CN103071522B - A kind of catalyst and method of C4 C6 hydrocarbon mixture catalytic pyrolysis propylene enhancings and ethene - Google Patents
A kind of catalyst and method of C4 C6 hydrocarbon mixture catalytic pyrolysis propylene enhancings and ethene Download PDFInfo
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- CN103071522B CN103071522B CN201210596304.XA CN201210596304A CN103071522B CN 103071522 B CN103071522 B CN 103071522B CN 201210596304 A CN201210596304 A CN 201210596304A CN 103071522 B CN103071522 B CN 103071522B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a kind of C4 C6 hydrocarbon mixture catalytic pyrolysis propylene enhancings and the catalyst of ethene, its preparation method is：Raw material proportioning is using molar ratio computing as SiO2∶Al2O3: the TPAOH: the second template: H2O=10~80: 1: 10: 0~200: 1900；The sodium metaaluminate of respective amount is dissolved in TPAOH solution first, after being completely dissolved Deng it, the water and gas phase silica gel of respective amount are added, certain time is stirred, is then placed in the reactor of polytetrafluoroethyllining lining, aging 24 hours at 60 DEG C, then the second template is added in mixed liquor, stirs to it and be completely dissolved, homogeneous crystallization is filtered after 48 hours, washed at 150 DEG C, dried 24 hours at 110 DEG C, be finally calcined at 550 DEG C and obtain within 10 hours the corresponding molecular sieves of multi-stage porous ZSM 5.With catalytic activity is good, diene yield is high and the advantages of long lifespan.
Description
Technical field
It is a kind of by C4-C6 hydrocarbon mixture accessory substances the present invention relates to petrochemical industry and coal chemical industry production propylene/ethylene technique
Reprocessing, the method for catalytic pyrolysis propylene enhancing and ethene, more particularly to C4-C6 hydrocarbon mixture catalytic pyrolysis propylene enhancings and
The catalyst and method of ethene.
Background technology
Propylene and ethene are important industrial chemicals, are obtained at present mainly by steam cracking, and supply falls short of demand for yield.With stone
The reduction of oily resource, coal-based methanol alkene route (MTP/MTO) are rapidly developed, but also in the commerical test stage, together
When also promote catalytic pyrolysis naphtha and refinery C4+Resource propylene enhancing/ethene at home flourish.
The method that CN1233603C discloses C4-C6 preparing propylene/ethane from catalytic cracking, using in K, Mg, La or Ce
ZSM-5/ZSM-11 (30-1000) coexisting molecular sieve of modification a kind of be catalyst, in 500-650 DEG C of reaction temperature, anti-
Answer pressure 0.1-8atm, air speed 1-50 hours-1Under conditions of, highest yield propylene reaches 33wt%, and ethene reaches 20wt%, and raw material is
Simple 1- butylene.
CN101190417B discloses the catalyst of preparing ethylene propylene from catalytic pyrolysis, using ZSM-5/ mercerisings, ZSM-5/ β,
The coexisting molecular sieves such as ZSM-5/Y are catalyst, carry out catalytic pyrolysis to naphtha, highest yield propylene is close to 26wt%, ethene
About 29wt%.
The method that US2004/0014593A1 discloses the hydrocarbons such as hybrid catalyst Deep catalytic cracking naphtha,
Hybrid catalyst is prepared for using micropore, mesopore material and inorganic binder, formed as aSiO2·bM2O3·cMoO3(M=Al,
Ce or La), highest yield propylene about 30wt%, ethene about 30wt%.
From reported above as can be seen that either olefin feedstock or feed naphtha, catalyst have one it is common
Feature, i.e. catalyst are hierarchical porous structure, are mainly prepared by way of steam treatment or synthesis coexisting molecular sieve, but
The shortcomings of cost high or complex process be present, and use the multistage porous molecular sieve directly synthesized as catalytic cracking catalyst almost
Do not report.
The content of the invention
The present invention provides urging for a kind of C4-C6 hydrocarbon mixtures catalytic pyrolysis propylene enhancing and ethene in view of the shortcomings of the prior art
Agent and method.
The technical scheme used for：
A kind of catalyst of C4-C6 hydrocarbon mixtures catalytic pyrolysis propylene enhancing and ethene, the method for preparing catalyst are：It is former
Material proportioning is using molar ratio computing as SiO2∶Al2O3: the TPAOH: the second template: H2O=10~80: 1: 10: 0~200: 1900；It is first
First the sodium metaaluminate of respective amount is dissolved in TPAOH solution, after waiting it to be completely dissolved, adds the water and gas phase silica gel of respective amount,
Certain time is stirred, is then placed in the reactor of polytetrafluoroethyllining lining, aging 24 hours at 60 DEG C, then by the second template
Agent is added in mixed liquor, stirs to it and is completely dissolved, and homogeneous crystallization is filtered after 48 hours, washed at 150 DEG C, is done at 110 DEG C
Dry 24 hours, finally it is calcined 10 hours at 550 DEG C and obtains corresponding multi-stage porous ZSM-5 molecular sieve.
Described catalyst, second template are cetyl trimethylammonium bromide CTAB, double dodecyl brominations
One of ammonium DDAB, diallyl dimethyl ammoniumchloride PDDA and nano carbon black CB.
Described catalyst, in addition to catalyst promoter, catalyst promoter is Group IVB element ti, Zr, group vib element Cr,
One or more in Mo, W, VIII element of Fe, Co, Ni, lanthanide series and nonmetalloid P, B, with corresponding oxide
Mass Calculation, the content of catalyst promoter in the catalyst are 0.01-30wt%.
A kind of method of C4-C6 hydrocarbon mixtures catalytic pyrolysis propylene enhancing and ethene, C4-C6Hydrocarbon mixture is in claim 1 or 2
Under the catalyst action, in 500-700 DEG C of reaction temperature, normal pressure, gas volume air speed 1000-3000h-1Under conditions of increase production
Propylene and ethene.
Described method, it is adapted to preparing propylene from methanol (MTP), methanol-to-olefins (MTO) and refinery processes hydro carbons by-product C4-C6
The catalytic pyrolysis propylene enhancing and ethene of total hydrocarbon feed.
Described method, major catalyst MFI topological structure multistages porous molecular sieve are ZSM-5 multistage porous molecular sieves, the second hole
Footpath size is 0.5-30nm, content 70-100wt%.
Described method, reaction temperature are 550-600 DEG C, normal pressure, and gas volume air speed is 1300-2000h-1。
Reaction is carried out in fixed bed, 30 grams of loaded catalyst, is flowed out after beds are flowed through after raw material is preheated
The products such as the product of carbon one, propylene/ethylene, alkane and aromatic hydrocarbons, product is through gas-chromatography qualitative, quantitative.Reaction condition preferably reacts
550-650 DEG C of temperature, reaction pressure 0.01-0.2MPa, gas volume air speed 1300-1900h-1.The more traditional ZSM-5 of diene yield
It is significantly increased, and catalyst life is obviously prolonged.
Domestic C4+Hydrocarbon aboundresources, and as preparing propylene from methanol (MTP), methanol-to-olefins (MTO) commercial plant are built
Into operation, these resources are more abundant, C4-C6Hydrocarbon production capacity further expands, therefore passes through catalytic pyrolysis system third using these resources
Alkene/ethene will improve the added value of product, increase economic benefit.The present invention is using the ZSM-5 (MFI topological structures) directly synthesized
Multistage porous molecular sieve is that main catalyst is modified and is molded, and simplifies the production technology of catalyst, while have catalytic activity
The advantages of good, diene yield height and long lifespan.
Brief description of the drawings
Fig. 1 is that the electromicroscopic photograph of C50-ZSM-5 (50) molecular sieve (is swept using the 1530VP type high-resolution of German LEO companies
Retouch Electronic Speculum), wherein A is clearly catalyst individual particle photo, and B is then the enlarged photograph of particle in A.
Fig. 2 is the lifetime data of the lower four kinds of different molecular sieve catalysts of the same terms.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Table 1 show prepared with MTP industrial by-products C4-C6The group of raw material similar in the constituent content of total hydrocarbon feed
Divide actual content, the raw material tested as catalytic pyrolysis propylene enhancing and ethene.
The experiment C of table 14-C6The component (wt%) of total hydrocarbon feed
| Butylene | 30.75 |
| Butane | 26.37 |
| C5 alkane | 24.98 |
| C6 alkane | 17.90 |
Embodiment 1-7
Synthesize multi-stage porous ZSM-5 molecular sieve：The TPAOH solution that 2 grams of sodium metaaluminates are dissolved in 200mL20-25% is weighed first
In, after waiting it to be completely dissolved, 670 grams of water and 73 grams of gas phase silica gel are added, stirs 2 hours, is then placed in polytetrafluoroethyllining lining
Reactor in, aging 24h at 60 DEG C, then by the second template (including cetyl trimethylammonium bromide CTAB, double 12
Alkyl bromination ammonium DDAB, diallyl dimethyl ammoniumchloride PDDA and nano carbon black CB etc.) it is added in mixed liquor, stirring is extremely
It is completely dissolved, and filters, washs after homogeneous crystallization 48h at 150 DEG C, 24h is dried at 110 DEG C, is finally calcined 10h at 550 DEG C
Corresponding multi-stage porous ZSM-5 (50) molecular sieve is obtained, the second template is not added with and then obtains traditional ZSM-5 (50) molecular sieve, is changed
Silicon source addition then obtains the multi-stage porous ZSM-5 molecular sieve of different silica alumina ratios.
Multi-stage porous ZSM-5 is labeled as Xy-ZSM-5 (silica alumina ratio), and X is the English initial of the second template：(C-CTAB,
D-DDAB, P-PDDA, CB- nanometer carbon black), y represents the SiO that the second template dosage added adds relative to Zeolite synthesis2
Molar percentage, traditional ZSM-5 is labeled as ZSM-5 (silica alumina ratio).
The 50 grams of ZSM-5 prepared as stated above catalyst are weighed, tabletting is granulated, and size is 20-40 mesh, takes 30 grams of loadings
Evaluated in special catalytic pyrolysis fixed bed reactors, beds are flowed through after raw material is preheated, carbon one is flowed out after reaction
The products such as product, propylene/ethylene, alkane and aromatic hydrocarbons, product is through gas-chromatography qualitative, quantitative.600 DEG C of reaction temperature, normal pressure, body
Product air speed 1800h-1, obtained partial data is shown in Table 2.The surface nature and pore size distribution data of partial catalyst are shown in Table 3, wherein
C50-ZSM-5 (50) pattern is shown in Fig. 1.A is the photo of catalyst granules in Fig. 1, and overall is in spherical particle, and B is catalyst particles
Photo after grain amplification, display catalyst granules are made up of many 400nm or so microballoon, and each microballoon has nanoscale twins
Architectural feature.After adding the second template it can be seen from photo and data, ZSM-5 has obvious meso-hole structure, so as to have
Beneficial to mass transfer, the generation of secondary response is avoided, so as to improve the yield of product especially diene, is found simultaneously, it is different
Second template and silica alumina ratio have a great influence to the conversion ratio of catalyst, and this is due to that there occurs change to cause for the Acidity on surface
's.
2 traditional ZSM-5 of table and multi-stage porous ZSM-5 catalytic pyrolysis performance
The surface nature and pore size distribution data of several multi-stage porous ZSM-5 samples of table 3
SBET：Specific surface area, Sint：Inner ratio surface area, Sext：External surface area, Vmicro：Micropore volume, Vmeso：Mesoporous hole
Hold, D2：The aperture of most probable second, D1：ZSM-5 micropore most probable pore sizes.
Embodiment 8-12
(microcosmic salt is ammonium dihydrogen phosphate to the salting liquid of preparation respective concentration, and other is corresponding nitrate, and content is with corresponding
Oxide is calculated).The multi-stage porous ZSM-5 molecular sieve that 50 restraints are got ready is weighed, incipient impregnation, is then roasted at 550 DEG C
It is standby to burn 6h.Tabletting granulation is carried out before evaluation, evaluation method is the same, the results are shown in Table 4.Catalyst surface is modified, due to regulation
Its Surface acidity and acid distribution so that diene yield increases substantially.
The catalytic pyrolysis performance of the modified catalyst of table 4
| Catalyst | Conversion ratio | Ethene is received | Propylene is received | Diene is received |
| / wt% | Rate/wt% | Rate/wt% | Rate/wt% | ||
| Embodiment 8 | 2.5wt%P/C50-ZSM-5 (38) | 81 | 27.2 | 30.4 | 57.6 |
| Embodiment 9 | 5wt%Fe/C50-ZSM-5 (50) | 83 | 27.8 | 28.1 | 55.9 |
| Embodiment 10 | 8wt%La/C50-ZSM-5 (50) | 86 | 24.0 | 27.6 | 51.6 |
| Embodiment 11 | 10wt%Ce/C50-ZSM-5 (50) | 79 | 25.3 | 19.9 | 45.2 |
| Embodiment 12 | 16wt%Zr/C50-ZSM-5 (50) | 74 | 26.3 | 23.6 | 49.9 |
Embodiment 13-17
With C50-ZSM-5 (50) for catalyst, the change to reaction temperature and air speed is investigated, embodiment 13-17
Partial data is provided to refer to.Temperature has a great influence to pyrolysis reactivity, next to that the influence of air speed.
Catalytic pyrolysis performance under the conditions of the differential responses of table 5
| Temperature/DEG C | Volume space velocity, h-1 | Conversion ratio, wt% | Yield of ethene, wt% | Propene yield, wt% | Diene yield, wt% | |
| Embodiment 13 | 450 | 2100 | 41 | 7.1 | 10.6 | 17.7 |
| Embodiment 14 | 500 | 2100 | 56 | 12.3 | 14.9 | 27.2 |
| Embodiment 15 | 600 | 2100 | 79 | 25.1 | 18.8 | 43.9 |
| Embodiment 16 | 650 | 2100 | 77 | 28.4 | 16.9 | 45.3 |
| Embodiment 17 | 500 | 1600 | 59 | 15.9 | 17.5 | 33.4 |
Embodiment 18-21
It is that catalyst has carried out the longevity with ZSM-5, C50-ZSM-5 (50), C100-ZSM-5 (50) and C150-ZSM-5 (50)
Life is investigated, 600 DEG C of reaction temperature, normal pressure, volume space velocity 1800h-1, as a result see Fig. 2.It can significantly find out from result, add
The catalytic pyrolysis performance of catalyst after second template significantly improves, and diene yield greatly improves, and the life-span also it is big greatly
Long, wherein C50-ZSM-5 (50) still has higher diene yield after running 100 hours, it is believed that can be obtained by keeping punching
To performance and life-span more preferably catalytic cracking catalyst.
It should be appreciated that for those of ordinary skills, can according to the above description be improved or converted,
And all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (5)
- A kind of 1. catalyst of C4-C6 hydrocarbon mixtures catalytic pyrolysis propylene enhancing and ethene, it is characterised in that the catalyst preparation Method is：Raw material proportioning is using molar ratio computing as SiO2∶Al2O3: the TPAOH: the second template: H2O=80: 1: 10: 200: 1900； The sodium metaaluminate of respective amount is dissolved in TPAOH solution first, after waiting it to be completely dissolved, adds the water and gas-phase silicon of respective amount Glue, certain time is stirred, is then placed in the reactor of polytetrafluoroethyllining lining, aging 24 hours at 60 DEG C, then by second Template is added in mixed liquor, stirs to it and is completely dissolved, and homogeneous crystallization is filtered after 48 hours, washed, 110 DEG C at 150 DEG C Lower drying 24 hours, finally it is calcined at 550 DEG C and obtains within 10 hours corresponding multi-stage porous ZSM-5 molecular sieve, second template Agent is cetyl trimethylammonium bromide CTAB, double dodecyl bromination ammonium DDAB, diallyl dimethyl ammoniumchloride PDDA And one of nano carbon black CB.
- 2. catalyst according to claim 1, it is characterised in that also including catalyst promoter, catalyst promoter is Group IVB One kind in element ti, Zr, group vib element Cr, Mo, W, VIII element of Fe, Co, Ni, lanthanide series and nonmetalloid P, B Or it is several, calculated with corresponding oxide mass, the content of catalyst promoter in the catalyst is 0.01-30wt%.
- 3. a kind of method of C4-C6 hydrocarbon mixtures catalytic pyrolysis propylene enhancing and ethene, it is characterised in that C4-C6 hydrocarbon mixtures are being weighed Profit is required under 1 or 2 catalyst actions, in 500-700 DEG C of reaction temperature, normal pressure, gas volume air speed 1000-3000h-1's Under the conditions of propylene enhancing and ethene.
- 4. according to the method for claim 3, it is characterised in that be adapted to preparing propylene from methanol MTP, methanol-to-olefins MTO techniques The catalytic pyrolysis propylene enhancing and ethene of hydro carbons accessory substance C4-C6 hydrocarbon mixtures.
- 5. according to the method for claim 4, it is characterised in that reaction temperature is 550-600 DEG C, and gas volume air speed is 1300-2000h-1。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104192859B (en) * | 2014-08-21 | 2018-02-06 | 陕西延长石油(集团)有限责任公司研究院 | A kind of Fast back-projection algorithm method of the molecular sieve of fine grain ZSM-5 5 |
| CN104437605B (en) * | 2014-11-07 | 2017-05-17 | 中国石油天然气集团公司 | W-ZSM-5 molecular-sieve-based catalyst as well as preparation method and application of W-ZSM-5 molecular-sieve-based catalyst |
| CN104437602B (en) * | 2014-12-16 | 2016-10-26 | 湖南科技大学 | A kind of multistage mesoporous ZSM-5 catalyst and methods for making and using same thereof |
| CN104888842B (en) * | 2015-05-11 | 2017-12-05 | 中国石油天然气股份有限公司 | A kind of catalytic cracking catalyst and preparation method and application |
| CN108273543B (en) * | 2018-01-23 | 2020-04-24 | 西南化工研究设计院有限公司 | Preparation method of catalyst for preparing nonene by oligomerization of propylene |
| CN109368657B (en) * | 2018-08-22 | 2021-09-10 | 中国矿业大学 | Preparation method of framework metal high-dispersion type hierarchical pore H-ZSM-5 molecular sieve |
| CN115990508A (en) * | 2021-10-19 | 2023-04-21 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve catalyst and preparation method and application thereof |
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