CN104549467A - In-situ synthesized composite molecular sieve catalyst and preparation method thereof - Google Patents
In-situ synthesized composite molecular sieve catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN104549467A CN104549467A CN201310512284.8A CN201310512284A CN104549467A CN 104549467 A CN104549467 A CN 104549467A CN 201310512284 A CN201310512284 A CN 201310512284A CN 104549467 A CN104549467 A CN 104549467A
- Authority
- CN
- China
- Prior art keywords
- zsm
- microballoon
- hours
- molecular sieve
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to an in-situ synthesized Y/ZSM-5 composite molecular sieve catalyst and a preparation method thereof, and aims at mainly solving the technical problems that the catalyst cracking activity is low and the yields of ethylene and propylene are low when an existing fluidized bed catalyst is used for catalytically cracking petroleum hydrocarbon to prepare ethylene and propylene. The problems are solved very well by adopting the technical scheme that the in-situ synthesized Y/ZSM-5 composite molecular sieve catalyst is prepared from the following components in parts by weight: (1) 1.0-10.0 parts of at least one of P, La, Mn and Fe oxides; and (2) 90.0-99.0 parts of an in-situ synthesized catalyst containing an in-situ synthesized symbiotic Y/ZSM-5 molecular sieve and micro-balls with the particles size of 10-200 microns. The catalyst can be used for industrial production of catalytically cracking the petroleum hydrocarbon to prepare ethylene and propylene.
Description
Technical field
The present invention relates to composite molecular sieve catalyst of a kind of fabricated in situ and preparation method thereof, particularly a kind of original position symbiosis Y/ ZSM-5 catalytic cracking catalyst and preparation method thereof.
Background technology
Ethene, propylene are very important two kinds of petrochemical materials, and current global ethene and propylene are mainly produced by steam-cracking process.Due to traditional steam cracking reaction temperatures as high 820 ~ 1000 DEG C, process energy consumption is very high, accounts for 50% of whole ethylene industry energy consumption.This process is non-catalytic free radical thermally splitting mechanism, ethylene/propene lower (0.5 ~ 0.7) in its product.Current, face the requirement of during country proposes 11th Five-Year to petrochemical industry energy-saving and cost-reducing 20% and the propylene demand day by day increased, traditional steam-cracking process just undergos acid test.Catalytic pyrolysis utilizes catalyzer to carry out the process of producing low-carbon olefins by cracking to petroleum naphtha.Compared with steam cracking, catalytic pyrolysis has temperature of reaction low (600-780 DEG C), energy consumption significantly reduce and reaction product propylene/ethylene than the advantage of high (0.6 ~ 1.3).This technology occurs, the innovation of producing ethylene, propylene process for traditional steam cracking brings hope.
Russia organic synthesis research institute and catalytic cracking catalyst active ingredient be the variable valency metal compound such as manganese, vanadium, niobium, tin, iron mainly, and wherein catalytic performance optimum is potassium vanadate (or sodium) fluid catalyst that is carrier with ceramic (andaluzite-corundum).Although this catalyzer has good heat resistance, the advantage of low coking rate and high stability, when its cracking reaction temperature is still up to 770 DEG C.[Picciotti M.[J].
Oil Gas J,1997 ,
95 (25) :53～56.]
Toyo Engineering Corporation of Japan is from THR-RC fluid catalyst, and Exemplary chemical consists of CaO: Al
2o
3: SiO
2: Fe
2o
3mgO=51.46: 47.74: 0.06: 0.185:0.25.This catalyzer take petroleum naphtha as raw material, and the temperature of reaction of cracking is still up to 750 DEG C.[Zhang Jian, Deng. [J]. petrochemical complex is dynamic, 1995, (11): 24 ~ 30,34.] Μ S4087350 discloses normal pressure and vacuum residuum catalysis to increase production the fluidized-bed Mg of alkene catalyst based, this catalyst reaction temperatures is up to 745, and ethylene, propylene yield also only has 28.6%.
The aperture that patent CN02152479 reports Li, alkaline earth, phosphorus and Modified by Rare Earth Elements is the molecular sieve catalyst of 0.45 ~ 0.75nm, and this catalyzer is mainly applicable to the technique of fixed bed hydrocarbon catalytic cracking alkene.Also the material of aluminum oxide, aluminum oxide and amorphous aluminum silicide class is inevitably used for improving intensity and the abrasion of catalyzer in its catalyzer.
Patent Μ S6566693B1 reports the catalyzer of a kind of ZSM-5 of the phosphorous modification for petroleum hydrocarbon catalytic pyrolysis alkene, in this fluid catalyst, ZSM-5 molecular sieve content only has 40% at the most, and all the other are the component such as amorphous alumina and silicon oxide for binding agent.
At present, for in the molecular sieve type fluid catalyst composition of naphtha cracking alkene, mostly to introduce the silicon-aluminum oxide materials such as aluminum oxide, silicon-dioxide and amorphous aluminum silicide as binding agent, make the fluidized catalyst of spray shaping have good physical strength and shape.In addition, FCC catalyzer also will add some clays, as some materials such as kaolin, polynite, carclazytes, for increasing the wear resistance of fluidized catalyst.This traditional method is prepared fluid catalyst and is called as the preformed catalyst that narrows above.Binding agent and wear resistant components is introduced in fluidized catalyst, because binding agent and wear-resisting possibility constituent part can enter zeolite cavity or blocking portion zeolite aperture, therefore diffusional limitation is introduced, adsorptive power is caused to weaken, adsorption selectivity is deteriorated, sorption and desorption speed declines, and then causes cracking activity to reduce in catalytic cracking reaction, and ethylene, propylene yield reduces.As by the binding agent of shaping for traditional spray introducing or wear resistant components is all or part of is converted into molecular sieve, effectively can alleviate the stopping state in reaction duct, activity and the stability of fluid catalyst may be improved.The method of this synthesis fluidized-bed is called as in-situ synthesis, and catalyzer is called as fabricated in situ fluid catalyst.
The straight-chain paraffin that size is less is not only had in light naphthar, the naphthenic hydrocarbon also having size relatively large and branched paraffin, and the size being usually used in the ZSM-5 molecular sieve of catalytic pyrolysis is suitable with the former, therefore cause catalyzer just lower to the catalytic cracking activity of light naphthar, transformation efficiency is not high, and ethene and propene yield low, have impact on the efficiency of this process.
Summary of the invention
One of technical problem to be solved by this invention is that the fluid catalyst of the catalytic pyrolysis preparing ethylene prepared of prior art and propylene forms that to there is catalytic cracking activity low with ethene with the low technical problem of propene yield.The invention provides a kind of original position symbiosis Y/ ZSM-5 catalytic cracking catalyst, this catalyst application, in naphtha catalytic pyrolysis preparing ethylene propylene process, has the advantage that catalytic cracking activity is high and ethylene, propylene yield is high.
For solve the problems of the technologies described above two, the invention provides a kind of preparation method for corresponding catalyzer of one of dealing with problems.
For solve the problems of the technologies described above three, the invention provides a kind of purposes for corresponding catalyzer of one of dealing with problems.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of original position Y/ ZSM-5 modified molecular screen base catalytic cracking catalyst, comprises following component with weight parts: a) 0.5 ~ 10.0 part is selected from least one in the oxide compound of P, Fe or Mn; B) 90.0 ~ 99.5 parts are selected from the microballoon of 10 ~ 200 μm of fabricated in situ Y/ZSM-5 coexisting molecular sieve.
In technique scheme, preferred technical scheme is, in catalyst weight number, be selected from P, Fe or Mn element oxide compound in the content of at least one be 2 ~ 5 parts; The silicon oxide of ZSM-5 molecular sieve used and the mol ratio of aluminum oxide are 20 ~ 300; The silicon oxide of ZSM-5 molecular sieve used and the preferred scope of the mol ratio of aluminum oxide are 30 ~ 120.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the preparation method of described catalyzer, comprises following step:
A) according to 10 ~ 70 parts of ZSM-5 molecular sieves, 20 ~ 80 parts of kaolin, 10 ~ 70SiO
2part material: 0 ~ 18.0Al
2o
3: the weight ratio of 0 ~ 5 part of Y molecular sieve crystal seed, takes the ZSM-5 molecular sieve of aequum, kaolin, SiO
2sill, Al
2o
3sill, Y molecular sieve crystal seed, mix with a certain amount of water and be made into the slurries that solid content is 20 ~ 50%, is the microballoon of 10 ~ 200 μm through obtained particle diameter of spraying, and through 550 ~ 900 DEG C of roastings 4 hours, obtains presoma microballoon WQ;
B) according to 100 parts of presoma microballoon WQ:0 ~ 40 part directed agents: 2 ~ 16 parts of Na
2o:500 ~ 5000 part H
2the weight ratio of O takes after the presoma microballoon WQ of aequum, sodium hydroxide, directed agents and deionized water mix, proceed to airtight crystallizing kettle, at 60 ~ 110 DEG C, crystallization obtains the crystallization microballoon containing Y/ ZSM-5 composite molecular screen for 20 ~ 180 hours, through 100 ~ 140 DEG C of dryings at 2 ~ 24 hours, 500 ~ 750 DEG C roasting 2-12 hour removed template method and moisture obtain roasting microballoon YZQ;
C) roasting microballoon YZQ ammonia at 60 ~ 90 DEG C exchanges three times, through 100 ~ 140 DEG C of dryings at 2 ~ 24 hours, 500 ~ 750 DEG C roasting 2-12 hour obtain Hydrogen microballoon HYZQ;
D) the Hydrogen microballoon HYZQ of aequum is taken, flood with the solution of at least one oxide precursor be selected from the oxide compound of P, Fe or Mn, ageing 2 ~ 12 hours at 0 ~ 80 DEG C, at 100 ~ 140 DEG C of dry 2-12 hour, at 500 ~ 750 DEG C, roasting 2-12 hour obtains catalyzer.
In technique scheme, preferred technical scheme is, SiO
2at least one in silicon sol, white carbon black, water glass and water glass that raw material comes, aluminum oxide is from aluminium salt or hydrated aluminum oxide; In HYZQ, the relative crystallinity of Y molecular sieve is 15 ~ 65%; By weight percentage, the preferred scope of the consumption of directed agents is 2 ~ 10 parts; In HYZQ, the preferred scope of the relative crystallinity of Y molecular sieve is 20 ~ 40%;
In technique scheme, preferred technical scheme is, the presoma of metallic element can be nitrate, vitriol, muriate or acetate.The presoma of phosphoric can be originated as at least one in the mixture of phosphoric acid, ammonium di-hydrogen phosphate, DAP, ammonium phosphate or phosphoric acid and ammoniacal liquor.The method of load can adopt the mode of dipping or ion-exchange.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: a kind of method of naphtha catalytic pyrolysis preparing ethylene and propylene, is 610 ~ 720 DEG C in temperature of reaction, and reaction pressure is 0.1 ~ 2.0MPa, water and petroleum hydrocarbon weight ratio are 0.1 ~ 6.0, weight space velocity 0.1 ~ 6.0h
-1condition under, in a fluidized bed reactor, raw material contacts with above-mentioned catalyzer the logistics of reacting and generating containing ethene and propylene.
In technique scheme, preferred technical scheme is, the preferred scope of temperature of reaction is 630 ~ 680 DEG C, and reaction pressure is 0.2 ~ 0.6MPa, and water and the preferred scope of petroleum hydrocarbon weight ratio are 0.2 ~ 1.5, the preferred scope 0.3 ~ 1.0h of weight space velocity
-1.
Compared with fluid catalyst in prior art, the present invention adopts the catalyzer containing ZSM-5 molecular sieve prepared by in-situ techniques, binding agent in shaping presoma and anti-wear agent (kaolin, carclazyte, polynite etc.) are partially converted into Y molecular sieve component, alleviate the stopping state in reaction duct, and define than more rich meso-hole structure, these are all conducive to improving the activity of fluid catalyst, diene yield and stability.Simultaneously, by the introducing of P, Fe or Mn element oxide, can modify the acid sites of catalyzer, regulate density and the strength of acid of the acid sites of catalyzer, thus reach generation such as side reaction such as suppression hydrogen transference and carbon distribution etc., improve stability and the diene yield of catalyzer.
The present invention adopts the fluid catalyst containing phosphorus, alkaline earth or Modified by Rare Earth Elements prepared by in-situ method, and at 650 DEG C, weight space velocity is 0.5 hour
-1water and weight of oil are than being 1:1, under the reaction conditions of normal pressure, take petroleum naphtha as raw material, the catalyzer that the transformation efficiency of petroleum naphtha is prepared than prior art is high by 3 ~ 5%, the catalyzer that diene yield is prepared than prior art is high by 2 ~ 5%, and the transformation efficiency of catalyzer and ethene, proprene diene yield have had and significantly improve, and achieve good technique effect.
Below by specific embodiment, the present invention is further elaborated.
Embodiment
The Y molecular sieve (silica alumina ratio is 2.6) that the degree of crystallinity of Y molecular sieve adopts Catalyst Factory, Nankai Univ to produce is benchmark, its diffraction angle 5 ~ 50
othe peak area sum of the diffraction peak in scope is 100%.
[embodiment 1]
According to 100SiO
2: 11.3Al
2o
3: 110Na
2o:640H
2the weight ratio of O claims the water glass (25.3w%SiO of aequum
2, 7.3w%Na
2o), after sodium hydroxide, aluminum nitrate and water mixes, within aging 24 hours at 45 DEG C, Y zeolite directed agents is obtained.
By 160 grams of kaolin (55.3%SiO
2, 42.5%Al
2o
3, 2.2% other oxide compounds), 20 grams of ZSM-5 molecular sieves (mol ratio of silicon oxide and aluminum oxide is 20.0), 25 grams of silicon sol (40% SiO
2), 2 grams of Y zeolite crystal seeds and 370 grams of water mix, spray shaping obtained the bead ZQ1 of 10 ~ 200 μm, 900 DEG C of roastings 4 hours.
Get 100 grams of atomized microball a, after 20.7 grams of NaOH and 500 gram water mix, proceed in closed reactor 60 DEG C of crystallization 180 hours.After crystallization, product was through washing, 120 DEG C of dryings 4 hours, and 550 DEG C of roastings obtain the crystallization microballoon YZQ1 that sodium form obtains containing Y/ ZSM-5 composite molecular screen for 8 hours.NWQ1 is carried out exchange three times with the ammonium nitrate solution of 1 mole, through washing, 120 DEG C of dryings 8 hours, 600 DEG C of roastings roasting in 3 hours obtains the microballoon HYZQ1 of Hydrogen, and the degree of crystallinity of XRD determining Y zeolite is 15%, and the silicon oxide of Y zeolite and the mol ratio of aluminum oxide are 4.8.
Take 97.2 grams of original position microballoon HYZ1, flood with 80.6 grams of aqueous solution containing 4.5 grams of primary ammonium phosphates, in room temperature ageing after 12 hours, through 120 DEG C of dryings 4 hours, 550 DEG C of roastings 4 hours, obtain situ catalytic agent a, it consists of: 2.8 parts of P
2o
5: 97.2 parts of original position microballoon HYZQ1.
Catalyzer adopts fluidized-bed evaluation, and appreciation condition: 650 DEG C, weight space velocity is 0.5 hour
-1, water and weight of oil ratio=1, normal pressure, the visible table 1 of raw material oil composition, the visible table 2 of reaction result.
[embodiment 2]
By 40 grams of kaolin (55.3%SiO
2, 42.5%Al
2o
32.2% other oxide compounds), 20 grams of ZSM-5 molecular sieves (mol ratio of silicon oxide and aluminum oxide is 100.0), 141.5 grams of white carbon blacks (99.0%SiO2), 171.4 grams of aluminum chloride and 370 grams of water mix, spray shaping obtained the bead ZQ2 of 10 ~ 200 μm, 900 DEG C of roastings 4 hours.
Get 100 grams of atomized microball a, 40 grams of directed agents, after 20.6 grams of NaOH and 500 gram water mix, proceed in closed reactor 110 DEG C of crystallization 20 hours.After crystallization, product was through washing, 120 DEG C of dryings 4 hours, and 550 DEG C of roastings obtain the crystallization microballoon of sodium form containing Y/ ZSM-5 composite molecular screen for 8 hours, YZQ2.YZQ2 is carried out exchange three times with the ammonium nitrate solution of 1 mole, through washing, 120 DEG C of dryings 8 hours, 600 DEG C of roastings roasting in 3 hours obtains the microballoon HYZQ2 of Hydrogen, and the degree of crystallinity of XRD determining Y zeolite is 65%, and the silicon oxide of Y zeolite and the mol ratio of aluminum oxide are 5.2.
Take 90.0 grams of original position microballoon HYZQ2, flood with 75 grams of aqueous solution containing 16.2 grams of phosphoric acid (85%), in room temperature ageing after 12 hours, through 120 DEG C of dryings 4 hours, 550 DEG C of roastings 4 hours, obtain situ catalytic agent b, it consists of: 10.0 parts of P
2o
5: 90.0 parts of original position microballoon HYZQ2.
[embodiment 3]
By 20 grams of kaolin (55.3%SiO
2, 42.5%Al
2o
3, 2.2% other oxide compounds), 120 grams of ZSM-5 molecular sieves (mol ratio of silicon oxide and aluminum oxide is 400.0), 212.4 grams of water glass (25.3w%SiO
2, 7.3w%Na
2o), 130.2 grams of aluminum nitrates and 370 grams of water mix, and spray shaping obtained the bead ZQ3 of 10 ~ 200 μm, 900 DEG C of roastings 4 hours.
Get 100 grams of atomized microball a, 15 grams of directed agents, after 5.0 grams of NaOH and 500 gram water mix, proceed in closed reactor 95 DEG C of crystallization 48 hours.After crystallization, product was through washing, 120 DEG C of dryings 4 hours, and 550 DEG C of roastings obtain sodium form molecular sieve microsphere YZQ3 in 8 hours.YZQ3 is carried out exchange three times with the ammonium nitrate solution of 1 mole, through washing, 120 DEG C of dryings 8 hours, 600 DEG C of roastings roasting in 3 hours obtains the microballoon HYZQ1 of Hydrogen, and the degree of crystallinity of XRD determining Y zeolite is 32%, and the silicon oxide of Y zeolite and the mol ratio of aluminum oxide are 4.6.
Take 99.5 grams of original position microballoon HYZQ3, flood with 81.6 grams of aqueous solution containing 1.3 grams of lanthanum nitrates, in room temperature ageing after 12 hours, through 120 DEG C of dryings 4 hours, 550 DEG C of roastings 4 hours, obtain situ catalytic agent c, it consists of: 0.5 part of La
2o
5: 99.5 parts of original position microballoon HYZQ3.
[embodiment 4]
By 100 grams of kaolin (55.3%SiO
2, 42.5%Al
2o
32.2% other oxide compounds), 60 grams of ZSM-5 molecular sieves (mol ratio of silicon oxide and aluminum oxide is 150.0), 141.4 grams of Starsos, 70 grams of Tai-Ace S 150 and 370 grams of water mix, spray shaping obtained the bead ZQ3 of 10 ~ 200 μm, 900 DEG C of roastings 4 hours.
Get 100 grams of atomized microball a, 20 grams of directed agents, after 2.0 grams of NaOH and 500 gram water mix, proceed in closed reactor 80 DEG C of crystallization 96 hours.After crystallization, product was through washing, 120 DEG C of dryings 4 hours, and 550 DEG C of roastings obtain sodium form molecular sieve microsphere YZQ3 in 8 hours.NWQ3 is carried out exchange three times with the ammonium nitrate solution of 1 mole, through washing, 120 DEG C of dryings 8 hours, 600 DEG C of roastings roasting in 3 hours obtains the microballoon HYZQ1 of Hydrogen, and the degree of crystallinity of XRD determining Y zeolite is 56%, and the silicon oxide of Y zeolite and the mol ratio of aluminum oxide are 5.2.
Take 94.7 grams of original position microballoon HYZQ3, the aqueous solution containing 14.1 grams of iron nitrates and 7.1 grams of tricresyl phosphate ammonia with 77.0 grams floods, in room temperature ageing after 12 hours, through 120 DEG C of dryings 4 hours, 550 DEG C of roastings 4 hours, obtain situ catalytic agent d, it consists of: 2.8 parts of Fe
2o
3part: 2.5P
2o
5: 94.7% original position microballoon HYZQ3.
[embodiment 5]
By 110 grams of kaolin (55.3%SiO
2, 42.5%Al
2o
3, 2.2% other oxide compounds), 80 grams of ZSM-5 molecular sieves (mol ratio of silicon oxide and aluminum oxide is 75.0), 25 grams of silicon sol, 8.0 grams of aluminum nitrates and 370 grams of water mix, and spray shaping obtained the bead ZQ5 of 10 ~ 200 μm, 900 DEG C of roastings 4 hours.
Get 100 grams of atomized microball a, 18 grams of directed agents, after 13.0 grams of NaOH and 500 gram water mix, proceed in closed reactor 95 DEG C of crystallization 48 hours.After crystallization, product was through washing, 120 DEG C of dryings 4 hours, and 550 DEG C of roastings obtain sodium form molecular sieve microsphere YZQ5 in 8 hours.NWQ5 is carried out exchange three times with the ammonium nitrate solution of 1 mole, through washing, 120 DEG C of dryings 8 hours, 600 DEG C of roastings roasting in 3 hours obtains the microballoon HYZQ5 of Hydrogen, and the degree of crystallinity of XRD determining Y zeolite is 42%, and the silicon oxide of Y zeolite and the mol ratio of aluminum oxide are 5.2.
Take 93.3 grams of original position microballoon HYZQ5, the aqueous solution containing 9.7 grams of DAP and 8.8 grams of manganous nitrates (50%) with 77.6 grams floods, in room temperature ageing after 12 hours, through 120 DEG C of dryings 4 hours, 550 DEG C of roastings 4 hours, obtain situ catalytic agent e, it consists of: 5.2 parts of P
2o
5: 1.5 parts of MnO
2: 93.3 parts of original position microballoon HYZQ5.
[embodiment 6]
By 60 grams of kaolin (55.3%SiO
2, 42.5%Al
2o
32.2% other oxide compounds), 100 grams of ZSM-5 molecular sieves (mol ratio of silicon oxide and aluminum oxide is 120.0), 50 grams of silicon sol, 70.8 grams of Starsos, 24.0 grams of aluminum nitrates and 370 grams of water mix, spray shaping obtained the bead ZQ6 of 10 ~ 200 μm, 1050 DEG C of roastings 4 hours.
Get 100 grams of atomized microball a, 20 grams of directed agents, after 2.0 grams of NaOH and 500 gram water mix, proceed in closed reactor 95 DEG C of crystallization 48 hours.After crystallization, product was through washing, 120 DEG C of dryings 4 hours, and 550 DEG C of roastings obtain sodium form molecular sieve microsphere YZQ6 in 8 hours.YZQ6 is carried out exchange three times with the ammonium nitrate solution of 1 mole, through washing, 120 DEG C of dryings 8 hours, 600 DEG C of roastings roasting in 3 hours obtains the microballoon HYZQ6 of Hydrogen, and the degree of crystallinity of XRD determining Y zeolite is 45%, and the silicon oxide of Y zeolite and the mol ratio of aluminum oxide are 5.2.
Take 90.9 grams of original position microballoon HYZQ6, flood, in room temperature ageing after 12 hours with the aqueous solution of 83.2 grams of 4.5 grams of phosphoric acid, 26.7 grams of iron nitrates and 2.7 grams of lanthanum nitrates, through 120 DEG C of dryings 4 hours, 550 DEG C of roastings 4 hours, obtain situ catalytic agent f, it consists of: 2.8 parts of P
2o
5: 5.3 parts of Fe
2o
3: 1.0 parts of La
2o
3: 90.9 parts of original position microballoon HYZQ6.
[embodiment]
Embodiment 7 ~ 11, for adopting catalyzer b, changes reaction conditions and obtains differential responses result, concrete reaction conditions with the results are shown in table 3.
[comparative example 1]
Adopt the Y zeolite content (32%) identical with embodiment 3, zeolite (silica alumina ratio the is 200.0) content about 60% of ZSM-5).Take the Y zeolite (mol ratio of silicon oxide and aluminum oxide is 4.6) of 64 grams of Hydrogens, the zeolite (mol ratio of silicon oxide and aluminum oxide is 400.0) of 120 grams of ZSM-5,6 grams of kaolin, 25 grams of silicon sol mix with 800 grams of water, spray shaping obtained the bead HWQ1 of 10 ~ 200 μm, 900 DEG C of roastings 4 hours.According to the method for similar embodiment 3, on HWQ1 microballoon, the oxide compound of the modification element of load same amount obtains catalyzer x.The evaluation method of catalyzer is with embodiment 2.
[comparative example 2]
Adopt the Y zeolite content (65%) identical with embodiment 2, zeolite (silica alumina ratio the is 200.0) content about 10% of ZSM-5.Take the Y zeolite (mol ratio of silicon oxide and aluminum oxide is 4.6) of 130 grams of Hydrogens, the zeolite (mol ratio of silicon oxide and aluminum oxide is 100.0) of 20 grams of ZSM-5,30 grams of kaolin, 50 grams of silicon sol mix with 800 grams of water, spray shaping obtained the bead HWQ2 of 10 ~ 200 μm, 900 DEG C of roastings 4 hours.According to the method for similar embodiment 2, the oxide catalyst y of the modification element of load same amount on HWQ2 microballoon.The evaluation method of catalyzer is with embodiment 2.
As can be seen from Table 2, the present invention adopts in-situ ZSM-5-5 and Y compound molecular sieve fluid catalyst, under the same reaction conditions, with petroleum naphtha and water for raw material, the transformation efficiency of petroleum naphtha must the catalyzer prepared of prior art high by 3 ~ 5%, the catalyzer that diene yield is prepared than prior art is high by 2 ~ 5%, and the transformation efficiency of catalyzer and ethene, proprene diene yield have had and significantly improve, and achieve good technique effect.
Table 1
| Physical parameter | Representative data |
| Determination of Alkane Content/% | 65.18 |
| Normal paraffin/% | 32.54 |
| Alkene/% | 0.17 |
| Naphthenic hydrocarbon/% | 28.44 |
| Aromatic hydrocarbons/% | 6.21 |
Table 2
Table 3
Claims (10)
1. a Y/ ZSM-5 modified molecular screen base catalytic cracking catalyst for fabricated in situ, with weight parts bag, containing following component:
A) 0.5 ~ 10.0 part is selected from least one in the oxide compound of P, Fe or Mn;
B) 90.0 ~ 99.5 parts are selected from the microballoon of 10 ~ 200 μm of the Y/ZSM-5 coexisting molecular sieve of fabricated in situ.
2. the Y/ZSM-5 catalytic cracking catalyst of fabricated in situ according to claim 1, is characterized in that with weight parts, be selected from P, Fe or Mn element oxide compound in the content of at least one be 2 ~ 5 parts.
3. the Y/ ZSM-5 modified molecular screen base catalytic cracking catalyst of fabricated in situ according to claim 1, is characterized in that the silicon oxide of ZSM-5 molecular sieve used and the mol ratio of aluminum oxide are 20 ~ 300.
4. the preparation method of the Y/ ZSM-5 modified molecular screen base catalytic cracking catalyst of fabricated in situ according to claim 1, comprises following step:
A) according to 10 ~ 70 parts of ZSM-5 molecular sieves, 20 ~ 80 parts of kaolin, 10 ~ 70SiO
2part material: 0 ~ 18.0Al
2o
3: the weight ratio of 0 ~ 5 part of Y molecular sieve crystal seed, takes the ZSM-5 molecular sieve of aequum, kaolin, SiO
2sill, Al
2o
3sill, Y molecular sieve crystal seed, mix with a certain amount of water and be made into the slurries that solid content is 20 ~ 50%, is the microballoon of 10 ~ 200 μm through obtained particle diameter of spraying, and through 550 ~ 900 DEG C of roastings 4 hours, obtains presoma microballoon WQ;
B) according to 100 parts of presoma microballoon WQ:0 ~ 40 part directed agents: 2 ~ 16 parts of Na
2o:500 ~ 5000 part H
2the weight ratio of O takes after the presoma microballoon WQ of aequum, sodium hydroxide, directed agents and deionized water mix, proceed to airtight crystallizing kettle, at 60 ~ 110 DEG C, crystallization obtains the crystallization microballoon containing Y/ ZSM-5 composite molecular screen for 20 ~ 180 hours, through 100 ~ 140 DEG C of dryings at 2 ~ 24 hours, 500 ~ 750 DEG C roasting 2-12 hour removed template method and moisture obtain roasting microballoon YZQ;
C) roasting microballoon YZQ ammonia at 60 ~ 90 DEG C exchanges three times, through 100 ~ 140 DEG C of dryings at 2 ~ 24 hours, 500 ~ 750 DEG C roasting 2-12 hour obtain Hydrogen microballoon HYZQ;
D) the Hydrogen microballoon HYZQ of aequum is taken, flood with the solution of at least one oxide precursor be selected from the oxide compound of P, Fe or Mn, ageing 2 ~ 12 hours at 0 ~ 80 DEG C, at 100 ~ 140 DEG C of dry 2-12 hour, at 500 ~ 750 DEG C, roasting 2-12 hour obtains catalyzer.
5. the preparation method of the Y/ ZSM-5 modified molecular screen base catalytic cracking catalyst of fabricated in situ according to claim 4, it is characterized in that at least one in silicon sol, white carbon black, water glass and water glass that silicon source is next, aluminum oxide is from aluminium salt or hydrated aluminum oxide.
6. the preparation method of the Y/ ZSM-5 modified molecular screen base catalytic cracking catalyst of fabricated in situ according to claim 4, is characterized in that the relative crystallinity of Y molecular sieve in Hydrogen microballoon HYZQ is 15 ~ 65%.
7. the preparation method of original position Y/ ZSM-5 modified molecular screen base catalytic cracking catalyst according to claim 4, is characterized in that, by weight percentage, the consumption of directed agents is 2 ~ 10 parts.
8. the preparation method of the Y/ ZSM-5 modified molecular screen base catalytic cracking catalyst of fabricated in situ according to claim 6, is characterized in that the relative crystallinity of Y molecular sieve in Hydrogen microballoon HYZQ is 20 ~ 40%.
9. a method for naphtha catalytic pyrolysis preparing ethylene and propylene is 610 ~ 720 DEG C in temperature of reaction, and reaction pressure is 0.1 ~ 2.0MPa, and water and petroleum hydrocarbon weight ratio are 0.1 ~ 6.0, weight space velocity 0.1 ~ 6.0h
-1condition under, in a fluidized bed reactor, raw material contacts with any one catalyzer in claim 1 ~ 3, and reaction generates the logistics containing ethene and propylene.
10. the method for naphtha catalytic pyrolysis preparing ethylene according to claim 9 and propylene, it is characterized in that temperature of reaction is 630 ~ 680 DEG C, reaction pressure is 0.2 ~ 0.6MPa, and water and petroleum hydrocarbon weight ratio are 0.2 ~ 1.5, weight space velocity 0.3 ~ 1.0h
-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310512284.8A CN104549467B (en) | 2013-10-28 | 2013-10-28 | Composite molecular sieve catalyst of fabricated in situ and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310512284.8A CN104549467B (en) | 2013-10-28 | 2013-10-28 | Composite molecular sieve catalyst of fabricated in situ and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104549467A true CN104549467A (en) | 2015-04-29 |
| CN104549467B CN104549467B (en) | 2017-07-14 |
Family
ID=53067170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310512284.8A Active CN104549467B (en) | 2013-10-28 | 2013-10-28 | Composite molecular sieve catalyst of fabricated in situ and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104549467B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020078437A1 (en) * | 2018-10-18 | 2020-04-23 | 中国石油化工股份有限公司 | Phosphorus-containing rare-earth-containing mfi structure molecular sieve rich in mesopore, preparation method, and catalyst containing same and application thereof |
| CN111097370A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Spherical meta-xylene adsorbent and preparation method thereof |
| CN112657544A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | Aromatic hydrocarbon olefin removal catalyst and preparation method and application thereof |
| CN112657547A (en) * | 2018-06-11 | 2021-04-16 | 山东多友科技有限公司 | Method for preparing low-carbon olefin by using phosphorus-containing hierarchical pore ZSM-5/Y composite molecular sieve |
| CN115869988A (en) * | 2022-12-02 | 2023-03-31 | 厦门大学 | Catalyst for preparing low-carbon olefins by catalytic cracking of naphtha and preparation method thereof |
| RU2800708C2 (en) * | 2018-10-18 | 2023-07-26 | Чайна Петролеум Энд Кемикал Корпорейшн | Molecular sieve containing phosphorus and rare earth elements with mfi structure and high mesopore content, method for its production, catalyst containing it and its application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279284A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene propylene from catalytic pyrolysis |
| CN102371171A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Catalytic cracking fluidized bed catalyst synthesized in situ |
-
2013
- 2013-10-28 CN CN201310512284.8A patent/CN104549467B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279284A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene propylene from catalytic pyrolysis |
| CN102371171A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Catalytic cracking fluidized bed catalyst synthesized in situ |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112657547A (en) * | 2018-06-11 | 2021-04-16 | 山东多友科技有限公司 | Method for preparing low-carbon olefin by using phosphorus-containing hierarchical pore ZSM-5/Y composite molecular sieve |
| WO2020078437A1 (en) * | 2018-10-18 | 2020-04-23 | 中国石油化工股份有限公司 | Phosphorus-containing rare-earth-containing mfi structure molecular sieve rich in mesopore, preparation method, and catalyst containing same and application thereof |
| RU2800708C2 (en) * | 2018-10-18 | 2023-07-26 | Чайна Петролеум Энд Кемикал Корпорейшн | Molecular sieve containing phosphorus and rare earth elements with mfi structure and high mesopore content, method for its production, catalyst containing it and its application |
| US11964262B2 (en) | 2018-10-18 | 2024-04-23 | China Petroleum & Chemical Corporation | Phosphorus-containing rare-earth-containing MFI structure molecular sieve rich in mesopore, preparation method, and catalyst containing same and application thereof |
| CN111097370A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Spherical meta-xylene adsorbent and preparation method thereof |
| CN111097370B (en) * | 2018-10-29 | 2022-06-28 | 中国石油化工股份有限公司 | Spherical meta-xylene adsorbent and preparation method thereof |
| CN112657544A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | Aromatic hydrocarbon olefin removal catalyst and preparation method and application thereof |
| CN112657544B (en) * | 2019-10-15 | 2023-09-29 | 中国石油化工股份有限公司 | Aromatic hydrocarbon olefin removal catalyst and preparation method and application thereof |
| CN115869988A (en) * | 2022-12-02 | 2023-03-31 | 厦门大学 | Catalyst for preparing low-carbon olefins by catalytic cracking of naphtha and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104549467B (en) | 2017-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100389067C (en) | ZSM-5 type molecular sieve and method for preparing the same | |
| CN104549467A (en) | In-situ synthesized composite molecular sieve catalyst and preparation method thereof | |
| CN101108734B (en) | Beta type molecular sieve and method of manufacturing the same | |
| CN102371171B (en) | Catalytic cracking fluidized bed catalyst synthesized in situ | |
| CN101468318B (en) | Modified rare-earth-containing molecular sieve catalyst as well as preparation method and use thereof | |
| CN1332757C (en) | Cracking catalyst and its application | |
| CN102744092A (en) | Phosphor and rare earth modified molecular sieve | |
| CN101172918B (en) | Method for producing propylene with methanol conversion | |
| CN101745412B (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN102372555A (en) | Method for preparing light olefins through fluid catalytic cracking of naphtha | |
| CN104437594B (en) | Low abrasion methanol aromatic hydrocarbons fluid catalyst and preparation method thereof | |
| CN102744094B (en) | Phosphor and rare earth composite modification method of molecular sieve | |
| CN102463133B (en) | Catalyst for preparing olefin by catalytic cracking, preparation method and application thereof | |
| CN102134082A (en) | Preparation method of ZSM-5 molecular sieve | |
| CN101868434A (en) | Process for producing light olefins from synthesis gas using dual sequential bed reactor | |
| CN102371172B (en) | Fluidized bed catalyst for preparing alkene through catalytic cracking | |
| CN104549466A (en) | In-situ synthesized ZSM-5/Beta symbiotic molecular sieve based catalyst and preparation method thereof | |
| CN114425376B (en) | Hydrocarbon conversion catalyst containing MFI zeolite and its preparation method | |
| CN102372552A (en) | Catalytic pyrolysis method for producing ethene and propylene | |
| CN102746082B (en) | Production method of ethylene and propylene | |
| CN114073976B (en) | Modified ZSM-5 molecular sieve and preparation method and application thereof | |
| CN111068758B (en) | Mesoporous-rich phosphorus-and-rare earth-containing MFI structure molecular sieve and preparation method thereof | |
| CN104557369A (en) | Methanol aromatization method | |
| CN107971008A (en) | A kind of catalytic cracking catalyst and preparation method thereof and petroleum hydrocarbon catalytic pyrolysis method | |
| CN112675902B (en) | Catalyst for preparing propylene by inverse disproportionation of ethylene and butene and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |