CN105728022A - A preparing method of a catalytic cracking catalyst containing a silica sol binder - Google Patents
A preparing method of a catalytic cracking catalyst containing a silica sol binder Download PDFInfo
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Abstract
A preparing method of a catalytic cracking catalyst containing a silica sol binder is disclosed. The method includes mixing an aluminum-based binder, a molecular sieve, clay and silica sol, pulping, spray-drying and calcinating to obtain the catalyst. The silica sol is acid-modified alkaline silica sol. According to acid modification conditions of the alkaline silica sol, an acid is added into alkaline silica sol at 0-30 DEG C under stirring to allow the pH value of the fully mixed sol to be 1-5, thus preparing the acid-modified alkaline silica sol.
Description
Technical field
The preparation method that the present invention relates to a kind of catalyst, is specifically related to the preparation method containing silica sol binder catalytic cracking catalyst.
Background technology
In recent years, along with the exhaustion day by day of petroleum resources, catalytic cracking unit processes heaviness, the ratio of in poor quality raw material is gradually increased, and causes that the coking yield of catalytic cracking is higher, yield of light oil is on the low side.Comparing with the aluminium base Cracking catalyst being widely used at present, silica-based or Silicon-rich catalyst has good coke selectivity and gasoline selective, comes into one's own gradually hence with silica-based Cracking catalyst processing heavy oil.Conventional silica sol binder in the preparation of silica-based Cracking catalyst.
Grace company proposes the preparation method containing Ludox substrate catalytic cracking catalyst first in US3867303, US3867308, and the method sulphuric acid is that acidulant is prepared containing sodium Ludox, and is applied to prepare catalytic cracking catalyst.Preparation process is as follows: (1) acidization prepares Ludox, and pH value is 1.8-3.0；(2) joining in Ludox by clay, can be directly added into after may be made as serosity and add, after clay addition, the pH value of colloidal sol can improve 0.2 unit；(3) prepare molecular sieve pulp so that it is pH value 3.0-4.5, the serosity of molecular sieve pulp with (2) is mixed so that it is pH value 2.8-4.0；(4) spray drying.It is crucial that the pH value by Ludox-clay-molecular sieve pulp is maintained at 2.8-4.0, because lower than 2.8, molecular sieve can be damaged, and then can thicken higher than 4.0 serosity.Prepared catalyst has good wear resistance and higher activity, but bulk density is big, does not flow in fluidisation, is not suitable for present stage most of FCC apparatus and uses, and, surface area is low, and pore volume is little, and matrix-active is low, is unfavorable for the catalytic cracking of residual oil.Afterwards, the preparation method that US3957689 improves Ludox, replace sulphuric acid as acidulant using acidifying aluminum sulfate, improve with single Ludox for binding agent prepare catalyst time the span of control of pH, make the stability of Ludox improve.But prepared catalyst faces the problems referred to above equally.
US4946814 improves the anti-wear performance containing silica sol binder catalytic cracking catalyst by adding the method for surfactant.Ludox, kaolin slurry, molecular sieve pulp and four bursts of logistics of activated alumina are adopted to mix then spray drying continuously and prepare catalyst, the method is binding agent only with Ludox, expensive surfactant must be added to ensure the anti-wear performance of catalyst, and preparation technology is more complicated.
The Catalysts and its preparation method that it is binding agent with Ludox that US5961817 and US6022471 discloses, by adding gibbsite, the catalyst prepared is made to have more mesopore, but preparation method employs two kinds of Ludox respectively, a kind of is the low sodium Ludox exchanged through ion, another kind is the Ludox of sulfur acid aluminum buffer solution, therefore preparation technology relative complex.
The 1980s, the research of the domestic Cracking catalyst started containing silica sol binder, Chang Ling oil-refining chemical head factory and Beijing Research Institute of Petro-Chemical Engineering have developed the catalyst for cracking heavy oil containing silica sol binder substrate cooperatively, middle lab scale and commercial Application it is shown that the coke selectivity of this catalyst is good, heavy oil conversion performance and preventing from heavy metal ability strong.But the preparation condition of this catalyst is harsh, the production cycle is long, and Ludox very easily gelling, causes catalyst slurry poor stability, and the resting period is short, unstable product quality.
The preparation method that CN1552801A discloses a kind of catalytic cracking catalyst containing silica sol binder, its preparation method is that Ludox, Kaolin, boehmite and molecular sieve are respectively prepared 2,3 or 4 bursts of logistics, proportion of composing according to catalyst, by each stock logistics mix homogeneously, spray-dried, washing, again drying and other steps prepare catalyst.In this method for preparing catalyst, two plume hybrid modes are: Ludox is a plume, and clay, boehmite and molecular sieve pulp are another plume；Three plume hybrid modes are: Ludox, molecular sieve are respectively a plume, the mixed serum of clay and boehmite is a plume, or Ludox, clay are respectively a plume, the mixed serum of boehmite and molecular sieve is a plume, or Ludox, boehmite serosity be respectively the serosity of a plume, clay and molecular sieve are a plume；Four plume hybrid modes are: Ludox, molecular sieve pulp, clay slurry and boehmite serosity are respectively a plume.Its Ludox adopts acidic silicasol.No matter being which kind of hybrid mode, its core is exactly that acidic silicasol individually becomes one, and when purpose is contemplated to avoid acidic silicasol to contact with other material, gel affects its use.This preparation technology is more complicated.
CN101745415A discloses a kind of alkaline silica sol composition and the application in prepared by Cracking catalyst thereof, containing 0.9-7 weight % alkali metal oxide, 3-20 weight %SiO in described alkaline silica sol composition2, the acid group of 0.5-7 weight % and aequum water, the pH value of alkaline silica sol composition is 10-11.5.Serosity during catalyst preparing is weak-type, and therefore alkaline silica sol gel easily occurs when application, causes catalyst preparing difficulty.
Difference according to pH value, Ludox can be divided into alkaline silica sol and acidic silicasol.Alkaline silica sol is divided into again alkalescence sodium form Ludox and alkaline ammonia type Ludox, and ammonia type Ludox is to be prepared by Ammonium Salt Ionic resins exchange by sodium form Ludox, and sodium oxide content is low, and colloid purity is high.Alkaline silica sol has good stability, but in preparing silica-based catalytic cracking catalyst process, itself and very easily gelling after the mixing such as molecular sieve, boehmite, loses flowability.Bring very big difficulty to production on the one hand, reduce the solid content of catalyst slurry on the other hand.Acidic silicasol is industrial again is passed through H by alkaline silica sol+Resins exchange also adds appropriate amount of acid and is adjusted and prepares.Compare with alkaline silica sol, the stability of acidic silicasol is poor, temperature is also comparatively sensitive, need just can remain stable under relatively low pH value and relatively low storage temperature, when being applied to catalytic cracking catalyst and preparing, cross the crystal structure that the stronger acids environment meeting saboteur under low ph value sieves.
Summary of the invention
The technical problem to be solved in the present invention is that in the preparation process for existing catalytic cracking catalyst, acidic silicasol poor stability is not easy to store, the colloid that alkaline silica sol exists in preparing Silicon-rich base catalytic cracking catalyst process is prone to gel, the problem lost flowability, it is provided that a kind of preparation method containing silica sol binder catalytic cracking catalyst.
The present invention provides a kind of preparation method containing silica sol binder catalytic cracking catalyst, including by the mixing making beating of aluminium base binding agent, molecular sieve, clay and Ludox, spray drying, roasting prepare corresponding catalyst, it is characterized in that described Ludox is the alkaline silica sol modifiied through peracid, the sour modified condition of alkaline silica sol is: at 0～30 DEG C of temperature and stirring condition, add an acid in alkaline silica sol, make after mix homogeneously the pH value of colloid 1～5, prepare into through the modified alkaline silica sol of peracid.
The present invention provides a kind of preparation method containing silica sol binder catalytic cracking catalyst, described aluminium base binding agent, molecular sieve, the process of the alkaline silica sol mixing making beating that clay and acid modifiy, to the feed postition of material and addition sequence, there is no particular limitation, aluminium base binding agent, molecular sieve, clay and through the alkaline silica sol that peracid is modified preparation of can pulling an oar respectively be 4 strands of materials, can also be 3 bursts of logistics, wherein aluminium base binding agent and clay are one logistics, molecular sieve and the alkaline silica sol modifiied through peracid are respectively one logistics, reach to optimize the purpose of catalyst preparation process by the addition sequence of each stock logistics of modulation.
A kind of preparation method containing silica sol binder catalytic cracking catalyst disclosed in this invention, it is preferably, comprise the following steps: prepare the alkaline silica sol that aluminium base binding agent serosity, modified molecular screen serosity and acid are modified respectively, these three strands of materials and clay are mixed making beating, then spray drying, roasting, ion exchange, dry, preparing catalyst, its concrete preparation process of described preparation method comprises the following steps:
(1) aluminium base binding agent and deionized water being mixed, be slowly added to acid under agitation, the consumption of acid makes the pH value of serosity not higher than 5；
(2) molecular sieve and deionized water are mixed, making beating, prepare molecular sieve pulp；
(3) at 0～30 DEG C of temperature and stirring condition, add an acid in alkaline silica sol, make after mix homogeneously the pH value of solution between 1 to 5, it is preferable that between 2～4, prepare into through the modified alkaline silica sol of peracid；
(4) by the mixing making beating of step (1), (2), (3) serosity and clay, then spray drying, roasting, ion exchange, dry, and prepare catalyst.
A kind of preparation method containing silica sol binder catalytic cracking catalyst provided by the present invention, in described step (1), the addition of acid is conventionally known to one of skill in the art, as long as according to actual needs so that aluminium base binding agent peptization.
A kind of preparation method containing silica sol binder catalytic cracking catalyst provided by the present invention, described step (1), step (2) and step (3) not order limits, if prepare respectively aluminium base binding agent serosity, molecular sieve pulp, through the modified alkaline silica sol of peracid.
Wherein, described alkaline silica sol selects one or more in the group that free sodium form alkaline silica sol, ammonium type alkaline silica sol are constituted, described alkaline silica sol is for being purchased alkaline silica sol, it can be one or more in sodium form alkaline silica sol, ammonium type alkaline silica sol, it is preferable that lower-cost sodium form alkaline silica sol.With alkaline silica sol weight for 100%, SiO in alkaline silica sol2Concentration be 20～40 weight %, it is preferable that 25～35 weight %, pH value is 7.5～12, it is preferable that 8.0～10.0；Sodium oxide content is less than or equal to 1 weight %, it is preferable that less than or equal to 0.5 weight %.
Step (1) described acid is hydrochloric acid or nitric acid.
When the acid of step (3) described alkaline silica sol is modified, acid used is mineral acid, it is preferable that the one in hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid etc., it is preferred to hydrochloric acid；The concentration of acid used is 10～50 weight %, it is preferred to 20～40 weight %；Through the alkaline silica sol that peracid is modified, its pH value is 1～5, it is preferably 2～4, pH value close to molecular sieve pulp or molecular sieve and other component mixed serum, therefore, through the modified alkaline silica sol of peracid with other component mixed processes in avoid the Ludox sour environment destruction to molecular sieve structure.
A kind of preparation method containing silica sol binder catalytic cracking catalyst provided by the present invention, described aluminium base binding agent, molecular sieve, clay and kind and addition through the modified alkaline silica sol of peracid are conventionally known to one of skill in the art, the present invention is not particularly limited, but the present invention recommends following preferred material and content.A kind of preparation method containing silica sol binder catalytic cracking catalyst provided by the present invention, the described alkaline silica sol modified through peracid is with SiO2Quality is calculated as the 3～30% of catalyst weight, it is preferred to 5～20%；Described molecular sieve is in the butt of molecular sieve, and its addition is the 5～50% of catalyst butt weight, it is preferable that 20～40%；Described aluminium base binding agent, with aluminum oxide gauge, for the 5～40% of catalyst butt weight, it is preferable that 15～35%；Described clay, is calculated as 10～50% relative to catalyst butt weight with clay butt quality, it is preferable that 20～40%.
Adding rare earth oxide before mixing making beating, rare earth oxide is the 0.5～4% of catalyst butt weight.
nullA kind of preparation method containing silica sol binder catalytic cracking catalyst provided by the present invention，Described molecular sieve is Y type molecular sieve、X-type molecular sieve、ZSM-5 molecular sieve、Beta-molecular sieve、Aluminium phosphate molecular sieve、Ω molecular sieve、Or one or more in the above-mentioned molecular sieve of Typical physical or chemical modification，Preferred y-type zeolite、ZSM-5 zeolite、β zeolite、Y-type zeolite through Typical physical or chemical modification、ZSM-5 zeolite through Typical physical or chemical modification、One or more in the β zeolite of Typical physical or chemical modification，Described refers to the super steady process of high temperature and/or to modifiying that it carries out through Typical physical or chemical modification molecular sieve，Such as various hydrogen type molecular sieves，Typically there is HY、HZSM-5，Containing rare earth and/or phosphorus modified molecular sieves，Typically there is REHY、REY、P-REY、P-ZSM-5，The super stable molecular sieve of hydrothermal treatment consists，Typically there is USY、Super steady REHY、Super steady REY etc.，Butt in molecular sieve，Its addition is the 5～50% of Cracking catalyst butt weight，Preferably 20～40%.The method of molecular sieve making beating is compared with existing method does not have particular/special requirement.
A kind of preparation method containing silica sol binder catalytic cracking catalyst provided by the present invention, described aluminium base binding agent is boehmite, Alumina gel, have a diaspore structure hydrated alumina, have gibbsite structure hydrated alumina, have boehmite structure hydrated alumina, one or more in gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, it is preferably boehmite, Alumina gel, the addition of aluminium base binding agent is with aluminum oxide gauge, 5～40 weight % for Cracking catalyst butt weight, it is preferable that 15～35%.
A kind of preparation method containing silica sol binder catalytic cracking catalyst provided by the present invention, described aluminium base binding agent acidifying is technology known in those skilled in the art, one or more in acid preferably mineral acid, it is preferably hydrochloric acid, the consumption of described acid makes the pH value after addition acid for not higher than 5, it is preferable that 1～4.
A kind of preparation method containing silica sol binder catalytic cracking catalyst provided by the present invention, described clay is one or more in Kaolin, halloysite, kieselguhr, montmorillonite, rectorite, bentonite, galapectite, meerschaum, saponite, attapulgite, brucite, optimal addn is calculated as 10～50 weight % relative to catalyst butt weight with butt quality, it is preferable that 20～40%.Clay of the present invention can also be the clay after above-mentioned various concrete clay is modified, and is called that modified clay, modal modified clay are the clay after acid and/or alkali density.No matter it is clay or modified clay, as long as the butt substrate meeting clay is 10～50 weight % relative to catalyst butt weight.Clay and or modified clay can make one material and be individually added into, it is also possible to be dividedly in some parts in different materials.
A kind of preparation method containing silica sol binder catalytic cracking catalyst provided by the present invention, the step introducing rare earth oxide can also be included, rare earth oxide added before mixing making beating, and described rare earth oxide is introduced by the aqueous solution added containing rare earth ion in catalyst preparation process.Described rare earth compound is rare earth chloride or nitric acid rare earth or sulfuric acid rare earth, preferably rare earth chloride or nitric acid rare earth, it is possible to be rich lanthanum or cerium-rich mischmetal, it is also possible to be pure lanthanum or pure cerium mischmetal, with rare earth oxide Mass Calculation, the addition of rare earth is 0～4 weight % of catalyst weight.Described rare earth oxide adds preferably in (1), (2) or (4) either step.
A kind of preparation method containing silica sol binder catalytic cracking catalyst provided by the present invention, spray drying described in step (4) is drying means conventional in the preparation of existing catalytic cracking catalyst, and the present invention does not have particular/special requirement.
A kind of preparation method containing silica sol binder catalytic cracking catalyst provided by the present invention, the post-treatment condition such as described roasting is treatment conditions conventional in catalytic cracking catalyst preparation process, and the present invention does not have particular/special requirement.Such as CN201110419856.9, CN200710099437.5 all disclose catalyst sintering temperature, roasting time: 200～750 DEG C of roastings 0.1～10 hour, it is preferable that 300～600 DEG C of roastings 0.1～4 hour.
A kind of preparation method containing silica sol binder catalytic cracking catalyst provided by the present invention, by adding the alkaline silica sol modifiied through peracid, overcomes the not easily-storied problem of acidic silicasol poor stability；Solve easy gel when alkaline silica sol mixes with other component in preparing catalytic cracking catalyst process simultaneously, making the problem that catalyst slurry loses flowability, thus improve the solid content of catalyst slurry, reducing production cost.The present invention only adds acid at alkaline silica sol through the alkaline silica sol that peracid is modified it is modified, it does not have the exchange process of acid ion resin, reduce Ludox actual should in cost；Simultaneously, due to other counter ion counterionsl gegenions that the Ludox itself that acid is modified introduces containing higher sodium ion and the difference modifiying acid kind used, therefore the standard according to industry silicasol, the character such as its parameter and commerical grade acidic silicasol character there are differences, but not affecting its result of use in Cracking catalyst, its heavy oil conversion ratio, coke selectivity and yield of light oil also effect are more excellent.The method that the present invention is applied to preparation Cracking catalyst by acid modified alkaline Ludox, technique is simple, is suitable for the commercial production of Cracking catalyst.
Detailed description of the invention
The present invention will be further described by example below, but not thereby limiting the invention.
(1) analysis used in example and evaluation methodology.
1.Na2O content: flame spectrometry.
2.RE2O3Content: colorimetry.
3.P content: spectrophotography.
4. abrasion index: goose tube method.
5. micro-activity: sample in advance 800 DEG C, process 17 hours under 100% water vapor conditions.Reaction raw materials is huge port light diesel fuel, reaction temperature 460 DEG C, 70 seconds response time, catalyst loading amount 5.0 grams, agent weight of oil ratio 3.2, using total conversion as micro-activity.
6.ACE heavy oil microreactor: reaction temperature 530 DEG C, oil ratio is 5, and raw oil is heavily urge device raw materials used in 3,000,000/year of Lanzhou Petrochemical.
(2) raw materials used specification in example
1. earth solution: rare earth chloride (rare earth oxide 272.5 g/l), industrial goods, picks up from Catalyst Factory of Lanzhou Petrochemical Company.
2. hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid are chemical pure；Kaolin, halloysite, kieselguhr, montmorillonite, rectorite, bentonite, galapectite, meerschaum, saponite, attapulgite, brucite, boehmite, Alumina gel, there is a diaspore structure hydrated alumina, there is gibbsite structure hydrated alumina, there is boehmite structure hydrated alumina, gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide are industrial goods.
3. sodium form alkaline silica sol (silicon oxide 30 weight %, pH value 9.6), ammonia type alkaline silica sol (silicon oxide 25 weight %, pH value 9.85) and acidic silicasol (silicon oxide 30 weight %, pH value 2.5), it is acceptable industrial product, purchased from Jinan Yin Feng silicon goods company.
The Y type molecular sieves such as 4.REY, REHY, USY, REUSY and L-type molecular sieve, ZSM-5 molecular sieve, beta-molecular sieve, aluminium phosphate molecular sieve are acceptable industrial product, pick up from Catalyst Factory of Lanzhou Petrochemical Company.
5. Modified Clay Slurry liquid 1 (solid content is 34 weight %), Modified Clay Slurry liquid 2 (solid content is 27 weight %), it is the serosity of the clay modifiied through peracid extracting, picks up from Catalyst Factory of Lanzhou Petrochemical Company.
Embodiment 1
In the retort with heating in water bath, add 3.0L water, 824g Modified Clay Slurry liquid (solid content 34 weight %), 952g Alumina gel (solid content 21 weight %), 51.4ml rare earth (272.5g/L), under agitation add 1212g activated alumina (solid content 66 weight %), it is then slowly added into hydrochloric acid and carries out peptization, stir 1h.nullSodium form alkaline silica sol (dioxide-containing silica 30 weight %) original ph is 9.60，Weigh alkaline silica sol 1333g，Concentrated hydrochloric acid (concentration 37 mass %) 11ml is rapidly joined under 20 DEG C of stirring conditions，Stir the hydrochloric Acid Modification alkaline silica sol of prepared pH value 2.5，This hydrochloric Acid Modification alkaline silica sol and 4.05kg molecular sieve pulp (1.66kg solid content be the REY molecular sieve of 82 weight % add the making beating shearing of 2.39kg water carry out dispersing and disintegrating and process) are joined in retort，1113g clay (solid content 85 weight %) is added after mix homogeneously，Stir，Catalyst slurry (butt 4kg) has good mobility，Surveying its solid content is 31%，Spray shaping，Exchange through roasting and ion、The dry Cracking catalyst that namely prepared by the prepared present invention，It is denoted as A1.
Comparative example 1
Ludox used adopts and is purchased acidic silicasol, and its parameter meets industry silicasol standard.nullIn the retort with heating in water bath，Add 2.22L water、618g Modified Clay Slurry liquid (solid content 34 weight %)、714g Alumina gel (solid content 21 weight %)、38.5ml rare earth (272.5g/L)，Under agitation add 909g activated alumina (solid content 66 weight %)，It is subsequently adding concentrated hydrochloric acid peptization，Stirring 1h，It is sequentially added into 1000g acidic silicasol (dioxide-containing silica 30 weight %，PH value 2.5) and 3.14kg modified molecular screen serosity (1.25kg solid content be the REY molecular sieve of 82 weight % add the making beating shearing of 1.9kg water carry out dispersing and disintegrating and process)，835g clay (solid content 85 weight %) is added after mix homogeneously，Stir，Catalyst slurry (butt 3kg) has good mobility，Surveying its solid content is 31%，Spray shaping，Exchange through roasting and ion、Dry namely preparing contrasts Cracking catalyst，It is denoted as B1.
Comparative example 2
It is modified that sodium form alkaline silica sol (dioxide-containing silica 30 weight %) does not carry out acid.nullIn the retort with heating in water bath，Add 2.22L water、618g Modified Clay Slurry liquid (solid content 34 weight %)、714g Alumina gel (solid content 21 weight %)、38.5ml rare earth (290g/L)，Under agitation add 909g activated alumina (solid content 66 weight %)，It is subsequently adding hydrochloric acid peptization，Stirring 1h，Add 1000g alkaline silica sol (dioxide-containing silica 30 weight %，PH value 9.60) and 3.14kg modified molecular screen serosity (1.25kg solid content be the REY molecular sieve of 82 weight % add the making beating shearing of 1.9kg water carry out dispersing and disintegrating and process)，835g clay (solid content 85 weight %) is added after mix homogeneously，Stirring, (catalyst slurry is thickness comparatively，For ensureing that what it can be smooth carries out spray shaping，Additionally add about 600mL water，Finally surveying its solid content is 29%，Butt 3kg)，Spray shaping，Exchange through roasting and ion、Dry namely preparing contrasts Cracking catalyst，It is denoted as B2.
Embodiment 2
In the retort with heating in water bath, add 2.6L water, 778g Modified Clay Slurry liquid 2 (solid content 27 weight %), 38.5ml rare earth (272.5g/L), 864g activated alumina (solid content 66 weight %), under agitation add hydrochloric acid peptization, stir 1h.nullAlkaline silica sol (dioxide-containing silica 30 weight %，Original ph is 9.60)，Weigh alkaline silica sol 1000g，Concentrated hydrochloric acid (concentration is 37 mass %) 11.0mL is rapidly joined under 25 DEG C of stirring conditions，Stir and prepare the alkaline silica sol (pH value 1.8) modifiied through peracid，This modified silicasol and 3.1kg molecular sieve pulp (1.2kg solid content be the REY molecular sieve of 87 weight % add the making beating shearing of 1.9kg water carry out dispersing and disintegrating and process) are joined in retort，Add 643g Alumina gel (solid content 21 weight %)，888g clay (solid content 85 weight %) is added after mix homogeneously，Stirring, (catalyst slurry has good mobility，Surveying its solid content is 30.8%，Butt 3kg)，Spray shaping，Exchange through roasting and ion、The dry Cracking catalyst that namely prepared by the prepared present invention，It is denoted as A2.
Comparative example 3
Ludox used adopts and is purchased acidic silicasol, and its parameter meets industry silicasol standard.In the retort with heating in water bath, add 2.6L water, 778g Modified Clay Slurry liquid 2 (solid content 27 weight %), 38.5ml rare earth (272.5g/L), 864g activated alumina (solid content 66 weight %), under agitation add hydrochloric acid peptization, stir 1h.It is subsequently adding acidic silicasol (dioxide-containing silica 30 weight %, original ph is 2.50) 1000g and 3.1kg molecular sieve pulp (1.2kg solid content be the REY molecular sieve of 87 weight % add the making beating shearing of 1.9kg water carry out dispersing and disintegrating and process) joins in retort, add 643g Alumina gel (solid content 21 weight %), 888g clay (solid content 85 weight %) is added after mix homogeneously, stirring, (catalyst slurry has good mobility, surveying its solid content is 30.5%), spray shaping, exchange through roasting and ion, the dry Cracking catalyst that namely prepared by the prepared present invention, it is denoted as B3
Comparative example 4
It is modified that sodium form alkaline silica sol (dioxide-containing silica 30 weight %) does not carry out acid.In the retort with heating in water bath, add 2.6L water, 778g Modified Clay Slurry liquid 2 (solid content 27 weight %), 38.5ml rare earth (272.5g/L), 864g activated alumina (solid content 66 weight %), under agitation add hydrochloric acid peptization, stir 1h.It is subsequently adding alkaline silica sol (dioxide-containing silica 30 weight %, original ph is 9.60) 1000g and 3.1kg molecular sieve pulp (1.2kg solid content be the REY molecular sieve of 87 weight % add the making beating shearing of 1.9kg water carry out dispersing and disintegrating and process) joins in retort, add 643g Alumina gel (solid content 21 weight %), 888g clay (solid content 85 weight %) is added after mix homogeneously, stirring, (catalyst slurry is thickness comparatively, for ensureing that what it can be smooth carries out spray shaping, additionally add about 600mL water, finally surveying its solid content is 28.6%), spray shaping, exchange through roasting and ion, the dry Cracking catalyst that namely prepared by the prepared present invention, it is denoted as B4.
Embodiment 3
In the retort with heating in water bath, add 1.8L water, 778g Modified Clay Slurry liquid 2 (solid content 27 weight %), 38.5ml rare earth (272.5g/L), 909g activated alumina (solid content 66 weight %), under agitation add hydrochloric acid peptization, stir 1h.nullWeigh ammonia type alkaline silica sol (dioxide-containing silica 25 weight %，Original ph is 9.85) 1200g，Concentrated hydrochloric acid (concentration is 37 mass %) 12mL is rapidly joined under 15 DEG C of stirring conditions，Stir the alkaline silica sol (pH value 3.0) of prepared hydrochloric Acid Modification，By this modified silicasol and 3.0kg molecular sieve pulp, (1.2kg solid content is the REY molecular sieve of 87 weight % and USY molecular sieve adds the making beating shearing of 1.8kg water and carries out dispersing and disintegrating and process，The mass ratio of REY molecular sieve and USY molecular sieve is 10:1) join in retort，Add 714g Alumina gel (solid content 21 weight %)，835g clay (solid content 85 weight %) is added after mix homogeneously，Stirring, (catalyst slurry has good mobility，Surveying its solid content is 31.2%)，Spray shaping，Exchange through roasting and ion、The dry Cracking catalyst that namely prepared by the prepared present invention，It is denoted as A3.
Comparative example 5
Technical process is the same but ammonia type alkaline silica sol does not carry out sour modified.In the retort with heating in water bath, add 1.8L water, 778g Modified Clay Slurry liquid 2 (solid content 27 weight %), 38.5ml rare earth (272.5g/L), 909g activated alumina (solid content 66 weight %), under agitation add hydrochloric acid peptization, stir 1h.nullAdd ammonia type alkaline silica sol (dioxide-containing silica 25 weight %，Original ph is 9.85) (1.2kg solid content is the REY molecular sieve of 87 weight % to 1200g and 3.0kg molecular sieve pulp and USY molecular sieve adds the making beating shearing of 1.8kg water and carries out dispersing and disintegrating and process，The mass ratio of REY molecular sieve and USY molecular sieve is 10:1) join in retort，Add 714g Alumina gel (solid content 21 weight %)，835g clay (solid content 85 weight %) is added after mix homogeneously，Stirring, (catalyst slurry is thickness comparatively，For ensureing that what it can be smooth carries out spray shaping，Additionally add about 600mL water，Finally surveying its solid content is 29.1%)，Spray shaping，Exchange through roasting and ion、The dry Cracking catalyst that namely prepared by the prepared present invention，It is denoted as B5.
Embodiment 4
In the retort with heating in water bath, add 1.9L water, 1000g activated alumina (solid content 66 weight %), 444g Modified Clay Slurry liquid 2 (solid content 27 weight %), under agitation add hydrochloric acid peptization, stir 1h.nullAlkaline silica sol (dioxide-containing silica 30 weight %，Original ph is 9.60)，Weigh alkaline silica sol 1000g，Concentrated hydrochloric acid (concentration is 37 mass %) 9.0mL is rapidly joined under 15 DEG C and stirring condition，Stir and prepare the alkaline silica sol (pH value 3.0) modifiied through peracid，This modified silicasol and 3.1kg molecular sieve pulp (1.2kg solid content be the REY molecular sieve of 87 weight % add the making beating shearing of 1.9kg water carry out dispersing and disintegrating and process) are joined in retort，Add 571g Alumina gel (solid content 21 weight %)，918g clay (solid content 85 weight %) is added after mix homogeneously，Stirring, (catalyst slurry has good mobility，Surveying its solid content is 30.5%，Butt 3kg)，Spray shaping，Exchange through roasting and ion、The dry Cracking catalyst that namely prepared by the prepared present invention，It is denoted as A4.
Comparative example 6
Ludox used adopts and is purchased acidic silicasol, and its parameter meets industry silicasol standard.In the retort with heating in water bath, add 1.9L water, 444g Modified Clay Slurry liquid 2 (solid content 27 weight %), 1000g activated alumina (solid content 66 weight %), under agitation add hydrochloric acid peptization, stir 1h.It is subsequently adding acidic silicasol (dioxide-containing silica 30 weight %, original ph is 2.50) 1000g and 3.1kg molecular sieve pulp (1.2kg solid content be the REY molecular sieve of 87 weight % add the making beating shearing of 1.9kg water carry out dispersing and disintegrating and process) joins in retort, add 571g Alumina gel (solid content 21 weight %), 918g clay (solid content 85 weight %) is added after mix homogeneously, stirring, (catalyst slurry has good mobility, surveying its solid content is 30.2%), spray shaping, exchange through roasting and ion, the dry Cracking catalyst that namely prepared by the prepared present invention, it is denoted as B6.
Comparative example 7
It is modified that sodium form alkaline silica sol (dioxide-containing silica 30 weight %) does not carry out acid.In the retort with heating in water bath, add 1.9L water, 444g Modified Clay Slurry liquid 2 (solid content 27 weight %), 1000g activated alumina (solid content 66 weight %), under agitation add hydrochloric acid peptization, stir 1h.It is subsequently adding alkaline silica sol (dioxide-containing silica 30 weight %, original ph is 9.60) 1000g and 3.1kg molecular sieve pulp (1.2kg solid content be the REY molecular sieve of 87 weight % add the making beating shearing of 1.9kg water carry out dispersing and disintegrating and process) joins in retort, add 571g Alumina gel (solid content 21 weight %), 918g clay (solid content 85 weight %) is added after mix homogeneously, stirring, (catalyst slurry is thickness comparatively, for ensureing that what it can be smooth carries out spray shaping, additionally add about 600mL water, finally surveying its solid content is 28.7%), spray shaping, exchange through roasting and ion, the dry Cracking catalyst that namely prepared by the prepared present invention, it is denoted as B7.
Embodiment 5
In the retort with heating in water bath, add 2.8L water, 1000g Alumina gel (solid content 21 weight %), 909g activated alumina (solid content 66 weight %), 1200g clay (solid content 85 weight %), under agitation add hydrochloric acid peptization, stir 1h.Alkaline silica sol (dioxide-containing silica 30 weight %, original ph is 9.60), weigh alkaline silica sol 500g, concentrated hydrochloric acid (concentration is 37 mass %) 5.5mL is rapidly joined under 16～18 DEG C of stirring conditions, stir and prepare the alkaline silica sol (pH value 1.8) through hydrochloric Acid Modification, this modified silicasol and 3.1kg molecular sieve pulp (1.2kg solid content be the REY molecular sieve of 87 weight % add the making beating shearing of 1.9kg water carry out dispersing and disintegrating and process) are joined in retort, after mix homogeneously, (catalyst slurry has good mobility, surveying its solid content is 31.1%, butt 3kg) spray shaping, exchange through roasting and ion, the dry Cracking catalyst that namely prepared by the prepared present invention, it is denoted as A5.
Comparative example 8
Ludox used adopts and is purchased acidic silicasol, and its parameter meets industry silicasol standard.In the retort with heating in water bath, add 2.8L water, 1000g Alumina gel (solid content 21 weight %), 909g activated alumina (solid content 66 weight %), 1200g clay (solid content 85 weight %), under agitation add hydrochloric acid peptization, stir 1h.It is subsequently adding acidic silicasol (dioxide-containing silica 30 weight %, original ph is 2.50) 500g and 3.1kg molecular sieve pulp (1.2kg solid content be the REY molecular sieve of 87 weight % add the making beating shearing of 1.9kg water carry out dispersing and disintegrating and process) joins in retort, after mix homogeneously, (catalyst slurry has good mobility, surveying its solid content is 30.8%), spray shaping, exchange through roasting and ion, dry the Cracking catalyst that namely prepared by the prepared present invention, be denoted as B8.
Embodiment 6
In the retort with heating in water bath, add 3.0L water, 440ml rare earth (272.5g/L), 429g Alumina gel (solid content 21 weight %), 682g activated alumina (solid content 66 weight %), under agitation adds hydrochloric acid peptization, stirs 1h.Alkaline silica sol (dioxide-containing silica 30 weight %, original ph is 9.60), weigh alkaline silica sol 2000g, rapidly join concentrated nitric acid 23.0mL under agitation, stir and prepare the alkaline silica sol (pH value 2.5) through Nitric Acid Modified, this modified silicasol and 2.15kg molecular sieve pulp (0.65kg solid content be the REUSY molecular sieve of 93 weight % add the making beating shearing of 1.50kg water carry out dispersing and disintegrating and process) are joined in retort, it is subsequently adding 1341g clay (solid content 85 weight %), (butt 3kg) spray shaping after mix homogeneously, exchange through roasting and ion, the dry Cracking catalyst that namely prepared by the prepared present invention, it is denoted as A6.
Embodiment 7
In the retort with heating in water bath, add 2.1L water, 714g Alumina gel (solid content 21 weight %), 1000g activated alumina (solid content 66 weight %), 220ml rare earth (272.5g/L), under agitation add hydrochloric acid peptization, stir 1h.Alkaline silica sol (dioxide-containing silica 30 weight %, original ph is 9.60), weigh alkaline silica sol 1500g, concentrated sulphuric acid 10.0mL is rapidly joined under C stirring condition, stir and prepare through sulfuric acid modified alkaline silica sol (pH value 2.5), this modified silicasol and 2.77kg molecular sieve pulp (0.97kg solid content be the REUSY molecular sieve of 82 weight % add the making beating shearing of 1.80kg water carry out dispersing and disintegrating and process) are joined in retort, it is subsequently adding 918g clay (solid content 85 weight %), (butt 3kg) spray shaping after mix homogeneously, exchange through roasting and ion, the dry Cracking catalyst that namely prepared by the prepared present invention, it is denoted as A7.
Embodiment 8
In the retort with heating in water bath, add 1.8L water, 1143g Alumina gel (solid content 21 weight %), 110ml rare earth (272.5g/L), 909g activated alumina (solid content 66 weight %), under agitation add hydrochloric acid peptization, stir 1h.Alkaline silica sol (dioxide-containing silica 30 weight %, original ph is 9.60), weigh alkaline silica sol 1100g, rapidly join concentrated hydrochloric acid (concentration is 37 mass %) 11.0mL under agitation, stir and prepare the alkaline silica sol (pH value 2.5) through hydrochloric Acid Modification, this modified silicasol and 3.84kg molecular sieve pulp (1.29kg solid content be the REUSY molecular sieve of 82 weight % add the making beating shearing of 2.55kg water carry out dispersing and disintegrating and process) are joined in retort, it is subsequently adding 706g clay (solid content 85 weight %), (butt 3kg) spray shaping after mix homogeneously, exchange through roasting and ion, the dry Cracking catalyst that namely prepared by the prepared present invention, it is denoted as A8.
Catalyst property in Table 1, catalyst in ACE evaluation response performance in Table 2.
Table 1 catalyst analysis of physical and chemical property result
| Numbering | Na2O | RE2O3 | Intensity (directly) | Micro-instead, 17h | Compare table |
| A1 | 0.12 | 2.96 | 0.9 | 67 | 279 |
| B1 | 0.09 | 2.91 | 0.9 | 67 | 266 |
| B2 | 0.11 | 2.95 | 0.8 | 67 | 275 |
| A2 | 0.12 | 2.71 | 2.1 | 71 | 288 |
| B3 | 0.13 | 2.75 | 1.7 | 71 | 301 |
| B4 | 0.14 | 2.75 | 1.3 | 69 | 290 |
| A3 | 0.10 | 2.70 | 1.0 | 70 | 270 |
| B5 | 0.11 | 2.68 | 1.1 | 69 | 252 |
| A4 | 0.11 | 2.40 | 1.5 | 69 | 281 |
| B6 | 0.14 | 2.35 | 1.6 | 70 | 277 |
| B7 | 0.13 | 2.44 | 2.0 | 68 | 267 |
| A5 | 0.14 | 2.45 | 0.7 | 65 | 247 |
| B8 | 0.13 | 2.56 | 0.8 | 66 | 265 |
| A6 | 0.08 | 4.28 | 0.9 | 54 | 219 |
| A7 | 0.10 | 2.45 | 1.0 | 61 | 255 |
| A8 | 0.11 | 1.60 | 1.2 | 64 | 316 |
Table 2 catalyst ACE evaluation result
Claims (12)
1. the preparation method containing silica sol binder catalytic cracking catalyst, including by the mixing making beating of aluminium base binding agent, molecular sieve, clay and Ludox, spray drying, roasting prepare catalyst, it is characterized in that described Ludox is the alkaline silica sol modifiied through peracid, the sour modified condition of alkaline silica sol is: at 0～30 DEG C of temperature and stirring condition, add an acid in alkaline silica sol, make after mix homogeneously the pH value of colloid 1～5, prepare into through the modified alkaline silica sol of peracid.
2. the preparation method containing silica sol binder catalytic cracking catalyst according to claim 1, it is characterized in that this preparation method includes preparing the alkaline silica sol that aluminium base binding agent serosity, modified molecular screen serosity and acid are modified respectively, these three strands of materials and clay are mixed making beating, then spray drying, roasting, ion exchange, dry, preparing catalyst, its concrete preparation process includes:
(1) aluminium base binding agent and deionized water are mixed, be slowly added to acid, the use of acid under agitation
Amount makes the pH value of serosity not higher than 5；
(2) molecular sieve and deionized water are mixed, making beating, prepare molecular sieve pulp；
(3) at 0～30 DEG C of temperature and stirring condition, add an acid in alkaline silica sol, make mixing equal
The pH value of even rear solution, 1～5, prepares into the alkaline silica sol modifiied through peracid；
(4) by step (1), (2), (3) serosity and clay mixing making beating, then spray drying, roasting, from
Son exchanges, dries, and prepares catalyst.
3. the preparation method containing silica sol binder catalytic cracking catalyst according to claim 1 and 2, it is characterised in that: described alkaline silica sol selects one or more in the group that free sodium form alkaline silica sol, ammonium type alkaline silica sol are constituted.
4. the preparation method containing silica sol binder catalytic cracking catalyst according to claim 1 and 2, it is characterised in that: SiO in described alkaline silica sol2Concentration be 20～40 weight %, pH value is 7.5～12, and sodium oxide content is less than or equal to 1 weight %.
5. the preparation method containing silica sol binder catalytic cracking catalyst according to claim 4, it is characterised in that: SiO in described alkaline silica sol2Concentration be 25～35 weight %, pH value is 8.0～10.0；Sodium oxide content is less than or equal to 0.5 weight %.
6. the preparation method containing silica sol binder catalytic cracking catalyst according to claim 1 and 2, it is characterised in that: step (1) described acid is hydrochloric acid or nitric acid.
7. the preparation method containing silica sol binder catalytic cracking catalyst according to claim 1 and 2, it is characterised in that: step (3) described acid is mineral acid.
8. the preparation method containing silica sol binder catalytic cracking catalyst according to claim 7, it is characterised in that: step (3) described mineral acid is hydrochloric acid, sulphuric acid, nitric acid or phosphoric acid.
9. the preparation method containing silica sol binder catalytic cracking catalyst according to claim 1 and 2, it is characterised in that: the alkaline silica sol pH value that the acid described in step (3) modifiies is 2～4.
10. the preparation method containing silica sol binder catalytic cracking catalyst according to claim 1 and 2, it is characterised in that: the alkaline silica sol that described acid is modified, with SiO2Quality meter, for the 3～30% of catalyst butt weight；Described molecular sieve, in the butt of molecular sieve, its addition is the 5～50% of catalyst butt weight；Described aluminium base binding agent, with aluminum oxide gauge, for the 5～40% of catalyst butt weight；Described clay, in clay butt quality, for the 10～50% of catalyst butt weight.
11. the preparation method containing silica sol binder catalytic cracking catalyst according to claim 10, it is characterised in that: the alkaline silica sol that described acid is modified, with SiO2Quality meter, for the 5～20% of catalyst butt weight；Described molecular sieve, in the butt of molecular sieve, its addition is the 20～40% of catalyst butt weight；Described aluminium base binding agent, with aluminum oxide gauge, for the 15～35% of catalyst butt weight；Described clay, in clay butt quality, for relative to the 20～40% of catalyst butt weight.
12. the preparation method containing silica sol binder catalytic cracking catalyst according to claim 1 and 2, it is characterised in that: adding rare earth oxide before mixing making beating, rare earth oxide is the 0～4% of catalyst butt weight.
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