CN101624536B - Method for preparing catalytic cracking catalyst - Google Patents
Method for preparing catalytic cracking catalyst Download PDFInfo
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- CN101624536B CN101624536B CN 200810116448 CN200810116448A CN101624536B CN 101624536 B CN101624536 B CN 101624536B CN 200810116448 CN200810116448 CN 200810116448 CN 200810116448 A CN200810116448 A CN 200810116448A CN 101624536 B CN101624536 B CN 101624536B
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Abstract
The invention discloses a method for preparing a catalytic cracking catalyst, which comprises steps of mixing and pulping aluminum binder and acid. The method is characterized by also comprising steps of adding alkali into slurry to improve the pH value of the slurry, and then adding the acid into the slurry to reduce the pH value of the slurry. The method can stabilize the quality of the prepared catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of catalytic cracking catalyst.
Background technology
In recent years; Catalytically cracked material is heaviness, poor qualityization day by day, in order to obtain high value added product in the case to greatest extent, improves the economic benefit of oil refining enterprise; Need further to improve the performance of existing catalytic cracking catalyst, wherein the improvement to matrix more and more comes into one's own.The matrix of catalyzer can not only presplitting heavy oil macromole, holds metal pollutant, and shaping of catalyst and physical and chemical performance are played a crucial role.
Al binder is a catalytic cracking catalyst sticker commonly used, is that the semi-synthetic matrix catalytic cracking catalyst of sticker has the advantages that intensity is good, heavy oil cracking ability is strong with aluminium colloidal sol and peptization pseudo-boehmite.Pseudo-boehmite is meant and contains a hydrated aluminum oxide to two water moleculess; Be used for cracking catalyst production and will pass through peptization usually; The fluctuation of its peptization performance or peptization degree can cause the prepared catalyzer physical strength and the fluctuation of pore volume; And often there is very big difference in its peptization performance of the pseudo-boehmite of different batches, need confirm best peptization conditions through test of many times, brings very big uncertainty to production.
In patent CN1098130A, CN1247885A, the disclosed method for preparing catalyst of CN1246515A, with the pseudo-boehmite peptization, the order of addition(of ingredients) of different is aluminium colloidal sol, clay, molecular sieve pulp is different with mineral acid.The disclosed method for preparing catalyst of CN1388213A, be with clay slurry with s.t. after, add pseudo-boehmite, water glass solution, add or do not add aluminium colloidal sol, add molecular sieve pulp again after, carry out spraying drying, washing.The disclosed preparation method who contains the molecular sieve hydrocarbon cracking catalyzer of CN1690168A comprises aluminium colloidal sol, hydrated aluminum oxide, clay, acid, molecular sieve and water making beating are mixed, and processes a kind of slurries, the dry then slurries that obtain.Said hydrated aluminum oxide contains a kind of modification hydrated aluminum oxide, and said modification hydrated aluminum oxide is through at least 10 minutes hydrated aluminum oxide of 150-400 ℃ of roasting, and when making beating, said acid adds after aluminium colloidal sol and hydrated aluminum oxide.The subject matter that above patent exists is when fluctuation appears in the peptization performance of pseudo-boehmite, causes the fluctuation of quality product.
In the disclosed production of cracking catalyst of CN1160436C; The fluctuation of the catalyst strength that causes for the fluctuation of avoiding because of the pseudo-boehmite acid consumption and pore volume etc.; Control the acid that adds of pseudo-boehmite peptization through the control slurry viscosity and measure, but not easy to operate in scale operation.
Summary of the invention
The technical problem that the present invention will solve is the problem that causes prepared catalyst strength and pore volume fluctuation to the fluctuation of al binder, and a kind of new production of cracking catalyst is provided.
The present invention provides a kind of preparation method of catalytic cracking catalyst, comprises al binder and the sour step that contacts, pulls an oar, and it is characterized in that, also is included in to add the pH value that alkali improves slurries in the slurries, and adding is sour then, the step of the pH value of reduction slurries.
The present invention also provides a kind of catalytic cracking catalyst, is benchmark with the weight of catalyzer, by butt weight, contains molecular sieve 10-50 weight %, and clay 10-80 weight % is derived from the aluminum oxide 10-40 weight % of peptization al binder and aluminium colloidal sol; The aluminum oxide that wherein is derived from aluminium colloidal sol is 0-15 with the weight ratio that is derived from the aluminum oxide of peptization al binder, the method for preparing catalyst preparation provided by the invention of said catalyzer.
Method for preparing catalyst of the present invention; Through in the al binder of peptization, adding alkali, add the mode of acid again, can stablize the peptization effect of al binder (for example pseudo-boehmite); Eliminate that stray crystal, grain size in the al binder is different, microtexture (cube, needle-like, diamond platy) is different and the influence of the difference of the peptization performance that brings; For the al binder of peptization performance difference, still can obtain good peptization effect, the peptization of the good al binder of peptization performance there is not disadvantageous effect; Peptization redispersion process uniform and complete; And can obtain preferable condition of molding, make prepared catalyst pore volume and abrasion strength resistance stable, the steady quality of catalyst prod.And the particle order in the prepared catalyst prod increases, and size of particles is even.
Embodiment
Among the catalytic cracking catalyst preparation method provided by the invention; The add-on of alkali makes the pH value of slurries be 7-11, is preferably 7-9, and described alkali is selected from one or more in the mineral alkali; For example one or more in ammoniacal liquor, sodium hydroxide and the Pottasium Hydroxide are preferably ammoniacal liquor.Making beating adds acid again after adding alkali more than 10 minutes, and preferred beating time is 20-60 minute.
Among the catalytic cracking catalyst preparation method provided by the invention, the slurries behind the adding alkali add acid again and reduce the pH value, and the add-on of acid makes the pH value of slurries be 2-5, is preferably 3-4; Add the making beating of acid back more than 10 minutes, be preferably 20-60 minute.Described acid is mineral acid commonly used in the existing al binder peptization, for example one or more in hydrochloric acid, nitric acid, phosphoric acid and the sulfuric acid, preferably hydrochloric acid and/or nitric acid.Used acid preferably with al binder with sour contact, pull an oar in used acid be with a kind of acid.
Among the catalytic cracking catalyst preparation method provided by the invention, in slurries, add the pH value that alkali improves slurries, add acid then, the step that reduces the pH value of slurries can repeat one or many, preferably is no more than twice.
In the method for preparing catalyst provided by the invention, at first al binder contact and pull an oar with acid, make the al binder peptization, add the pH value that alkali improves slurries then, again the pH value of the sour reduction of adding slurries.Said with al binder with acid contact, pull an oar; Generally include the slurries that preparation contains al binder and water, add sour acidifying step then, the consumption of acid should be able to make the al binder peptization; The consumption of preferred acid makes the pH value of slurries be 2-6, and more preferably the consumption of acid makes the pH value of slurries be 3-4; Add acid back beating time and be not less than 10 minutes, preferably adding acid back beating time is 20-60 minute.The solid content of slurries is preferably 20-55 weight %.Described al binder is to be preferably pseudo-boehmite by the al binder of sour peptization one or more in pseudo-boehmite, boehmite, gipsite, bayerite, gama-alumina and the η-aluminum oxide for example.Said acid is one or more in the acid of using always in existing al binder (for example pseudo-boehmite) peptization, for example hydrochloric acid and/or nitric acid.
In the method for preparing catalyst provided by the present invention, also comprise the step of introducing active ingredient, said active ingredient preferably adds the pH value that alkali improves slurries in slurries, add acid again, reduces the pH value back of slurries and introduces.Described active ingredient is one or more in the cracking catalyst molecular sieve commonly used; One or more in y-type zeolite, ZSM-5 zeolite and the β zeolite for example; Can also contain modified component in the wherein said zeolite; For example contain P, RE, Fe, Ni modifying element, these are known for those skilled in the art, and the present invention repeats no more.
In the method for preparing catalyst provided by the invention, also can comprise the step of introducing cracking catalyst matrix commonly used, said matrix is one or more in clay, aluminium colloidal sol, rare earth and the inorganic oxide for example.Said clay is one or more in kaolin, halloysite, polynite, zeyssatite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite; Said inorganic oxide is one or more in silicon oxide, aluminum oxide, silica-alumina, titanium oxide, the zirconium white for example.What step is said matrix can introduce in, for example when introducing clay, can in the process of al binder being mixed making beating with acid, introduce; Its preparation method comprises: clay and deionized water are mixed making beating; The preferred 10-60 of beating time minute, more preferably 20-40 minute, add al binder then; Pulled an oar 10-30 minute, and added acidifying again; Also can add acid again, reduce the pH value back introducing clay of slurries in the pH value that adds alkali raising slurries.
Among the preparation method provided by the invention, preferably the solid content of the slurries that obtain of each raw materials mix making beating is 20-55 weight %.
Method provided by the invention also comprises the exsiccant step, and said drying is spraying drying for example.The exsiccant method is known for those skilled in the art, and the present invention does not have particular requirement.
In the method for preparing catalyst provided by the invention, be benchmark with the weight of catalyzer, the consumption of peptization al binder, active ingredient and matrix makes and contains 10-50 weight % molecular sieve in the prepared catalyzer, and 10-80 weight % clay is with Al
2O
3The aluminum oxide that is derived from peptization al binder and aluminium colloidal sol of meter 10-40 weight % wherein is derived from aluminium colloidal sol and the Al that is derived from the peptization al binder
2O
3Weight ratio be 0-15.
Following instance will further be explained the present invention, but therefore not limit the present invention.
In each instance and Comparative Examples, Na in the zeolite
2O, Fe
2O
3, NiO, Al
2O
3, SiO
2Content measure { referring to " petrochemical complex analytical procedure (RIPP experimental technique) ", volumes such as Yang Cuiding, Science Press, nineteen ninety publishes } with x-ray fluorescence method.
Instance 1
With 8.64Kg pseudo-boehmite N-1 (Shandong Aluminum Plant's Industrial products, solid content 63 weight %) making beating, the pH value of slurries is transferred to 3 with 40Kg decationized Y sieve water, pulled an oar again 20 minutes with hydrochloric acid (technical grade, 31 weight %); Under agitation add industrial ammonia (mass concentration 25%) then, the pH value that makes slurries is 8.5, pulls an oar 20 minutes; With above-mentioned hydrochloric acid slurry pH value is transferred to 3 again, pulled an oar 20 minutes; Add 44.44Kg halloysite (Suzhou china clay company Industrial products, solid content 45m%) then, pulled an oar 15 minutes; Add water 25kg, add ZSM-5 molecular sieve pulp 16.0kg (molecular sieve content is 37.97 weight % in the slurries) and REY molecular sieve (butt) 7.0kg again and stirred 15 minutes, add the 7.5Kg aluminium colloidal sol (commerical prod that catalyzer branch office in Shandong obtains down in stirring then; Alumina content 20 heavy %), the compound re chloride of 1Kg (concentration is 300g/kg, and La accounts for 65 weight %, and Ce accounts for 35 weight %); Stirred 5 minutes; Spray drying forming, the flush away Na ion that dissociates is drying to obtain catalyst sample A.
The abrasion index of gained catalyst A is 1.5, and water droplet method pore volume is 0.42 a milliliter/gram, and heap is than being 0.70 grams per milliliter.
Instance 2
With 8.64Kg pseudo-boehmite N-2 (Shandong Aluminum Plant's Industrial products, solid content 57 weight %) making beating, (technical grade, 31 weight %) transfer to 3.5 with its pH with hydrochloric acid, pull an oar 20 minutes again with 40Kg decationized Y sieve water; Add industrial ammonia (mass concentration 25%) 4.0Kg then, making its pH value is 8, pulls an oar 20 minutes.With hydrochloric acid slurries pH is transferred to 3.5 again, pulled an oar 20 minutes, add 44.44Kg halloysite (Suzhou china clay company Industrial products, solid content 45m%); Pulled an oar 15 minutes, and added water 25kg, add ZSM-5 molecular sieve pulp 16.0kg (concentration of slurry is 37.97 weight %) and REY molecular sieve (butt) 7.0kg then; Stirred 15 minutes, and added 7.5Kg aluminium colloidal sol (commerical prod that catalyzer branch office in Shandong obtains, alumina content 20 heavy %) down in stirring again, (concentration is 300g/kg to 1Kg compound rare-earth solution; La accounts for 65%, and Ce accounts for 35%), stirred 5 minutes; Spray drying forming, the flush away Na ion that dissociates is drying to obtain catalyst sample B.
The abrasion index of gained catalyst B is 1.6, and water droplet method pore volume is 0.41 a milliliter/gram, and heap is than 0.69 grams per milliliter.
Comparative Examples 1
With 40Kg decationized Y sieve water 8.64Kg pseudo-boehmite N-1 (Shandong Aluminum Plant's Industrial products, solid content 63m%) is pulled an oar, with hydrochloric acid (technical grade; 31m%) its pH is transferred to 3; Pulled an oar then 20 minutes, and added 44.44Kg halloysite (Suzhou china clay company Industrial products, solid content 45m%) then; Pulled an oar 15 minutes, and added water 25kg; Add ZSM-5 molecular sieve pulp 16.0kg (molecular sieve content is 37.97 weight %) and REY molecular sieve (butt) 7.0kg again, stirred 15 minutes, add the 7.5Kg aluminium colloidal sol (commerical prod that catalyzer branch office in Shandong obtains down in stirring; Alumina content 20 heavy %), the compound re chloride of 1Kg (concentration is 300g/kg, and La accounts for 65%, and Ce accounts for 35%); Stirred 5 minutes; Spray drying forming, the flush away Na ion that dissociates is drying to obtain catalyst sample DB-1.
The abrasion index of gained catalyzer DB is 1.3, and water droplet method pore volume is 0.40 a milliliter/gram, and heap is than 0.69 grams per milliliter.
Comparative Examples 2
With 8.64Kg pseudo-boehmite N-2 (Shandong Aluminum Plant's Industrial products, solid content 57m%) making beating, (technical grade 31m%) transfers to 3.5 with its pH with hydrochloric acid with 40Kg decationized Y sieve water; Pulled an oar then 20 minutes, and added 44.44Kg halloysite (Suzhou china clay company Industrial products, solid content 45m%) again; Pulled an oar 15 minutes, and added water 25kg, add ZSM-5 molecular sieve pulp 16.0kg (concentration of slurry is 37.97%) and REY molecular sieve (butt) 7.0kg then; Stirred 15 minutes, and added 7.5Kg aluminium colloidal sol (commerical prod that catalyzer branch office in Shandong obtains, alumina content 20 heavy %) down in stirring again, (concentration is 300g/kg to 1Kg compound rare-earth solution; La accounts for 65%, and Ce accounts for 35%), stirred 5 minutes; Spray drying forming, the flush away Na ion that dissociates is drying to obtain catalyst sample DB-2.
The abrasion index of gained catalyzer DB-2 is 2.5, and water droplet method pore volume is 0.34 a milliliter/gram, and heap is than being 0.75 grams per milliliter.
Instance 3
With 8.64Kg pseudo-boehmite N-2 (Shandong Aluminum Plant's Industrial products, solid content 57 weight %) making beating, (technical grade, 31 weight %) transfer to 3.5 with its pH with hydrochloric acid, pull an oar 20 minutes again with 40Kg decationized Y sieve water; Add industrial ammonia (mass concentration 25%) 4.0Kg then, making its pH value is 8, pulls an oar 20 minutes; With hydrochloric acid slurries pH is transferred to 3.5 again, pulled an oar 20 minutes, with ammoniacal liquor the pH value of slurries is adjusted to 9 then; Stirred 20 minutes, using the salt acid for adjusting pH value again is 3.0, pulls an oar 30 minutes; Add 44.44Kg halloysite (Suzhou china clay company Industrial products, solid content 45m%) then, pulled an oar 15 minutes; Add water 25kg, add ZSM-5 molecular sieve pulp 16.0kg (concentration of slurry is 37.97 weight %) and REY molecular sieve (butt) 7.0kg then, stirred 15 minutes; Add 7.5Kg aluminium colloidal sol (commerical prod that catalyzer branch office in Shandong obtains, alumina content 20 heavy %) down in stirring again, (concentration is 300g/kg to 1Kg compound rare-earth solution, and La accounts for 65%; Ce accounts for 35%), stirred spray drying forming 5 minutes; The flush away Na ion that dissociates is drying to obtain catalyst sample C.
The abrasion index of gained catalyzer C is 1.2, and water droplet method pore volume is 0.40 a milliliter/gram, and heap is than being 0.67 grams per milliliter.
It is thus clear that; Adopt existing peptization method to prepare catalyzer; The pseudo-boehmite materials variance possibly cause the catalyst prod performance to have than big difference; Prepare catalyzer and use the inventive method, the pseudo-boehmite materials variance is less to the catalyst performance influence, and is also better with the catalyst performance of inferior raw material preparation.
Claims (10)
1. the preparation method of a catalytic cracking catalyst comprises al binder and the sour step that contacts, pulls an oar, and it is characterized in that, also is included in to add the pH value that alkali improves slurries in the slurries, and adding is sour then, the step of the pH value of reduction slurries; By butt weight, said catalytic cracking catalyst contains molecular sieve 10-50 weight %, and clay 10-80 weight % is derived from the aluminum oxide 10-40 weight % of peptization al binder and aluminium colloidal sol; The aluminum oxide that wherein is derived from aluminium colloidal sol is 0-15 with the weight ratio that is derived from the aluminum oxide of peptization al binder: 1.
2. according to the described method of claim 1, it is characterized in that the consumption of alkali makes the pH value of slurries be 7-11.
3. according to the described method of claim 2, it is characterized in that the consumption of alkali makes the pH value of slurries be 7-9.
4. according to claim 1,2 or 3 described methods, it is characterized in that, add behind the alkali and stirred at least 10 minutes.
5. according to the described method of claim 1, it is characterized in that the amount that adds the acid that adds again behind the alkali makes the pH value of slurries be 2-5.
6. according to the described method of claim 5, it is characterized in that the amount that adds the acid that adds again behind the alkali makes the pH value of slurries be 3-4.
7. according to claim 1,5 or 6 described methods, it is characterized in that, add acid back making beating at least 10 minutes.
8. according to the described method of claim 1, it is characterized in that al binder and acid contact, the pull an oar pH value of the slurries that obtain is 2-6.
9. according to the described method of claim 1, it is characterized in that said al binder is one or more in pseudo-boehmite, boehmite, gipsite, bayerite and the η-aluminum oxide.
10. catalytic cracking catalyst is a benchmark with the weight of catalyzer, by butt weight, contains molecular sieve 10-50 weight %, and clay 10-80 weight % is derived from the aluminum oxide 10-40 weight % of peptization al binder and aluminium colloidal sol; The aluminum oxide that wherein is derived from aluminium colloidal sol is 0-15 with the weight ratio that is derived from the aluminum oxide of peptization al binder: 1, and said catalyzer is by each described method preparation of claim 1～9.
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| CN103031062B (en) * | 2011-09-29 | 2014-10-01 | 中国石油化工股份有限公司 | Peptizing aluminum adhering agent and preparation method of peptizing aluminum adhering agent, catalytic cracking catalyst and preparation method of catalytic cracking catalyst |
| CN103028437B (en) * | 2011-09-29 | 2015-07-29 | 中国石油化工股份有限公司 | Peptization al binder and preparation method thereof and catalytic cracking catalyst and preparation method thereof |
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