CN101279880B - Method for preparing ethylene propylene by catalytic pyrolysis of light oil - Google Patents
Method for preparing ethylene propylene by catalytic pyrolysis of light oil Download PDFInfo
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Abstract
The invention relates to a method for preparing ethylene propylene by light oil through catalytic cracking, which mainly solves the problems of low catalyst activity, low ethylene propylene yield and high reaction temperature of the current ethylene propylene preparing technique by catalytic cracking. The invention properly solves the problems by adopting the technical proposals that: a ZSM-5/mordenite/analcime intergrown molecular sieve, a ZSM-5/mordenite/zeolite beta intergrown molecular sieve, a ZSM-5/mordenite/zeolite Y intergrown molecular sieve, a ZSM-5/mordenite/MCM-22intergrown molecular sieve or a mixture thereof serves as a catalyst, the light oil with the compositions of C4 to C10 hydrocarbon is adopted as a raw material, and the material is in contact reaction with a catalyst under the conditions of a reaction temperature of between 600 and 700 DEG C, a reaction pressure of between 0.001 and 0.5MPa, a reaction weight space velocity of between 0.1 and 4/h, and water/light oil being present in a weight ratio of 0.5-6: 1, and the method of preparation can be used for the industrial production of preparing the ethylene propylene by the light oil through catalytic cracking.
Description
Technical field
The present invention relates to the method for a kind of naphtha catalytic cracking system ethene and propylene.
Background technology
Ethene and propylene industry have 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, 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, the preparing ethylene propylene from catalytic pyrolysis technology is as realizing industrialization, 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 with modification is a 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.With molecular sieve be by 0～25 weight %Y zeolite of high silica alumina ratio or have the ZSM molecular sieve of MFI structure, form by phosphorus/Al, Mg or Ca dipping, but the ethylene, propylene selectivity of catalyzer and yield are not high.
Document CN1565967A, CN1565970A report adopts ZSM-5 molecular sieve or mordenite as crystal seed, adds respectively in the resulting solution of mordenite or ZSM-5 molecular sieve, has 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 to add different crystal seeds in the building-up process as inductor, also needs to 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 composition.Synthetic method is to prepare the reaction mixture gel of synthetic microporous molecular sieve earlier, under 30～300 ℃ of conditions, carry out the crystallization of fs then, after the crystallization 3～300 hours, the pH value of adjusting reaction mixture is 9.5～12, and the synthetic used template of mesoporous molecular sieve of adding, and then at 30～170 ℃ from depressing the hydrothermal crystallizing that carries out subordinate phase, crystallization time is 15～480 hours, mesoporous-microporous composite molecular sieve composition in obtaining, but the building-up process of molecular sieve needs the segmentation crystallization, and the pH value also will be regulated in the centre, and synthetic 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 lattice of molecular sieve.Building-up process of the present invention also needs to 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 the catalyzer use temperature height that exists in the prior art, and the problem that the yield of ethene and propylene is low provides a kind of new naphtha catalytic cracking system ethene and the method for propylene.This method has the catalyst activity height, ethene and propene yield height, the characteristics that temperature of reaction is low.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the method for a kind of naphtha catalytic cracking system ethene and propylene, and with C
4～C
10The light oil of hydrocarbon is raw material, is 600～700 ℃ in temperature of reaction, and reaction pressure is 0.001～0.5MPa, and the reaction weight space velocity is 0.1～4 hour
-1Water/light oil weight ratio is under 0.5～6: 1 the condition, raw material passes through beds, reaction generates ethene, propylene, and wherein used catalyzer is for being selected from ZSM-5/ mordenite/euthalite coexisting molecular sieve, ZSM-5/ mordenite/beta zeolite coexisting molecular sieve, ZSM-5/ mordenite/Y zeolite coexisting molecular sieve, ZSM-5/ mordenite/MCM-22 coexisting molecular sieve or its mixture.
In the technique scheme, the silica alumina ratio SiO of used ZSM-5/ mordenite/euthalite coexisting molecular sieve, ZSM-5/ mordenite/beta zeolite coexisting molecular sieve, ZSM-5/ mordenite/Y zeolite coexisting molecular sieve or ZSM-5/ mordenite/MCM-22 coexisting molecular sieve
2/ Al
2O
3Preferable range is 8～500, and more preferably scope is 12～50; In used ZSM-5/ mordenite/euthalite coexisting molecular sieve, ZSM-5/ mordenite/beta zeolite coexisting molecular sieve, ZSM-5/ mordenite/Y zeolite coexisting molecular sieve or the ZSM-5/ mordenite/MCM-22 coexisting molecular sieve ZSM-5 molecular sieve content by weight percentage preferable range be 10～99.5%, more preferably scope is 60～99%; The temperature of reaction preferable range is 630～680 ℃, and reaction weight space velocity preferable range is 0.2～2 hour
-1, water/light oil weight ratio preferable range is 2～3: 1, the reaction pressure preferable range is 0.01～0.2MPa.
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, make solution with dissolved in distilled water respectively, then two kinds of solution are mixed, the powerful stirring adds the template of aequum then, stirs after 30 minutes with rare acid for adjusting pH value 10～12, 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/ mordenite/euthalite coexisting molecular sieve, ZSM-5/ mordenite/beta zeolite coexisting molecular sieve, ZSM-5/ mordenite/Y zeolite coexisting molecular sieve, ZSM-5/ mordenite/MCM-22 coexisting molecular sieve or its mixture.Because their channel diameter distributes different, can handle 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, strength of acid is higher, can reach good catalytic activity under cryogenic condition, and the ethylene, propylene total recovery can reach more than 55%, has 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 component that adopts Shanghai Gaoqiao petro-chemical corporation to produce is C
4～C
10Light oil be raw material (the raw material physical index sees Table 1), be 12 millimeters down examination of fixed-bed reactor normal pressure with diameter, range of reaction temperature is 600～700 ℃, reaction pressure is 0.001～0.5MPa, mass space velocity is 0.15～2 hour
-1, water/stock oil mass ratio is 0.5～6: 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 |
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Get 284 gram Starsos, become solution A with 300 gram dissolved in distilled water, get 33.4 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 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: 0.1: 0.4: 40: 1.2, 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 ZSM-5/ mordenite/euthalite coexisting molecular sieve.With the XRD diffraction quantitatively as can be known in the coexisting molecular sieve ZSM-5 quality percentage composition be 50.2%, mordenite MOR content is 23.6%, euthalite ANA content is 26.2%.It with concentration 5% ammonium nitrate solution, twice of 70 ℃ of exchange, 550 ℃ of roastings are 3 hours then, after repeating twice, make Hydrogen ZSM-5/ mordenite/euthalite coexisting molecular sieve, then compressing tablet, break into pieces, sieve, get 20～40 purpose particles and put into fixed-bed reactor, in temperature of reaction is that 650 ℃, reaction pressure are 0.02MPa, weight space velocity 0.5 hour
-1, check and rate under water/condition of 3: 1 of stock oil mass ratio, the results are shown in Table 3.
[embodiment 2～7]
According to the method for embodiment 1 synthetic coexisting molecular sieve, raw materials used as shown in table 14, the different mole proportionings of control solution, synthetic ZSM-5/ mordenite/euthalite coexisting molecular sieve sees Table 2 respectively.The ratio of ZSM-5, mordenite and euthalite sees Table 3 in the coexisting molecular sieve.According to the method examination of embodiment 1, the result is as shown in table 4.
Table 2
| Embodiment | Solution mole proportioning | Sample number into spectrum |
| Embodiment 2 | Si：Al：M：H 2O：OH -1＝1：0.005：0.4：40：5 | FH-2 |
| Embodiment 3 | Si：Al：M：H 2O：OH -1＝1：0.01：0.4：40：0.01 | FH-3 |
| Embodiment 4 | Si：Al：M：H 2O：OH -1＝1：0.1：0.1：50：0.001 | FH-4 |
| Embodiment 5 | Si：Al：M：H 2O：OH -1＝1：0.125：0.2：40：0.5 | FH-5 |
| Embodiment 6 | Si：Al：M：H 2O：OH -1＝1：0.167：0：60：2 | FH-6 |
| Embodiment 7 | Si：Al：M：H 2O：OH -1＝1：0.2：0.01：80：4 | FH-7 |
Table 3
| Sample number into spectrum | ZSM-5 content (weight %) | Mordenite content (weight %) | Euthalite content (weight %) |
| FH-1 | 50.2 | 23.6 | 26.2 |
| FH-2 | 96.2 | 1.8 | 2.0 |
| FH-3 | 95.8 | 2.4 | 1.8 |
| FH-4 | 88.2 | 6.5 | 5.3 |
| FH-5 | 65.4 | 22.0 | 12.6 |
| FH-6 | 33.6 | 25.3 | 41.1 |
| FH-7 | 12.3 | 11.3 | 76.4 |
Table 4
| Sample number into spectrum | Yield of ethene (weight %) | Propene yield (weight %) | Total recovery (weight %) |
| Embodiment 1 | 24.51 | 23.24 | 47.75 |
| Embodiment 2 | 28.62 | 27.58 | 56.20 |
| Embodiment 3 | 28.23 | 27.16 | 55.39 |
| Embodiment 4 | 27.89 | 27.04 | 54.93 |
| Embodiment 5 | 26.56 | 25.12 | 51.68 |
| Embodiment 6 | 23.61 | 22.67 | 46.28 |
| Embodiment 7 | 22.74 | 21.23 | 43.97 |
[embodiment 8]
Get 284 gram Starsos, become solution A with 300 gram dissolved in distilled water, get 16.7 gram Tai-Ace S 150, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 12.2 gram quadrols and 29.4 gram tetraethyl ammonium hydroxides (mixed templates is designated as M) then, after stirring for some time, regulate the pH value 11 with dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: M: H
2O=1: 0.05: 0.4: 40, add 3.0 gram β zeolite seed crystals, mixing solutions is put into autoclave, 160 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/ mordenite/beta zeolite coexisting molecular sieve.With the XRD diffraction quantitatively as can be known in the coexisting molecular sieve ZSM-5 quality percentage composition be 60.5%, mordenite content is 23.4%, the β zeolite content is 16.1%.It with concentration 5% ammonium nitrate solution, twice of 70 ℃ of exchange, 550 ℃ of roastings are 3 hours then, after repeating twice, make Hydrogen ZSM-5/ mordenite/beta zeolite coexisting molecular sieve, then compressing tablet, break into pieces, sieve, get 20～40 purpose particles and put into fixed-bed reactor, in temperature of reaction is that 650 ℃, reaction pressure are 0.02MPa, weight space velocity 0.5 hour
-1, check and rate under water/condition of 3: 1 of stock oil mass ratio, the results are shown in Table 7.
[embodiment 9～14]
According to the method for embodiment 8, raw materials used as shown in table 14, the different mole proportionings of control solution, (as using mixed templates, usage ratio is 1: 1 or 1: 1: 1, down with) synthetic ZSM-5/ mordenite/beta zeolite coexisting molecular sieve respectively sees Table 5.The ratio of ZSM-5, mordenite and β zeolite sees Table 6 in the coexisting molecular sieve.According to the method examination of embodiment 8, the result is as shown in table 7.
Table 5
| Embodiment | Solution mole proportioning | Sample number into spectrum |
| Embodiment 9 | Si：Al：M：H 2O：OH -1＝1：0.004：0.4：40：1.5 | FH-9 |
| Embodiment 10 | Si：Al：M：H 2O：OH -1＝1：0.01：0.4：40：0.01 | FH-10 |
| Embodiment 11 | Si：Al：M：H 2O：OH -1＝1：0.125：0.2：40：0.5 | FH-11 |
| Embodiment 12 | Si：Al：M：H 2O：OH -1＝1：0.143：0.1：40：1.2 | FH-12 |
| Embodiment 13 | Si：Al：M：H 2O：OH -1＝1：0.167：0：60：2 | FH-13 |
| Embodiment 14 | Si：Al：M：H 2O：OH -1＝1：0.25：0.4：100：3 | FH-14 |
Table 6
| Sample number into spectrum | ZSM-5 content (weight %) | Mordenite content (weight %) | β zeolite content (weight %) |
| FH-8 | 60.5 | 22.4 | 17.1 |
| FH-9 | 97.2 | 1.2 | 1.6 |
| FH-10 | 84.4 | 8.0 | 7.6 |
| FH-11 | 48.7 | 40.5 | 10.8 |
| FH-12 | 32.1 | 54.5 | 14.4 |
| FH-13 | 14.5 | 73.3 | 12.2 |
| FH-14 | 10.4 | 84.5 | 5.1 |
[0039]Table 7
| Sample number into spectrum | Yield of ethene (weight %) | Propene yield (weight %) | Total recovery (weight %) |
| Embodiment 8 | 25.47 | 24.66 | 50.13 |
| Embodiment 9 | 29.48 | 27.57 | 57.05 |
| Embodiment 10 | 28.45 | 27.12 | 55.57 |
| Embodiment 11 | 24.39 | 24.26 | 48.65 |
| Embodiment 12 | 23.24 | 22.07 | 45.31 |
| Embodiment 13 | 21.12 | 23.51 | 44.63 |
| Embodiment 14 | 20.81 | 23.23 | 44.04 |
[embodiment 15]
Get 284 gram Starsos, become solution A with 300 gram dissolved in distilled water, get 33.4 gram Tai-Ace S 150, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 12.2 gram quadrols and 29.4 gram tetraethyl ammonium hydroxides (mixed templates is designated as M) then, after stirring for some time, regulate the pH value 11 with dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: M: H
2O=1: 0.1: 0.4: 40, add 2.8 gram Y zeolite crystal seeds, mixing solutions is put into autoclave, 160 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/ mordenite/Y zeolite coexisting molecular sieve, with the XRD diffraction quantitatively as can be known in the coexisting molecular sieve ZSM-5 quality percentage composition be 50.5%, mordenite content is 24.2%, and Y zeolite content is 25.3%.It with concentration 5% ammonium nitrate solution, twice of 70 ℃ of exchange, 550 ℃ of roastings are 3 hours then, after repeating twice, make Hydrogen ZSM-5/ mordenite/Y zeolite coexisting molecular sieve, then compressing tablet, break into pieces, sieve, get 20～40 purpose particles and put into fixed-bed reactor, in temperature of reaction is that 650 ℃, reaction pressure are 0.02MPa, weight space velocity 0.5 hour
-1, check and rate under water/condition of 3: 1 of stock oil mass ratio, the results are shown in Table 10.
[embodiment 16～21]
According to the method for embodiment 15, raw materials used as shown in table 14, the different mole proportionings of control solution, synthetic ZSM-5/ mordenite/Y zeolite coexisting molecular sieve sees Table 8 respectively.The ratio of ZSM-5, mordenite and Y zeolite sees Table 9 in the coexisting molecular sieve.According to the method examination of embodiment 15, the result is as shown in table 10.
Table 8
| Embodiment | Solution mole proportioning | Sample number into spectrum |
| Embodiment 16 | Si：Al：M：H 2O：OH -1＝1：0.005：0.4：40：1.5 | FH-16 |
| Embodiment 17 | Si：Al：M：H 2O：OH -1＝1：0.01：0.4：40：0.01 | FH-17 |
| Embodiment 18 | Si：Al：M：H 2O：OH -1＝1：0.1：0.1：50：0.001 | FH-18 |
| Embodiment 19 | Si：Al：M：H 2O：OH -1＝1：0.125：0.2：40：0.5 | FH-19 |
| Embodiment 20 | Si：Al：M：H 2O：OH -1＝1：0.143：0.1：40：1.2 | FH-20 |
| Embodiment 21 | Si：Al：M：H 2O：OH -1＝1：0.25：0.01：80：1 | FH-21 |
Table 9
| Sample number into spectrum | ZSM-5 content (weight %) | Mordenite content (weight %) | Y zeolite content (weight %) |
| FH-15 | 50.5 | 24.2 | 25.3 |
| FH-16 | 97.1 | 1.4 | 1.5 |
| FH-17 | 88.3 | 6.5 | 5.2 |
| FH-18 | 76.2 | 12.3 | 11.5 |
| FH-19 | 40.4 | 38.5 | 21.1 |
| FH-20 | 22.3 | 45.8 | 31.9 |
| FH-21 | 10.3 | 56.3 | 33.4 |
Table 10
| Sample number into spectrum | Yield of ethene (weight %) | Propene yield (weight %) | Total recovery (weight %) |
| Embodiment | 23.22 | 24.45 | 47.67 |
| Embodiment 16 | 29.62 | 27.17 | 56.79 |
| Embodiment 17 | 28.50 | 27.02 | 55.52 |
| Embodiment 18 | 27.29 | 26.76 | 54.05 |
| Embodiment 19 | 23.21 | 24.14 | 47.35 |
| Embodiment 20 | 21.60 | 22.59 | 44.19 |
| Embodiment 21 | 20.83 | 21.33 | 42.16 |
[embodiment 22]
Get 284 gram Starsos, become solution A with 300 gram dissolved in distilled water, get 16.7 gram Tai-Ace S 150, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 12.2 gram quadrols and 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, mixing solutions is put into autoclave, 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/ mordenite/MCM-22 coexisting molecular sieve.With the XRD diffraction quantitatively as can be known in the coexisting molecular sieve ZSM-5 quality percentage composition be 60.3%, mordenite content is 8.9%, MCM-22 content is 30.8%.It with concentration 5% ammonium nitrate solution, twice of 70 ℃ of exchange, 550 ℃ of roastings are 3 hours then, after repeating twice, make Hydrogen ZSM-5/ mordenite/MCM-22 coexisting molecular sieve, then compressing tablet, break into pieces, sieve, get 20～40 purpose particles and put into fixed-bed reactor, in temperature of reaction is that 650 ℃, reaction pressure are 0.02MPa, weight space velocity 0.5 hour
-1, water/stock oil mass ratio 3:1 condition under check and rate, the results are shown in Table 13.
[embodiment 23～28]
According to the method for embodiment 22, raw materials used as shown in table 14, the different mole proportionings of control solution, synthetic ZSM-5/ mordenite/MCM-22 coexisting molecular sieve sees Table 11 respectively.The ratio of ZSM-5, mordenite and Y zeolite sees Table 12 in the coexisting molecular sieve.According to the method examination of embodiment 22, the result is as shown in table 13.
Table 11
| Embodiment | Solution mole proportioning | Sample number into spectrum |
| Embodiment 23 | Si：Al：M：H 2O：OH -1＝1：0.005：0.4：40：1 | FH-23 |
| Embodiment 24 | Si：Al：M：H 2O：OH -1＝1：0.1：0.1：50：0.001 | FH-24 |
| Embodiment 25 | Si：Al：M：H 2O：OH -1＝1：0.05：2：30：0.1 | FH-25 |
| Embodiment 26 | Si：Al：M：H 2O：OH -1＝1：0.05：3：20：1.8 | FH-26 |
| Embodiment 27 | Si：Al：M：H 2O：OH -1＝1：0.167：0：60：2 | FH-27 |
| Embodiment 28 | Si：Al：M：H 2O：OH -1＝1：0.25：0.4：100：1.3 | FH-28 |
Table 12
| Sample number into spectrum | ZSM-5 content (weight %) | Mordenite content (weight %) | MCM-22 content (weight %) |
| FH-22 | 60.3 | 8.9 | 30.8 |
| FH-23 | 96.8 | 1.4 | 1.8 |
| FH-24 | 56.2 | 24.3 | 19.5 |
| FH-25 | 33.6 | 25.3 | 41.1 |
| FH-26 | 40.3 | 7.8 | 51.9 |
| FH-27 | 16.7 | 70.3 | 13.0 |
| FH-28 | 10.8 | 87.0 | 2.2 |
[0059]Table 13
| Sample number into spectrum | Yield of ethene (weight %) | Propene yield (weight %) | Total recovery (weight %) |
| Embodiment 22 | 22.44 | 24.25 | 46.69 |
| Embodiment 23 | 28.79 | 27.47 | 56.26 |
| Embodiment 24 | 22.25 | 24.01 | 46.26 |
| Embodiment 25 | 21.89 | 23.75 | 45.64 |
| Embodiment 26 | 22.26 | 23.64 | 45.90 |
| Embodiment 27 | 21.50 | 22.67 | 44.17 |
| Embodiment 28 | 20.81 | 23.04 | 43.85 |
Table 14
[embodiment 29～33]
Get Hydrogen ZSM-5/ mordenite/euthalite coexisting molecular sieve, ZSM-5/ mordenite/beta zeolite coexisting molecular sieve, ZSM-5/ mordenite/Y zeolite coexisting molecular sieve and the ZSM-5/ mordenite/MCM-22 coexisting molecular sieve of embodiment 3, embodiment 10, embodiment 17 and embodiment 24 preparations respectively, Pei Zhi mixture is as shown in Table 15 by weight percentage, mode by embodiment 1 is checked and rated, and appraisal result sees Table 16.
Table 15
| Embodiment | Used molecular sieve type | Part by weight | Sample number into spectrum |
| Embodiment 29 | ZSM-5/ mordenite/euthalite+ZSM-5/ mordenite/beta zeolite | 1∶1 | HH-1 |
| Embodiment 30 | ZSM-5/ mordenite/beta zeolite+ZSM-5/ mordenite/Y zeolite | 1∶1 | HH-2 |
| Embodiment 31 | ZSM-5/ mordenite/Y zeolite+ZSM-5/ mordenite/MCM-22 | 1∶1 | HH-3 |
| Embodiment 32 | ZSM-5/ mordenite/euthalite+ZSM-5/ mordenite/beta zeolite+ZSM-5/ mordenite/Y zeolite | 1∶1∶1 | HH-4 |
| Embodiment 33 | SM-5/ mordenite/euthalite+ZSM-5/ mordenite/beta zeolite+ZSM-5/ mordenite/Y zeolite+ZSM-5/ mordenite/MCM-22 | 1∶1∶1∶1 | HH-5 |
Table 16
| Sample number into spectrum | Yield of ethene (weight %) | Propene yield (weight %) | Total recovery (weight %) |
| HH-1 | 28.35 | 27.16 | 55.51 |
| HH-2 | 28.49 | 27.24 | 55.73 |
| HH-3 | 27.25 | 26.30 | 53.55 |
| HH-4 | 28.54 | 27.32 | 55.86 |
| HH-5 | 27.65 | 27.44 | 55.19 |
[embodiment 34～37]
Getting Hydrogen ZSM-5/ mordenite/euthalite coexisting molecular sieve, ZSM-5/ mordenite/beta zeolite coexisting molecular sieve, ZSM-5/ mordenite/Y zeolite coexisting molecular sieve and the ZSM-5/ mordenite/MCM-22 coexisting molecular sieve of embodiment 2, embodiment 9, embodiment 16 and embodiment 23 preparations respectively, is that 650 ℃, water/stock oil weight ratio are that 3: 1, weight space velocity were followed successively by respectively 2 hours in temperature of reaction
-11 hour
-10.8 hour
-1With 0.25 hour
-1Condition under check and rate, the results are shown in Table 17.
[embodiment 38～41]
Getting Hydrogen ZSM-5/ mordenite/euthalite coexisting molecular sieve, ZSM-5/ mordenite/beta zeolite coexisting molecular sieve, ZSM-5/ mordenite/Y zeolite coexisting molecular sieve and the ZSM-5/ mordenite/MCM-22 coexisting molecular sieve of embodiment 2, embodiment 9, embodiment 16 and embodiment 23 preparations respectively, is that 3: 1, weight space velocity are 0.5 hour in water/stock 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 results are shown in Table 17.
[embodiment 42～45]
Getting Hydrogen ZSM-5/ mordenite/euthalite coexisting molecular sieve, ZSM-5/ mordenite/beta zeolite coexisting molecular sieve, ZSM-5/ mordenite/Y zeolite coexisting molecular sieve and the ZSM-5/ mordenite/MCM-22 coexisting molecular sieve of embodiment 2, embodiment 9, embodiment 16 and embodiment 23 preparations respectively, is 0.5 hour at weight space velocity
-1, temperature is that 650 ℃, water/stock oil mass ratio were followed successively by respectively 4: 1; 3.5: 1; Checked and rated under the condition, and the results are shown in Table 17 in 2: 1 and 1: 1.
[embodiment 46～49]
Getting Hydrogen ZSM-5/ mordenite/euthalite coexisting molecular sieve, ZSM-5/ mordenite/beta zeolite coexisting molecular sieve, ZSM-5/ mordenite/Y zeolite coexisting molecular sieve and the ZSM-5/ mordenite/MCM-22 coexisting molecular sieve of embodiment 2, embodiment 9, embodiment 16 and embodiment 23 preparations respectively, is 0.5 hour at weight space velocity
-1, temperature of reaction is 650 ℃, water/stock oil mass ratio 3:1, reaction pressure is followed successively by 0.01MPa respectively; 0.05MPa; 0.1MPa and check and rate under the condition of 0.2MPa, the results are shown in Table 17.
Table 17
| Embodiment | Yield of ethene (weight %) | Propene yield (weight %) | Diene yield (weight %) |
| Embodiment 34 | 24.61 | 26.05 | 50.66 |
| Embodiment 35 | 25.73 | 26.82 | 52.55 |
| Embodiment 36 | 26.49 | 27.10 | 53.59 |
| Embodiment 37 | 28.23 | 27.05 | 55.28 |
| Embodiment 38 | 21.35 | 24.74 | 45.09 |
| Embodiment 39 | 23.50 | 24.89 | 48.39 |
| Embodiment 40 | 29.44 | 28.25 | 57.69 |
| Embodiment 41 | 30.20 | 25.23 | 55.43 |
| Embodiment 42 | 28.75 | 28.69 | 57.44 |
| Embodiment 43 | 28.47 | 28.89 | 57.36 |
| Embodiment | Yield of ethene (weight %) | Propene yield (weight %) | Diene yield (weight %) |
| Embodiment 44 | 28.26 | 25.92 | 54.18 |
| Embodiment 45 | 27.30 | 22.41 | 49.71 |
| Embodiment 46 | 29.25 | 27.18 | 56.43 |
| Embodiment 47 | 28.46 | 28.27 | 56.73 |
| Embodiment 48 | 28.34 | 27.74 | 56.08 |
| Embodiment 49 | 27.58 | 27.64 | 55.22 |
Claims (9)
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/light oil weight ratio is under 0.5～6: 1 the condition, raw material passes through beds, reaction generates ethene, propylene, it is characterized in that used catalyzer is for being selected from ZSM-5/ mordenite/euthalite coexisting molecular sieve, ZSM-5/ mordenite/beta zeolite coexisting molecular sieve, ZSM-5/ mordenite/Y zeolite coexisting molecular sieve, ZSM-5/ mordenite/MCM-22 coexisting molecular sieve or its mixture.
2. according to the method for described naphtha catalytic cracking system ethene of claim 1 and propylene, it is characterized in that the weight percentage of ZSM-5 in ZSM-5/ mordenite/euthalite coexisting molecular sieve, ZSM-5/ mordenite/beta zeolite coexisting molecular sieve, ZSM-5/ mordenite/Y zeolite coexisting molecular sieve or the ZSM-5/ mordenite/MCM-22 coexisting molecular sieve is 10～99.5%.
3. according to the method for described naphtha catalytic cracking system ethene of claim 2 and propylene, it is characterized in that the weight percentage of ZSM-5 in ZSM-5/ mordenite/euthalite coexisting molecular sieve, ZSM-5/ mordenite/beta zeolite coexisting molecular sieve, ZSM-5/ mordenite/Y zeolite coexisting molecular sieve or the ZSM-5/ mordenite/MCM-22 coexisting molecular sieve is 60～99%.
4. according to the method for described naphtha catalytic cracking system ethene of claim 1 and propylene, it is characterized in that the SiO of ZSM-5/ mordenite/euthalite coexisting molecular sieve, ZSM-5/ mordenite/beta zeolite coexisting molecular sieve, ZSM-5/ mordenite/Y zeolite coexisting molecular sieve or ZSM-5/ mordenite/MCM-22 coexisting molecular sieve
2/ Al
2O
3Mol ratio is 8～500.
5. according to the method for described naphtha catalytic cracking system ethene of claim 4 and propylene, it is characterized in that the SiO of ZSM-5/ mordenite/euthalite coexisting molecular sieve, ZSM-5/ mordenite/beta zeolite coexisting molecular sieve, ZSM-5/ mordenite/Y zeolite coexisting molecular sieve or ZSM-5/ mordenite/MCM-22 coexisting molecular sieve
2/ Al
2O
3Mol ratio is 12～50.
6. according to the method for described naphtha catalytic cracking system ethene of claim 1 and propylene, it is characterized in that temperature of reaction is 630～680 ℃.
7. according to the method for described naphtha catalytic cracking system ethene of claim 1 and propylene, it is characterized in that reacting weight space velocity is 0.2～2 hour
-1
8. according to the method for described naphtha catalytic cracking system ethene of claim 1 and propylene, it is characterized in that water/light oil weight ratio is 2～3: 1.
9. according to the method for described naphtha catalytic cracking system ethene of claim 1 and propylene, it is characterized in that reaction pressure is 0.01～0.2MPa.
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