CN101190864B - Catalyst for preparing ethene and propene by catalysis cracking - Google Patents

Catalyst for preparing ethene and propene by catalysis cracking Download PDF

Info

Publication number
CN101190864B
CN101190864B CN200610118532A CN200610118532A CN101190864B CN 101190864 B CN101190864 B CN 101190864B CN 200610118532 A CN200610118532 A CN 200610118532A CN 200610118532 A CN200610118532 A CN 200610118532A CN 101190864 B CN101190864 B CN 101190864B
Authority
CN
China
Prior art keywords
zsm
molecular sieve
propylene
zeolite
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN200610118532A
Other languages
Chinese (zh)
Other versions
CN101190864A (en
Inventor
陈亮
谢在库
马广伟
胡永君
姚晖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN200610118532A priority Critical patent/CN101190864B/en
Publication of CN101190864A publication Critical patent/CN101190864A/en
Application granted granted Critical
Publication of CN101190864B publication Critical patent/CN101190864B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • 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

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a catalyst used for producing ethylene and propylene by catalytic cracking, and mainly solves the problem that temperature required by the catalyst is high while selectivity to the ethylene and the propylene is low in the existing catalytic cracking reaction. The invention adopts the technical proposal of sieving ZSM-5/beta zeolite accrete molecular as catalyst, and SiO2/Al2O3 mole ratio of which is more than 100 to 500, thereby properly solving the problem. The invention is used for industrial production of the ethylene and the propylene by the catalytic cracking.

Description

The catalyzer that is used for preparing ethylene propylene from catalytic pyrolysis
Technical field
The present invention relates to a kind of catalyzer that is used for preparing ethylene propylene from catalytic pyrolysis.
Background technology
Along with the development of society, the market requirement of China's ethylene, propylene sharply increases, and the import volume of ethylene, propylene and derived product thereof increases year by year, and the home products share of market is less than half.Whole world ethene is raw material with petroleum naphtha (or ethane) mainly at present, adopts steam heat cracking technique (under the temperature about 800 ℃) production, and its output surpasses 90% of ultimate production.Catalytic pyrolysis is compared with the steam heat cracking, and this process reaction temperature is than low 50～200 ℃ approximately of standard scission reactions, and therefore than common steam cracking less energy consumption, cracking furnace pipe inwall coking rate will reduce, thereby but prolong operation cycle increases the boiler tube life-span; Carbon emission also can reduce, and can adjust the product mix flexibly, can increase the total recovery of ethene and propylene, and production cost of ethylene reduces significantly.
U.S. Pat P6211104 and domestic patent CN1504540A adopt a kind of 10～70 weight % clays that contain, 5～85 weight % inorganic oxides, 1～50 weight % molecular sieve is formed catalyzer, to the various raw materials of traditional steam heat cracked, the activity, the especially ethene that well are converted into light olefin have been demonstrated.With molecular sieve be by 0～25 weight %Y zeolite of high silica alumina ratio or have the ZSM molecular sieve of MFI structure, form by P, Al, Mg or Ca dipping, but the ethylene, propylene selectivity of catalyzer and yield are not high.
Japan Asahi Chemical Industry (patent CN1274342A) has announced that a kind of high silica alumina ratio, the aperture molecular sieve between 0.5～0.65 is a catalyzer, be the feedstock production ethylene, propylene with the light hydrocarbons that contains alkene, but the ethylene, propylene yield is lower.
Exxon Mobil (00816642.0) announces that a kind of aperture of a kind of usefulness contains the hydrocarbon raw material of petroleum naphtha less than the zeolite treatment of 0.7 nanometer, produces ethylene, propylene between 550-600 ℃, and conversion of raw material is lower.
Mobil Oil Corp. (CN1413244A) has announced that a kind of mesopore phosphate material with modification is that catalyzer and primary catalytic pyrolysis material combine, the hydrocarbon raw material of catalytic pyrolysis sulfur-bearing prepares micromolecular hydrocarbon mixture, but the use temperature of catalyzer, conversion of raw material and product yield are all lower.
Summary of the invention
Technical problem to be solved by this invention is that the catalyst activity that uses in the existing catalytic cracking reaction is lower, and the problem that the yield of ethylene, propylene is lower, use temperature is high provides a kind of new catalyzer that is used for preparing ethylene propylene from catalytic pyrolysis.This catalyzer has catalytic activity height, ethylene, propylene yield height, advantage that use temperature is low.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyzer that is used for preparing ethylene propylene from catalytic pyrolysis, catalyzer are SiO 2/ Al 2O 3Mol ratio is the coexisting molecular sieve of＞100～500 ZSM-5/ β zeolite; Wherein, in the ZSM-5/ beta zeolite coexisting molecular sieve by weight percentage the content of ZSM-5 molecular sieve be 20～99.5%.
In the technique scheme, the SiO of ZSM-5/ beta zeolite coexisting molecular sieve 2/ Al 2O 3Mol ratio is that preferable range is＞100～200, and more preferably scope is＞100～150.In the ZSM-5/ beta zeolite coexisting molecular sieve by weight percentage the content preferable range of ZSM-5 molecular sieve be 60～99%.
At least a as in silicate, metasilicate sodium or the silicon sol of the preparation coexisting molecular sieve silicon source of using, the aluminium source is at least a in aluminium salt or the aluminate, template is at least a in quadrol, ethamine, n-Butyl Amine 99, triethylamine, 4-propyl bromide, TPAOH, tetraethyl ammonium hydroxide or the tetraethylammonium bromide, and the pH value of regulating colloidal sol with diluted acid is 10～13.
The synthetic method of coexisting molecular sieve is, get the silicon source and the aluminium source of aequum by material proportion, make solution with dissolved in distilled water respectively, then two kinds of solution are mixed, the powerful stirring adds the template of aequum then, stirs after 30 minutes with rare acid for adjusting pH value in 10～13 scopes, add the β zeolite as crystal seed, supply distilled water again.Colloidal sol is put into autoclave, control required temperature crystallization after 10～100 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours, can obtain ZSM-5/ beta zeolite coexisting molecular sieve.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, roasting then makes hydrogen type molecular sieve after repeating twice, then compressing tablet, break into pieces, sieve, get 20～40 purpose particles and put into fixed-bed reactor and check and rate.
Catalyzer involved in the present invention, owing to adopted the coexisting molecular sieve that contains ZSM-5 molecular sieve and β zeolite simultaneously, this molecular sieve is owing to contain acid strong β zeolite, so its acid amount is bigger, acidity is stronger, is suitable for the higher alkane cracking of cracking energy.Because coexisting molecular sieve contains multistage pore canal, can handle the different mixture material of molecular diameter.Because the degree that comes to the surface, acidity, duct and the specific surface of coexisting molecular sieve and having than big difference of two kinds of molecular sieve mechanically mixing so catalytic performance is preferably arranged, are used for the naphtha catalytic pyrolysis preparing ethylene propylene reaction, with C 4～C 10The petroleum naphtha of hydrocarbon is raw material (the raw material physical index sees Table 1), is 12 millimeters down examination of fixed-bed reactor normal pressure with diameter, and range of reaction temperature is 600～700 ℃, and reaction pressure is 0.001MPa～0.5MPa, and mass space velocity is 0.25～2 hour -1, water/stock oil weight ratio is that ethene and propylene total recovery can reach 51.94% and obtain better technical effect under 1～4: 1 the condition.
Description of drawings
Fig. 1 is the XRD figure spectrum of ZSM-5/ beta zeolite coexisting molecular sieve
Curve 1 is the XRD diffracting spectrum of FH-1 sample among Fig. 1, and curve 2 is the XRD diffracting spectrum of FH-12 sample.
Table 1 feed naphtha index
Project Data
Density (20 ℃) kilogram/rice 3 704.6
Boiling range is boiling range ℃ just 40
Whole boiling range ℃ 160
Saturated vapor pressure (20 ℃) kPa 50.2
Alkane % (weight %) 65.18
Normal paraffin % (weight %) in the alkane ＞32.5
Naphthenic hydrocarbon % (weight %) 28.44
Alkene % (weight %) 0.17
Project Data
Aromatic hydrocarbons % (weight %) 6.21
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Get 284 gram Starsos, become solution A with 300 gram dissolved in distilled water, get 5.56 gram Tai-Ace S 150, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 12.2 gram quadrols and 29.4 gram tetraethyl ammonium hydroxides (mixed templates is designated as M) then, after stirring for some time, regulate the pH value 11 with dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: M: H 2O=1: 0.0167: 0.4: 40, add 2.8 gram β zeolite seed crystals, mixing solutions is put into autoclave, 160 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/ beta zeolite coexisting molecular sieve, the XRD diffracting spectrum is shown in curve among Fig. 11, with the XRD diffraction quantitatively as can be known in the coexisting molecular sieve ZSM-5 weight percentage be 94.6%, the β zeolite is 5.4%.It with concentration 5% ammonium nitrate solution, twice of 70 ℃ of exchange, 550 ℃ of roastings are 3 hours then, make Hydrogen ZSM-5/ beta zeolite coexisting molecular sieve after repeating twice, then compressing tablet, break into pieces, sieve, getting 20～40 purpose particles and put into fixed-bed reactor, is that 650 ℃, reaction pressure are that 0.02MPa, weight space velocity are 0.5 hour in temperature of reaction -1, water/stock oil weight ratio is to check and rate under 3: 1 the condition, the results are shown in Table 4.
[embodiment 2～4]
According to the method for embodiment 1, the pH of control solution is respectively 10.5,11.5 and 12, synthesizes ZSM-5/ beta zeolite coexisting molecular sieve respectively, is designated as FH-2 respectively, FH-3, FH-4.The ratio of ZSM-5 and β zeolite sees Table 3.Method examination according to embodiment 1 the results are shown in Table 4.
[embodiment 5～11]
According to the method for embodiment 1, the different mole proportionings of control solution, the two constant rate in the mixed templates, synthetic ZSM-5/ beta zeolite coexisting molecular sieve sees Table 2 respectively, and the ratio of ZSM-5 and β zeolite sees Table 3.Method examination according to embodiment 1 the results are shown in Table 4.
Table 2
Embodiment Solution mole proportioning Sample number into spectrum
Embodiment
5 Si∶Al∶M∶H 2O＝1∶0.005∶0.4∶40 FH-5
Embodiment 6 Si∶Al∶M∶H 2O＝1∶0.01∶0.4∶40 FH-6
Embodiment 7 Si∶Al∶M∶H 2O＝1∶0.0111∶0.4∶40 FH-7
Embodiment 8 Si∶Al∶M∶H 2O＝1∶0.0133∶0.4∶40 FH-8
Embodiment 9 Si∶Al∶M∶H 2O＝1∶0.0182∶0.4∶40 FH-9
Embodiment Solution mole proportioning Sample number into spectrum
Embodiment
10 Si∶Al∶M∶H 2O＝1∶0.0167∶0.2∶30 FH-10
Embodiment 11 Si∶Al∶M∶H 2O＝1∶0.0167∶0.5∶60 FH-11
[embodiment 12～15]
Method according to embodiment 1, the mole proportioning of control solution is identical, adding β zeolite seed crystal amount respectively is 5.68 grams, 11.3 grams, 22.6 grams and 28.4 grams, synthetic ZSM-5/ beta zeolite coexisting molecular sieve, be designated as FH-12, FH-13, FH-14, FH-15 respectively, the XRD diffracting spectrum of FH-12 is shown in curve among Fig. 11, and the ratio of ZSM-5 and β zeolite sees Table 3.Method examination according to embodiment 1 the results are shown in Table 4.
[embodiment 16～19]
According to the method for embodiment 1, the mole proportioning of control solution is identical, and mixed templates mol ratio 1: 1 or 1: 1: 1 (selecting three kinds of template for use) are used n-Butyl Amine 99 and tetraethylammonium bromide successively respectively; Ethamine, quadrol and tetraethyl ammonium hydroxide; 4-propyl bromide and tetraethyl ammonium hydroxide; TPAOH, n-Butyl Amine 99 and tetraethyl ammonium hydroxide; Synthetic ZSM-5/ beta zeolite coexisting molecular sieve is designated as FH-16, FH-17, FH-18, FH-19 respectively, and the ratio of ZSM-5 and β zeolite sees Table 3.Method examination according to embodiment 1 the results are shown in Table 4.
[embodiment 20～21]
According to the method for embodiment 1, the mole proportioning of control solution is identical, and crystallization temperature is set to 150 ℃ and 170 ℃ respectively, has synthesized ZSM-5/ beta zeolite coexisting molecular sieve respectively, is designated as FH-20, FH-21, and the ratio of ZSM-5 and β zeolite sees Table 3.Method examination according to embodiment 1 the results are shown in Table 4.
Table 3
Sample number into spectrum Contain ZSM-5 ratio (weight %) Contain β zeolite ratio (weight %)
FH-1 94.6 5.4
FH-2 98.7 1.3
FH-3 92.3 7.7
FH-4 86.4 13.6
FH-5 99.3 0.7
FH-6 99.0 1.0
FH-7 90.1 9.9
FH-8 95.6 4.4
FH-9 98.2 1.8
Sample number into spectrum Contain ZSM-5 ratio (weight %) Contain β zeolite ratio (weight %)
FH-10 93.4 6.6
FH-11 95.3 4.7
FH-12 89.8 10.2
FH-13 75.6 24.4
FH-14 63.7 36.3
FH-15 50.5 49.5
FH-16 95.2 4.8
FH-17 96.1 3.9
FH-18 94.9 5.1
FH-19 96.4 3.6
FH-20 93.7 6.3
FH-21 95.1 4.9
Table 4
Sample number into spectrum Yield of ethene (weight %) Propene yield (weight %) Total recovery (weight %)
FH-1 23.47 26.25 49.72
FH-4 21.25 22.53 43.78
FH-6 25.11 26.83 51.94
FH-8 24.54 25.37 49.91
FH-12 22.06 24.32 46.38
FH-14 20.52 21.12 41.64
FH-18 24.57 25.73 50.30
FH-20 23.27 25.16 48.43
[comparative example 1]
With the synthesis mode of embodiment 1, do not add the β zeolite seed crystal, template is only used quadrol, synthetic pure ZSM-5 molecular sieve, making the catalyzer postscript is C-1, checks and rates according to the mode of embodiment 1, the results are shown in Table 5.
[comparative example 2]
In the mode of embodiment 1, template is only used tetraethyl ammonium hydroxide, adds 5.68 gram β zeolite seed crystals, synthetic pure β zeolite, and making the catalyzer postscript is C-2, checks and rates according to the mode of embodiment 1, the results are shown in Table 5.
[comparative example 3]
Prepare the two mechanical mixture in the ratio of ZSM-5 among the embodiment 12 and β zeolite, make catalyzer, be designated as C-3, check and rate, the results are shown in Table 5 by the mode of embodiment 1.
Table 5
Sample Yield of ethene (weight %) Propene yield (weight %) Total recovery (weight %)
C-1 21.84 22.62 44.46
C-2 19.12 21.32 40.44
C-3 22.47 23.44 45.91

Claims (4)

1. a catalyzer that is used for preparing ethylene propylene from catalytic pyrolysis is characterized in that catalyzer is SiO 2/ Al 2O 3Mol ratio is greater than 100 and smaller or equal to 500 ZSM-5/ beta zeolite coexisting molecular sieve; Wherein, in the ZSM-5/ beta zeolite coexisting molecular sieve by weight percentage the content of ZSM-5 molecular sieve be 20～99.5%.
2. according to the described catalyzer that is used for preparing ethylene propylene from catalytic pyrolysis of claim 1, it is characterized in that the SiO of ZSM-5/ beta zeolite coexisting molecular sieve 2/ Al 2O 3Mol ratio is greater than 100 and smaller or equal to 200.
3. according to the described catalyzer that is used for preparing ethylene propylene from catalytic pyrolysis of claim 2, it is characterized in that the SiO of ZSM-5/ beta zeolite coexisting molecular sieve 2/ Al 2O 3Mol ratio is greater than 100 and smaller or equal to 150.
4. according to the described catalyzer that is used for preparing ethylene propylene from catalytic pyrolysis of claim 1, it is characterized in that in the ZSM-5/ beta zeolite coexisting molecular sieve that the content of ZSM-5 molecular sieve is 60～99% by weight percentage.
CN200610118532A 2006-11-21 2006-11-21 Catalyst for preparing ethene and propene by catalysis cracking Active CN101190864B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200610118532A CN101190864B (en) 2006-11-21 2006-11-21 Catalyst for preparing ethene and propene by catalysis cracking

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200610118532A CN101190864B (en) 2006-11-21 2006-11-21 Catalyst for preparing ethene and propene by catalysis cracking

Publications (2)

Publication Number Publication Date
CN101190864A CN101190864A (en) 2008-06-04
CN101190864B true CN101190864B (en) 2010-05-12

Family

ID=39486084

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200610118532A Active CN101190864B (en) 2006-11-21 2006-11-21 Catalyst for preparing ethene and propene by catalysis cracking

Country Status (1)

Country Link
CN (1) CN101190864B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9227181B2 (en) 2011-09-13 2016-01-05 Basf Corporation Catalyst to increase propylene yields from a fluid catalytic cracking unit
EP3539651A1 (en) 2018-03-14 2019-09-18 Saudi Arabian Oil Company Method of heavy reformate conversion into btx over metal-impregnated zsm-5+layered mordenite zeolite composite catalyst; said composite catalyst
EP3539649B1 (en) 2018-03-14 2020-11-18 Saudi Arabian Oil Company Methods of producing composite zeolite catalysts for heavy reformate conversion into xylenes
EP3539652A1 (en) 2018-03-14 2019-09-18 Saudi Arabian Oil Company Method of heavy reformate conversion into btx over metal-impregnated zsm-5+mesoporous mordenite zeolite composite catalyst
EP3834931A1 (en) * 2018-03-14 2021-06-16 Saudi Arabian Oil Company Composite zeolite catalysts for heavy reformate conversion into xylenes
CN113830778B (en) * 2020-06-24 2023-06-09 中国石油化工股份有限公司 ZSM-5/beta core-shell molecular sieve and synthesis method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1611470A (en) * 2003-10-27 2005-05-04 中国石油化工股份有限公司 Method for producing propene
CN1647856A (en) * 2004-01-19 2005-08-03 中国石油化工股份有限公司 Method for preparing ZSM-5 and beta zeolite mixed crystal material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1611470A (en) * 2003-10-27 2005-05-04 中国石油化工股份有限公司 Method for producing propene
CN1647856A (en) * 2004-01-19 2005-08-03 中国石油化工股份有限公司 Method for preparing ZSM-5 and beta zeolite mixed crystal material

Also Published As

Publication number Publication date
CN101190864A (en) 2008-06-04

Similar Documents

Publication Publication Date Title
CN101191069B (en) Method for preparing ethene and propene by naphtha catalysis cracking
CN101279287B (en) Catalyst for producing olefin hydrocarbon by catalytic pyrolysis
CN101491772B (en) Catalyst for naphtha catalytic cracking
CN101190864B (en) Catalyst for preparing ethene and propene by catalysis cracking
CN101348407A (en) Method for preparing ethylene and propylene by catalytic pyrolysis
CN102548937A (en) Process for catalytic cracking of hydrocarbons using uzm-35
CN100554229C (en) The method of naphtha catalytic pyrolysis preparing ethylene propylene
CN101347746B (en) Catalyst for producing olefin hydrocarbon by catalytic pyrolysis of naphtha
CN101279284B (en) Catalyst for preparing ethylene propylene from catalytic pyrolysis
CN101428233B (en) Catalyst for catalytic pyrolysis
CN100475337C (en) Catalyst of naphtha catalytic pyrolysis preparing ethylene and propylene
CN101279880B (en) Method for preparing ethylene propylene by catalytic pyrolysis of light oil
CN101514009B (en) Mordenite/beta zeolite/Y zeolite coexisting material and method for synthesizing same
CN101348408B (en) Method for preparing ethylene and propylene by catalytic pyrolysis of benzin naphtha
CN101514004B (en) Coexisting molecular sieve and synthesis method thereof
CN100531910C (en) Naphtha catalytic pyrolysis catalyst for preparing ethylene propylene
CN101514007B (en) Beta zeolite/Y zeolite coexisting molecular sieve and method for synthesizing same
CN101190417B (en) Catalyst for preparing ethylene and propylene by catalytic cracking method
CN101514010A (en) Mordenite/beta zeolite/analcime porous coexisting material and method for synthesizing same
CN100586858C (en) Porous intergrowth material and synthetic method thereof
CN101347745B (en) Catalyst for producing ethylene and propylene by catalytic pyrolysis of naphtha
CN101279285B (en) Naphtha catalytic pyrolysis catalyst for preparing ethylene propylene
CN101555187B (en) Method for preparing ethylene propylene through white oil catalytic cracking
CN101514008A (en) Mordenite/Y zeolite coexisting molecular sieve and method for synthesizing same
CN101306972B (en) Process for preparing ethylene and propylene by catalytic scission reaction

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant