CN102371172B - Fluidized bed catalyst for preparing alkene through catalytic cracking - Google Patents
Fluidized bed catalyst for preparing alkene through catalytic cracking Download PDFInfo
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Abstract
The invention relates to a fluidized bed catalyst for preparing alkene through catalytic cracking and mainly aims to overcome the technical problems that when conventional fluidized bed catalysts are used for preparing ethene and propylene through catalytic cracking of naphtha, the conversion rate of naphtha and the yield of ethene and propylene are low. Following components by weight are utilized in the invention: 1) 15.0 to 60.0% of kaolin; 2) 10.0 to 30.0% of at least one selected from the group consisting of silicon oxide and alumina; 3) 0.5 to 15.0% of at least one selected from the group consisting of oxides of phosphor, rare earth and alkaline earth; 4) 25.0 to 70.0% of a catalyst which has a grain size of 200 to 1000 nm, is synthesized by using the method of directing agents and comprises ZSM-5 zeolite. According to the invention, the above-mentioned problems are well overcome, and the fluidized bed catalyst can be used in industrial production of ethene and propylene through catalytic cracking.
Description
Technical field
The present invention relates to a kind of fluid catalyst of producing olefin hydrocarbon by catalytic pyrolysis, specifically a kind of small-grain ZSM-5 with directing agent method preparation be active component, be raw material is produced ethene and propylene through catalytic pyrolysis process fluid catalyst with the naphtha.
Background technology
Ethene, propylene are very important two kinds of petrochemical materials, and present global ethene and propylene mainly are to be produced by the steam cracking process.Because traditional steam cracking reaction temperature is up to 820～1000 ℃, the process energy consumption is very high, accounts for 50% of whole ethylene industry energy consumption.This process is non-catalytic free radical thermal cracking mechanism, ethylene/propene lower (0.5～0.7) in its product.Current, face country petrochemical industry is proposed during the 11th Five-Year energy-saving and cost-reducing 20% requirement and the propylene demand that increases day by day, traditional steam cracking process is just standing acid test.Catalytic pyrolysis is to utilize catalyst naphtha to be carried out the process of producing low-carbon olefins by cracking.Compare with steam cracking, catalytic pyrolysis has reaction temperature low (600～780 ℃), and energy consumption significantly reduces and the product propylene/ethylene compares the advantage of high (0.6～1.3).This technology occurs, and the innovation of producing the ethylene, propylene process for traditional steam cracking has brought hope.
Russia organic synthesis research institute and catalytic cracking catalyst active component mainly are variable valency metal compounds such as manganese, vanadium, niobium, tin, iron, and wherein the catalytic performance optimum is to be potassium vanadate (or sodium) fluid catalyst of carrier with ceramic (andalusite-corundum).Though this catalyst has good heat resistance, the advantage of low coking rate and high stability, its cracking reaction temperature are during still up to 770 ℃.[Picciotti M.[J].Oil Gas J，1997，95(25)：53～56.]
Japan Toyo Engineering Corporation is from the THR-RC fluid catalyst, and typical chemistry consists of CaO: Al
2O
3: SiO
2: Fe
2O
3MgO=51.46: 47.74: 0.06: 0.185: 0.25.This catalyst is raw material with the light petrol, and the reaction temperature of cracking is still up to 750 ℃.[Zhang Jian waits .[J] petrochemical industry is dynamic, 1995, (11): 24～30,34.] US4087350 disclosed that the fluid bed Mg of normal pressure and decompression residuum catalysis volume increase alkene is catalyst based, and this catalyst reaction temperatures is up to 745, and the ethylene, propylene yield also has only 28.6%.
Patent CN02152479 has reported that the aperture that Li, alkaline earth, phosphorus and rare earth element are modified is the zeolite catalyst of 0.45～0.75nm, and this catalyst mainly is applicable to the technology of fixed bed hydrocarbon catalytic cracking alkene processed.The crystallite dimension of the not mentioned zeolite of this catalyst.
Patent US6566693B1 has reported the catalyst of a kind of ZSM-5 of the phosphorous modification for petroleum hydrocarbon catalytic pyrolysis alkene processed, and the crystallite dimension of the used zeolite of this patent is micron order.
At present, compare with the catalytic cracking catalyst of oxide type, the catalytic cracking fluid bed catalyst that contains the ZSM-5 zeolite has the advantage that activity is high, the diene yield is high, is the catalytic cracking catalyst that is hopeful to realize industrial applications most.The crystallite dimension of the ZSM-5 zeolite that conventional industry is used is generally several to dozens of microns.Still there is the problem that reactivity is low and the diene yield is low at present in the ZSM-5 zeolite catalyst that contains big crystallite dimension.Compare with the zeolite catalyst of big crystallite dimension (being generally micron order), little crystal grain zeolite catalyst because have specific surface big, expose that the aperture is many, advantage such as diffusion-restricted restriction and the acid centre that can contact are many, thereby in numerous catalytic reactions, show higher catalytic activity, selectively and excellent properties such as anti-carbon.With the zeolite of the little crystal grain active component as catalytic cracking catalyst, will make catalytic pyrolysis have higher reactivity and diene yield.
In sum, be used for the fluid catalyst of stone brain hydrocarbon preparing ethylene propylene from catalytic pyrolysis at present, still exist the naphtha conversion ratio to hang down and ethene, low the asking of propene yield.
Summary of the invention
Technical problem to be solved by this invention is that existing fluid catalyst is in the process that is used for preparing ethylene propylene from catalytic pyrolysis, exist the naphtha conversion ratio low with ethene, technical problem that propene yield is low, a kind of new fluid catalytic cracking catalyst is provided, this catalyst have the naphtha conversion ratio high with ethene, advantage that propene yield is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of fluid catalyst of producing olefin hydrocarbon by catalytic pyrolysis comprises following component by weight percentage: a) 15.0～60.0% kaolin; B) 10.0～30.0% be selected from least a in silica or the aluminium oxide; C) 0.5～15.0% be selected from least a in the oxide of phosphorus, rare earth element and alkaline earth element; D) 25～70% be selected from the ZSM-5 zeolite that crystallite dimension is the directing agent method preparation of 200～1000nm.
The silica preferred version derives from Ludox in the technique scheme, and the preferred version of aluminium oxide derives from least a in aluminium colloidal sol or the acidifying aluminium oxide; Preferred at least a in phosphorus and rare earth or alkaline earth element or its oxide, the content preferred range of P elements oxide is 0.3～5.0% with percentage by weight; Rare earth oxide is a kind of in La or Ce element oxide preferably, and its content preferred range is 0.1～8.0% by weight percentage; Alkaline earth element oxide preferred version is selected from least a in Mg or the Ca element oxide, and its content preferred range is 0.2～5.0% by weight percentage; The silica alumina ratio of ZSM-5 zeolite is 20～300.
Preparation of catalysts method of the present invention is as follows: with ethyl orthosilicate, sodium aluminate, NaOH, TPAOH and water according to 100SiO
2: 0.1Al
2O
3: 1.0NaOH: 25.0 TPAOHs: 2500H
2After the O mixed in molar ratio is even, obtained crystallization director in 120 hours 90 ℃ of following crystallization.With Ludox (SiO
2Percentage by weight is 40%), sodium aluminate, NaOH, ethylenediamine and water is according to 100SiO
2: 0.1～5.0Al
2O
3: 40.0 NaOH: 50.0 ethylenediamines: 4000H
2The mixed in molar ratio of O evenly obtains raw mix, adding is after 0.5～10% crystallization director of raw mix stirs, to obtain the sodium type small-grain ZSM-5 zeolite that crystallite dimension is 200～1000nm in 24～240 hours 120～180 ℃ of following crystallization with the percentage by weight.
Be the Hydrogen ZSM-5 zeolite of 200～1000nm with the crystallite dimension of synthetic sodium type, ammonium nitrate solution with 1M exchanges 3 times down at 60～90 ℃, each 2 hours, the solid-liquid mass ratio is 1: 10, but by 120 ℃ of dryings 4～12 hours, 500～700 ℃ of roastings obtained Hydrogen ZSM-5 zeolite in 4～12 hours.By dipping or the mode of ion-exchange, load 0.1～15% is selected from least a in phosphorus, rare earth or the alkaline earth element on Hydrogen ZSM-5 zeolite, and through 120 ℃ of dryings 4～12 hours, 500～700 ℃ of roastings obtained the ZSM-5 zeolite of support type in 4～12 hours.With the kaolin of aequum, be selected from least a binding agent in Ludox, acidifying aluminium oxide and the aluminium colloidal sol, load and modify the ZSM-5 zeolite of component and water and mix that to obtain solids content be 20～50% slurries, spray-dried moulding obtains 10～200 microns catalyst microballoon, obtains catalytic cracking fluid bed catalyst through 500～800 ℃ of roastings after 1～12 hour.
Compare with the big crystal grain zeolite fluid catalyst of using in the prior art, the present invention adopts catalytic cracking fluid bed catalyst to contain the small-grain ZSM-5 zeolite that crystallite dimension is 200～1000nm that contains of directed agents preparation, the introducing of little crystal grain zeolite has increased the number in catalyst exposure aperture, reduced diffusion-restricted, increased simultaneously and can contact the number of acid centre, thereby had higher naphtha conversion ratio and ethene, propene yield.Simultaneously, by the introducing of rare earth, phosphorus or alkali earth metal oxide, can modify the acid centre of catalyst, regulate density and the acid strength of the acid centre of catalyst, take place thereby reach side reactions such as suppressing hydrogen migration and carbon distribution, also can further improve the yield of ethene, propylene.
The crystallite dimension that the present invention prepares by the employing directing agent method is that the ZSM-5 zeolite of 200～1000nm is active component, phosphorus, alkaline earth or rare earth element or oxide are for modifying the fluid catalyst of component, be raw material with naphtha and water, at 650 ℃, weight space velocity=1.0 hour
-1Water is 4: 1 with the weight ratio of oil, under the reaction condition of normal pressure, the conversion ratio of naphtha can reach 36.3～42.3%, higher by 2～9% than the catalyst of prior art for preparing, ethene and propene yield can reach 18.6～21.2%, and be higher by 2～6% than the catalyst of prior art for preparing, the conversion ratio of naphtha and ethene, propylene diene yield have had and have significantly improved, this method have the naphtha conversion ratio high with ethene, advantage that propene yield is high.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With ethyl orthosilicate, sodium aluminate, NaOH, TPAOH and water according to 100SiO
2: 5.0Al
2O
3: 1.0NaOH: 25.0 TPAOHs: 2500H
2After the O mixed in molar ratio is even, obtained crystallization director in 120 hours 90 ℃ of following crystallization.
With Ludox (SiO
2Percentage by weight is 40%), sodium aluminate, NaOH, ethylenediamine and water is according to 100SiO
2: 5Al
2O
3: 40.0 NaOH: 50.0 ethylenediamines: 4000H
2The mixed in molar ratio of O evenly obtains raw mix, adding is after 10% crystallization director of raw mix stirs with the percentage by weight, obtained the sodium type small-grain ZSM-5 that crystallite dimension is 200-400nm (silica alumina ratio is 20) zeolite in 96 hours 180 ℃ of following crystallization, through washing, separate, 120 ℃ of dryings 4 hours, 550 ℃ of roastings obtained na-pretreated zeolite in 8 hours.With na-pretreated zeolite with 1 mole ammonium nitrate solution 60～90 ℃ of exchanges 3 times down, each 2 hours, the solid-liquid mass ratio was 1: 10, through washing, 120 ℃ of dryings 8 hours, 600 ℃ of roastings roasting in 3 hours obtained the ZSM-5 zeolite a of Hydrogen.
With Ludox (SiO
2Percentage by weight be 40%), sodium aluminate, NaOH, ethylenediamine and water is according to 100SiO
2: 2Al
2O
3: 40 NaOH: 50 ethylenediamines: 4000H
2The mixed in molar ratio of O evenly obtains raw mix, adding is after 10% crystallization director of raw mix stirs with the percentage by weight, obtained the sodium type small-grain ZSM-5 zeolite (silica alumina ratio is 50) that crystallite dimension is 200～400nm in 96 hours 180 ℃ of following crystallization, through washing, separate, 120 ℃ of dryings 4 hours, 550 ℃ of roastings obtained na-pretreated zeolite in 8 hours.With na-pretreated zeolite with 1 mole ammonium nitrate solution 60～90 ℃ of exchanges 3 times down, each 2 hours, the solid-liquid mass ratio was 1: 10, through washing, 120 ℃ of dryings 8 hours, 600 ℃ of roastings roasting in 3 hours obtained the ZSM-5 zeolite b of Hydrogen.
With Ludox (SiO
2Percentage by weight is 40%), sodium aluminate, NaOH, ethylenediamine and water is according to 100.0SiO
2: 05Al
2O
3: 40.0NaOH: 50.0 ethylenediamines: 4000H
2The mixed in molar ratio of O evenly obtains raw mix, adding is after 2.0% crystallization director of raw mix stirs with the percentage by weight, obtained the sodium type small-grain ZSM-5 zeolite (silica alumina ratio is 200) that crystallite dimension is 300～500nm in 96 hours 180 ℃ of following crystallization, through washing, separate, 120 ℃ of dryings 4 hours, 550 ℃ of roastings obtained na-pretreated zeolite in 8 hours.With na-pretreated zeolite with 1 mole ammonium nitrate solution 60～90 ℃ of exchanges 3 times down, each 2 hours, the solid-liquid mass ratio was 1: 10, through washing, 120 ℃ of dryings 8 hours, 600 ℃ of roastings roasting in 3 hours obtained the ZSM-5 zeolite c of Hydrogen.
With Ludox (SiO
2Weight content is 40%), sodium aluminate, NaOH, ethylenediamine and water is according to 100SiO
2: 0.25Al
2O
3: 40NaOH: 50 ethylenediamines: 4000H
2The mixed in molar ratio of O evenly obtains raw mix, adding is after the crystallization director of raw mix weight 0.5% stirs with the percentage by weight, obtained the sodium type small-grain ZSM-5 zeolite (silica alumina ratio is 400) that crystallite dimension is 800～1000nm in 96 hours 180 ℃ of following crystallization, through washing, separate, 120 ℃ of dryings 4 hours, 550 ℃ of roastings obtained na-pretreated zeolite in 8 hours.With na-pretreated zeolite with 1 mole ammonium nitrate solution 60～90 ℃ of exchanges 3 times down, each 2 hours, the solid-liquid mass ratio was 1: 10, through washing, 120 ℃ of dryings 8 hours, 600 ℃ of roastings roasting in 3 hours obtained the ZSM-5 zeolite d of Hydrogen.
Take by weighing aequum phosphoric acid, lanthanum nitrate is mixed with the aqueous solution, loads to the Hydrogen ZSM-5 zeolite a that embodiment 2 obtains by infusion process, through 120 ℃ of dryings 8 hours, 600 ℃ of roastings obtained modification type zeolite in 4 hours.Get aequum kaolin, aluminium colloidal sol (Al
2O
3Content is 21%), modification of zeolite and water mixes that to obtain solid content be 30% slurries.After spray-dried, obtaining particle diameter in 600 ℃ of roastings roasting in 3 hours is 20～200 microns catalyst for cracking e, consisting of by weight percentage: 60% kaolin: 10%SiO
2: 25.0% zeolite a: 2.0%P
2O
5: 3.0%La
2O
3
[embodiment 2]
Take by weighing aequum ammonium dihydrogen phosphate (ADP), lanthanum chloride and magnesium nitrate and be mixed with the aqueous solution, load to Hydrogen ZSM-5 zeolite b by infusion process, through 120 ℃ of dryings 8 hours, 600 ℃ of roastings obtained modification type zeolite in 4 hours.Take by weighing aequum kaolin, Ludox (SiO
2Weight content be 40%), modification of zeolite and water mixes that to obtain solid content be 30% slurries.After spray-dried, obtaining particle diameter in 600 ℃ of roastings roasting in 3 hours is 20～200 microns catalyst for cracking f, consisting of by weight percentage: 30% kaolin: 20%SiO
2: 40% zeolite a: 5.0%P
2O
5: 8.0%La
2O
3: 2.0%MgO.
[embodiment 3]
The phosphoric acid, magnesium nitrate and the lanthanum oxalate that take by weighing aequum are mixed with the aqueous solution, load to the Hydrogen ZSM-5 zeolite b that embodiment 3 obtains by infusion process, and through 120 ℃ of dryings 8 hours, 600 ℃ of roastings obtained modification type zeolite in 4 hours.Get aequum kaolin, aluminium oxide (Al
2O
3Weight content is 71%), hydrochloric acid (weight content 36.5%, consumption are alumina weight 20%), modification of zeolite and water mixes that to obtain solid content be 30% slurries.After spray-dried, obtaining particle diameter in 600 ℃ of roastings roasting in 3 hours is 20～200 microns catalyst for cracking g, consisting of by weight percentage: 25% kaolin: 20%Al
2O
3: 50% zeolite b: 4.0%P
2O
5: 1.0%MgO: 10%La
2O
3
[embodiment 4]
The ammonium dihydrogen phosphate (ADP), calcium nitrate, the cerous nitrate that take by weighing aequum are mixed with the aqueous solution, load to the Hydrogen ZSM-5 zeolite b that embodiment 2 obtains by infusion process, and through 120 ℃ of dryings 8 hours, 600 ℃ of roastings obtained modification type zeolite in 4 hours.Get aequum kaolin, aluminium colloidal sol (Al
2O
3Content is 21%), modification of zeolite and water mixes that to obtain solid content be 30% slurries.After spray-dried, obtaining particle diameter in 600 ℃ of roastings roasting in 3 hours is 20～200 microns catalyst for cracking h, consisting of by weight percentage: 20% kaolin: 30%Al
2O
3: 45% zeolite b: 2.5%P
2O
5: 0.2%CaO: 4.3%CeO
2
[embodiment 5]
The beryllium nitrate, phosphoric acid, the yttrium nitrate that take by weighing aequum are mixed with the aqueous solution, load to the Hydrogen ZSM-5 zeolite c that embodiment 2 obtains by infusion process, and through 120 ℃ of dryings 8 hours, 600 ℃ of roastings obtained modification type zeolite in 4 hours.Get aequum kaolin, aluminium colloidal sol (Al
2O
3Content is 21%), modification of zeolite and water mixes that to obtain solid content be 30% slurries.After spray-dried, obtaining particle diameter in 600 ℃ of roastings roasting in 3 hours is 20～200 microns catalyst for cracking i, consisting of by weight percentage: 30% kaolin: 15%Al
2O
3: 50% zeolite b: 1.0%P
2O
5: 0.2%BeO: 3.8%Y
2O
3
[embodiment 6]
The phosphoric acid, strontium nitrate, barium nitrate and the lanthanum nitrate that take by weighing aequum are mixed with the aqueous solution, and by infusion process load Hydrogen ZSM-5 zeolite c, through 120 ℃ of dryings 8 hours, 600 ℃ of roastings obtained modification type zeolite in 4 hours.Get aequum kaolin, aluminium colloidal sol (Al
2O
3Content is 21%), modification of zeolite and water mixes that to obtain solid content be 30% slurries.After spray-dried, obtaining particle diameter in 600 ℃ of roastings roasting in 3 hours is 20～200 microns catalyst for cracking j, consisting of by weight percentage: 25% kaolin: 20%Al
2O
3: 50% zeolite b: 1.2%P
2O
5: 3.8%SrO 0.5%BaO: 8.0%La
2O
3
[embodiment 7]
The ammonium dihydrogen phosphate (ADP), the lanthanum nitrate that take by weighing aequum are mixed with the aqueous solution, load to Hydrogen ZSM-5 zeolite d by infusion process, and through 120 ℃ of dryings 8 hours, 600 ℃ of roastings obtained modification type zeolite in 4 hours.Get aequum kaolin, boehmite (Al
2O
3Content is 71%), hydrochloric acid (weight content 36%, consumption are boehmite weight 20%), modification of zeolite and water mixes that to obtain solid content be 30% slurries.After spray-dried, obtaining particle diameter in 600 ℃ of roastings roasting in 3 hours is 20～200 microns catalyst for cracking k, by weight percentage consist of 15% kaolin: 10%SiO
2: 0.3%P
2O
5: 4.7%La
2O
3: 70% zeolite d.
[embodiment 8]
The phosphoric acid, gallium nitrate and the lanthanum nitrate that take by weighing aequum are mixed with the aqueous solution, load to Hydrogen ZSM-5 zeolite d by infusion process, and through 120 ℃ of dryings 8 hours, 600 ℃ of roastings obtained modification type zeolite in 4 hours.Get aequum kaolin, boehmite (Al
2O
3Content be 71%), hydrochloric acid (weight content 36%, consumption are boehmite weight 20%), modification of zeolite and water mixes that to obtain solid content be 30% slurries.After spray-dried, obtaining particle diameter in 600 ℃ of roastings roasting in 3 hours is 10～200 microns cracking catalyst l, by weight percentage consist of 20% kaolin: 10%Al
2O
3: 1.0%P
2O
5: 3.0%Ga
2O
3: 1.0%La
2O
3: 65% zeolite d.
[comparative example 1]
The ZSM-5 (silica alumina ratio is 50) of 2000～4000nm is got the identical catalyst Comparative Examples 1 of each constituent content according to the preparation method of embodiment 3.
[comparative example 2]
The ZSM-5 (silica alumina ratio is 400) of 2000～4000nm is obtained the identical catalyst Comparative Examples 2 of each constituent content according to the preparation method of embodiment 7.
Catalyst adopts the fluid bed evaluation, and appreciation condition: 650 ℃, weight space velocity is 1.0 hours
-1, water is 4: 1 with the weight of oil ratio, normal pressure, and the raw material oil composition can see Table 1.
Table 1 high bridge petrochemical industry steam cracking is specialized in the rerum natura of naphtha
| Physical parameter | Typical data |
| Initial boiling point ℃ | 40 |
| The end point of distillation ℃ | 162 |
| Sulfur content (m/m) | 0.0097 |
| Arsenic content (ug/Kg) | 1.07 |
| Alkane content/% | 65.18 |
| N-alkane/% | 32.54 |
| Alkene/% | 0.17 |
| Cycloalkane/% | 28.44 |
| Aromatic hydrocarbons/% | 6.21 |
| Color (Saybolt number) | 30 |
The performance of the producing ethene, propylene through catalytic cracking of 2 different catalysts
| Catalyst | Conversion ratio/% | Ethylene yield (weight)/% | Productivity of propylene (weight)/% | Second+third productive rate (weight)/% |
| e | 36.3 | 9.8 | 8.8 | 18.6 |
| f | 38.5 | 9.2 | 9.7 | 18.9 |
| g | 41.3 | 10.4 | 9.8 | 20.2 |
| h | 42.3 | 9.5 | 10.1 | 19.6 |
| i | 41.0 | 10.6 | 10.2 | 20.8 |
| j | 40.2 | 10.3 | 10.6 | 20.9 |
| k | 38.7 | 9.8 | 11.4 | 21.2 |
| l | 38.2 | 9.5 | 11.3 | 20.8 |
| Comparative example 1 | 32.5 | 6.7 | 7.6 | 14.3 |
| Comparative example 2 | 34.2 | 7.5 | 8.6 | 16.1 |
As can be seen from Table 2, the fluid catalyst that contains phosphorus, alkaline earth or rare earth oxide modification of the present invention's preparation is raw material with naphtha and water, and at 650 ℃, weight space velocity is 1.0 hours
-1Water is 4: 1 with the weight of oil ratio, under the reaction condition of normal pressure, the conversion ratio of naphtha can reach 36.3～42.3%, higher by 2～9% than the catalyst of prior art for preparing, ethene and propene yield can reach 18.6～21.2%, and be higher by 2～6% than the catalyst of prior art for preparing, the conversion ratio of naphtha and ethene, propylene diene yield are significantly improved, and have obtained better technical effect.
Claims (4)
1. the preparation method of the fluid catalyst of a producing olefin hydrocarbon by catalytic pyrolysis, described fluid catalyst comprises following component by weight percentage:
A) 15.0～60.0% kaolin;
B) 10.0～30.0% be selected from least a in silica or the aluminium oxide;
C) 0.5～15.0% be selected from least a in phosphorus, rare earth or the alkaline earth element oxide;
D) 25.0～70.0% be selected from the ZSM-5 zeolite that crystallite dimension is the directing agent method preparation of 200～1000nm;
The preparation method of described fluid catalyst is as follows:
With ethyl orthosilicate, sodium aluminate, NaOH, TPAOH and water according to 100SiO
2: 0.1Al
2O
3: 1.0NaOH: 25.0 TPAOHs: 2500H
2After the O mixed in molar ratio is even, obtained crystallization director in 120 hours 90 ℃ of following crystallization; With SiO
2Percentage by weight is that 40% Ludox, sodium aluminate, NaOH, ethylenediamine and water are according to 100SiO
2: 0.1～5.0Al
2O
3: 40.0 NaOH: 50.0 ethylenediamines: 4000H
2The mixed in molar ratio of O evenly obtains raw mix, adding is 0.5～10% crystallization director of raw mix by weight percentage, after stirring, obtained the sodium type small-grain ZSM-5 zeolite that crystallite dimension is 200～1000nm in 24～240 hours 120～180 ℃ of following crystallization;
Be the ZSM-5 zeolite of 200～1000nm with the crystallite dimension of synthetic sodium type, ammonium nitrate solution with 1M exchanges 3 times down at 60～90 ℃, and each 2 hours, the solid-liquid mass ratio was 1: 10, through 120 ℃ of dryings 4～12 hours, 500～700 ℃ of roastings obtained Hydrogen ZSM-5 zeolite in 4～12 hours; By dipping or the mode of ion-exchange, load 0.1～15% is selected from least a in phosphorus, rare earth or the alkaline earth element on Hydrogen ZSM-5 zeolite, and through 120 ℃ of dryings 4～12 hours, 500～700 ℃ of roastings obtained the ZSM-5 zeolite of support type in 4～12 hours; The kaolin of aequum, the ZSM-5 zeolite that is selected from least a binding agent, above-mentioned support type in Ludox, acidifying aluminium oxide and the aluminium colloidal sol and water mixed to obtain solids content be 20～50% slurries, spray-dried moulding obtains 10～200 microns catalyst microballoon, obtains fluid catalyst through 500～800 ℃ of roastings after 1～12 hour.
2. the preparation method of the fluid catalyst of producing olefin hydrocarbon by catalytic pyrolysis according to claim 1, it is characterized in that being selected from least a in phosphorus and rare earth element or the alkaline earth element oxide, the content of P elements oxide is 0.3～5.0% by weight percentage.
3. the preparation method of the fluid catalyst of producing olefin hydrocarbon by catalytic pyrolysis according to claim 1 is characterized in that rare earth oxide is selected from least a in La or the Ce element oxide, and its content is 0.1～8.0% by weight percentage.
4. the preparation method of the fluid catalyst of producing olefin hydrocarbon by catalytic pyrolysis according to claim 1 is characterized in that alkali earth metal is selected from least a in Mg or the Ca element oxide, and its content is 0.2～5.0% by weight percentage.
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| EP2991762B1 (en) * | 2013-04-29 | 2022-11-16 | Saudi Basic Industries Corporation | Catalytic methods for converting naphtha into olefins |
| CN104888842B (en) * | 2015-05-11 | 2017-12-05 | 中国石油天然气股份有限公司 | A kind of catalytic cracking catalyst and preparation method and application |
| CN106221786B (en) * | 2015-06-02 | 2021-03-02 | 中国科学院大连化学物理研究所 | Naphtha conversion method |
| CN111203225B (en) * | 2020-01-09 | 2023-07-04 | 中国石油大学(华东) | Catalyst for preparing low-carbon olefin by hydrocarbon catalytic pyrolysis and preparation method thereof |
| CN116371454A (en) * | 2023-04-07 | 2023-07-04 | 山东京博石油化工有限公司 | Preparation method and application of light hydrocarbon cracking catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634811A (en) * | 2004-10-18 | 2005-07-06 | 中国石油化工集团公司 | Process for catalytic conversion production of ethylene and propylene |
| CN1915819A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 zeolite in small crystal grain |
| CN101092318A (en) * | 2006-06-21 | 2007-12-26 | 中国科学院大连化学物理研究所 | Method for producing olefin by using vegetable fat and animal fat |
| CN101186313A (en) * | 2007-12-21 | 2008-05-28 | 中国科学院山西煤炭化学研究所 | Small crystal grain zirconium-containing ZSM-5 molecular sieve catalyst and preparation method thereof |
| CN101462916A (en) * | 2007-12-18 | 2009-06-24 | 中国石油化工股份有限公司 | Method for producing light olefin by catalytic pyrolysis of petroleum hydrocarbon |
-
2010
- 2010-08-23 CN CN2010102619249A patent/CN102371172B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634811A (en) * | 2004-10-18 | 2005-07-06 | 中国石油化工集团公司 | Process for catalytic conversion production of ethylene and propylene |
| CN1915819A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 zeolite in small crystal grain |
| CN101092318A (en) * | 2006-06-21 | 2007-12-26 | 中国科学院大连化学物理研究所 | Method for producing olefin by using vegetable fat and animal fat |
| CN101462916A (en) * | 2007-12-18 | 2009-06-24 | 中国石油化工股份有限公司 | Method for producing light olefin by catalytic pyrolysis of petroleum hydrocarbon |
| CN101186313A (en) * | 2007-12-21 | 2008-05-28 | 中国科学院山西煤炭化学研究所 | Small crystal grain zirconium-containing ZSM-5 molecular sieve catalyst and preparation method thereof |
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