CN101555187B - Method for preparing ethylene propylene through white oil catalytic cracking - Google Patents
Method for preparing ethylene propylene through white oil catalytic cracking Download PDFInfo
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- CN101555187B CN101555187B CN2008100432512A CN200810043251A CN101555187B CN 101555187 B CN101555187 B CN 101555187B CN 2008100432512 A CN2008100432512 A CN 2008100432512A CN 200810043251 A CN200810043251 A CN 200810043251A CN 101555187 B CN101555187 B CN 101555187B
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Abstract
The invention relates to a method for preparing ethylene propylene through white oil catalytic cracking, which mainly aims at solving the problems of low catalyst activity, low ethylene propylene yield rate and high reaction temperature in the prior technologies for preparing the ethylene propylene through catalytic cracking. The method adopts a symbiotic molecular sieve as the catalyst and taking white oil comprising C4-C10 hydrocarbon as the raw material; the raw material and the catalyst contact and react to generate the ethylene propylene at the reaction temperature of 600-700 DEG C, the reaction pressure of 0.001-0.5MPa, the reaction weight space velocity of 0.1-4h<-1> and the weight ratio of water to the white oil is 1-4:1, such a technical scheme better solves the problems and can be used in the industrial production for preparing the ethylene propylene through the white oil catalytic cracking.
Description
Technical field
The present invention relates to a kind of method of preparing ethylene propylene by catalytic pyrolysis of light oil.
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 the.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, needs expensive high-temperature alloy steel molecular sieve, and the operational cycle is short, and the boiler tube life-span is low, discharge great amount of carbon dioxide, and the ethylene, propylene yield is lower, has restricted further developing of ethylene industry.
Catalytic pyrolysis also is one of important method of producing ethylene, propylene.It is under the condition that catalyzer exists, and petroleum hydrocarbon is carried out the process that catalytic pyrolysis is produced low-carbon alkene.Catalytic pyrolysis is compared with the steam heat cracking, and this process reaction temperature is than low 50～200 ℃ approximately of equivalent steam scission reactions, and therefore than 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.Compare with steam cracking technology, this new technology can also increase the total recovery of ethene and propylene, produces the used feed naphtha of equal amts ethene and can reduce, and production cost of ethylene reduces significantly.Therefore, preparing ethylene propylene from catalytic pyrolysis technology as realize industriallization is that the petrochemical industry of raw material brings huge economic benefit with giving ethylene, propylene.
The ZSM-5 molecular sieve is applied in field of petrochemical industry widely owing to have good shape selective catalysis performance and thermostability preferably.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.
Mobil Oil Corp. (CN1413244A) has announced that a kind of mesopore phosphate molecule sieve of modification that uses is catalyzer; Combine with primary catalytic pyrolysis molecular sieve (Y zeolite); The hydrocarbon raw material of catalytic pyrolysis sulfur-bearing prepares micromolecular hydrocarbon mixture, but the yield of the use temperature of catalyzer, conversion of raw material and product is all lower.
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.The molecular sieve of usefulness is by 0～25 weight %Y zeolite of high silica alumina ratio or has the ZSM molecular sieve of MFI structure, formed by phosphorus/Al, Mg or Ca dipping, but the ethylene, propylene selectivity of catalyzer and yield is not high.
Document CN1565967A, CN1565970A report adopt ZSM-5 molecular sieve or mordenite as crystal seed, add respectively in the resulting solution of mordenite or ZSM-5 molecular sieve, have synthesized the mixed crystal molecular sieve of ZSM-5 and mordenite.Its catalytic effect is better than the effect of two kinds of molecular sieve mechanically mixing, but needs in the building-up process to add different crystal seeds as inductor, also need add fluorochemical in addition, and building-up process is comparatively complicated.
Document CN1393403 report adopts the method for segmentation crystallization to synthesize middle mesoporous-microporous composite molecular sieve compsn.Compound method is to prepare the reaction mixture gel of synthetic microporous molecular sieve earlier, under 30～300 ℃ of conditions, carries out the crystallization of fs then, and crystallization is after 3～300 hours; The pH value of adjustment reaction mixture is 9.5～12; And add the synthetic used template of mesoporous molecular sieve, and then depress the hydrothermal crystallizing that carries out subordinate phase certainly at 30～170 ℃, crystallization time is 15～480 hours; Mesoporous-microporous composite molecular sieve compsn in obtaining; But the building-up process of molecular sieve needs the segmentation crystallization, and the centre also will regulate the pH value, and compound method is also comparatively complicated.Be used for heavy oil upgrading, its reactive behavior is lower.
Document CN03133557.8 has reported and has synthesized the composite structure molecular sieve with TON and two kinds of structures of MFI under the static conditions; This molecular sieve has added a spot of crystal seed and salt in the preparation gelation process; Control suitable crystallization parameter; Can obtain the molecular sieve of two kinds of crystal formation different ratioss, silica alumina ratio obtains the reaction process that composite molecular screen of the present invention can be used for mixture such as petroleum fractions greater than 50 on the character of molecular sieve.Building-up process of the present invention also need add crystal seed and salt.
Document CN1583562 has reported a kind of double-micropore zeolites molecular sieve and preparation method, it is characterized in that adopting orderly synthesis method, tentatively synthesizes y-type zeolite by certain material proportion earlier; After it is mixed with the tetraethyl-amine bromide solution that is dissolved with ammoniacal liquor; Adding a certain amount of silicon sol at last more fully stirs and makes it even; In 130 ℃～140 ℃ following crystallization 4～7 days, obtain having the composite zeolite molecular sieve of the two microvoid structures of Y/ β, this method is also similar with the segmentation crystallization.
Summary of the invention
Technical problem to be solved by this invention is that the catalyzer use temperature that exists in the prior art is high, and the problem that the yield of ethylene, propylene is low provides a kind of method of new preparing ethylene propylene by catalytic pyrolysis of light oil.This method has the catalyst activity height, and the ethylene, propylene yield is high, the characteristics that temperature of reaction is low.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of method of preparing ethylene propylene by catalytic pyrolysis of light oil, and with C
4～C
10The light oil of hydrocarbon is raw material, is 600～700 ℃ in temperature of reaction, and reaction pressure is 0.001MPa～0.5MPa, and the reaction weight space velocity is 0.1～4 hour
-1Water/raw material weight ratio is under 0.1～4: 1 the condition; Raw material passes through beds; Reaction generates ethylene, propylene, and wherein used catalyzer is for being selected from least a in mordenite/beta zeolite/Y zeolite, mordenite/beta zeolite/euthalite, mordenite/beta zeolite/MCM-22, mordenite/MCM-22/MCM-49, mordenite/MCM-22, mordenite/Y zeolite, β zeolite/Y zeolite, ZSM-5/ mordenite/Magadiite, ZSM-5 zeolite/β zeolite/MCM-22, ZSM-5/ β zeolite/Magadiite, ZSM-5 zeolite/β zeolite/Y zeolite, ZSM-5 zeolite/β zeolite/MCM-49, ZSM-5 zeolite/β zeolite/MCM-56, ZSM-5 zeolite/β zeolite/ZSM-23, ZSM-5 zeolite/mordenite/MCM-49, ZSM-5 zeolite/mordenite/MCM-56, ZSM-5 zeolite/mordenite/ZSM-23, ZSM-5 zeolite/ZSM-23/MCM-22, the ZSM-5 zeolite/ZSM-23/Y zeolite coexisting molecular sieve.
In the technique scheme, the silica alumina ratio SiO of used coexisting molecular sieve
2/ Al
2O
3Preferable range is 8～1000, and more preferably scope is 12～200; The temperature of reaction preferable range is 620～680 ℃, and reaction weight space velocity preferable range is 0.2～2 hour
-1, water/raw material weight is 0.1～3: 1 than preferable range, more preferably scope is 0.5～3: 1; 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, zeyssatite or the water glass; Used aluminium source is at least a in oxide compound or the aluminiferous mineral of the oxyhydroxide that is selected from aluminate, meta-aluminate, aluminium salt, aluminium, aluminium; Used alkali source is to be selected from least a in the alkali-metal oxyhydroxide; Template used dose of M is selected from least a in organic amine or the inorganic ammonium; The pH value of using diluted acid to regulate colloidal sol is 8～14.
The compound method concrete operations of coexisting molecular sieve are by silicon source and the aluminium source that material proportion is got aequum, to melt with zero(ppm) water respectively and process solution; Mix two kinds of solution then; The powerful stirring adds the template M of aequum then, stirs after 30 minutes with rare acid for adjusting pH value 8～14; Supply zero(ppm) water again, add small amount of seeds.Put into autoclave to colloidal sol, 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.Using concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, 550 ℃ of roastings are 3 hours then, makes the Hydrogen coexisting 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 coexisting molecular sieve or its mixture, and the difference because their channel diameter distributes can be handled molecular diameter complex component not of uniform size as light oil; Because their catalytic performance is different, can play the concerted catalysis effect, in addition again; The acid amount of coexisting molecular sieve is bigger, and strength of acid is higher, can be under cryogenic condition; Reach good catalytic activity, and the ethylene, propylene total recovery can reach more than 55%, 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, the component that adopts Shanghai Gaoqiao petro-chemical corporation to produce is C
4～C
10Light oil be raw material (the raw material physical index is seen table 1), using diameter is 12 millimeters fixed-bed reactor normal pressure examination down, range of reaction temperature is 600～700 ℃, reaction pressure is 0.001MPa～0.5MPa, mass space velocity is 0.1～4 hour
-1, water/raw oil mass ratio is 0.1～4: 1.
Table 1 light oil raw material 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 |
| Aromatic hydrocarbons % (weight %) | 6.21 |
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
Get 284 gram Starsos, become solution A, get 33.4 gram Tai-Ace S 150 with 300 gram dissolved in distilled water; Process solution B with 100 gram zero(ppm) water, slowly pour B solution in the A solution, the powerful stirring; Adding 29.4 gram tetraethyl ammonium hydroxides then is template M; 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: 0.1: 0.2: 40; Add 3.0 gram Y zeolite crystal seeds, put into autoclave to mixing solutions, 150 ℃ of insulations 40 hours; Take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then; Make β zeolite/Y zeolite coexisting material, use the XRD diffraction can know that quantitatively β zeolite quality percentage composition is 46.5% in the coexisting material, Y zeolite content is 53.5%.
With C
4～C
10Petroleum naphtha be raw material (the raw material physical index is seen table 1), using diameter is 12 millimeters fixed-bed reactor, at 650 ℃, weight space velocity 0.5h
-1, water/weight of oil is to check and rate under the condition of 0.02MPa than 3: 1, pressure, the ethene mass yield reaches 27.2%, the propylene mass yield reaches 29.4%, ethene and propylene diene quality total recovery reach 55.8%, have obtained better technical effect.
[embodiment 2]
Get 284 gram Starsos, become solution A, get 16.7 gram Tai-Ace S 150 with 300 gram dissolved in distilled water; Process solution B with 100 gram zero(ppm) water, slowly pour B solution in the A solution, the powerful stirring; Add 29.4 gram tetraethyl ammonium hydroxides and 19.9 gram hexamethylene imines (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: 0.05: 0.4: 40, add 3.0 gram MCM-22 crystal seeds, put into autoclave to mixing solutions; 150 ℃ of insulations 40 hours; Take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make β zeolite/mordenite/MCM-22 coexisting material, use the XRD diffraction can know that quantitatively β zeolite weight percentage is 54.5% in the coexisting material; Mordenite content is 12.8%, and MCM-22 content is 22.7%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, and the result sees table 2.
[embodiment 3]
Get 284 gram Starsos, become solution A, get 16.7 gram Tai-Ace S 150 with 300 gram dissolved in distilled water; Process solution B with 100 gram zero(ppm) water, slowly pour B solution in the A solution, the powerful stirring; Add 12.2 gram quadrols and 19.9 gram hexamethylene imines (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: 0.05: 0.4: 40; Add 3.0 gram MCM-22 crystal seeds, put into autoclave to mixing solutions, 150 ℃ of insulations 40 hours; Take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then; Make MCM-49 molecular sieve/mordenite/MCM-22 coexisting material, use the XRD diffraction can know that quantitatively mordenite quality percentage composition is 61.5% in the coexisting material, MCM-22 content is 38.5%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, and the result sees table 2.
[embodiment 4]
Get 284 gram Starsos, become solution A, get 25.1 gram Tai-Ace S 150 with 300 gram dissolved in distilled water; Process solution B with 100 gram zero(ppm) water, slowly pour B solution in the A solution, the powerful stirring; Add 12.2 gram quadrols and 19.9 gram hexamethylene imines (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: 0.067: 0.4: 40, add 3.0 gram MCM-22 crystal seeds, put into autoclave to mixing solutions; 150 ℃ of insulations 40 hours; Take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make mordenite/MCM-22/MCM-49 coexisting material, use the XRD diffraction can know that quantitatively MCM-49 molecular sieve weight percentage is 22.3% in the coexisting material; Mordenite content is 47.9%, and MCM-22 content is 29.8%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, and the result sees table 2.
[embodiment 5]
Get 284 gram Starsos, become solution A, get 33.4 gram Tai-Ace S 150 with 300 gram dissolved in distilled water; Process solution B with 100 gram zero(ppm) water, slowly pour B solution in the A solution, the powerful stirring; Add 12.2 gram quadrols 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: 0.1: 0.2: 40; Add 3.0 gram Y zeolite crystal seeds, put into autoclave to mixing solutions, 160 ℃ of insulations 40 hours; Take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then; Make mordenite/Y zeolite coexisting material, use the XRD diffraction can know that quantitatively the mordenite weight percentage is 54.5% in the coexisting material, Y zeolite content is 45.5%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, and the result sees table 2.
[embodiment 6]
Get 284 gram Starsos, become solution A, get 16.7 gram Tai-Ace S 150 with 300 gram dissolved in distilled water; Process solution B with 100 gram zero(ppm) water, slowly pour B solution in the A solution, the powerful stirring; Add 29.4 gram tetraethyl ammonium hydroxides and 19.9 gram hexamethylene imines (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: 0.05: 0.4: 40, add 3.0 gram MCM-22 crystal seeds, put into autoclave to mixing solutions; 150 ℃ of insulations 40 hours; Take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/ β zeolite/MCM-22 coexisting material, use the XRD diffraction can know that quantitatively β zeolite weight percentage is 41.5% in the coexisting material; ZSM-5 content is 37.7%, and MCM-22 content is 20.8%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, and the result sees table 2.
[embodiment 7]
Get 284 gram Starsos, become solution A, get 33.4 gram Tai-Ace S 150 with 300 gram dissolved in distilled water; Process solution B with 100 gram zero(ppm) water, slowly pour B solution 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: 0.1: 0.4: 40, add 3.0 gram Y zeolite crystal seeds, put into autoclave to mixing solutions; 150 ℃ of insulations 40 hours; Take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/ β zeolite/Y zeolite coexisting material, use the XRD diffraction can know that quantitatively β zeolite weight percentage is 20.5% in the coexisting material; ZSM-5 content is 38.7%, and Y zeolite content is 40.8%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, and the result sees table 2.
[embodiment 8]
Get 33.3 gram Starsos, become solution A, get the silicon sol of 57.4 grams 40% with 100 gram dissolved in distilled water; Process the solution mercerising with 100 gram zero(ppm) water, get 0.48 gram Tai-Ace S 150, process solution C with 20 ml distilled waters; Slowly pour A and C solution in the mercerising solution respectively, the powerful stirring adds 2.6 gram sodium hydroxide; Add 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; Put into autoclave to mixing solutions,, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then 160 ℃ of insulations 40 hours; Make the ZSM-5/Magadiite/ beta zeolite coexisting material; Use the XRD diffraction can know that quantitatively ZSM-5 molecular sieve weight percentage is 50.6% in the coexisting material, β zeolite weight percentage is 24.9%, and 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, and the result sees table 2.
[embodiment 9]
Get 33.3 gram Starsos, become solution A, get the silicon sol of 57.4 grams 40%, process the solution mercerising with 100 gram zero(ppm) water with 100 gram dissolved in distilled water; Get 0.48 gram Tai-Ace S 150, process solution C, slowly pour A and C solution in the mercerising solution respectively with 20 ml distilled waters; The powerful stirring adds 2.6 gram sodium hydroxide, and then adds 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; Put into autoclave to mixing solutions,, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then 180 ℃ of insulations 40 hours; Make the ZSM-5/Magadiite/ mordenite coexisting material; Use the XRD diffraction can know that quantitatively ZSM-5 molecular sieve weight percentage is 40.4% in the coexisting material, the mordenite weight percentage is 21.2%, and 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, and the result sees table 2.
[embodiment 10]
Get 284 gram Starsos, become solution A, get 25.1 gram Tai-Ace S 150 with 300 gram dissolved in distilled water; Process solution B with 100 gram zero(ppm) water, slowly pour B solution in the A solution, the powerful stirring; Add 12.2 gram triethylamines and 29.4 gram tetraethyl ammonium hydroxides (mixed templates is designated as M) then; After stirring for some time, regulate the pH value 11.5 with dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: M: H
2O=1: 0.067: 0.4: 40, add 2.8 gram Y zeolite crystal seeds, put into autoclave to mixing solutions; 160 ℃ of insulations 40 hours; Take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make mordenite/beta zeolite/Y zeolite coexisting material, use the XRD diffraction can know that quantitatively the mordenite weight percentage is 35.4% in the coexisting material; The β zeolite content is 30.3%, and Y zeolite content is 34.3%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, and the result sees table 2.
[embodiment 11]
Get 284 gram Starsos, become solution A, get 16.7 gram Tai-Ace S 150 with 300 gram dissolved in distilled water; Process solution B with 100 gram zero(ppm) water, slowly pour B solution in the A solution, the powerful stirring; Add 24.4 gram quadrols and 29.4 gram tetraethyl ammonium hydroxides then as template M; After stirring for some time, regulate the pH value 12 with sodium hydroxide and dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: M: H
2O: OH-=1: 0.05: 0.4: 40; Put into autoclave to mixing solutions,, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then 160 ℃ of insulations 40 hours; Make mordenite/beta zeolite/euthalite porous coexisting material; Use the XRD diffraction can know that quantitatively β zeolite weight percentage is 30.2% in the coexisting material, mordenite content is 48.7%, and euthalite content is 21.1%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, and the result sees table 2.
[embodiment 12]
Get 284 gram Starsos, become solution A, get 16.7 gram Tai-Ace S 150 with 300 gram dissolved in distilled water; Process solution B with 100 gram zero(ppm) water, slowly pour B solution in the A solution, the powerful stirring; Add 29.4 gram tetraethyl ammonium hydroxides and 19.9 gram hexamethylene imines (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: 0.05: 0.4: 40, add 3.0 gram MCM-49 crystal seeds, put into autoclave to mixing solutions; 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/ β zeolite/MCM-49 coexisting material, use the XRD diffraction can know that quantitatively β zeolite weight percentage is 41.6% in the coexisting material; ZSM-5 content is 37.9%, and MCM-49 content is 20.5%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, and the result sees table 2.
[embodiment 13]
Get 284 gram Starsos, become solution A, get 16.7 gram Tai-Ace S 150 with 300 gram dissolved in distilled water; Process solution B with 100 gram zero(ppm) water, slowly pour B solution in the A solution, the powerful stirring; Add 29.4 gram tetraethyl ammonium hydroxides and 19.9 gram hexamethylene imines (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: 0.05: 0.4: 40, add 3.0 gram MCM-56 crystal seeds, put into autoclave to mixing solutions; 140 ℃ of insulations 40 hours; Take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/ β zeolite/MCM-56 coexisting material, use the XRD diffraction can know that quantitatively β zeolite weight percentage is 40.3% in the coexisting material; ZSM-5 content is 38.1%, and MCM-56 content is 21.6%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, and the result sees table 2.
[embodiment 14]
Get 284 gram Starsos, become solution A, get 16.7 gram Tai-Ace S 150 with 300 gram dissolved in distilled water; Process solution B with 100 gram zero(ppm) water, slowly pour B solution in the A solution, the powerful stirring; Add 29.4 gram tetraethyl ammonium hydroxides and 12.2 gram tetramethyleneimine (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: 0.05: 0.4: 40, add 3.0 gram MCM-23 crystal seeds, put into autoclave to mixing solutions; 165 ℃ of insulations 70 hours; Take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/ β zeolite/MCM-23 coexisting material, use the XRD diffraction can know that quantitatively β zeolite weight percentage is 28.7% in the coexisting material; ZSM-5 content is 46.4%, and MCM-23 content is 24.9%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, and the result sees table 2.
[embodiment 15]
Get 284 gram Starsos, become solution A, get 16.7 gram Tai-Ace S 150 with 300 gram dissolved in distilled water; Process solution B with 100 gram zero(ppm) water, slowly pour B solution in the A solution, the powerful stirring; Add 29.4 gram tetraethyl ammonium hydroxides and 19.9 gram hexamethylene imines (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: 0.05: 0.4: 40, add 3.0 gram MCM-49 crystal seeds, put into autoclave to mixing solutions; 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/ mordenite/MCM-49 coexisting material, use the XRD diffraction can know that quantitatively the mordenite weight percentage is 36.7% in the coexisting material; ZSM-5 content is 44.7%, and MCM-49 content is 18.6%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, and the result sees table 2.
[embodiment 16]
Get 284 gram Starsos, become solution A, get 16.7 gram Tai-Ace S 150 with 300 gram dissolved in distilled water; Process solution B with 100 gram zero(ppm) water, slowly pour B solution in the A solution, the powerful stirring; Add 29.4 gram tetraethyl ammonium hydroxides and 19.9 gram hexamethylene imines (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: 0.05: 0.4: 40, add 3.0 gram MCM-56 crystal seeds, put into autoclave to mixing solutions; 140 ℃ of insulations 40 hours; Take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/ mordenite/MCM-56 coexisting material, use the XRD diffraction can know that quantitatively the mordenite weight percentage is 34.5% in the coexisting material; ZSM-5 content is 48.7%, and MCM-56 content is 16.8%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, and the result sees table 2.
[embodiment 17]
Get 284 gram Starsos, become solution A, get 16.7 gram Tai-Ace S 150 with 300 gram dissolved in distilled water; Process solution B with 100 gram zero(ppm) water, slowly pour B solution in the A solution, the powerful stirring; Add 40.6 gram TPAOHs and 12.2 gram tetramethyleneimine (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: 0.05: 0.4: 40, add 3.0 gram MCM-23 crystal seeds, put into autoclave to mixing solutions; 170 ℃ of insulations 70 hours; Take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/ mordenite/MCM-23 coexisting material, use the XRD diffraction can know that quantitatively the mordenite weight percentage is 31.5% in the coexisting material; ZSM-5 content is 45.2%, and MCM-23 content is 23.3%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, and the result sees table 2.
[embodiment 18]
Get 284 gram Starsos, become solution A, get 16.7 gram Tai-Ace S 150 with 300 gram dissolved in distilled water; Process solution B with 100 gram zero(ppm) water, slowly pour B solution in the A solution, the powerful stirring; Add 14.7 gram tetraethyl ammonium hydroxides, 7.1 gram pyrrole Lip river alkane and 19.9 gram hexamethylene imines (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: 0.05: 0.4: 40, add 3.0 gram MCM-22 crystal seeds, put into autoclave to mixing solutions; 160 ℃ of insulations 70 hours; Take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make the ZSM-5/ZSM-23/MCM-22 coexisting material, use the XRD diffraction can know that quantitatively the ZSM-23 weight percentage is 32.5% in the coexisting material; ZSM-5 content is 44.7%, and MCM-22 content is 22.8%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, and the result sees table 2.
[embodiment 19]
Get 284 gram Starsos, become solution A, get 16.7 gram Tai-Ace S 150 with 300 gram dissolved in distilled water; Process solution B with 100 gram zero(ppm) water, slowly pour B solution in the A solution, the powerful stirring; Add 12.2 gram quadrols and 14.2 gram tetramethyleneimine (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: 0.05: 0.4: 40, add 3.0 gram Y zeolite crystal seeds, put into autoclave to mixing solutions; 150 ℃ 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/ZSM-23/Y zeolite coexisting material, use the XRD diffraction can know that quantitatively the ZSM-23 weight percentage is 30.5% in the coexisting material; ZSM-5 content is 40.7%, and Y zeolite content is 28.8%.
Method by embodiment 1 makes the Hydrogen coexisting molecular sieve, and presses processing condition and the method examination of embodiment 1, and the result sees table 2.
Table 2
| Embodiment | SiO 2/Al 2O 3(mol ratio) | Yield of ethene (weight %) | Propene yield (weight %) | Total recovery (weight %) |
| Embodiment 1 | 20 | 27.2 | 29.4 | 56.6 |
| Embodiment 2 | 40 | 26.4 | 28.9 | 55.3 |
| Embodiment 3 | 40 | 26.5 | 28.9 | 55.4 |
| Embodiment 4 | 30 | 29.0 | 27.5 | 56.5 |
| Embodiment 5 | 20 | 25.8 | 29.6 | 55.4 |
| Embodiment 6 | 40 | 25.4 | 30.5 | 55.9 |
| Embodiment 7 | 20 | 27.1 | 29.4 | 56.5 |
| Embodiment 8 | 400 | 27.2 | 28.0 | 55.2 |
| Embodiment 9 | 200 | 25.1 | 30.2 | 55.3 |
| Embodiment 10 | 30 | 27.5 | 28.6 | 56.1 |
| Embodiment 11 | 40 | 27.9 | 27.6 | 55.5 |
| Embodiment 12 | 40 | 25.6 | 30.2 | 55.8 |
| Embodiment 13 | 40 | 25.6 | 30.7 | 56.3 |
| Embodiment 14 | 40 | 27.8 | 28.1 | 55.9 |
| Embodiment 15 | 40 | 26.8 | 29.4 | 56.2 |
| Embodiment 16 | 40 | 27.4 | 28.4 | 55.8 |
| Embodiment 17 | 40 | 28.2 | 27.1 | 55.3 |
| Embodiment 18 | 40 | 26.2 | 28.5 | 55.7 |
| Embodiment 19 | 40 | 26.8 | 29.1 | 55.9 |
[embodiment 20～22]
Get Hydrogen β zeolite/Y zeolite, β zeolite/mordenite/MCM-22, MCM-49 molecular sieve/mordenite/MCM-22, the mordenite/MCM-22/MCM-49 of embodiment 1, embodiment 2, embodiment 3 and embodiment 4 preparations respectively; The mixture of preparation is as shown in table 3 by weight percentage; Mode by embodiment 1 is checked and rated, and appraisal result is seen table 3.
Table 3
| Embodiment | Used molecular sieve type | Part by weight | Yield of ethene (weight %) | Propene yield (weight %) | Total recovery (weight %) |
| Embodiment 20 | β zeolite/Y zeolite+β zeolite/mordenite/MCM-22 | 1∶1 | 27.3 | 28.7 | 56.0 |
| Embodiment 21 | β zeolite/Y zeolite+β zeolite/mordenite/MCM-22+MCM-49 molecular sieve/mordenite/MCM-22 | 1∶1∶1 | 28.2 | 28.2 | 56.4 |
| Embodiment 22 | β zeolite/Y zeolite+β zeolite/mordenite/MCM-22+MCM-49 molecular sieve/mordenite/MCM-22+ mordenite/MCM-22/MCM-49 | 1∶1∶1∶1 | 27.7 | 28.9 | 56.6 |
[embodiment 23～26]
Getting the Hydrogen coexisting molecular sieve of embodiment 2, embodiment 9, embodiment 16 and embodiment 19 preparations respectively, is that 650 ℃, water/raw oil weight ratio are that 3: 1, weight space velocity were followed successively by respectively 2 hours in temperature of reaction
-11 hour
-10.25 hour
-1With 0.1 hour
-1Condition under check and rate, the result sees table 4.
[embodiment 27～30]
Getting the Hydrogen coexisting molecular sieve of embodiment 2, embodiment 9, embodiment 16 and embodiment 19 preparations respectively, is that 3: 1, weight space velocity are 0.5 hour in water/raw oil weight ratio
-1, temperature of reaction is followed successively by 600 ℃ respectively; 630 ℃; Check and rate under the condition of 680 ℃ and 700 ℃, the result sees table 4.
[embodiment 31～34]
Getting the Hydrogen coexisting molecular sieve of embodiment 2, embodiment 9, embodiment 16 and embodiment 19 preparations respectively, is 0.5 hour at weight space velocity
-1, temperature is that 650 ℃, water/raw oil mass ratio were followed successively by respectively 4: 1; 2: 1; 0.5: 1 and condition under check and rate at 0.1: 1, the result sees table 4.
[embodiment 35～38]
Getting the Hydrogen coexisting molecular sieve of embodiment 2, embodiment 9, embodiment 16 and embodiment 19 preparations respectively, is 0.5 hour at weight space velocity
-1, temperature of reaction is 650 ℃, water/raw oil mass ratio 3: 1, reaction pressure is followed successively by 0.01MPa respectively; 0.05MPa; 0.1MPa with check and rate under the condition of 0.2MPa, the result sees table 4.
Table 4
| Embodiment | Yield of ethene (weight %) | Propene yield (weight %) | Diene yield (weight %) |
| Embodiment 23 | 24.6 | 26.1 | 50.7 |
| Embodiment 24 | 25.7 | 26.8 | 52.5 |
| Embodiment 25 | 28.2 | 27.1 | 55.3 |
| Embodiment 26 | 26.5 | 25.1 | 51.6 |
| Embodiment 27 | 21.4 | 24.7 | 45.1 |
| Embodiment 28 | 23.5 | 24.9 | 48.4 |
| Embodiment 29 | 29.4 | 27.3 | 56.7 |
| Embodiment 30 | 30.2 | 25.2 | 55.4 |
| Embodiment 31 | 27.8 | 29.7 | 57.5 |
| Embodiment 32 | 28.5 | 28.9 | 57.4 |
| Embodiment 33 | 27.3 | 26.9 | 54.2 |
| Embodiment 34 | 26.3 | 21.4 | 47.7 |
| Embodiment 35 | 28.3 | 28.1 | 56.4 |
| Embodiment 36 | 28.4 | 28.3 | 56.7 |
| Embodiment 37 | 28.3 | 27.7 | 56.0 |
| Embodiment 38 | 28.6 | 26.6 | 55.2 |
Claims (5)
1. the method for naphtha catalytic cracking system ethene and propylene is with C
4～C
10The light oil of hydrocarbon is raw material, is 600～700 ℃ in temperature of reaction, and reaction pressure is 0.001～0.5MPa, and the reaction weight space velocity is 0.1～4 hour
-1Water/raw material weight ratio is under 0.1～4: 1 the condition; Raw material contacts with catalyzer; Reaction generates ethene and propylene, it is characterized in that used catalyzer is for being selected from least a in mordenite/beta zeolite/Y zeolite, mordenite/beta zeolite/euthalite, mordenite/beta zeolite/MCM-22, mordenite/MCM-22/MCM-49, mordenite/MCM-22, mordenite/Y zeolite, β zeolite/Y zeolite, ZSM-5/ mordenite/Magadiite, ZSM-5/ β zeolite/MCM-22, ZSM-5/ β zeolite/Magadiite, ZSM-5/ β zeolite/Y zeolite, ZSM-5/ β zeolite/MCM-49, ZSM-5/ β zeolite/MCM-56, ZSM-5/ β zeolite/ZSM-23, ZSM-5/ mordenite/MCM-49, ZSM-5/ mordenite/MCM-56, ZSM-5/ mordenite/ZSM-23, ZSM-5/ZSM-23/MCM-22, the ZSM-5/ZSM-23/Y zeolite coexisting molecular sieve.
2. according to the method for said naphtha catalytic cracking system ethene of claim 1 and propylene, it is characterized in that temperature of reaction is 620～680 ℃, the reaction weight space velocity is 0.2～2 hour
-1, water/raw material weight ratio is 0.1～3: 1, reaction pressure is 0.01～0.2MPa.
3. according to the method for said naphtha catalytic cracking system ethene of claim 2 and propylene, it is characterized in that water/raw material weight ratio is 0.5～3: 1.
4. according to the method for said naphtha catalytic cracking system ethene of claim 1 and propylene, the silica alumina ratio that it is characterized in that coexisting molecular sieve is SiO
2/ Al
2O
3Be 8～1000.
5. according to the method for said naphtha catalytic cracking system ethene of claim 4 and propylene, the silica alumina ratio that it is characterized in that coexisting molecular sieve is SiO
2/ Al
2O
3Be 12～200.
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