CN100554229C - The method of naphtha catalytic pyrolysis preparing ethylene propylene - Google Patents
The method of naphtha catalytic pyrolysis preparing ethylene propylene Download PDFInfo
- Publication number
- CN100554229C CN100554229C CNB2006100279104A CN200610027910A CN100554229C CN 100554229 C CN100554229 C CN 100554229C CN B2006100279104 A CNB2006100279104 A CN B2006100279104A CN 200610027910 A CN200610027910 A CN 200610027910A CN 100554229 C CN100554229 C CN 100554229C
- Authority
- CN
- China
- Prior art keywords
- catalytic pyrolysis
- zsm
- propylene
- ethylene propylene
- preparing ethylene
- 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
Links
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 present invention relates to a kind of method of naphtha catalytic pyrolysis preparing ethylene propylene, mainly catalyst activity is low in the existing preparing ethylene propylene from catalytic pyrolysis technology of solution, the ethylene, propylene selectivity is low, the problem that temperature of reaction is high.The present invention is a catalyzer by adopting a kind of ZSM-5/ mordenite composite molecular sieve, with C
4～C
10Be raw material, temperature of reaction is 600～700 ℃, and reaction velocity is 0.1～2 hour
-1, water/petroleum naphtha weight ratio is that the technical scheme that reaction generates ethylene, propylene under 1～4: 1 the condition has solved this problem preferably, can be used in the industrial production of ethylene, propylene.
Description
Technical field
The present invention relates to a kind of method of naphtha catalytic pyrolysis preparing ethylene propylene.
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.
Japan Asahi Chemical Industry (patent CN1274342A) has announced that a kind of high silica alumina ratio, the aperture molecular sieve between 0.5～0.65nm 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 Corporation's (Chinese patent application 00816642.0) announces and a kind ofly to contain the hydrocarbon raw material of petroleum naphtha with the aperture less than the zeolite treatment of 0.7 nanometer that produce ethylene, propylene between 550～600 ℃, conversion of raw material is lower.
Mobil Oil Corp. (CN1413244A) has announced that a kind of mesopore phosphate material with modification is a catalyzer, combine with primary catalytic pyrolysis material (Y zeolite), the hydrocarbon raw material of catalytic pyrolysis sulfur-bearing prepares micromolecular hydrocarbon mixture, and the use temperature of its catalyzer and conversion of raw material are all lower.
Summary of the invention
Technical problem to be solved by this invention is the catalyzer use temperature height that exists in the prior art or the selectivity and the low problem of transformation efficiency of ethylene, propylene, and a kind of method of new naphtha catalytic pyrolysis preparing ethylene propylene is provided.This method has the catalyst activity height, and it is good to have the ethylene, propylene selectivity simultaneously, the advantage that temperature of reaction is low.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of naphtha catalytic pyrolysis preparing ethylene propylene, and with C
4～C
10Being raw material, is 600～700 ℃ in temperature of reaction, and reaction velocity is 0.1～2 hour
-1, water/petroleum naphtha weight ratio is that raw material contacts with catalyzer by beds under 1～4: 1 the condition, and reaction generates ethylene, propylene, and wherein used catalyzer is the composite molecular screen of ZSM-5 and mordenite, and its synthetic method is:
With metasilicate or silicon sol is the silicon source, the aluminium source is at least a in aluminium salt or the aluminate, with the quadrol is template, above-mentioned raw materials is made solution by required proportioning, regulator solution pH value is between 9～13, got the ZSM-5/ mordenite composite molecular sieve in 10～100 hours 150～220 ℃ of following crystallization, wherein the mole proportioning of solution is:
Si: Al: template: H
2O=1: 0.1: 0.4: 40.
In the technique scheme, the weight percentage preferable range of ZSM-5 is 20～99.5% in the composite molecular screen, and more preferably scope 60～99%; The SiO of used composite molecular screen
2/ Al
2O
3The mol ratio preferable range is 12～100, and more preferably scope is 14～40; The reaction velocity preferable range is 0.15～1 hour
-1, water/petroleum naphtha weight ratio preferable range is 1.5～3: 1.
The raw material that the preparation composite molecular screen uses is chemical pure, and the silicon source is at least a in metasilicate or the silicon sol, and the aluminium source is at least a in aluminium salt or the aluminate, and template is at least a in quadrol or the ethamine, the pH value of regulating colloidal sol with diluted acid.
The synthetic method of composite molecular screen is by silicon source and the aluminium source that material proportion is got aequum, to melt with distilled water respectively and make solution, then two kinds of solution are mixed, the powerful stirring adds the template of aequum then, stirs with rare acid for adjusting pH value in 9～13 scopes.Colloidal sol is put into autoclave, and the temperature crystallization of controlling 150～220 ℃ was taken out washing, oven dry, roasting after 10～100 hours, can obtain the composite molecular screen of ZSM-5 and mordenite.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.
The present invention is because the catalyzer that adopts is the composite molecular screen of ZSM-5 and mordenite, because their channel diameter distributes different, can handle the such molecular diameter of image-stone cerebrol complex component not of uniform size, again because ZSM-5 and their catalytic performance of mordenite are different, can play the concerted catalysis effect, in addition, the acid amount of composite molecular screen is bigger, strength of acid is higher, under cryogenic condition, reach good catalytic activity, ethene, propylene total recovery can reach 50%, have obtained better technical effect.
Catalyzer involved in the present invention has adopted above-mentioned preparation method.In order to check and rate activity of such catalysts, the C that adopts Shanghai Gaoqiao petro-chemical corporation to produce
4～C
10Petroleum naphtha be that [the wherein wt percentage composition is alkane 65.2% (normal paraffin is 32.5%) to raw material, and naphthenic hydrocarbon is 28.4%, and alkene is 0.17%, aromatic hydrocarbons is 6.2%], with the examination down of fixed-bed reactor normal pressure, range of reaction temperature is 600～700 ℃, and air speed is 0.15～2 hour
-1, water-oil ratio is 1～4: 1.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Get 284 gram Starsos, become solution A with 300 gram dissolved in distilled water, get 33.3 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 24.4 gram quadrols then, stir down, regulate the pH value 11.5 with dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: quadrol: H
2O=1: 0.1: 0.4: 40, mixing solutions is put into autoclave, 180 ℃ of insulations 40 hours, take out washing, oven dry, roasting then, make the composite molecular screen of ZSM-5 and mordenite, quantitatively contain the mordenite of the ZSM-5 and 14.5% (weight) of 85.5% (weight) with the XRD diffraction as can be known in the composite molecular screen.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, 650 ℃, air speed 0.5 hour
-1, check and rate under the condition of water/weight of oil than 3: 1, the results are shown in Table 1.
[embodiment 2～8]
Get the different composite molecular screen of ZSM-5 molecular sieve weight percentage, make catalyzer, be designated as FH-2 respectively, FH-3, FH-4, FH-5, FH-6, FH-7, FH-8 by the mode of embodiment 1.The weight content of ZSM-5 molecular sieve sees Table 1 in the composite molecular screen, and the condition examination with embodiment 1 the results are shown in Table 3.
Table 1
| Embodiment | Contain ZSM-5 ratio (weight %) | Sample number into spectrum |
| Embodiment 2 | 99.5 | FH-2 |
| Embodiment 3 | 97.5 | FH-3 |
| Embodiment 4 | 95.5 | FH-4 |
| Embodiment 5 | 90.5 | FH-5 |
| Embodiment 6 | 81.2 | FH-6 |
| Embodiment 7 | 72.4 | FH-7 |
| Embodiment 8 | 61.5 | FH-8 |
[embodiment 9～13]
Get the composite molecular screen of Different Silicon aluminum ratio,, make catalyzer, count FH-9 respectively, FH-10, FH-11, FH-12, FH-13, the SiO of composite molecular screen according to the method for embodiment 1
2/ Al
2O
3Mol ratio sees Table 2, checks and rates in the mode of embodiment 1, the results are shown in Table 3.
Table 2
| Embodiment | SiO 2/Al 2O 3(mol ratio) | Sample number into spectrum |
| Embodiment 9 | 14 | FH-9 |
| Embodiment 10 | 25 | FH-10 |
| Embodiment 11 | 30 | FH-11 |
| Embodiment 12 | 40 | FH-12 |
Table 3
| Sample number into spectrum | Yield of ethene (weight %) | Propene yield (weight %) | Total recovery (weight %) |
| FH-1 | 21.76 | 27.09 | 48.85 |
| FH-2 | 26.38 | 22.41 | 48.79 |
| FH-3 | 22.83 | 26.61 | 49.08 |
| FH-4 | 23.32 | 26.61 | 49.93 |
| FH-5 | 19.61 | 26.3 | 45.91 |
| FH-6 | 24.95 | 21.57 | 46.52 |
| FH-7 | 21.12 | 22.64 | 43.77 |
| FH-8 | 18.99 | 22.45 | 41.44 |
| FH-9 | 17.25 | 24.15 | 41.40 |
| FH-10 | 26.98 | 23.51 | 50.49 |
| FH-11 | 25.12 | 20.91 | 46.03 |
| FH-12 | 19.4 | 26.43 | 45.83 |
[embodiment 13～16]
Mode with embodiment 1 prepares catalyzer, and with same examination mode, is 650 ℃ in temperature of reaction, water-oil ratio 3: 1, and weight space velocity was respectively 1 hour
-1, 0.8 hour
-1, 0.25 hour
-1, 0.15 hour
-1Condition under check and rate, the results are shown in Table 4.
Table 4
| Embodiment | Air speed hour -1 | Yield of ethene (weight %) | Propene yield (weight %) | Total recovery (weight %) |
| FH-13 | 1 | 18.44 | 24.94 | 43.38 |
| FH-14 | 0.8 | 18.50 | 24.70 | 43.20 |
| FH-15 | 0.25 | 21.91 | 21.06 | 42.97 |
| FH-16 | 0.15 | 23.24 | 22.50 | 45.74 |
[embodiment 17～19]
Mode with embodiment 1 prepares catalyzer, and with same examination mode, and temperature of reaction is at 650 ℃, weight space velocity 0.5 hour
-1, water/weight of oil ratio was respectively 2.5: 1, checked and rated under the condition of 2: 1 and 1.5: 1, the results are shown in Table 5.
Table 5
| Embodiment | Water-oil ratio (weight ratio) | Yield of ethene (weight %) | Propene yield (weight %) | Total recovery (weight %) |
| FH-17 | 2.5∶1 | 19.61 | 26.30 | 45.91 |
| FH-18 | 2∶1 | 20.71 | 26.42 | 47.13 |
| FH-19 | 1.5∶1 | 22.03 | 23.68 | 45.71 |
[embodiment 20～23]
Mode with embodiment 1 prepares catalyzer, and with same examination mode, is 600 ℃, 630 ℃, 670 ℃, 700 ℃ in temperature of reaction respectively, air speed 0.5 hour
-1, check and rate under the condition of water/weight of oil than 3: 1, the results are shown in Table 6.
Table 6
| Embodiment | Temperature of reaction (℃) | Yield of ethene (weight %) | Propene yield (weight %) | Diene yield (weight %) |
| Embodiment 20 | 600 | 14.85 | 25.57 | 40.41 |
| Embodiment 21 | 630 | 20.93 | 21.68 | 42.61 |
| Embodiment 22 | 670 | 25.62 | 22.80 | 48.42 |
| Embodiment 23 | 700 | 23.82 | 19.09 | 47.09 |
Claims (6)
1, a kind of method of naphtha catalytic pyrolysis preparing ethylene propylene is with C
4～C
10Being raw material, is 600～700 ℃ in temperature of reaction, and reaction velocity is 0.1～2 hour
-1Water/petroleum naphtha weight ratio is under 1～4: 1 the condition, raw material contacts with catalyzer by beds, reaction generates ethylene, propylene, it is characterized in that used catalyzer is the composite molecular screen of ZSM-5 and mordenite, its synthetic method is: with metasilicate or silicon sol is the silicon source, the aluminium source is at least a in aluminium salt or the aluminate, with the quadrol is template, above-mentioned raw materials is made solution by required proportioning, regulator solution pH value got the ZSM-5/ mordenite composite molecular sieve in 10～100 hours 150～220 ℃ of following crystallization between 9～13, wherein the mole proportioning of solution is:
Si: Al: template: H
2O=1: 0.1: 0.4: 40.
2,, it is characterized in that the weight percentage of ZSM-5 in the composite molecular screen of ZSM-5 and mordenite is 20～99.5% according to the method for the described naphtha catalytic pyrolysis preparing ethylene propylene of claim 1.
3,, it is characterized in that the weight percentage of ZSM-5 in the composite molecular screen of ZSM-5 and mordenite is 60～99% according to the method for the described naphtha catalytic pyrolysis preparing ethylene propylene of claim 2.
4,, it is characterized in that the SiO of composite molecular screen according to the method for the described naphtha catalytic pyrolysis preparing ethylene propylene of claim 1
2/ Al
2O
3Mol ratio is 14～40.
5,, it is characterized in that reaction velocity is 0.15～1 hour according to the method for the described naphtha catalytic pyrolysis preparing ethylene propylene of claim 1
-1
6,, it is characterized in that water/petroleum naphtha weight ratio is 1.5～3: 1 according to the method for the described naphtha catalytic pyrolysis preparing ethylene propylene of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100279104A CN100554229C (en) | 2006-06-21 | 2006-06-21 | The method of naphtha catalytic pyrolysis preparing ethylene propylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100279104A CN100554229C (en) | 2006-06-21 | 2006-06-21 | The method of naphtha catalytic pyrolysis preparing ethylene propylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101092324A CN101092324A (en) | 2007-12-26 |
| CN100554229C true CN100554229C (en) | 2009-10-28 |
Family
ID=38990785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100279104A Active CN100554229C (en) | 2006-06-21 | 2006-06-21 | The method of naphtha catalytic pyrolysis preparing ethylene propylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100554229C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10907109B2 (en) | 2017-03-09 | 2021-02-02 | Sabic Global Technologies B.V. | Integration of catalytic cracking process with crude conversion to chemicals process |
| US11208599B2 (en) | 2017-05-10 | 2021-12-28 | Sabic Global Technologies B.V. | Process for catalytic cracking of naphtha using radial flow moving bed reactor system |
| US11267770B2 (en) | 2016-12-21 | 2022-03-08 | Sabic Global Technologies B.V. | Process to produce olefins from a catalytically cracked hydrocarbons stream |
| US11396630B2 (en) | 2016-12-13 | 2022-07-26 | Sabic Global Technologies B.V. | Naphtha catalytic cracking for light olefins production over cyclic regenerative process with dry gas diluent |
| US11807816B2 (en) | 2016-12-19 | 2023-11-07 | Sabic Global Technologies B.V. | Process integration for cracking light paraffinic hydrocarbons |
| US11905467B2 (en) | 2018-09-06 | 2024-02-20 | Sabic Global Technologies B.V. | Process for catalytic cracking of naphtha using multi-stage radial flow moving bed reactor system |
| US12012376B2 (en) | 2018-04-30 | 2024-06-18 | Sabic Global Technologies B.V. | Process of producing light olefins from isomerized straight run naphtha |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276391B (en) * | 2010-06-11 | 2013-10-16 | 中国石油化工股份有限公司 | Method for catalyzing and converting methanol and naphtha into low-carbon olefins |
-
2006
- 2006-06-21 CN CNB2006100279104A patent/CN100554229C/en active Active
Non-Patent Citations (4)
| Title |
|---|
| Mesoporous Material from Zeolite. Goto Y,Fukushina Y,Ogura M, et al.J Porous Mater,Vol.9 . 2002 |
| Mesoporous Material from Zeolite. Goto Y,Fukushina Y,Ogura M, et al.J Porous Mater,Vol.9 . 2002 * |
| 中－微孔复合分子筛的合成研究. 马广伟，葛学贵，黄少云.天津化工，第6期. 2002 |
| 中－微孔复合分子筛的合成研究. 马广伟，葛学贵，黄少云.天津化工，第6期. 2002 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11396630B2 (en) | 2016-12-13 | 2022-07-26 | Sabic Global Technologies B.V. | Naphtha catalytic cracking for light olefins production over cyclic regenerative process with dry gas diluent |
| US11807816B2 (en) | 2016-12-19 | 2023-11-07 | Sabic Global Technologies B.V. | Process integration for cracking light paraffinic hydrocarbons |
| US11267770B2 (en) | 2016-12-21 | 2022-03-08 | Sabic Global Technologies B.V. | Process to produce olefins from a catalytically cracked hydrocarbons stream |
| US10907109B2 (en) | 2017-03-09 | 2021-02-02 | Sabic Global Technologies B.V. | Integration of catalytic cracking process with crude conversion to chemicals process |
| US11208599B2 (en) | 2017-05-10 | 2021-12-28 | Sabic Global Technologies B.V. | Process for catalytic cracking of naphtha using radial flow moving bed reactor system |
| US12012376B2 (en) | 2018-04-30 | 2024-06-18 | Sabic Global Technologies B.V. | Process of producing light olefins from isomerized straight run naphtha |
| US11905467B2 (en) | 2018-09-06 | 2024-02-20 | Sabic Global Technologies B.V. | Process for catalytic cracking of naphtha using multi-stage radial flow moving bed reactor system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101092324A (en) | 2007-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101191069B (en) | Method for preparing ethene and propene by naphtha catalysis cracking | |
| CN100554229C (en) | The method of naphtha catalytic pyrolysis preparing ethylene propylene | |
| CN101279287B (en) | Catalyst for producing olefin hydrocarbon by catalytic pyrolysis | |
| CN101491772B (en) | Catalyst for naphtha catalytic cracking | |
| CN101348407B (en) | Method for preparing ethylene and propylene by catalytic pyrolysis | |
| CN101530813A (en) | Method for preparing molecular sieve catalyst used in carbon 4 liquid gas aromatization reaction | |
| CN101279284B (en) | Catalyst for preparing ethylene propylene from catalytic pyrolysis | |
| CN101190864B (en) | Catalyst for preparing ethene and propene by catalysis cracking | |
| CN101347746B (en) | Catalyst for producing olefin hydrocarbon by catalytic pyrolysis of naphtha | |
| CN101928598B (en) | Method and system for producing gasoline and propylene by integrating heavy oil catalytic cracking with oxygen-containing compound conversion | |
| CN100475337C (en) | Catalyst of naphtha catalytic pyrolysis preparing ethylene and propylene | |
| CN101428233B (en) | Catalyst for catalytic pyrolysis | |
| CN101279881B (en) | Method for preparing ethylene and propylene by benzin naphtha catalytic pyrolysis | |
| CN101279880B (en) | Method for preparing ethylene propylene by catalytic pyrolysis of light oil | |
| CN101348408B (en) | Method for preparing ethylene and propylene by catalytic pyrolysis of benzin naphtha | |
| CN101190417B (en) | Catalyst for preparing ethylene and propylene by catalytic cracking method | |
| CN115624987A (en) | Preparation method and application of catalyst for preparing low-carbon olefin by catalytic cracking of straight-run diesel oil | |
| CN101683621A (en) | Catalyst for producing low-carbon olefins through catalytic cracking by fixed bed | |
| CN100531910C (en) | Naphtha catalytic pyrolysis catalyst for preparing ethylene propylene | |
| CN101279285B (en) | Naphtha catalytic pyrolysis catalyst for preparing ethylene propylene | |
| CN100593528C (en) | Method for producing ethene and propene by catalytic oxidation cracking naphtha | |
| CN101555187B (en) | Method for preparing ethylene propylene through white oil catalytic cracking | |
| CN102791373A (en) | Olefin cracking catalyst and manufacturing process | |
| CN101306972B (en) | Process for preparing ethylene and propylene by catalytic scission reaction | |
| CN111560267B (en) | Method for producing high-octane low-benzene gasoline |
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 |