CN105478162A - Catalyst for reducing green coke and producing more low-carbon olefins - Google Patents
Catalyst for reducing green coke and producing more low-carbon olefins Download PDFInfo
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- CN105478162A CN105478162A CN201410535604.6A CN201410535604A CN105478162A CN 105478162 A CN105478162 A CN 105478162A CN 201410535604 A CN201410535604 A CN 201410535604A CN 105478162 A CN105478162 A CN 105478162A
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Abstract
The invention relates to a catalyst for reducing green coke and producing more low-carbon olefins. The catalyst contains the ingredients in percentage by weight: 10-85wt% of aluminum binder, 15-60wt% of molecular sieves and 0-75wt% of clay, wherein the molecular sieves are MFI-structure zeolite or MFI-structure zeolite and Y-type zeolite. A preparation method for the catalyst comprises the following steps of preparing slurry from the aluminum binder, the clay, the molecular sieves, water and carboxymethyl cellulose, carrying out spray drying, and carrying out optional roasting. The catalyst provided by the invention has the advantages that the degree of sphericity is high, the yield of the low-carbon olefins is high, and the yield of the coke is low.
Description
Technical field
The present invention relates to a kind of catalyst and Synthesis and applications thereof of heavy oil fluidized producing low-carbon alkene by catalytic pyrolysis.
Background technology
Low-carbon alkene (ethene and propylene) is important industrial chemicals, and its demand is very vigorous and constantly increase.Ethene, the propylene of existing market more than 95% are provided by naphtha steam cracking and heavy-oil catalytic preparing low-carbon olefins technology.In recent years, heavily become bad along with petroleum becomes gradually, heavy-oil catalytic preparing low-carbon olefins technology, because energy consumption is low, ingredient requirement is low, product slates flexible adjustment obtains large development, has larger development prospect meeting in the ever-increasing demand in future market.
CN1093101A (Chinese ZL93102783.7) discloses a kind of catalyst for cracking for the production of low-carbon alkene, is made up of clay, the inorganic oxide of 5-99% and the zeolite of 1-50% of 0-70% (taking catalyst weight as benchmark).Zeolite is wherein the mixture of the five-membered ring silica-rich zeolite of the REY of the heavy % of 0-25 or the phosphorous and rare earth of Y-type high-Si zeolite and the heavy % of 75-100.This catalyst has hydrothermal activity stability, conversion ratio and the C higher compared with the catalyst being active component with HZSM-5 zeolite
2 =-C
4 =productive rate.
Summary of the invention
The technical problem to be solved in the present invention is to provide the Catalysts and its preparation method that a kind of heavy oil catalytic pyrolysis containing al binder and molecular sieve newly produces low-carbon alkene, and this catalyst has better sphericity.
The invention provides a kind of catalyst of producing low-carbon alkene by catalytic pyrolysis, this catalyst comprises in butt 10-85 % by weight al binder, in butt 15-60 % by weight molecular sieve with in the clay of butt 0-75 % by weight, described molecular sieve is MFI structure zeolite or MFI structure zeolite and y-type zeolite; The preparation method of described catalyst comprises the following steps: al binder, clay, molecular sieve, water and carboxymethyl cellulose are formed slurries, by formed slurries spray drying forming, and optional roasting.
The present invention also provides a kind of method of producing low-carbon alkene by catalytic pyrolysis, the step contacted with catalytic cracking catalyst provided by the invention by hydrocarbon ils under being included in the condition of catalytic pyrolysis.
Catalyst provided by the invention, has lower coke yield for heavy oil catalytic pyrolysis, has higher productivity of low carbon olefin hydrocarbon.Catalyst of the present invention can be used as auxiliary agent or catalyst for hydrocarbon oil catalytic cracking, is particularly suited for fluid catalytic cracking of heavy oil.The preparation method of catalyst provided by the invention, adds carboxymethyl cellulose in preparation process, and can well arrange in pairs or groups with al binder makes catalyst spherical degree good, and anti-wear performance is good, improves pore volume and increases specific area, can improve product slates simultaneously; Can be used for preparing macropore carrier Cracking catalyst.Heavy oil catalytic pyrolysis provided by the invention produces the method for low-carbon alkene, can be used for fluid catalytic cracking of heavy oil and produces low-carbon alkene, especially produce propylene.One or more in described heavy oil such as AGO (atmospheric gas oil), vacuum gas oil (VGO), reduced crude, decompression residuum.
Detailed description of the invention
The catalyst of producing low-carbon alkene by catalytic pyrolysis provided by the invention, its preparation process comprises al binder, clay, molecular sieve and water mixing making beating, wherein, also adds carboxymethyl cellulose, the slurries spraying dry then will obtained in mixing pulping process.Wherein the butt weight ratio of al binder, molecular sieve and clay is 10-85:15-60:0-75; Carboxymethyl cellulose with in the weight ratio of the al binder of butt for 2-40:100.Described butt weight is the weight of the solid product that the 800 DEG C of roastings of described raw material obtain for 1 hour.
The catalyst of producing low-carbon alkene by catalytic pyrolysis provided by the invention comprises in butt 10-85 % by weight al binder, and in butt 15-60 % by weight molecular sieve with in the clay of butt 0-75 % by weight, the content of described clay is preferably 15-60 % by weight.Under preferable case, the catalyst of producing low-carbon alkene by catalytic pyrolysis provided by the invention comprises in butt 10-55 % by weight al binder, in butt 15-55 % by weight molecular sieve with in the clay of butt 10-55 % by weight; Such as, described catalyst is made up of the clay of 15-50 % by weight al binder, 15-50 % by weight molecular sieve and 20-50 % by weight, and described molecular sieve is MFI structure zeolite or MFI structure zeolite and y-type zeolite.
The catalyst of producing low-carbon alkene by catalytic pyrolysis provided by the invention, in its preparation process, the solid content of the slurries that al binder, clay, molecular sieve, water and carboxymethyl cellulose are formed is preferably 5-45 % by weight, is more preferably 10-35 % by weight.Described solid content is the percentage in 800 DEG C of roastings, 1 hour gained solid product weight and slurry weight after slurry dried.
Preferably, in described catalyst, the content of clay is preferably 15-60 % by weight.Described that al binder, clay, molecular sieve and carboxymethyl cellulose are formed slurry method is as follows: clay, carboxymethyl cellulose and water are formed slurries, is mixed by the slurries obtained and pull an oar, then mix with binding agent with molecular sieve.Preferably, described by clay, that carboxymethyl cellulose and water form slurry method is as follows: clay is mixed with water and pulls an oar, carboxymethyl cellulose aqueous solution is added in the process that making beating is stirred, carboxymethyl cellulose weight accounts for the 3-30 % by weight of the slurry weight that the making beating of kaolin, carboxymethyl cellulose weight and water is formed, preferred 3-10 % by weight; Then, stir 10-20 minute, stop stirring, leave standstill 10-20 minute, then stir 10-20 minute, stop stirring, leave standstill 10-20 minute, then stir 10-20 minute, whole slurry temperature remain on 60 DEG C below be such as 15-60 DEG C, 15-50 DEG C or 20-40 DEG C.The catalyst obtained like this has that carboxymethyl cellulose is evenly distributed, catalyst productivity of low carbon olefin hydrocarbon is high, the effect that anti-wear performance is good, coke yield is low.In described carboxymethyl cellulose aqueous solution, the concentration of carboxymethyl cellulose is 2-20 % by weight is such as 5-15 % by weight.Wherein in the slurries that formed of clay, water and carboxymethyl cellulose, the content of clay is preferably 5-40 % by weight is such as 5 ~ 25 % by weight.
More preferably, by al binder, clay, it is as follows that molecular sieve and carboxymethyl cellulose form slurry method: by clay and water making beating, add the carboxymethyl cellulose aqueous solution that concentration is 2-20 % by weight, 10-20 minute is stirred in making beating, stop stirring, leave standstill 10-20 minute, stir 10-20 minute again, stop stirring, leave standstill 10-20 minute, stir 10-20 minute again, it is such as 0-60 DEG C that whole slurry temperature remains on less than 60 DEG C, then mix with molecular sieve pulp and pull an oar, finally mix with al binder slurries, obtain the slurries that clay content is 5-40 % by weight such as 5 ~ 25 % by weight.The slurries obtained like this are after spraying dry, and the sphericity of the microballoon of the catalyst obtained is better; Have better selective.
Catalyst spherical degree provided by the invention is better.In the present invention, sphericity (representing with Φ) measuring method is as follows:
Φ＝4·π·A/P
2
In formula, Φ is sphericity (also claiming degree of rounding of grains), and A is the projected area of particle, and P is particle projection girth.
The catalyst of producing low-carbon alkene by catalytic pyrolysis provided by the invention, described clay is one or more in the clay commonly used of this area, such as, be one or more in kaolin, rectorite, imvite, diatomite, galapectite, saponite, sepiolite, attapulgite, hydrotalcite and bentonite.In described clay, metal impurities are as Fe, Ca, Mg etc., and in clay of the present invention, impurity element weight content is preferably: Fe
2o
3<0.8%, CaO<0.2%, MgO<0.5%.
In the catalyst of producing low-carbon alkene by catalytic pyrolysis provided by the present invention, described al binder is selected from one or more in aluminium oxide and precursor thereof, is preferably 5-80 % by weight in the described al binder content of aluminium oxide.Preferably, aluminium oxide and precursor thereof be Alumina gel, phosphorus Alumina gel, containing aluminium salt (sulfate, nitrate, the halide of such as various aluminate, aluminium), gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, the hydrated alumina with structure of similar to thin diaspore, the hydrated alumina with a diaspore structure, the hydrated alumina with gibbsite structure and have in the hydrated alumina of boehmite structure one or more; Described al binder is more excellent is boehmite, or is boehmite and the mixture of one or more be selected from other precursor of aluminium oxide and aluminium oxide.Under preferable case, when described al binder comprises boehmite, al binder, clay, molecular sieve, water and carboxymethyl cellulose are formed in slurry processes, described boehmite first forms acidification pseudo-boehmite slurries with water and inorganic acid, and then forms slurries with clay, molecular sieve, optional other al binder, water and carboxymethyl cellulose; Described boehmite and water and inorganic acid form acidification pseudo-boehmite slurries, and this slurry solid content is preferably 5-40 % by weight, and pH value is preferably 2-5 such as 3-4; Usually, inorganic acid with in the mol ratio of the boehmite of aluminium oxide for 0.15-0.35 such as can for 0.15-0.25:1; One or more in described inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid.
The catalyst of producing low-carbon alkene by catalytic pyrolysis provided by the invention, containing molecular sieve, described molecular sieve to be described molecular sieve be MFI structure zeolite or MFI structure zeolite and y-type zeolite.Described MFI structure zeolite is such as: one or more in ZSM-5 zeolite, ZSP zeolite, ZRP zeolite, and described Y zeolite is REY zeolite, HY zeolite, REHY zeolite such as; One or more in DASY zeolite, USY zeolite.Contain in described DASY zeolite or do not contain rare earth, containing or P Modification component, such as, is DASY0.0, DASY1.0, DASY2.0; Described USY zeolite contains or not containing rare earth, containing or P Modification component, such as, is USY-1, USY-2.Molecular sieve mixes in pulping process with other component used in catalyst preparation process, first can be prepared into the molecular sieve pulp that solid content is 30-45 % by weight, also can add molecular sieve dry powder.Under preferable case, with catalyst butt weight for benchmark, in described catalyst, the content of MFI structure zeolite is the content of 15-60 % by weight Y zeolite is 0-45 % by weight, and MFI structure zeolite and the ratio of y-type zeolite weight can be 100:0-50 is such as 100:1-50; In described MFI structure zeolite, the mol ratio of silica and aluminium oxide is preferably 15-300:1.
The catalyst of producing low-carbon alkene by catalytic pyrolysis provided by the invention, there is the size distribution of conventional fluid catalytic cracking (FCC) catalyst, such as its average grain diameter (diameter) is 60-80 micron, particle diameter (diameter) is not low 90% volume of particle of 0-149 micron (particle diameter is greater than 0 and is no more than 149 microns), and particle diameter is that the particle of 0-40 micron (particle diameter is greater than 0 and is no more than 40 microns) is no more than 20% volume.
Described spray drying forming, can with reference to existing method, and the present invention repeats no more.
Catalytic cracking catalyst provided by the invention, its preparation method also can comprise the step of roasting.Roasting condition is roasting condition usual in catalytic cracking catalyst preparation process, but the temperature of roasting is not less than 300 DEG C such as 300-800 DEG C, and be generally 350-650 DEG C, roasting time is preferably 1-6 hour.
In catalytic cracking method of the present invention, the described condition contacted with hydrocarbon ils by catalyst is prior art, and such as reaction temperature is 400 DEG C-750 DEG C.According to catalyst cracking method of the present invention, the zeolite containing MFI structure in used catalyst, preferable reaction temperature is 480 DEG C-560 DEG C, introduces water vapour in course of reaction, and the part by weight of steam and feedstock oil is 0.7-14:1.
Catalytic cracking method of the present invention, containing catalyst provided by the invention in described catalyst, also can contain other Cracking catalyst.Such as, when in catalyst provided by the present invention containing when there is the zeolite of MFI structure, catalyst provided by the present invention can be used alone, or after mixing with other Cracking catalyst as auxiliary agent, for the production of low-carbon alkene; During as auxiliary agent, with the gross weight of catalyst for benchmark, the content of catalyst provided by the invention is 1 weight-30 % by weight, is preferably 5 weight-30 % by weight.Described low-carbon alkene is butylene, propylene and ethene.
Example below will be further described the present invention, but not thereby limiting the invention.
In each example and comparative example, Na in zeolite
2o, Fe
2o
3, NiO, A1
2o
3, SiO
2content with x-ray fluorescence method measure [see " and Petrochemical Engineering Analysis method (RIPP experimental technique), the volumes such as Yang Cuiding, Science Press, nineteen ninety publish].
The sphericity of the CamsizerXT dynamic digital imaging particle analyzer testing catalytic Cracking catalyst of German Lai Chi company is adopted in embodiment and comparative example.In embodiment, adopt dry method to measure, condition determination is: sample fast forward rate in feed well is 60% of the maximum vibration speed that instrument specifies, and the speed that sample enters measurement window is 55% of the maximum vibration speed that instrument specifies, and sample introduction is 1.2g.It adopts digital camera to take the two-dimensional projection image of particle, uses digital imaging processing software to obtain projected area and the projection girth of particle, just can the circularity of count particles; A large amount of roundness calculation is carried out to the particle in sample, gets the sphericity that its statistics (mean value) obtains sample.
Embodiment 1
By 19Kg halloysite, (Suzhou china clay company industrial products, solid content 72.3 % by weight, impurity weight content is Fe by analysis
2o
3=0.76%, CaO does not detect, MgO does not detect) add 30Kg decationized Y sieve water, pull an oar after 30 minutes and add cmc soln 98Kg (aqueous solution of 15 % by weight), making beating stirring 20 minutes, stop stirring, leave standstill 15 minutes, then stir 20 minutes, stop stirring, leave standstill 15 minutes, then stir 20 minutes, obtain slurries A.Whole slurry temperature remains on 15-40 DEG C; Wherein in slurries, the content of carboxymethyl cellulose is 10 % by weight, and kaolinic content is 9.34 % by weight;
20Kg decationized Y sieve water and 10Kg boehmite (Shandong Aluminum Plant's industrial products, solid content 63 % by weight) are mixed, making beating, regulate its pH value to be 3 with hydrochloric acid (concentration 30 % by weight, lower same); (Qilu Petrochemical catalyst plant is produced, A1 to add 10Kg Alumina gel
2o
3content is 21.7 % by weight), stir 40 minutes, obtain al binder slurries B, its pH value is 2.7; Slurry solid content is 21.2 % by weight
Molecular sieve pulp 20Kg is added (wherein containing ZRP zeolite 8Kg, ZRP Zeolite (SiO in slurries A
2/ Al
2o
3mol ratio) 40, phosphorous 2.5 % by weight, containing rare earth (RE
2o
3) 1 % by weight, be asphalt in Shenli Refinery of Sinopec catalyst Co., Ltd product), stir and obtain slurries C.
Slurries C mixes with slurries B, stir 30 minutes, and obtain solid content 14.5 % by weight slurries, spraying dry, obtains particle A, and 500 DEG C of roastings 4 hours, then wash away free Na ion, dry, obtains catalyst CA1.CA1 forms: kaolin 45.5% weight, aluminium oxide 28 % by weight, molecular sieve 26.5 % by weight.
Embodiment 2
According to the method for embodiment 1, unlike, do not carry out described making beating repeatedly and stopped process in slurries A preparation process.
By 19Kg halloysite (Suzhou china clay company industrial products, the same) add 30Kg decationized Y sieve water, pull an oar after 30 minutes and add cmc soln 98Kg (aqueous solution of 15%), pull an oar 60 minutes, obtain slurries A, whole slurry temperature remains on 15-40 DEG C.
20Kg decationized Y sieve water and 10Kg boehmite (Shandong Aluminum Plant's industrial products, solid content 63 % by weight) are mixed, making beating, regulate its pH value to be 3 with hydrochloric acid (concentration 30 % by weight, lower same); (Qilu Petrochemical catalyst plant is produced, A1 to add 10Kg Alumina gel
2o
3content is 21.7 % by weight), stir 40 minutes, obtain al binder slurries B, its pH value is 2.7;
Add molecular sieve pulp 20Kg in slurries A and (wherein contain ZRP zeolite 8Kg, ZRP Zeolite 40, phosphorous 2.5 % by weight, containing rare earth (RE
2o
3) 1 % by weight, be catalyst asphalt in Shenli Refinery of China Petrochemical Industry product), stir and obtain slurries C.
Slurries C mixes with slurries B, stir 30 minutes, spraying dry, obtains particle A, and 500 DEG C of roastings 4 hours, then wash away free Na ion, dry, obtains catalyst CA2.
Embodiment 3
By 19Kg halloysite, (impurity content is Fe by analysis for Maoming Kaolin, solid content 75.4 % by weight
2o
3=0.76 % by weight, CaO=0.32 % by weight, MgO=0.25 % by weight) add 30Kg decationized Y sieve water, pull an oar after 30 minutes and add cmc soln 98Kg (aqueous solution of 15 % by weight), making beating stirring 20 minutes, stop stirring, leave standstill 15 minutes, then stir 20 minutes, stop stirring, leave standstill 15 minutes, then stir 20 minutes, obtain slurries A.Whole slurry temperature remains on less than 60 DEG C.
20Kg decationized Y sieve water and 10Kg boehmite (Shandong Aluminum Plant's industrial products, solid content 63 % by weight) are mixed, making beating, regulate its pH value to be 3 with hydrochloric acid (concentration 30 % by weight, lower same); (Qilu Petrochemical catalyst plant is produced, A1 to add 10Kg Alumina gel
2o
3content is 21.7 % by weight), stir 40 minutes, obtain al binder slurries B, its pH value is 2.7;
Add molecular sieve pulp 20Kg in slurries A and (wherein contain ZRP zeolite 8Kg, ZRP Zeolite 40, phosphorous 2.5 % by weight, containing rare earth (RE
2o
3) 1 % by weight, be catalyst asphalt in Shenli Refinery of China Petrochemical Industry product), stir and obtain slurries C.
Slurries C mixes with slurries B, stir 30 minutes, spraying dry, obtains particle B, and 500 DEG C of roastings 4 hours, then wash away free Na ion, dry, obtains catalyst CA3.
Embodiment 4
According to the method for embodiment 1, unlike, carboxymethyl cellulose joins in al binder slurries B, and does not introduce carboxymethyl cellulose in slurries A.Obtain catalyst CA4.
Embodiment 5
According to the method for embodiment 1, be 3 % by weight unlike carboxymethyl cellulose level in the slurries that the consumption adjusting carboxymethyl cellulose makes clay, water and carboxymethyl cellulose be formed; To pull an oar after adding methylcellulose stirring 10 minutes, leave standstill 20 minutes, then stir 10 minutes, leave standstill 15 minutes, then stir 10 minutes, obtain slurries A.Gained catalyst is designated as CA5.
Embodiment 6
According to the method for embodiment 1, unlike, slurries A temperature in whole process keeps 65-80 DEG C.Obtain catalyst CA-6.
Comparative example 1
This comparative example, according to existing method Kaolinite Preparation of Catalyst, does not add carboxymethyl cellulose.
By 30Kg decationized Y sieve water and 19Kg halloysite (Suzhou china clay company industrial products, solid content 72.3 % by weight) mixing making beating, add 10Kg boehmite (Shandong Aluminum Plant's industrial products, solid content 63 % by weight) again, with hydrochloric acid, its PH is adjusted to 3, stir, at 65 DEG C, leave standstill aging 1 hour, maintenance PH is 2-4, cools the temperature to 55 DEG C, (Qilu Petrochemical catalyst plant is produced, A1 to add 10Kg Alumina gel
2o
3content is 21.7 % by weight), stir 40 minutes.Add molecular sieve pulp 20Kg and (wherein contain ZRP zeolite 8Kg, ZRP Zeolite 40, phosphorous 2.5 % by weight, containing rare earth (RE
2o
3) 1 % by weight, be catalyst asphalt in Shenli Refinery of China Petrochemical Industry product), stir, pull an oar, spray drying forming, washes away free Na ion, is drying to obtain contrast medium DB-2.
Embodiment 7-13
Evaluate on the FFB device of laboratory after aging for catalyst CA1-CA6 and DB-2.Catalyst ageing condition: 800 DEG C, 100% steam aging 14h.Operation condition: feedstock oil is grand celebration VGO (character is in table 1), reaction temperature 620 DEG C, agent weight of oil than 10, weight (hourly) space velocity (WHSV) 4h
-1, water injection rate 25 % by weight (accounting for feedstock oil).Reaction result is in table 2.
Table 1 feedstock oil character
Table 2 evaluating catalyst result
Carry out specific area, pore volume and sphericity sign to the catalyst that embodiment 1-6 and comparative example 1 obtain, characterization result is in table 3.
Table 3 catalyst characterization result
。
Claims (13)
1. a catalyst for producing low-carbon alkene by catalytic pyrolysis, comprises 10-85 % by weight al binder, the clay of 15-60 % by weight molecular sieve and 0-75 % by weight, and described molecular sieve is MFI structure zeolite or MFI structure zeolite and y-type zeolite; The preparation method of described catalyst comprises the following steps: al binder, clay, molecular sieve, water and carboxymethyl cellulose are formed slurries, spraying dry, optional roasting.
2., according to catalyst according to claim 1, it is characterized in that, carboxymethyl cellulose with in the weight ratio of the al binder of butt for 2-40:100.
3. according to catalyst according to claim 1, it is characterized in that, containing 15-60 % by weight clay in described catalyst.
4. according to catalyst according to claim 3, it is characterized in that, described that al binder, clay, molecular sieve and carboxymethyl cellulose are formed slurry method is as follows: clay, carboxymethyl cellulose and water are formed slurries, the slurries obtained are mixed with molecular sieve and pulls an oar, then mix with binding agent.
5. catalyst according to claim 4, is characterized in that, carboxymethyl cellulose weight accounts for the 3-30% of the slurry weight that the making beating of kaolin, carboxymethyl cellulose and water is formed.
6. catalyst according to claim 5, it is characterized in that, described by clay, that carboxymethyl cellulose and water form slurry processes is as follows: clay is mixed with water and pulls an oar, add carboxymethyl cellulose aqueous solution, stir 10-20 minute, stop stirring 10-20 minute, then stir 10-20 minute, stop stirring 10-20 minute, then stir 10-20 minute; In whole process, slurry temperature remains on less than 60 DEG C.
7. catalyst according to claim 6, is characterized in that, described carboxymethyl cellulose weight accounts for the 3-10 % by weight of the slurry weight that the making beating of kaolin, carboxymethyl cellulose and water is formed.
8. catalyst according to claim 3, is characterized in that, the impurity content in described clay: Fe
2o
3<0.8 % by weight, CaO<0.2 % by weight, MgO<0.5 % by weight.
9. catalyst according to claim 3, is characterized in that, described clay is one or more in kaolin, rectorite, imvite, diatomite, galapectite, saponite, sepiolite, attapulgite, hydrotalcite and bentonite.
10. according to catalyst according to claim 1, it is characterized in that, described molecular sieve is MFI structure zeolite or MFI structure zeolite and y-type zeolite, with catalyst butt weight for benchmark, the content of described MFI structure zeolite is 15-60 % by weight, and the content of described y-type zeolite is 0-45 % by weight; In described MFI structure zeolite, the mol ratio of silica and aluminium oxide is 15-300:1.
11., according to the catalyst described in any one of claim 1 ~ 10, is characterized in that, are 15-45 % by weight by the solid content that al binder, clay, molecular sieve, water and carboxymethyl cellulose form slurries.
The preparation method of Cracking catalyst described in 12. any one of claim 1-11, comprises al binder, clay, molecular sieve, water and carboxymethyl cellulose mixing making beating, spraying dry, optional roasting.
The method of 13. 1 kinds of heavy oil fluidized producing low-carbon alkene by catalytic pyrolysis, comprises the step contacted with catalytic cracking catalyst by heavy oil, it is characterized in that, the catalyst that described catalytic cracking catalyst provides for any one of claim 1-11.
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| CN108927131A (en) * | 2018-07-09 | 2018-12-04 | 江苏俊镕环保设备有限公司 | A kind of preparation method of tar gas cracking composite catalyzing material |
| CN115041222A (en) * | 2022-06-07 | 2022-09-13 | 山东京博石油化工有限公司 | High-performance propylene additive and preparation method thereof |
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| CN115041222A (en) * | 2022-06-07 | 2022-09-13 | 山东京博石油化工有限公司 | High-performance propylene additive and preparation method thereof |
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