CN101602639A - Produce the method for ethylene, propylene - Google Patents
Produce the method for ethylene, propylene Download PDFInfo
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- CN101602639A CN101602639A CNA2008100434927A CN200810043492A CN101602639A CN 101602639 A CN101602639 A CN 101602639A CN A2008100434927 A CNA2008100434927 A CN A2008100434927A CN 200810043492 A CN200810043492 A CN 200810043492A CN 101602639 A CN101602639 A CN 101602639A
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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
- 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
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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Abstract
The present invention relates to a kind of method of producing ethylene, propylene, mainly the ethylene, propylene yield is low in the existing methanol dehydration preparing ethylene and propylene technology of solution, the problem of the easy inactivation of catalyzer.The present invention is a catalyzer by adopting ZSM-5/Magaditte, mordenite/Magaditte, β zeolite/Magaditte, ZSM-5/ mordenite/Magaditte, mordenite/beta zeolite/Magaditte and ZSM-5/ β zeolite/Magaditte coexisting material or its mixture, with methyl alcohol is raw material, in temperature of reaction is 400～600 ℃, reaction pressure is 0.001MPa～0.5MPa, and the reaction weight space velocity is 0.1～4 hour
-1, water/light oil weight ratio is that the catalytic technical scheme of raw material and catalyzer has solved this problem preferably, can be used in the industrial production of methyl alcohol preparing ethylene and propylene under 0.5～4: 1 the condition.
Description
Technical field
The present invention relates to a kind of method of producing ethylene, propylene.
Background technology
Ethylene, propylene industry has critical role as the tap of petrochemical industry in the national economic development.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.More than 100,000,000 ton of ethene is produced in the whole world per year at present, is raw material with petroleum naphtha (or ethane) mainly, adopts steam heat cracking technique (under the temperature about 800 ℃) production, and its output surpasses 90% of ultimate production.But steam cracking needs high temperature of reaction, and energy consumption is big, and the ethylene, propylene yield is lower, has restricted further developing of ethylene industry.
In recent years, development coal-based methanol-ethene-polyethylene industrial product route has many-sided effect and meaning.Since 2003, the development that domestic many enterprises pay attention are produced the technology of alkene (ethene, third rare be main) to methyl alcohol, and go up the design of carrying out coproduction alkene in the methyl alcohol project in new.Current, methyl alcohol has become reality as replenishing of oil.Long-range seeing, methyl alcohol also can become one of main continue resource of oil.The research of methyl alcohol system ethene, propylene is just beginning to show dawn, by present oil price and alkene price, the expection economic benefit of methanol-to-olefins can be that raw material system alkene cardinal principle is close with petroleum naphtha and solar oil.Therefore, consider that from the China's oil continue resource optimum development methanol industry has the important strategic meaning.
At present, the MTO technology of American UOP company (methanol-to-olefins technology), adopt silicoaluminophosphamolecular molecular sieve catalyzer (SAPO-34), methanol conversion is near 100%, and the selectivity of ethene and propylene is respectively 55% and 27%, and the ratio of ethene and propylene can be regulated within the specific limits in the product, the alkene once through yield has reached 60%, C2～C4 alkene total recovery is 93%, catalyst recirculation regeneration 450 times, and its performance is still very stable.
China Dalian Chemistry and Physics Institute is the patent (CN1166478) of existing similar technology also, adopt the SAPO-34 molecular sieve catalyst, on the ciculation fluidized reaction unit of dense bed, carry out this reacting middle catalyst continuously circulation react and regenerate, normal pressure and 500～570 ℃, the weight space velocity 1～10h of methyl alcohol or dme
-1Down, the transformation efficiency of methyl ether is greater than 98%, ethene, and the selectivity of low-carbon alkenes such as propylene is greater than 90%.
Germany LURGI also just is being devoted to MTP Study on Technology and industrialization.
But the silicoaluminophosphamolecular molecular sieve that above technology goes all to use is catalyzer, and the technology that suitable cheap stable coexisting material is a catalyzer yet there are no report.
Summary of the invention
Technical problem to be solved by this invention is that the diene yield that exists in the existing methanol dehydration preparing ethylene and propylene technology is low, catalyzer use temperature height, the easy problem of carbon distribution, and a kind of method of new production ethylene, propylene is provided.This method has the catalyst activity height, ethylene, propylene yield height, and temperature of reaction is low, the characteristics that catalyst life is long.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of producing ethylene, propylene is a raw material with methyl alcohol, is 400～600 ℃ in temperature of reaction, and reaction pressure is 0.001MPa～0.5MPa, and the reaction weight space velocity is 0.1～10 hour
-1Water/raw material weight ratio is under 0.5～4: 1 the condition, raw material passes through beds, reaction generates ethylene, propylene, and wherein used catalyzer is for being selected from least a in ZSM-5/Magaditte, mordenite/Magaditte, β zeolite/Magaditte, ZSM-5/ mordenite/Magaditte, mordenite/beta zeolite/Magaditte or the ZSM-5/ β zeolite/Magaditte coexisting material.
In the technique scheme, the silica alumina ratio SiO of used ZSM-5/Magaditte, mordenite/Magaditte, β zeolite/Magaditte, ZSM-5/ mordenite/Magaditte, mordenite/beta zeolite/Magaditte and ZSM-5/ β zeolite/Magaditte coexisting material
2/ Al
2O
3Preferable range is 40～1000, and more preferably scope is 100～500; The temperature of reaction preferable range is 450～550 ℃, and reaction weight space velocity preferable range is 0.2～4 hour
-1, water/raw material weight is 1～3: 1 than preferable range, the reaction pressure preferable range is 0.01MPa～0.2MPa.
The raw material that the preparation coexisting molecular sieve uses: used silicon source is to be selected from least a in organosilicon, soft silica, silicon sol, solid oxidation silicon, silica gel, diatomite or the water glass; Used aluminium source is at least a in the oxide compound of the oxyhydroxide that is selected from aluminate, meta-aluminate, aluminium salt, aluminium, aluminium or the aluminiferous mineral; Used alkali source is to be selected from least a in the alkali-metal oxyhydroxide; Template used dose for being selected from least a in organic amine or the inorganic ammonium; The pH value of regulating colloidal sol with diluted acid is 10～12.
The synthetic method concrete operations of coexisting molecular sieve are, get the silicon source and the aluminium source of aequum by material proportion, 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 after 30 minutes with rare acid for adjusting pH value 8～14, supply distilled water again, add small amount of seeds.Colloidal sol is put into autoclave, control certain temperature crystallization after 10～100 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours, can obtain required coexisting molecular sieve.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, 550 ℃ of roastings are 3 hours 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 ZSM-5/Magaditte, mordenite/Magaditte, β zeolite/Magaditte, ZSM-5/ mordenite/Magaditte, mordenite/beta zeolite/Magaditte and ZSM-5/ β zeolite/Magaditte coexisting material or its mixture.Because their channel diameter distributes different, can improve the selectivity of ethylene, propylene, again because their catalytic performance is different, can play the concerted catalysis effect, in addition, the multi-stage artery structure of coexisting material can strengthen the appearance carbon ability of catalyzer, can be under cryogenic condition, reach good catalytic activity and long stability, and the ethylene, propylene total recovery can reach more than 50%, obtain 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, employing methyl alcohol is raw material, is 10 millimeters down examination of fixed-bed reactor normal pressure with diameter, and range of reaction temperature is 400～600 ℃, and reaction pressure is 0.001MPa～0.5MPa, and mass space velocity is 0.1～10 hour
-1, water/raw materials quality ratio is 0.5～4: 1.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Get 33.3 gram Starsos, become solution A with 100 gram dissolved in distilled water, get the silicon sol of 57.4 grams 40%, make the solution mercerising with 100 gram distilled water, get 0.48 gram Tai-Ace S 150, make solution C with 20 ml distilled waters, respectively A and C solution are slowly poured in the mercerising solution, the powerful stirring, add 2.6 gram sodium hydroxide and 29.4 gram tetraethyl ammonium hydroxides, and then add 1.2 gram mordenite crystal seeds, after stirring for some time, regulate the pH value 11 with dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: Na: M: H
2O=1: 0.005: 0.6: 0.2: 40, 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 β zeolite/Magadiite/ mordenite coexisting material.With the XRD diffraction quantitatively as can be known in the coexisting material beta-zeolite molecular sieve weight percentage be 54.5%, the mordenite weight percentage is 24.9%, Magadiite content is 20.6%.
With weight percent is that 5% ammonium nitrate solution carries out ammonium exchange 3 hours at 90 ℃.Product after filtration, washing, 130 ℃ down after dry 3 hours, repeat an ammonium exchange again, after filtration, washing, 130 ℃ be down after dry 3 hours, 550 ℃ of following roastings 3 hours, make the Hydrogen coexisting material, then compressing tablet, break into pieces, sieve, it is standby to get 20～40 purpose particles.With methyl alcohol was raw material, is 10 millimeters fixed-bed reactor with diameter, 480 ℃, weight space velocity 1 hour
-1, water/methyl alcohol weight ratio 3: 1, pressure is to check and rate under the condition of 0.02MPa, appraisal result sees Table 1.
[embodiment 2]
Get 33.3 gram Starsos, become solution A with 100 gram dissolved in distilled water, get the silicon sol of 57.4 grams 40%, make the solution mercerising with 100 gram distilled water, get 0.48 gram Tai-Ace S 150, make solution C with 20 ml distilled waters, respectively A and C solution are slowly poured in the mercerising solution, the powerful stirring adds 2.6 gram sodium hydroxide, adds 14.7 gram tetraethyl ammonium hydroxides then, and then add 1.2 gram β zeolite seed crystals, after stirring for some time, regulate the pH value 11 with dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: Na: H
2O=1: 0.005: 0.6: 40, 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 the ZSM-5/Magadiite/ beta zeolite coexisting material, with the XRD diffraction quantitatively as can be known in the coexisting material ZSM-5 molecular sieve weight percentage be 50.6%, β zeolite weight percentage is 24.9%, Magadiite content is 24.5%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, the results are shown in Table 1.
[embodiment 3]
Get 33.3 gram Starsos, become solution A, get the silicon sol of 57.4 grams 40% with 100 gram dissolved in distilled water, make the solution mercerising with 100 gram distilled water, get 0.48 gram Tai-Ace S 150, make solution C, respectively A and C solution are slowly poured in the mercerising solution with 20 ml distilled waters, the powerful stirring, add 2.6 gram sodium hydroxide, and then add 1.2 gram mordenite crystal seeds, after stirring for some time, regulate the pH value 11 with dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: Na: H
2O=1: 0.001: 0.6: 40, mixing solutions is put into autoclave, 180 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make the ZSM-5/Magadiite/ mordenite coexisting material, with the XRD diffraction quantitatively as can be known in the coexisting material ZSM-5 molecular sieve weight percentage be 40.4%, the mordenite weight percentage is 21.2%, Magadiite content is 38.4%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, the results are shown in Table 1.
[embodiment 4]
Get 33.3 gram Starsos, become solution A, get the silicon sol of 57.4 grams 40% with 100 gram dissolved in distilled water, make solution β with 100 gram distilled water, get 0.48 gram Tai-Ace S 150, make solution C, respectively A and C solution are slowly poured in the β solution with 20 ml distilled waters, the powerful stirring, add 2.6 gram sodium hydroxide, and then add 1.2 gram β zeolite seed crystals, after stirring for some time, regulate the pH value 11 with dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: Na: H
2O=1: 0.005: 0.6: 40, 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 the Magadiite/ beta zeolite coexisting material with the XRD diffraction quantitatively as can be known in the coexisting material β zeolite quality percentage composition be 55.4%, Magadiite content is 44.6%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, the results are shown in Table 1.
[embodiment 5]
Get 33.3 gram Starsos, become solution A, get the silicon sol of 57.4 grams 40% with 100 gram dissolved in distilled water, make the solution mercerising with 100 gram distilled water, get 0.48 gram Tai-Ace S 150, make solution C, respectively A and C solution are slowly poured in the mercerising solution with 20 ml distilled waters, the powerful stirring, add 2.6 gram sodium hydroxide, and then add 1.2 gram mordenite crystal seeds, after stirring for some time, regulate the pH value 11 with dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: Na: H
2O=1: 0.005: 0.6: 40, mixing solutions is put into autoclave, 180 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make the Magadiite/ mordenite coexisting material.With the XRD diffraction quantitatively as can be known in the coexisting material mordenite quality percentage composition be 30.8%, Magadiite content is 69.2%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, the results are shown in Table 1.
[embodiment 6]
Get 33.3 gram Starsos, become solution A, get the silicon sol of 57.4 grams 40% with 100 gram dissolved in distilled water, make solution β with 100 gram distilled water, get 0.48 gram Tai-Ace S 150, make solution C, respectively A and C solution are slowly poured in the β solution with 20 ml distilled waters, the powerful stirring, add 2.6 gram sodium hydroxide, and then add 1.2 gram β zeolite seed crystals, after stirring for some time, regulate the pH value 11 with dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: Na: H
2O=1: 0.005: 0.6: 40, mixing solutions is put into autoclave, 180 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make the Magadiite/ beta zeolite coexisting material.With the XRD diffraction quantitatively as can be known in the coexisting material β zeolite quality percentage composition be 40.6%, Magadiite content is 59.4%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, the results are shown in Table 1.
Table 1
| Embodiment | ??SiO 2/Al 2O 3(mol ratio) | Yield of ethene (mole %) | Propene yield (mole %) | Total recovery (mole %) |
| Embodiment 1 | ??400 | ??24.3 | ??36.4 | ??60.7 |
| Embodiment 2 | ??400 | ??23.4 | ??33.9 | ??57.3 |
| Embodiment 3 | ??400 | ??21.5 | ??36.9 | ??58.4 |
| Embodiment 4 | ??400 | ??23.5 | ??34.7 | ??58.2 |
| Embodiment 5 | ??400 | ??27.4 | ??34.7 | ??62.1 |
| Embodiment 6 | ??400 | ??24.4 | ??33.5 | ??57.9 |
[embodiment 7～9]
Get the Hydrogen coexisting material of embodiment 1, embodiment 2, embodiment 3 and embodiment 4 preparations respectively, Pei Zhi mixture is as shown in table 2 by weight percentage, method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, the results are shown in Table 2.
Table 3
| Embodiment | Used molecular sieve type | Part by weight | Yield of ethene (mole %) | Propene yield (mole %) | Total recovery (mole %) |
| Embodiment 7 | β zeolite/Magadiite/ mordenite+ZSM-5/Magadiite/ β zeolite | ??1∶1 | ??22.4 | ??36.7 | ??59.1 |
| Embodiment 8 | β zeolite/Magadiite/ mordenite+ZSM-5/Magadiite/ β zeolite+ZSM-5/Magadiite/ mordenite | ??1∶1∶1 | ??23.2 | ??37.3 | ??60.5 |
| Embodiment 9 | β zeolite/Magadiite/ mordenite+ZSM-5/Magadiite/ β zeolite+ZSM-5/Magadiite/ mordenite+Magadiite/ β zeolite | ??1∶1∶1∶1 | ??24.8 | ??38.9 | ??63.7 |
[embodiment 10～11]
Press the synthetic coexisting material of method of embodiment 1, the consumption of getting Tai-Ace S 150 respectively is 4.8 grams and 0.2 gram, synthesizes required coexisting material respectively, makes the Hydrogen coexisting molecular sieve by the method for embodiment 1.
[embodiment 12～13]
Press the synthetic coexisting material of method of embodiment 2, the consumption of getting Tai-Ace S 150 respectively is 4.8 grams and 0.2 gram, synthesizes required coexisting material respectively, makes the Hydrogen coexisting molecular sieve by the method for embodiment 1.
[embodiment 14～15]
Press the synthetic coexisting material of method of embodiment 3, the consumption of getting Tai-Ace S 150 respectively is 4.8 grams and 0.2 gram, synthesizes required coexisting material respectively, makes the Hydrogen coexisting molecular sieve by the method for embodiment 1.
[embodiment 16～17]
Press the synthetic coexisting material of method of embodiment 4, the consumption of getting Tai-Ace S 150 respectively is 4.8 grams and 0.2 gram, synthesizes required coexisting material respectively, makes the Hydrogen coexisting molecular sieve by the method for embodiment 1.
[embodiment 18～19]
Press the synthetic coexisting material of method of embodiment 5, the consumption of getting Tai-Ace S 150 respectively is 4.8 grams and 0.2 gram, synthesizes required coexisting material respectively, makes the Hydrogen coexisting molecular sieve by the method for embodiment 1.
[embodiment 20～21]
Press the synthetic coexisting material of method of embodiment 6, the consumption of getting Tai-Ace S 150 respectively is 4.8 grams and 0.2 gram, synthesizes required coexisting material respectively, makes the Hydrogen coexisting molecular sieve by the method for embodiment 1.
[embodiment 22～24]
Getting the Hydrogen coexisting material of embodiment 10, embodiment 11 and embodiment 12 preparations respectively, is that 480 ℃, water/raw material weight ratio are that 3: 1, weight space velocity were followed successively by respectively 10 hours in temperature of reaction
-12 hours
-1With 0.1 hour
-1Condition under check and rate, the results are shown in Table 3.
[embodiment 25～27]
Getting the Hydrogen coexisting material of embodiment 13, embodiment 14 and embodiment 15 preparations respectively, is that 3: 1, weight space velocity are 0.5 hour at water/raw material weight ratio
-1, temperature of reaction is followed successively by 400 ℃ respectively; Check and rate under the condition of 500 ℃ and 600 ℃, the results are shown in Table 3.
[embodiment 28～30]
Getting the Hydrogen coexisting material of embodiment 16, embodiment 17 and embodiment 18 preparations respectively, is 0.5 hour at weight space velocity
-1, temperature is that 480 ℃, water/raw materials quality were followed successively by 4: 1 than respectively; Checked and rated under the condition, and the results are shown in Table 3 in 2: 1 and 0.5: 1.
[embodiment 31～33]
Getting the Hydrogen coexisting material of embodiment 19, embodiment 20 and embodiment 21 preparations respectively, is 1 hour at weight space velocity
-1, temperature of reaction be 500 ℃, water/raw materials quality than 3: 1, reaction pressure is followed successively by 0.001MPa respectively; 0.1MPa and check and rate under the condition of 0.5MPa, the results are shown in Table 3.
Table 3
| Embodiment | The coexisting material type | ??SiO 2/Al 2O 3(mol ratio) | Yield of ethene (mole %) | Propene yield (mole %) | Total recovery (mole %) |
| Embodiment 22 | β zeolite/Magadiite/ mordenite | ??40 | ??25.1 | ??24.4 | ??49.5 |
| Embodiment 23 | β zeolite/Magadiite/ mordenite | ??1000 | ??26.4 | ??31.8 | ??57.2 |
| Embodiment 24 | ZSM-5/Magadiite/ β zeolite | ??40 | ??38.5 | ??28.4 | ??66.9 |
| Embodiment 25 | ZSM-5/Magadiite/ β zeolite | ??1000 | ??18.5 | ??32.3 | ??50.8 |
| Embodiment 26 | The ZSM-5/Magadiite/ mordenite | ??40 | ??37.4 | ??22.7 | ??60.1 |
| Embodiment 27 | The ZSM-5/Magadiite/ mordenite | ??1000 | ??34.4 | ??35.5 | ??69.5 |
| Embodiment 28 | Magadiite/ β zeolite | ??40 | ??34.3 | ??34.5 | ??68.8 |
| Embodiment 29 | Magadiite/ β zeolite | ??1000 | ??36.4 | ??38.9 | ??75.3 |
| Embodiment 30 | The Magadiite/ mordenite | ??40 | ??30.5 | ??30.9 | ??61.4 |
| Embodiment 31 | The Magadiite/ mordenite | ??1000 | ??33.5 | ??43.7 | ??77.2 |
| Embodiment 32 | Magadiite/ β zeolite | ??40 | ??33.4 | ??38.7 | ??72.1 |
| Embodiment 33 | Magadiite/ β zeolite | ??1000 | ??26.4 | ??35.5 | ??61.9 |
Claims (7)
1, a kind of method of producing ethylene, propylene is a raw material with methyl alcohol, is 400～600 ℃ in temperature of reaction, and reaction pressure is 0.001MPa～0.5MPa, and the reaction weight space velocity is 0.1～10 hour
-1Water/raw material weight ratio is under 0.5～4: 1 the condition, raw material passes through beds, reaction generates ethylene, propylene, it is characterized in that used catalyzer is for being selected from least a in ZSM-5/Magaditte, mordenite/Magaditte, β zeolite/Magaditte, ZSM-5/ mordenite/Magaditte, mordenite/beta zeolite/Magaditte or the ZSM-5/ β zeolite/Magaditte coexisting material.
2,, it is characterized in that the SiO of described coexisting material according to the method for the described production ethylene, propylene of claim 1
2/ Al
2O
3Mol ratio is 40～1000.
3,, it is characterized in that the SiO of described coexisting material according to the method for the described production ethylene, propylene of claim 2
2/ Al
2O
3Mol ratio is 100～500.
4,, it is characterized in that temperature of reaction is 450～550 ℃ according to the method for the described preparing ethylene propylene by catalytic pyrolysis of light oil of claim 1.
5, according to the method for the described preparing ethylene propylene by catalytic pyrolysis of light oil of claim 1, it is characterized in that reacting weight space velocity is 0.2～4 hour-1.
6,, it is characterized in that water/raw material weight ratio is 1～3: 1 according to the method for the described preparing ethylene propylene by catalytic pyrolysis of light oil of claim 1.
7,, it is characterized in that reaction pressure is 0.01MPa～0.2MPa according to the method for the described preparing ethylene propylene by catalytic pyrolysis of light oil of claim 1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372548A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin through methanol dehydration |
| CN106608777A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Method for production of propylene |
| US10723630B2 (en) * | 2018-03-14 | 2020-07-28 | Saudi Arabian Oil Company | Methods of producing composite zeolite catalysts for heavy reformate conversion into xylenes |
| US10723631B2 (en) * | 2018-03-14 | 2020-07-28 | Saudi Arabian Oil Company | Methods of producing composite zeolite catalysts for heavy reformate conversion into xylenes |
| US10927059B2 (en) | 2018-03-14 | 2021-02-23 | Saudi Arabian Oil Company | Catalyst for converting heavy reformate to produce BTX compounds |
| US11091413B2 (en) | 2018-03-14 | 2021-08-17 | Saudi Arabian Oil Company | Methods of heavy reformate conversion into aromatic compounds |
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- 2008-06-12 CN CNA2008100434927A patent/CN101602639A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372548A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin through methanol dehydration |
| CN102372548B (en) * | 2010-08-23 | 2013-12-18 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin through methanol dehydration |
| CN106608777A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Method for production of propylene |
| CN106608777B (en) * | 2015-10-21 | 2019-04-12 | 中国石油化工股份有限公司 | The production method of propylene |
| US10723630B2 (en) * | 2018-03-14 | 2020-07-28 | Saudi Arabian Oil Company | Methods of producing composite zeolite catalysts for heavy reformate conversion into xylenes |
| US10723631B2 (en) * | 2018-03-14 | 2020-07-28 | Saudi Arabian Oil Company | Methods of producing composite zeolite catalysts for heavy reformate conversion into xylenes |
| US10927059B2 (en) | 2018-03-14 | 2021-02-23 | Saudi Arabian Oil Company | Catalyst for converting heavy reformate to produce BTX compounds |
| US11091413B2 (en) | 2018-03-14 | 2021-08-17 | Saudi Arabian Oil Company | Methods of heavy reformate conversion into aromatic compounds |
| US11472755B2 (en) | 2018-03-14 | 2022-10-18 | Saudi Arabian Oil Company | Methods of heavy reformate conversion into aromatic compounds |
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