CN101428231A - Method for preparing adhesiveless ZSM-5 zeolite catalyst - Google Patents
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Abstract
The invention relates to a binder-free ZSM-5 zeolite catalyst and a preparation method thereof, and is characterized in that in the preparation process, the white carbon black is adopted as a raw material and the number of nucleation centers is controlled by adding external crystal seeds in the non-spontaneous nucleation synthesis region, and the catalyst is prepared by temperature-variable hydrothermal and crystallization reactions in the absence of organic templating agents. The preparation method comprises the following steps: adding 5% to 20% (by weight) of zeolite crystal seeds to white carbon black as silicon source, wherein the molar ratios of the feeding materials are as follows: the molar ratio of SiO2/AL2O3 ranges from 20 to 100, the molar ratio of Na2O/SiO2 ranges from 0.05 to 0.20, and the molar ratio of H2O/SiO2 ranges from 6 to 20, preferably the molar ratio of SiO2/AL2O3 ranges from 30 to 70,the molar ratio of Na2O/SiO2 ranges from 0.06 to 0.10, and the molar ratio of H2O/SiO2 ranges from 8 to 15; carrying out the temperature-variable crystallization reaction: firstly crystallizing at a temperature (100 DEG C to 120 DEG C) for a time period from 2 hours to 6 hours, then raising the temperature (160 DEG C to 190 DEG C) and further crystallizing for a time period from25 hours to 40 hours; slowing dropping the temperature (80 DEG C to 120 DEG C) within a time period from 4 hours to 6 hours and stopping crystallization; filtering the resulting slurry, washing and oven-drying; and removing sodium ions by the conventional hydrothermal exchange with ammonium salts, drying and calcining to obtain the final binder-free ZSM-5 zeolite catalyst. The particle size distribution of the catalyst is, on an average, 50 micrometers. The content of the component with a particle size less than 25 micrometers in the product is less than 15wt%. The content of ZSM-5 zeolite in the catalyst is increased up to the range from 30wt% to 90wt%.
Description
The present invention relates to a kind of zeolite catalyst preparation field, relate in particular to ZSM-5 zeolite catalyst of a kind of binder free and preparation method thereof.
Since 1972, after the ZSM-5 zeolite has been invented in the Mobil oil company by the U.S., see USP 3702886, because it has higher silica alumina ratio, unique pore passage structure and excellent heat and hydrothermal stability, the ZSM-5 zeolite has obtained in petrochemical process such as the shape slective cracking of hydro carbons, alkylation, isomerization, disproportionation, catalytic dewaxing, etherificate and has used widely.USP4639360 has reported to contain the cyclohexanediamine organic formwork agent and has prepared the ZSM-5 zeolite, is once thinking that synthetic ZSM-5 zeolite organic amine is absolutely necessary.The synthetic method of ZSM-5 zeolite is made organic method of template agent by the employing organic ammonium of classics afterwards, develops into no ammonium synthetic method, as USP4257885, USP4565681, USP5254327 and USP5240892 etc.Adopt in synthetic used silicon source is mainly waterglass (CN1072654), Ludox (USP4061724, CN1082510A, USP5240892) or white carbon (CN1194942A, CN1235875A).Generally need to use organic formwork agent (CN1923690A) when adopting white carbon to do the silicon source.But the resulting product of these existing synthetic methods generally all is a particle diameter less than zeolite crystal/particle of tens microns.
CN1100005C discloses the method that adopts directed agents fast synthesis of ZSM-5-5 zeolite, isolating the transparency liquid part of temperature programming after aging under the template agent effect as directed agents, can obtain the ZSM-5 zeolite of 0.1 μ m, and generated time shortens.CN1884075A similarly discloses a kind of high concentration fast synthesis of ZSM-5-5 zeolite method, has used crystal seed and template agent, has also shortened crystallization time.Directed agents, crystal seed mainly have been to quicken the effect that crystallization shortens the time.
CN1318302C has reported that elder generation in the following nucleation of higher temperature (180-210 ℃), again in the variable temperature crystallization mode of the following crystallization of lower temperature (130-170 ℃), can prepare the ZSM-5 zeolite of 1-6 micron size.CN1205122C has also adopted the variable temperature crystallization mode, but what obtain also is conventional ZSM-5 zeolite.Still there is not report by adding the method for crystal seed or variable temperature crystallization acquisition greater than tens micron particles ZSM-5 zeolites.
Adopt natural minerals report also to be arranged, disclose C as USP4091007 and USP5558851 as the technology of silicon, the synthetic ZSM-5 zeolite in aluminium source
2-C
4Synthesize the ZSM-5 zeolite with kaolin as part aluminium source under the alkyl quaternary ammonium salts template agent effect; EP0068817 discloses the synthetic ZSM-5 zeolite of acid treatment metakaolin under the TPABr effect; CN1281495C, CN1205122C etc. have then synthesized the ZSM-5 zeolite with diatomite.The method of the synthetic ZSM-5 zeolite of these natural materials is except that the cost that reduces part material, and products therefrom there is no different with the product that synthesizes with silicon sources such as waterglass.
For the needs that separate, often need the ZSM-5 zeolite is prepared into the catalyst granules of certain size and geometry in the catalytic reaction, the ZSM-5 zeolite powder that directly synthesizes often can not satisfy the demands owing to size is not more than tens microns.What CN1093514C reported makes directly synthetic large crystal ZSM-5-5 zeolite of template agent with amino acid, and crystal length also is no more than tens microns.
In order to obtain the ZSM-5 zeolite catalyst of ideal dimensions, various forming techniques have been developed, by binding agent catalyst is made in the moulding of ZSM-5 zeolite as CN1132904C, USP5521133, CN1950146AUSP2003/0047487 have then described by the spray shaping preparation and have contained the method for ZSM-5 zeolite up to the high abrasion microspherical catalyst of 40 heavy %.But just be affected in its wearability of ZSM-5 microsphere of zeolite body that contains that is higher than 25 heavy % generally speaking, and the complicated difficult cost of its preparation process is very high, and zeolite can be lossy, catalytic performance also can be subjected to influence to a certain degree.
USP4522705, USP5145659 etc. have reported the method for using organic formwork agent in-situ crystallization ZSM-5-5 zeolite on pre-formed clay microphere for this reason.USP6908603 adopts a small amount of directed agents in-situ crystallization synthetically grown ZSM-5 zeolite on kaolin microsphere without the template agent.Then under the TPAOH effect, with the synthetic ZSM-5 of pure silicon microballoon, zeolite crystallinity is 25 heavy % to USP6004527, and microballoon has kept shape and size.Similarly CN1798608A, USP4091007, USP5558851, EP0068817, EP0156595, USP6004527, USP4522705, USP5145659 etc. in addition.
CN1927714A, CN1974007A, CN1915820A disclose adhesiveless ZSM-5 prepare zeolite method, be with after silica and the moulding of ZSM-5 zeolite again in organic amine atmosphere the secondary conversion processing be integral the type catalyst.These binder free zeolites are meant and do not contain inert binder in the zeolite grain or only contain small amount of binder, have than high zeolite content.Therefore can utilize effective surface area big, have better catalytic performance.
No matter be the pre-formed back of in-situ crystallization method or zeolite/binder secondary transformation processing method, in a hydrothermal crystallization process, do not realize, the longer preparation process complexity of whole operation, in fact binding agent also is absolutely necessary when pre-formed.Do not use binding agent fully, obtain crystal/particle (secondary gathering) size in hydro-thermal building-up process and still do not appear in the newspapers up to the high abrasion catalyst preparation technology more than the 40 heavy % at tens microns and ZSM-5 zeolite content.
On the basis of existing technology, the purpose of this invention is to provide a kind of adhesiveless ZSM-5 zeolite catalyst and preparation method thereof, it is characterized in that adopting in the preparation process white carbon to control the nuclearing centre number at the synthetic phase region of non-spontaneous nucleation by adding plus seed, and the alternating temperature hydrothermal crystallizing form under the organic-free template condition as raw material.Different with the Y zeolite of non-spontaneous nucleation is, the ZSM-5 zeolite under an amount of basicity, temperature or organic formwork agent effect often at an easy rate spontaneous nucleation growth go out zeolite crystal, particularly under the organic formwork agent effect especially like this, nucleus quantity is many and uncontrolled, and nucleation temperature higher when no mould is pulled agent also can promote zeolite growth.As well known in the art be the size that nucleus quantity often influences zeolite crystal/particle, nucleus quantity zeolite crystal/particle at most is just little.The present invention suppresses spontaneous nucleation and zeolite growth by the nucleation crystallization section of selecting relatively lower temp under the organic-free template, control the nucleation centric quantity by the zeolite granular that adds appropriate amount as nucleus, and promote zeolite to assemble adding on the zeolite granular crystal seed growth by the hydrothermal crystallizing temperature that raises, in a hydrothermal crystallization process, obtain size and reach tens microns ZSM-5 zeolite granular, and the prepared adhesiveless ZSM-5 zeolite catalyst of the present invention has good anti-wear performance much larger than the average grain diameter of prior art.Because zeolite granular is to form by the gathering growth of silicon/aluminium poly acid group on zeolite seed crystal that white carbon dissolves in alkaline environment, the size of white carbon does not have a direct impact the product particle size, this is different with in-situ crystallization technology on the silicon ball of prefabricated big or small moulding, kaolin microsphere, also is different with technology with zeolite and the pre-formed back of inorganic filler being integral of secondary hydrothermal treatment consists catalyst.
Concrete steps of the present invention are:
(1), be the silicon source with the white carbon, add the heavy % of zeolite seed crystal 5-20, preferably the heavy % of 8-15.
(2), the diatomite that can add the heavy % of 0-15 adjusts apparent bulk density, total molar ratio is: SiO
2/ AL
2O
3=20-100, Na
2O/SiO
2=0.05-0.20, H
2O/SiO
2=6-20; SiO preferably
2/ AL
2O
3=30-70, Na
2O/SiO
2=0.06-0.10, H
2O/SiO
2=8-15.
(3), adopt the variable temperature crystallization mode, after 100-120 ℃ of following crystallization 2-6 hour, be warmed up to 160-190 ℃ again and continued crystallization 25-40 hour down earlier; Slowly cool to 80-120 ℃ in 4-6 hour and finish crystallization; Preferably elder generation was warmed up to 175-185 ℃ again and continued crystallization 28-32 hour down after 105-115 ℃ of following crystallization 3-5 hour; In 4.5-5.5 hour, slowly cool to 90-100 ℃ and finish crystallization.
(4), dope filtration, washing, oven dry, product can way routinely carries out the ammonium salt hydrothermal exchange and removes sodium ion, drying and roasting, obtains the ZSM-5 zeolite catalyst of binder free.
Catalyst grain size is distributed as 50 microns of average grain diameters,＜25 microns product less than 15 heavy %.Can make the content of ZSM-5 zeolite in the catalyst bring up to the heavy % of 30-90, preferably the heavy % of 40-80; And make catalyst keep excellent abrasive.
The adhesiveless ZSM-5 zeolite catalyst of the present invention preparation advantage be that zeolite content still keeps excellent abrasive up to catalyst under the heavy % situation of 40-90, and product has 50 microns of average grain diameters in preparation process, the size distribution of＜25 microns product less than 15 heavy %.Simplify Preparation of catalysts technology and reduced manufacturing cost.
The adhesiveless ZSM-5 zeolite catalyst of the present invention's preparation is applicable to the applied all spectra of ZSM-5 microsphere of zeolite catalyst.Be particularly suitable in fluidized catalytic cracking and the catalytic pyrolysis process, it is mixed to convert as the catalyst of catalytic cracking of hydrocarbon/catalytic pyrolysis process or co-catalyst and major catalyst use or add separately and use, can improve octane number or obtain higher liquefied gas and productivity of low carbon olefin hydrocarbon.
The following examples will the present invention is further illustrated, but protection scope of the present invention is not subjected to the restriction of these embodiment.
ZSM-5 zeolite relative crystallinity is measured (see " petrochemical industry analytical method (RIPP test method) ", Yang Cui delimits the organizational structure, and Science Press publishes, nineteen ninety version) with the X-ray diffraction method with reference to the RIPP146-90 standard method in the zeolite catalyst in an embodiment; The composition of zeolite catalyst presses RIPP134-90 with x ray fluorescence spectrometry and (the same) measured in the RIPP111-90 standard method; The specific surface of zeolite and pore volume are measured by (GB/T5816-1995) method; Apparent bulk density is pressed the RIPP32-97 standard method and is measured (the same); The size distribution of zeolite catalyst adopts laser particle analyzer to measure; The tear strength of catalyst adopts the RIPP29-90 standard method to measure (the same); Mat activity test is undertaken by the method for ASTM D-3907, and other detect referring to (" oil and oil product test method national standard " China Standard Press published 1989).
Embodiment 1
Get 1.0 premium on currency glass (Shandong Aluminum Plant, SiO
2Content 250.4 grams per liters, Na
2O 78.4 grams per liters, density (20 ℃) 1.259 grams per milliliters); Will be by 76.5 milliliters of aluminum sulfate solutions (Shandong Aluminum Plant's production, Al
2O
3Content 92.7 grams per liters, d
4 20=1.198) and 175.7 milliliters of dilute sulfuric acids (concentration is 26 heavy %, d for chemically pure reagent preparation, Beijing Chemical Plant
4 20=1.192) acidified aluminum sulfate solution formed, stir to join down and make reactant mixture in the above-mentioned waterglass, gained material cumulative volume is 1260 milliliters, this reactant mixture packed into stirred crystallization 16 hours down in 180 ℃ in the reactor, products therefrom after filtration, washing, add water after the drying and grinding and pull an oar into the slurries of 25 heavy % concentration as crystal seed.
Stir adding 900 ml waters in the synthesis reactor at 2 liters of stainless steel high pressure, (produce the Changbai, igloss 17 heavy %, SiO to get 45 gram diatomite
294 heavy %) add and add after 150 gram water grind to form slurries, start 60 rev/mins of stirring (〉), add the white carbon black of 80-120 order 240 grams (production of Qingdao silica gel factory, SiO again
294 heavy %), (Shandong Aluminum Plant produces, Na to add 100 milliliters of sodium metaaluminates
2The O160 grams per liter, AL
2O
3100 grams per liters, d
4 20=1.248), sodium hydroxide solution 30 grams (the chemically pure reagent preparation that adds 35 heavy % again, the Beijing Chemical Plant), adding above-mentioned zeolite seed crystal slurries 140 grams stirs after 1 hour 110 ℃ of following crystallization after 4 hours, be warmed up to 180 ℃ again and continued crystallization 30 hours down, last slowly cooling (about 5 hours) finishes crystallization to 100 ℃.Dope filtration, washing, oven dry promptly obtains product.Zeolite crystallinity 72%, silica alumina ratio 40, the X-ray diffracting spectrum is seen Fig. 1; Apparent bulk density is 0.58g/ml; Specific area is 260m
2/ g, pore volume are 0.15ml/g; Size distribution is 53 microns of average grain diameters,＜25 microns product 13 heavy %; Tear strength 1.2.
Embodiment 2
The product of embodiment 1 ground cause average grain diameter＜20 micron, add water and pull an oar into the slurries of 25 heavy % concentration as crystal seed.Stir adding 600 ml waters in the synthesis reactor at 2 liters of stainless steel high pressure, (produce the Changbai, igloss 17 heavy %, SiO to get 5 gram diatomite
294 heavy %) add and add after 15 gram water grind to form slurries, start 60 rev/mins of stirring (〉), add the white carbon black of 200 orders, 240 grams (production of Qingdao silica gel factory, SiO again
295 heavy %), add 100 milliliters of sodium metaaluminates (Shandong catalyst plant, Na
2The O160 grams per liter, AL
2O
3100 grams per liters), the sodium hydroxide solution 30 gram (chemical pures that add the 35 heavy % that are mixed with by reagent again, the Beijing Chemical Plant), adding above-mentioned zeolite seed crystal slurries 87 grams stirs after 1 hour 105 ℃ of following crystallization after 5 hours, be warmed up to 190 ℃ again and continued crystallization 28 hours down, last slowly cooling (about 5 hours) finishes crystallization to 95 ℃.Dope filtration, washing, oven dry promptly obtains product.Zeolite crystallinity 68%, silica alumina ratio 42; Bulk density is 0.52g/ml; Specific area is 250m
2/ g, pore volume are 0.14ml/g; Size distribution is 54 microns of average grain diameters,＜25 microns product 12 heavy %; Tear strength 1.1.
Embodiment 3
Stir adding 600 ml waters in the synthesis reactor at 2 liters of stainless steel high pressure, start 60 rev/mins of stirrings (〉), (silica gel factory in Qingdao produces, SiO to add the white carbon black of 300 orders, 240 grams again
292 heavy %), add 80 milliliters of sodium metaaluminates (Shandong catalyst plant, Na
2The O155 grams per liter, AL
2O
3100 grams per liters), the sodium hydroxide solution 35 gram (chemical pures that add the 30 heavy % that are mixed with by reagent again, the Beijing Chemical Plant), adding zeolite seed crystal slurries 80 grams among the embodiment 2 stirs after 1 hour 100 ℃ of following crystallization after 5 hours, be warmed up to 178 ℃ again and continued crystallization 32 hours down, last slowly cooling (about 4.5 hours) finishes crystallization to 100 ℃.Dope filtration, washing, oven dry promptly obtains product.Zeolite crystallinity 70%, silica alumina ratio 42; Bulk density is 0.50g/ml; Specific area is 268m
2/ g, pore volume are 0.15ml/g; Size distribution is 51 microns of average grain diameters,＜25 microns product 13 heavy %; Tear strength 1.4.
Embodiment 4
Embodiment 3 products therefroms (butt), ammonium phosphate salt and water are descended exchange 1 hour according to the weight ratio of 1:0.8:20 at 90 ℃, and sodium oxide content is less than 0.1 heavy %.After the drying, product is put into fixed bed, behind 800 ℃/4 hours hydrothermal agings under the 100 heavy % water vapor conditions, sample after aging is estimated its positive carbon tetradecane hydrocarbon pyrolysis activity on the pulsed micro-reactor-chromatography device, appreciation condition is: 480 ℃ of reaction temperatures, zeolite catalyst loading amount 0.1 gram, positive carbon tetradecane sample size 0.5 microlitre, the positive pure hydrocarbon pyrolysis conversion ratio of the carbon tetradecane is 100%.
Embodiment 2 products therefroms (butt), ammonium phosphate salt and water are descended exchange 2 hours according to the weight ratio of 1:1:20 at 95 ℃, and sodium oxide content is less than 0.1 heavy %; After the drying, with product under 100 heavy % water vapor conditions in 800 ℃/4 hours and 800 ℃/17 hours hydrothermal aging respectively, sample after aging is estimated its activity stability on anti-in that light oil is little, appreciation condition is: 460 ℃ of reaction temperatures, catalyst loading amount 5 grams, advance straight distillation light diesel oil 1.56 grams in huge port in 70 seconds, the results are shown in Table 1.
Table 1, embodiment 2 light oil micro anti-evaluation results:
| Aging conditions | 800 ℃/4 hours | 800 ℃/17 hours |
| Micro-activity, % | 50 | 45 |
Embodiment 6
Table 2, feedstock oil character:
| Density (20 ℃), kg/m 3 | 898.1 |
| |
367 |
| 30％，℃ | 401 |
| 50％，℃ | 454 |
| 350℃，％ | 5 |
| Carbon residue, m% | 2.72 |
| Freezing point, ℃ | +33 |
| Heavy metal Ni ppm | 1.94 |
| V?ppm | 0.7 |
With embodiment 1 products therefrom (butt), ammonium phosphate salt and water according to the weight ratio of 1:0.5:10 90 ℃ of exchanges 1 hour down, exchange twice, sodium oxide content is less than 0.1 heavy %.
Dried product under 100 heavy % water vapor conditions in 800 ℃/4 hours hydrothermal agings.Sample after aging is carried out performance evaluation on small fixed flowing bed catalytic cracking experimental provision, adopt commercial heavy oil as cracked stock, feedstock oil character sees Table 2.The industrial poising agent of choosing a kind of trade names and be GOR contrasts as blank.518 ℃ of reaction temperatures, air speed 10h
-1, water filling 10 heavy % in the charging.The results are shown in Table 3, data result shows that the product of embodiment 1 promptly has excellent catalytic performance under the situation of adding 1 heavy %.
Product distribution situation before and after table 3, embodiment 1 zeolite catalyst use:
| Product distributes, w% | 100% poising agent | + 1% embodiment 1 aging sample |
| Dry gas | 5.1 | 5.4 |
| Liquefied gas | 9.7 | 14.7 |
| Gasoline | 37.1 | 36.7 |
| Diesel oil | 35.9 | 31.6 |
| Slurry oil | 4.3 | 3.6 |
| Coke | 7.5 | 7.6 |
| Loss | 0.4 | 0.4 |
| Gasoline RON increases | - | +2.0 |
| Gasoline MON increases | - | +1.3 |
Description of drawings: Fig. 1 is the product X optical diffraction collection of illustrative plates of embodiment 1.
Claims (9)
1, the present invention relates to a kind of adhesiveless ZSM-5 zeolite catalyst and preparation method thereof, it is characterized in that in preparation process, adopting white carbon to control the nuclearing centre number at the synthetic phase region of non-spontaneous nucleation by adding plus seed, and the alternating temperature hydrothermal crystallizing form under the organic-free template condition as raw material.Concrete steps are: be the silicon source with the white carbon, add the heavy % of zeolite seed crystal 5-20; Molar ratio is: SiO
2/ AL
2O
3=20-100, Na
2O/SiO
2=0.05-0.20, H
2O/SiO
2=6-20; Adopt variable temperature crystallization, after 100-120 ℃ of following crystallization 2-6 hour, be warmed up to 160-190 ℃ again and continued crystallization 25-40 hour down earlier; Slowly cool to 80-120 ℃ in 4-6 hour and finish crystallization, dope filtration, washing, oven dry.Product can way routinely carries out the ammonium salt hydrothermal exchange and removes sodium ion, drying and roasting, obtains the ZSM-5 zeolite catalyst of binder free.Catalyst grain size is distributed as 50 microns of average grain diameters,＜25 microns product less than 15 heavy %.Can make the content of ZSM-5 zeolite in the catalyst bring up to the heavy % of 30-90; Can adjust apparent bulk density by the diatomite that adds the heavy % of 0-15 in the preparation.
2,, it is characterized in that said adhesiveless ZSM-5 zeolite catalyst adopts white carbon as raw material according to claim 1.
3,, it is characterized in that said adhesiveless ZSM-5 zeolite catalyst does not adopt organic formwork agent when preparing according to claim 1.
4,, it is characterized in that adding in the said adhesiveless ZSM-5 zeolite catalyst preparation the heavy % of zeolite seed crystal 5-20, the preferably heavy % of 8-15 according to claim 1.
5,, it is characterized in that said adhesiveless ZSM-5 zeolite catalyst prepares molar ratio and is: SiO according to claim 1
2/ AL
2O
3=20-100, Na
2O/SiO
2=0.05-0.20, H
2O/SiO
2=6-20; SiO preferably
2/ AL
2O
3=30-70, Na
2O/SiO
2=0.06-0.10, H
2O/SiO
2=8-15.
6, according to claim 1, it is characterized in that adopting when said adhesiveless ZSM-5 zeolite catalyst prepares variable temperature crystallization, after 100-120 ℃ of following crystallization 2-6 hour, be warmed up to 160-190 ℃ again and continued crystallization 25-40 hour down earlier, slowly cool to 80-120 ℃ in 4-6 hour and finish crystallization; Preferably elder generation was warmed up to 175-185 ℃ again and continued crystallization 28-32 hour down after 105-115 ℃ of following crystallization 3-5 hour, slowly cooled to 90-100 ℃ and finish crystallization in 4.5-5.5 hour.
7, according to claim 1, it is characterized in that the ZSM-5 zeolite content of said adhesiveless ZSM-5 zeolite catalyst is brought up to the heavy % of 30-90, preferably 40-80 weighs %, and makes catalyst keep excellent abrasive.
8, according to claim 1, the size distribution that it is characterized in that said adhesiveless ZSM-5 zeolite catalyst is 50 microns of average grain diameters,＜25 microns product less than 15 heavy %.
9,, it is characterized in that said adhesiveless ZSM-5 zeolite catalyst adjusts apparent bulk density by the diatomite that adds the heavy % of 0-15 according to claim 1.
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| CN104415779B (en) * | 2013-09-04 | 2017-01-25 | 中国石油天然气股份有限公司 | Molecular sieve based catalyst for catalytic cracking regenerated flue gas denitration and preparation method of molecular sieve based catalyst |
| CN110237857A (en) * | 2019-04-22 | 2019-09-17 | 中国科学院山西煤炭化学研究所 | A kind of acid regulation method of TON molecular sieve |
| CN110237857B (en) * | 2019-04-22 | 2021-07-27 | 中国科学院山西煤炭化学研究所 | Acidity regulation and control method of TON molecular sieve |
| CN112279262A (en) * | 2020-11-16 | 2021-01-29 | 四川奥力奋催化材料有限公司 | Silicoaluminophosphate molecular sieve, catalyst for preparing olefin from methanol, preparation method and application thereof |
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