPO-34 molecular screen primary powder, 610oIt is roasted 9 hours under C and obtains SAPO-34 molecular sieve.It is surveyed with Malvern laser particle analyzer
The particle size average for obtaining sample is 2.7 μm, and carrying out methanol-to-olefins experiment with it, evaluation results are shown in Table 1.
Comparative example 1
Into beaker be added 20g deionized water, 68g tetraethyl ammonium hydroxide aqueous solution, 12g boehmite, 20g phosphoric acid,
3.15g silica solution is stirred to uniformly mixed.Reaction mixture is transferred in stainless steel cauldron, 145oAging 12 under the conditions of C
Hour, then heat to 180oC, crystallization 32 hours.After crystallization, object to be mixed is cooled to room temperature, by crystallization product and mother
Liquid centrifuge separation, is washed solid product to neutrality with deionized water.Finally 110oIt is 8 hours dry under C, obtain SAPO-34
Molecular screen primary powder.By this molecular sieve in 600oIt is roasted 10 hours under the conditions of C and obtains SAPO-34 molecular sieve.With its carry out methanol system
Evaluation results are shown in Table 1 for alkene experiment.
Comparative example 2
85g deionized water, 16.6g boehmite, 26.8g phosphoric acid, 4.6g silica solution, 27.8g triethylamine are added into beaker,
It stirs evenly.Reaction mixture is transferred in stainless steel cauldron, 130 oC agings 16 hours, 190oC crystallization 30 hours.It is brilliant
After change, object to be mixed is cooled to room temperature, and crystallization product and mother liquor are centrifugated, washed solid product with deionized water
To neutrality, 110oC dries 8 hours, 600oC is roasted 10 hours and is obtained SAPO-34 molecular sieve, X-ray diffraction result such as Fig. 1 institute
Show.Carrying out methanol-to-olefins experiment with it, evaluation results are shown in Table 1.
Comparative example 3
80g deionized water, 16.6g boehmite, 26.8g phosphoric acid, 4.8g silica solution, 24g morpholine, stirring are added into beaker
It is transferred in stainless steel cauldron after uniformly, 130 oC agings 16 hours, 180oC crystallization 36 hours.It is to be mixed after crystallization
Object is cooled to room temperature, and crystallization product and mother liquor are centrifugated, washed solid product to neutrality with deionized water, 120oC is dry
Dry 5 hours, 580oC is roasted 14 hours and is obtained SAPO-34 molecular sieve.Its X-ray diffraction result as shown in Figure 1, Electronic Speculum result such as
Shown in Fig. 3, carrying out methanol-to-olefins experiment with it, evaluation results are shown in Table 1.
Experimental example
The product that above-mentioned each embodiment and comparative example obtain is used for the fixed bed activity rating of methanol-to-olefins (MTO), is commented
The condition of valence are as follows: molecular sieve powder tabletting is granulated, the particle of 20 ~ 40 mesh is screened out, 2.5g is weighed and is placed in fixed bed reactors
In, 550oIt is activated 1 hour under the conditions of C, is then cooled to 450oC, is fed with micro pump, raw material is 40% methanol aqueous solution, air speed
For 3h-1, on-line chromatographic analysis, each embodiment and comparative example obtains diene selective and the service life is shown in Table 1 are carried out to reaction product.
The MTO evaluation result of the SAPO-34 molecular sieve of table 1 comparative example 1-3, embodiment 1-5 synthesis
The technical means disclosed in the embodiments of the present invention is not limited only to technological means disclosed in above embodiment, further include by with
Technical solution composed by upper any combination of technical features.It should be pointed out that for those skilled in the art,
Various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as this hair
Bright protection scope.
Claims (10)
1. a kind of preparation method of low silicon small grain SAPO-34 molecular sieve, which comprises the following steps: (a) is by aluminium
Source, phosphorus source, silicon source, water and morpholine are mixed and stirred for uniformly, obtaining initial gel mixture；(b) SAPO-34 molecular sieve is handled
The crystal seed for being 70-900nm at granularity；(c) crystal seed obtained by step (b) is added in initial gel mixture obtained by step (a),
After mixing evenly, aging process is carried out；(d) after aging, temperature is increased, reaction mixture crystallization at autogenous pressures；
(e) after crystallization, solid crystallized product and mother liquor is centrifugated, is washed with deionized to neutrality, dries in an oven
After obtain SAPO-34 molecular screen primary powder.
2. the preparation method of low silicon small grain SAPO-34 molecular sieve as described in claim 1, which is characterized in that in step (a)
Source of aluminium is one of aluminium oxide, boehmite, aluminum soluble salt, aluminium isopropoxide or any several mixture；Phosphorus
Source is one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate or any several mixture；Silicon source is silica solution, positive silicic acid second
One of ester, white carbon black or any several mixture.
3. the preparation method of low silicon small grain SAPO-34 molecular sieve as claimed in claim 2, which is characterized in that silicon source, phosphorus
In the initial gel mixture that source, silicon source, water and morpholine are formed, the molar ratio of each component is Al2O3: P2O5: SiO2: Mor:H2O=
1:0.5 ~ 1.5:0.1 ~ 0.6:1 ~ 4:30 ~ 100.
4. the preparation method of low silicon small grain SAPO-34 molecular sieve as described in claim 1, which is characterized in that in step (b)
Processing method to SAPO-34 molecular sieve is one or more of Mechanical Crushing, acid corrosion or caustic corrosion processing.
5. the preparation method of low silicon small grain SAPO-34 molecular sieve as described in claim 1, which is characterized in that in step (c)
The temperature of aging process is 100 ~ 150oC, time are 8 ~ 36 hours.
6. the preparation method of low silicon small grain SAPO-34 molecular sieve as described in claim 1, which is characterized in that in step (c)
Crystal seed and the mass ratio of initial gel mixture are 0.1 ~ 10:100.
7. the preparation method of low silicon small grain SAPO-34 molecular sieve as described in claim 1, which is characterized in that in step (c)
Crystal seed and initial gel mixture are placed in the stainless steel cauldron with teflon lined, and reaction kettle sealing is placed on rotation
Turn to carry out aging process in baking oven.
8. the preparation method of low silicon small grain SAPO-34 molecular sieve as described in claim 1, which is characterized in that in step (d)
The temperature of crystallization is 150 ~ 210oC, time are 1 ~ 3 day.
9. the application for the low silicon small grain SAPO-34 molecular sieve that the preparation method as described in claim 1-8 any one obtains
Method, which is characterized in that after the roasting of SAPO-34 molecular screen primary powder, the catalyst as preparing low carbon olefinic hydrocarbon with methanol.
10. the application method of low silicon small grain SAPO-34 molecular sieve as claimed in claim 9, which is characterized in that the temperature of roasting
Degree is 500 ~ 650 DEG C, and calcining time is 4 ~ 24 hours.
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| CN110182823A (en) * | 2019-05-22 | 2019-08-30 | 陕西煤化工技术工程中心有限公司 | A method of reducing aluminium phosphate molecular sieve size of microcrystal |
| CN110342538A (en) * | 2019-06-18 | 2019-10-18 | 平顶山市汇通达科技开发有限公司 | A kind of synthetic method and its application of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve |
| CN110467194A (en) * | 2019-08-21 | 2019-11-19 | 正大能源材料(大连)有限公司 | A kind of low silicon SAPO-34 molecular sieve and its preparation method and application |
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| 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 |
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| CN114890437B (en) * | 2022-06-22 | 2023-08-25 | 中国石油大学(华东) | Small-granularity SAPO-34 molecular sieve rapidly synthesized by MTO spent catalyst and preparation method 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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