CN103586068A - Efficient synthetic method of MTP (methanol to propylene) catalyst - Google Patents
Efficient synthetic method of MTP (methanol to propylene) catalyst Download PDFInfo
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- CN103586068A CN103586068A CN201310568955.2A CN201310568955A CN103586068A CN 103586068 A CN103586068 A CN 103586068A CN 201310568955 A CN201310568955 A CN 201310568955A CN 103586068 A CN103586068 A CN 103586068A
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Abstract
The invention discloses an efficient synthetic method of an MTP (methanol to propylene) catalyst. According to the method, tetrapropyl ammonium hydroxide is taken as a template agent, and sodium hydroxide and ammonium fluoride are taken as mineralizing agents; firstly, an aluminum source, sodium hydroxide, ammonium fluoride, water and the template agent are prepared into a solution; then, the silicon source is added, sol with molar ratio being n(F-):n(Al203):n(SiO2):n(TPAOH):n(Na2O):n(H2O)=(0-18):1:150:15:7:100 is synthesized, and the mixture is uniformly stirred, aged and crystallized; and the mixture is centrifugally separated, washed and dried after completely crystallized, and then raw powder of molecular sieve ZSM-5 is obtained. With the adoption of the method, the small-grain pure-phase molecular sieve ZSM-5 is easy to synthetize, and the synthetic method has application values in the aspects of olefin conversion, xylene isomerization, benzene alkylation, MTP and the like.
Description
Technical field
The invention discloses a kind of little crystal grain high silica ZSM-5 molecular sieve catalyst, it is preparing propylene transformed that this catalyst can be used for high efficiency methanol.
Background technology
Propylene is important basic organic chemical raw material, is mainly derived from the petroleum path such as catalytic cracking, steam reforming and alkene coupling, accounts for the more than 95% of propylene production capacity.Along with increasing rapidly of the acryloyl derivative demands such as polypropylene, acrylonitrile, expoxy propane, the demand of propylene also rises year by year, needs the output that increases propylene badly.The approach of propylene enhancing mainly contains two kinds: one, on the basis of existing petroleum base technology, by measures such as technological innovation, process innovations, improves productivity of propylene; Two, develop new Non oil-based route Technologies For Increasing Propylene, as preparing propylene by dehydrogenating propane technique and preparing propylene by methanol transformation technology.
In view of the energy resource structure natural endowment of China's " few oily deficency of rich coal ", petroleum base route and preparing propylene by dehydrogenating propane are difficult to the supply that continues, efficiently keeps propylene.Preparing propylene by methanol transformation (MTP) by coal through gasification methanol (or dimethyl ether), then propylene technique is produced in dehydration, it is that generally acknowledge, promising Non oil-based route Technologies For Increasing Propylene, this technology is that the useful of petroleum path propylene enhancing supplemented, and has important practical significance and wide market prospects.
Preparing propylene by methanol transformation (MTP) technology comes from preparing olefin by conversion of methanol (MTO).It is catalyst that Mobil company adopts low silica-alumina ratio ZSM-5 molecular sieve the earliest, carries out the research work of preparing olefin by conversion of methanol, and its product is mainly the mixture of low-carbon alkene, and in product, Propylene Selectivity is lower.In addition, the acidity due to ZSM-5 molecular sieve is strong, aperture is large, C in product
4 +alkene, alkane and arene content very high (C.D.Chang, Methanol Conversion to Light Olefins, Catal. Rev-Sci.Eng., 1984,26 (3 & 4), 323-345).Adopt pore zeolite as erionite, T zeolite, chabasie, ZK-5, ZSM-34, SAPO-34, although can obtain very high ethene, propylene overall selectivity, but the ratio of propylene and ethene is very low in product, and above-mentioned catalyst easily generates carbon distribution and rapid deactivation.Generally speaking, preparing olefin by conversion of methanol, product distribution does not have low-carbon alkene and take propylene as main feature.
Germany LURGI has taken the lead in carrying out the research of preparing propylene by methanol transformation technology, they adopt fixed bed reactors to take high-silicon small grain ZSM-5 molecular sieve as catalyst, in order further to improve Propylene Selectivity and yield, prepared the ZSM-5 catalyst series (patent WO2004/018089) of Cd or Zn modification.Propylene one way is selectively 35-40% left and right, and heavy component circulation Returning reactor, can make propene yield reach 71.2%.But this technique still exists, and propylene once through yield is low, P/E is than the problem such as low.
Improving small-grain ZSM-5 molecular sieve catalyst common method of Propylene Selectivity and P/E ratio in preparing propylene by methanol transformation product is that it is carried out post processing modification or changes reaction process and reaction condition.Main method has:
1, soda acid is processed, and main purpose is acidic site intensity and the quantity that regulates catalyst, simultaneously the diffusion of regulating catalyst: if CN101239326A is first to ZSM-5 molecular sieve (SiO
2/ A1
20
3=110) carry out alkali treatment, then carry out acid treatment, propene yield is 41.8%, P/E=9.4; CN101269340A carries out acid treatment to molecular sieve, and the yield of propylene is 45.7%, P/E=10.9;
2, interpolation binding agent: patent CN101279281A, CN101172246A, CN101176849A have studied silica (with U.S.P4060568 and U.S.P 4100219), aluminium oxide (U.S.P4433189) or the impact of clay on propene yield and P/E ratio, wherein add separately binding agent, the highest yield of propylene is 47.1%, P/E=6.2; If ZSM-5 molecular sieve is carried out to alkali treatment, silanization processing before adding binding agent, can greatly improve yield (55.6%) and the P/E ratio (14.0 CN101176849A) of propylene.
3, metal or nonmetal oxide modification, mainly concentrate on phosphorus, magnesium, group of the lanthanides, cadmium, zinc etc., as: phosphorus, modified zirconia (CN101011667A), phosphorus, magnesium, lanthanum modification (CN101239875A, U.S.P 5367100), phosphorus, vanadium, molybdenum, tungsten modification (CN101234353A, CN101306381A) lanthanum, cerium, praseodymium, neodymium modification (CN101279281A), boron, magnesium, lanthanum modification (U.S.P6,048,816).
4, adjust production technology (WO2007086839, US20080242910, EP-B-1025068, USP4,433,188), adopt moving bed, flowing bed reactor or by the heavy hydrocarbon component (C in product
4 +) recycle after separation, improve yield and the P/E ratio of propylene in product.
Make a general survey of document, the preparation method of existing MTP catalyst mainly stresses the post processing modification of high silica ZSM-5 molecular sieve, has that catalyst preparation process route is long, technological operation is loaded down with trivial details and the shortcoming such as catalytic performance poor repeatability.Therefore be necessary exploitation efficiently, MTP method for preparing catalyst easily.
Summary of the invention
Technical problem to be solved by this invention is the synthetic method that a kind of technique is simply used Propylene Selectivity and the high preparing propylene transformed catalyst of high efficiency methanol of P/E ratio.
For solving above technical problem, the technical solution used in the present invention is:
A synthetic method for the preparing propylene transformed catalyst of high efficiency methanol, take TPAOH as template, and NaOH and ammonium fluoride are mineralizer; First by aluminium source, NaOH, ammonium fluoride, water and template wiring solution-forming, then add silicon source, mole proportioning of synthetic colloidal sol is n (F
-): n (Al
20
3): n (SiO
2): n (TPAOH): n (Na
2o): n (H
2o)=and (0-18): 1:150:15:7:100, after stirring, ageing 0.4-1.0 hour at room temperature, then at 160-180 ℃ of crystallization 18-26h; After crystallization is complete, after centrifugation, washing and drying, obtain the former powder of ZSM-5 molecular sieve.
As a kind of preferred technical scheme, aluminium source is aluminum sulfate, aluminium hydroxide, aluminium oxide or aluminium isopropoxide.
As a kind of preferred technical scheme, silicon source is ethyl orthosilicate, silicic acid, Ludox or white carbon.
As the preferred technical scheme of another kind, after stirring, at room temperature ageing 0.5 hour, then at 170 ℃ of crystallization 24h.
The present invention, under alkaline medium and fluorine ion existence, for ZSM-5 molecular sieve with small crystal grains, has using value at aspects such as alkene conversion, xylene isomerization, benzene alkylation and preparing propylene by methanol transformation by Vacuum-assisted method legal system.
Accompanying drawing explanation
Fig. 1 schemes according to the X-ray diffraction of embodiment 1 synthetic product (XRD).
Fig. 2 schemes according to the X-ray diffraction of embodiment 2 synthetic products (XRD).
Fig. 3 schemes according to the X-ray diffraction of embodiment 3 synthetic products (XRD).
Fig. 4 schemes according to the X-ray diffraction of embodiment 4 synthetic products (XRD).
Fig. 5 is methanol conversion temporal evolution curve.
Fig. 6 is ethylene selectivity temporal evolution curve.
Fig. 7 is Propylene Selectivity temporal evolution curve.
Fig. 8 is P/E ratio temporal evolution curve.
The specific embodiment
In order to make those skilled in the art better understand the present invention, below in conjunction with specific embodiment, the present invention is done to further clear, complete explanation.
0.48g aluminum sulfate, 0.40g NaOH are joined successively in TPAOH (TPAOH, the methanol solution of the 25 %) aqueous solution of 9 g, fully stir until formation clear solution is referred to as A solution.Then 25ml ethyl orthosilicate is added to A liquid, the about 0.5h of stirring at room, is referred to as B liquid, and wherein the amount of substance of each species is than being n (Al
20
3): n (SiO
2): n (TPAOH): n (Na
2o): n (H
2o)=1:150:15:7:100.B liquid is transferred in autoclave, at 170 ℃ of crystallization 24h.After crystallization completes, centrifugation, wash to PH=7-8.At 100 ℃, dry, sample is placed in to Muffle furnace, under air atmosphere, 550 ℃ of roastings are 8 hours, and 2 ℃/min of heating rate, finally obtains ZSM-5 molecular sieve, and the XRD figure of synthetic product is shown in Fig. 1.Then at 90 ℃ with 1M hydrochloric acid acid treatment ZSM-5 molecular sieve 2～3 times (liquid-solid ratio 10～20:1), then through washing, roasting, compressing tablet, obtain 20-40 object catalyst, catalyst numbering is designated as S1.
0.48g aluminum sulfate, 0.40g NaOH and 0.16g ammonium fluoride are joined successively in TPAOH (TPAOH, the methanol solution of the 25 %) aqueous solution of 9.0g, fully stir until formation clear solution is referred to as A solution.Then 25ml ethyl orthosilicate is added to A liquid, the about 0.5h of stirring at room, is referred to as B liquid, and wherein the amount of substance of each species is than being n (F
-): n (Al
20
3): n (SiO
2): n (TPAOH): n (Na
2o): n (H
2o)=6:1:150:15:7:100.B liquid is transferred in autoclave, at 170 ℃ of crystallization 24h.After crystallization completes, centrifugation, wash to PH=7-8.At 100 ℃, dry, sample is placed in to Muffle furnace, under air atmosphere, 550 ℃ of roastings are 8 hours, and 2 ℃/min of heating rate, finally obtains ZSM-5 molecular sieve, and the XRD figure of synthetic product is shown in Fig. 2.Then at 90 ℃ with 1M hydrochloric acid acid treatment ZSM-5 molecular sieve 2～3 times (liquid-solid ratio 10～20:1), then through washing, roasting, compressing tablet, obtain 20-40 object catalyst, catalyst numbering is designated as S2.
0.48g aluminum sulfate, 0.40g NaOH and 0.33g ammonium fluoride are joined successively in TPAOH (TPAOH, the methanol solution of the 25 %) aqueous solution of 9.0g, fully stir until formation clear solution is referred to as A solution.Then 25ml ethyl orthosilicate is added to A liquid, the about 0.5h of stirring at room, is referred to as B liquid, and wherein the amount of substance of each species is than being n (F
-): n (Al
20
3): n (SiO
2): n (TPAOH): n (Na
2o): n (H
2o)=12:1:150:15:7:100.B liquid is transferred in autoclave, at 170 ℃ of crystallization 24h.After crystallization completes, centrifugation, wash to PH=7-8.At 100 ℃, dry, sample is placed in to Muffle furnace, under air atmosphere, 550 ℃ of roastings are 8 hours, and 2 ℃/min of heating rate, finally obtains ZSM-5 molecular sieve, and the XRD figure of synthetic product is shown in Fig. 3.Then at 90 ℃ with 1M hydrochloric acid acid treatment ZSM-5 molecular sieve 2～3 times (liquid-solid ratio 10～20:1), then through washing, roasting, compressing tablet, obtain 20-40 object catalyst, catalyst numbering is designated as S3.
0.48g aluminum sulfate, 0.40g NaOH and 0.49 g ammonium fluoride are joined successively in TPAOH (TPAOH, the methanol solution of the 25 %) aqueous solution of 9.0g, fully stir until formation clear solution is referred to as A solution.Then 25ml ethyl orthosilicate is added to A liquid, the about 0.5h of stirring at room, is referred to as B liquid, and wherein the amount of substance of each species is than being n (F
-): n (Al
20
3): n (SiO
2): n (TPAOH): n (Na
2o): n (H
2o)=18:1:150:15:7:100.B liquid is transferred in autoclave, at 170 ℃ of crystallization 24h.After crystallization completes, centrifugation, wash to PH=7-8.At 100 ℃, dry, sample is placed in to Muffle furnace, under air atmosphere, 550 ℃ of roastings are 8 hours, and 2 ℃/min of heating rate, finally obtains ZSM-5 molecular sieve, and the XRD figure of synthetic product is shown in Fig. 4.Then at 90 ℃ with 1M hydrochloric acid acid treatment ZSM-5 molecular sieve 2～3 times (liquid-solid ratio 10～20:1), then through washing, roasting, compressing tablet, obtain 20-40 object catalyst, catalyst numbering is designated as S4.
0.48g aluminum sulfate, 0.40g NaOH and 0.027 g ammonium fluoride are joined successively in TPAOH (TPAOH, the methanol solution of the 25 %) aqueous solution of 9.0g, fully stir until formation clear solution is referred to as A solution.Then 25ml ethyl orthosilicate is added to A liquid, the about 0.5h of stirring at room, is referred to as B liquid, and wherein the amount of substance of each species is than being n (F
-): n (Al
20
3): n (SiO
2): n (TPAOH): n (Na
2o): n (H
2o)=1:1:150:15:7:100.B liquid is transferred in autoclave, at 170 ℃ of crystallization 24h.After crystallization completes, centrifugation, wash to PH=7-8.At 100 ℃, dry, sample is placed in to Muffle furnace, under air atmosphere, 550 ℃ of roastings are 8 hours, and 2 ℃/min of heating rate, finally obtains ZSM-5 molecular sieve.Then at 90 ℃ with 1M hydrochloric acid acid treatment ZSM-5 molecular sieve 2～3 times (liquid-solid ratio 10～20:1), then through washing, roasting, compressing tablet, obtain 20-40 object catalyst, catalyst numbering is designated as S5.
0.48g aluminum sulfate, 0.40g NaOH and 0.11 g ammonium fluoride are joined successively in TPAOH (TPAOH, the methanol solution of the 25 %) aqueous solution of 9.0g, fully stir until formation clear solution is referred to as A solution.Then 25ml ethyl orthosilicate is added to A liquid, the about 0.5h of stirring at room, is referred to as B liquid, and wherein the amount of substance of each species is than being n (F
-): n (Al
20
3): n (SiO
2): n (TPAOH): n (Na
2o): n (H
2o)=4:1:150:15:7:100.B liquid is transferred in autoclave, at 170 ℃ of crystallization 24h.After crystallization completes, centrifugation, wash to PH=7-8.At 100 ℃, dry, sample is placed in to Muffle furnace, under air atmosphere, 550 ℃ of roastings are 8 hours, and 2 ℃/min of heating rate, finally obtains ZSM-5 molecular sieve.Then at 90 ℃ with 1M hydrochloric acid acid treatment ZSM-5 molecular sieve 2～3 times (liquid-solid ratio 10～20:1), then through washing, roasting, compressing tablet, obtain 20-40 object catalyst, catalyst numbering is designated as S6.
S1, S2, S3, S4, S5, six kinds of catalyst of S6 are 0.1～10h at mass space velocity
-1, reaction pressure is 0.1MPa, and reaction temperature is 470 ℃, and in methanol conversion and product, ethylene selectivity, Propylene Selectivity and P/E ratio temporal evolution curve are shown in respectively Fig. 5, Fig. 6, Fig. 7, Fig. 8.S5 and S6 catalysate distribute close with S1, therefore unlisted.
In the present invention, aluminium source at least can be selected from aluminum sulfate, aluminium hydroxide, aluminium oxide, sodium metaaluminate or aluminium isopropoxide, and silicon source at least can be selected from ethyl orthosilicate, silicic acid, Ludox or white carbon, and is not limited to above embodiment.
Claims (4)
1. a synthetic method for the preparing propylene transformed catalyst of high efficiency methanol, is characterized in that: take TPAOH as template, NaOH and ammonium fluoride are mineralizer; First by aluminium source, NaOH, ammonium fluoride, water and template wiring solution-forming, then add silicon source, mole proportioning of synthetic colloidal sol is n (F
-): n (Al
20
3): n (SiO
2): n (TPAOH): n (Na
2o): n (H
2o)=and (0-18): 1:150:15:7:100, after stirring, ageing 0.4-1.0 hour at room temperature, then at 160-180 ℃ of crystallization 18-26h; After crystallization is complete, after centrifugation, washing and drying, obtain the former powder of ZSM-5 molecular sieve.
2. method according to claim 1, is characterized in that: aluminium source is aluminum sulfate, aluminium hydroxide, aluminium oxide or aluminium isopropoxide.
3. method according to claim 1, is characterized in that: silicon source is ethyl orthosilicate, silicic acid, Ludox or white carbon.
4. according to the method described in claim 1 or 2 or 3, it is characterized in that: after stirring, at room temperature ageing 0.5 hour, then at 170 ℃ of crystallization 24h.
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| CN109772263A (en) * | 2019-03-20 | 2019-05-21 | 东北大学 | Utilize cation exchange modified zeolite adsorbent method, zeolite adsorbents and application |
| CN114160183A (en) * | 2021-12-20 | 2022-03-11 | 西北师范大学 | Preparation of flaky HZSM-5 molecular sieve catalyst and application of catalyst in preparation of aromatic hydrocarbon by hydrogenation of carbon dioxide |
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| CN102745717A (en) * | 2012-07-19 | 2012-10-24 | 大同煤矿集团有限责任公司 | Method for reducing pore diameter of small crystal grain ZSM-5 (zeolite socony mobil-5) molecular sieve |
| CN102962091A (en) * | 2012-11-23 | 2013-03-13 | 中国天辰工程有限公司 | Preparation method of ZSM-5 (zeolites synthesized by mobil-5) molecular sieve catalyst with small grain diameter |
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| CN102745717A (en) * | 2012-07-19 | 2012-10-24 | 大同煤矿集团有限责任公司 | Method for reducing pore diameter of small crystal grain ZSM-5 (zeolite socony mobil-5) molecular sieve |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109772263A (en) * | 2019-03-20 | 2019-05-21 | 东北大学 | Utilize cation exchange modified zeolite adsorbent method, zeolite adsorbents and application |
| CN114160183A (en) * | 2021-12-20 | 2022-03-11 | 西北师范大学 | Preparation of flaky HZSM-5 molecular sieve catalyst and application of catalyst in preparation of aromatic hydrocarbon by hydrogenation of carbon dioxide |
| CN114160183B (en) * | 2021-12-20 | 2024-02-23 | 西北师范大学 | Preparation of flaky HZSM-5 molecular sieve catalyst and application of catalyst in preparing aromatic hydrocarbon by carbon dioxide hydrogenation |
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