CN101745415B - Alkaline silica sol composition and application thereof in preparation of cracking catalyst - Google Patents
Alkaline silica sol composition and application thereof in preparation of cracking catalyst Download PDFInfo
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Abstract
The invention relates to an alkaline silica sol composition and an application thereof in the preparation of a cracking catalyst, and the alkaline silica sol composition contains 0.9-7% by weight of alkali metal oxide, 3-20% by weight of SiO2, 0.5-7% by weight of acid radical and the balance of water, the pH value of the alkaline silica sol composition is 10-11.5; and the silica sol composition is used for preparing the cracking catalyst, and the preparation comprises the steps of mixing the silica sol composition with a NaY molecular sieve, beating, then spray drying, carrying out ion exchange and drying. The cracking catalyst prepared by the preparation method of the cracking catalyst has the advantages of high pore volume, strong heavy oil conversion capacity and high yield of gasoline.
Description
Technical field
The present invention relates to a kind of alkaline silica sol composition and the application in the catalytic cracking catalyst preparation thereof.
Background technology
Ludox has extensive use in fields such as casting, weaving, papermaking, metallurgy and Preparation of Catalyst, comprises acidic silicasol and alkaline silica sol, and Ludox preparation method commonly used has ion-exchange, elemental silicon dissolution method, electroosmose process and neutralisation.
At present the preparation alkaline silica sol mainly uses ion-exchange, and this method is with waterglass and strong-acid ion exchange resin prepared in reaction acidic silicasol, then with it with adjusting pH values such as ammoniacal liquor, evaporation and concentration obtains needed Ludox again.This method energy consumption height, ion exchange resin regeneration produces a large amount of waste water, the cost height.
CN1295042C discloses a kind of al-modified silica sol, contains silica 20～32%, aluminium oxide 0.1～1.5%, and sodium oxide molybdena 0.03～0.15%, its pH value is 7.5～9.6, this Ludox can be used as the model casting binding agent.
CN1644497A discloses a kind of preparation method of alkaline silica sol, and it is raw material with the acidic silicasol, and adding ammonia or ammoniacal liquor to pH value is 8-10, obtains alkaline silica sol.Above-mentioned acidic silicasol pH value is 2.0-4.8, and dioxide-containing silica is 15-40%.
CN1644498A discloses a kind of preparation method of stabilized silica sol, it is to be raw material with alkaline sodium type Ludox, remove to add behind the sodium ion ammonia or ammoniacal liquor to pH value 8.5～9.5, obtain stabilized silica sol, the sodium oxide content of described alkaline sodium type Ludox is 0.3～0.5%.
Along with crude oil heaviness and poor qualityization day by day, catalytic cracking needs the import oil that processing heavy oil, residual oil and content of beary metal are high more, this is to the anti-carbon deposit demands for higher performance of Cracking catalyst, and Silicon-rich matrix cracking catalyst has the high and low characteristics of coking yield of gasoline selective, therefore utilizes silica-based Cracking catalyst processing heavy oil to come into one's own gradually.Ludox commonly used is the acidic silicasol of sour neutralisation preparation in the present silica-based Cracking catalyst preparation, and its pH value is common below 3.5.For example all disclose among USP3867308, USP3957689, USP5961817, USP6022471, CN1552801A and the CN1749364A and prepared acidic silicasol and prepare the method for catalyst with it.Yet the catalyst pore volume of acidic silicasol preparation is low, be unfavorable for big molecule cracking, and acidic silicasol stability is poor, need could keep stable down in lower pH value and temperature (being generally below 30 ℃), and require the prepared catalyst slurry pH value should be enough low, otherwise the easy gelling of slurries that forms, this requires when using the slurry preparation catalyst of molecular sieve, alumina host and other component, various slurries should have lower pH value, and the common pH value that need regulate molecular sieve pulp is acid; But the zeolite isoreactivity component that Cracking catalyst is used always is destroyed easily under the low excessively situation of pH value, the active reduction, so acidic silicasol is unsuitable for directly utilizing the NaY molecular sieve to prepare the method for catalyst.
Summary of the invention
One of the technical problem to be solved in the present invention provides the method that a kind of NaY of utilization zeolite and silica binder prepare Cracking catalyst.The other technical problem that the present invention will solve provides a kind of alkaline silica sol composition that is applicable to said method.
The invention provides a kind of preparation method of Cracking catalyst, comprise a kind of alkaline silica sol composition is mixed, pulls an oar with the NaY molecular sieve, the step of spray-drying, ion-exchange, drying contains 0.9～7 weight %M in the described alkaline silica sol composition then
2O, 3～20 weight %SiO
2, the acid group of 0.5～7 weight % and the water of aequum, the pH value of described alkaline silica sol composition is 10～11.5, wherein said M is an alkali metal.
The invention provides a kind of alkaline silica sol composition, the pH value of described alkaline silica sol composition is 10～11.5; Weight with alkaline silica sol composition is benchmark, contains 0.9～7 weight %M in the described alkaline silica sol composition
2O, 3～20 weight %SiO
2, the acid group of 0.5～7 weight % and the water of aequum, M are alkali metal.
Alkaline silica sol composition provided by the invention can comparatively stably exist in 0～60 ℃ scope, keeps stable wider range; Silica sol composition preparation technology of the present invention is simple, compares with the preparation acidic silicasol, can save the consumption of acid, and be to prepare silica sol composition with lower-cost waterglass and inorganic acid reaction, can reduce discharging, reduce the pollution to environment, cost is lower.
In the method for preparing catalyst provided by the invention, after alkaline silica sol composition and other component are mixed with slurries, the pH value changes little, do not pay particular attention to and frequent pH value of regulating slurries, pH value requirement to other component is not so strict, prepared slurries stability is high by the slurries stability that acidic silicasol and matrix, active component are mixed with, and is not easy gelling more.Method for preparing catalyst of the present invention directly utilizes the NaY molecular sieve to prepare catalyst, need not anticipate the NaY molecular sieve, and the washing of catalyst and the exchange washing and the modification of NaY molecular sieve are carried out behind shaping of catalyst, do not need the particular processing process, can simplify preparation process; Because the heap of molecular sieve is lower, particle is less usually, about 3～5 microns of its average grain diameter, molecular sieve reclaims difficulty in the processing procedure, the cost recovery height, and the average grain diameter of Cracking catalyst is usually between 60～90 microns, heap is than higher, help cyclonic separation, improve the yield of molecular sieve, reduce the Preparation of Catalyst cost.Method for preparing catalyst of the present invention can exchange the washing of the sodium oxide molybdena in the catalyst, does not influence its performance; Compare with the catalyst that with the acidic silicasol is adhesive preparation, the catalyst of the inventive method preparation has bigger pore volume and lower bulk density, helps the macromolecular cracking reaction of heavy oil.Prepared catalyst is used for RFCC, the conversion ratio height, and heavy oil cracking ability is strong, the gasoline yield height, and have coke selectivity preferably.
The specific embodiment
In the production of cracking catalyst provided by the present invention, the pH value of described alkaline silica sol composition is preferably 10.2～11.3, and more preferably 10.8～11.2; SiO in the alkaline silica sol composition
2Concentration be preferably 5～20 weight %, 5～15 weight % more preferably; The content of acid group is preferably 0.8～5 weight %, more preferably 1～4 weight %; M
2O content is preferably 1.5～6 weight %, more preferably 1.5～6 weight %; The content of water is preferably 70～95 weight %.Acid group in the described alkaline silica sol composition is Cl
-, NO
3 -, SO
4 2-, PO
4 3-In one or more, be preferably NO
3 -Or SO
4 2-, SO more preferably
4 2-Described M is preferably Na.
In the production of cracking catalyst provided by the present invention, used alkaline silica sol composition can be by being 2.6～3.5 with modulus, concentration is that waterglass and the method that contact of acid of 3.5～21 weight % prepares, and to make the pH value of the mixture that obtains be 10～11.5 to the consumption of acid during preparation.Wherein said acid is one or more in hydrochloric acid, sulfuric acid, nitric acid and the phosphoric acid, is preferably hydrochloric acid, sulfuric acid or nitric acid, more preferably sulfuric acid.The concentration of acid is 1～50 weight %, is preferably 5～30 weight %.When the concentration of water glass solution is crossed when low, the concentration of silica is low in the prepared silica sol composition, the adhesive property of silica sol composition can reduce, and during the excessive concentration of water glass solution, in the process that adds acid, be easy to form gel, and the stability of formed silica sol composition, caking property variation, therefore, SiO in the described waterglass
2Concentration be preferably 5～20 weight %, 6～18 weight % more preferably.Described waterglass being contacted with inorganic acid, can be intermittent mode, also can be continuation mode.When intermittent mode is produced, preferably under agitation acid is joined in the water glass solution.When continuation mode is produced, waterglass and acid are proportionally mixed, mixed pH value is met the demands.When prepared silica sol composition concentration is low, in order to improve its concentration, also can comprise the step that an evaporation concentrates silica sol composition, described evaporation is preferably in temperature and is lower than 60 ℃ and carries out.
In the production of cracking catalyst provided by the present invention, used alkaline silica sol composition has preferably stability in 0～60 ℃ temperature range, can be under higher temperature stable existence, the temperature of preferred silica sol composition is 0～45 ℃.
In the production of cracking catalyst provided by the invention, silica sol composition is mixed making beating with the NaY molecular sieve, can carry out according to existing method, for example the slurries of NaY molecular sieve can be mixed making beating with silica sol composition, also can in silica sol composition, add the making beating of NaY molecular sieve dry powder.
In the production of cracking catalyst provided by the invention, can also comprise the step of introducing clay.When introducing clay, clay can be made slurries and mix with silica sol composition and molecular sieve again, also the clay and the alkaline silica sol composition making beating of solid can be mixed with molecular sieve again.Described clay is selected from kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and the bentonite one or more.Weight with catalyst is benchmark, and the introducing amount of clay makes containing of catalyst medium clay soil be no more than 70 weight %.
In the production of cracking catalyst provided by the invention, can also comprise the step of introducing alumina host, described alumina host is one or more of hydrated alumina, for example have structure of similar to thin diaspore hydrated alumina, have a diaspore structure hydrated alumina, have the hydrated alumina of gibbsite structure and have in the hydrated alumina of bayerite structure one or more, be preferably hydrated alumina with structure of similar to thin diaspore.Can alumina host be mixed, pull an oar with alkaline silica sol composition and then mix earlier, also can in silica sol composition-clay-molecular sieve pulp, introduce the making beating of al binder slurries with clay, molecular sieve pulp.Weight with catalyst is benchmark, and described introducing makes in the catalyst alumina host in aluminium oxide contain and is no more than 40 weight %.
Weight with prepared catalyst is benchmark, in the prepared catalyst of production of cracking catalyst provided by the invention, contains the clay of molecular sieve, 0～70 weight % of 10～95 weight %, with SiO
2The silicon bonding that is derived from alkaline silica sol composition of meter 5～90 weight % is with Al
2O
3The alumina host of meter 0～40 weight %; Preferably contain the clay of molecular sieve, 10～70 weight % of 10～60 weight %, with SiO
2The silicon bonding that is derived from alkaline silica sol composition of meter 5～40 weight % is with Al
2O
3The alumina host of meter 1～20 weight %; More preferably contain the clay of molecular sieve, 20～50 weight % of 20～40 weight %, with SiO
2The alkaline silica sol composition binding agent of meter 10～30 weight % is with Al
2O
3The alumina host of meter 5～15 weight %.
In the production of cracking catalyst provided by the invention, spray-drying obtains the micro-spherical catalyst particle, the method of carrying out ion-exchange can be existing method, generally include the step that catalyst granules is contacted with the inorganic salt solution that is used to exchange, for example can contact with deionized water or sulfate of ammoniac solution by the catalyst microballoon that spray-drying is obtained, removing impurity such as sodium oxide molybdena wherein, or, introduce rare earth ion with the earth solution exchange.Catalyst after the exchange can also wash, further to remove residual sodium oxide molybdena, cleaning solution and other impurity.
In the production of cracking catalyst provided by the invention, a kind of preferred ion-exchange process comprises catalyst granules that spray-drying is obtained and inorganic ammonium salt, H
2O is according to catalyst: inorganic ammonium salt: H
2O=1:(0.5～2): the weight ratio of (5～30) is mixed, and regulating its pH value is 9～11, keeps 30～80 minutes down in 60～95 ℃, filter then, wash, dry, 520～650 ℃ of following roastings 2～4 hours; And then according to catalyst: inorganic ammonium salt: H
2O=1:(0.5～2): the catalyst granules of the weight ratio of (5～30) after with roasting mixes with inorganic ammonium salt, stirs 20～80 minutes in 60～95 ℃, filters, washing; Catalyst granules drying after the washing obtains catalyst provided by the invention, and described catalyst can also further contact with rare earth and exchange so that introduce rare earth in catalyst.Described washing can be washed with the deionized water of 5～15 times of catalyst weights.Catalyst carries out ion-exchange according to this preferable methods, helps further improving the pore volume of catalyst, improves the cracking activity and the selectivity of catalyst.
In the production of cracking catalyst provided by the invention, described ion-exchange can also be adopted following method: catalyst granules that spray-drying is obtained and rare earth chloride, water are according to NaY molecular sieve (butt): RECl
3=1: 0.2～0.35 (weight ratio), water is that 3～50:1 mixes with the NaY weight ratio, under 40～100 ℃, carry out ion-exchange, stirring, filtration, washing, drying, again at 480～650 ℃, roasting more than 0.5 hour under 0～100% steam, roasting in preferred 0.5～4 hour, catalyst is pressed catalyst more then: ammonium salt: the weight ratio of water=1:0～2:2～30 is handled down at 60～100 ℃, makes through washing, filtration, drying.Described rare earth is selected from one of mishmetal, La, Ce, Pr, Nd or several mixture in them.
The pH value of alkaline silica sol composition provided by the invention is preferably 10.2～11.3, and more preferably 10.8～11.2; SiO in the alkaline silica sol composition
2Concentration be preferably 5～20 weight %, 5～15 weight % more preferably; The content of acid group is preferably 0.8～5 weight %, more preferably 1～4 weight %; M
2O content is preferably 1.5～6 weight %, more preferably 1.5～6 weight %; The content of water is preferably 70～95 weight %.Acid group in the described alkaline silica sol composition is Cl
-, NO
3 -, SO
4 2-, PO
4 3-In one or more, be preferably NO
3 -Or SO
4 2-, SO more preferably
4 2-Described M is preferably Na.
Alkaline silica sol composition provided by the present invention can be by being 2.6～3.5 with modulus, and concentration is the method preparation that the waterglass of 3.5～21 weight % contacts with acid.Wherein said acid is one or more in hydrochloric acid, sulfuric acid, nitric acid and the phosphoric acid, is preferably hydrochloric acid, sulfuric acid or nitric acid, sulfuric acid more preferably, and described waterglass is preferably sodium silicate.The concentration of acid is 1～50 weight %, is preferably 5～30 weight %.When the concentration of water glass solution is crossed when low, the concentration of silica is low in the prepared silica sol composition, the adhesive property of silica sol composition can reduce, and during the excessive concentration of water glass solution, in the process that adds acid, be easy to form gel, and the stability of formed silica sol composition, caking property variation, therefore, SiO in the described waterglass
2Concentration be preferably 5～20 weight %, 6～18 weight % more preferably.Described waterglass being contacted with inorganic acid, can be intermittent mode, also can be continuation mode.When intermittent mode is produced, preferably under agitation acid is joined in the water glass solution.When continuation mode is produced, waterglass and acid are proportionally mixed, mixed pH value is met the demands.When prepared alkaline silica sol composition concentration is low, in order to improve its concentration, also can comprise the step that an evaporation concentrates silica sol composition, described evaporation is preferably in temperature and is lower than 60 ℃ and carries out.
Alkaline silica sol composition provided by the invention is applicable to the preparation of silica-based Cracking catalyst.
Production of cracking catalyst provided by the invention is suitable for preparing the hydrocarbon oil catalytic cracking catalyst for heavy oil catalytic cracking especially that contains silicon bonding and y-type zeolite.Described y-type zeolite is HY, REHY, REY zeolite for example; Described heavy oil is reduced crude, decompression residuum, vacuum gas oil (VGO) for example, AGO (atmospheric gas oil), and straight run gas oil, propane is light/in heavy deasphalted oil and the coker gas oil one or more.
The present invention is further described for the following examples.
Embodiment 1
Under 35 ℃ the room temperature, (catalyst Shandong branch company of China Petrochemical Industry produces, SiO with the 4.6kg sodium silicate
2Content 20 weight %, modulus 3.2) mix with 10.1kg decationized Y sieve water, following in stirring then to wherein adding the sulfuric acid solution 0.9kg that concentration is 25 weight %, obtain SiO
2Concentration 6.0 weight %, the silica sol composition of pH value 10.2.
Add 3.3kg kaolin (China Kaolin Co., Ltd produces, solid content 84 weight %) in 4.7kg decationized Y sieve water, making beating makes kaolin slurry.
Add 1.2kg NaY molecular sieve (catalyst Shandong branch company produces, and solid content 78.2%, sodium oxide content are 13.7%) in 1.9kg decationized Y sieve water, making beating obtains molecular sieve pulp.
Above-mentioned silica sol composition, kaolin slurry, molecular sieve pulp are mixed, stir, obtain catalyst slurry, with this slurries spray-drying, obtain the micro-spherical catalyst particle then.
With the micro-spherical catalyst particle that obtains and ammonium nitrate and deionized water according to catalyst: NH
4NO
3: H
2The weight ratio of O=1:0.8:15 is mixed, and stirs, and regulating the slurries pH value is 9.6, is warming up to 90 ℃, stirred 35 minutes, filtration, filter cake with 10 times to the drip washing of catalyst butt weight deionized water, oven dry.
Under 600 ℃, to gained oven dry filter cake roasting 2 hours, then with catalyst and ammonium chloride and deionized water according to catalyst (butt): NH
4NO
3: H
2The weight ratio of O=1:1.2:15 mixes, and is warming up to 80 ℃, stirs 35 minutes, filters, and filter cake obtains catalyst A with 10 times of deionized water drip washing, oven dry to catalyst weight.Catalyst A consist of 60 weight % kaolin, 20 weight % molecular sieves, 20 weight %SiO
2Binding agent.Its performance sees Table 1.
Embodiment 2
Under 35 ℃ the room temperature, (catalyst Shandong branch company of China Petrochemical Industry produces, SiO with the 7.1kg sodium silicate
2Content 20 weight %, modulus 3.2) mix with 9.1kg decationized Y sieve water, following in stirring then to wherein adding the sulfuric acid solution 1.2kg that concentration is 20 weight %, obtain SiO
2Concentration 8.2 weight %, the silica sol composition of pH value 10.78.
Add 3.1kg kaolin (China Kaolin Co., Ltd produces, solid content 84 weight %) in 4.3kg decationized Y sieve water, making beating makes kaolin slurry.
Add 2.2kg NaY molecular sieve (catalyst Shandong branch company produces, and solid content 78.2%, sodium oxide content are 13.7%) in 3.5kg decationized Y sieve water, making beating obtains molecular sieve pulp.
Above-mentioned silica sol composition, kaolin slurry, molecular sieve pulp are mixed, stir, obtain catalyst slurry, with this slurries spray-drying, obtain the micro-spherical catalyst particle then.
With resulting catalyst granules according to NaY (butt): RECl
3=1: 0.25 weight ratio is carried out ion-exchange under 70 ℃, water and NaY weight ratio 20, regulating the slurries pH value is 3.7, is warming up to 70 ℃, stirred 60 minutes, filtration, filter cake with 10 times to the drip washing of catalyst butt weight deionized water, oven dry.
Under 550 ℃, to gained oven dry filter cake roasting 2 hours, then with catalyst and ammonium sulfate and water according to catalyst: (NH
4)
2SO
4: H
2The weight ratio of O=1:0.8:20 is mixed, and stirs, and is warming up to 70 ℃, and washing exchange 60 minutes is filtered, and filter cake obtains catalyst B with 10 times of deionized water drip washing, oven dry to catalyst weight.Catalyst B consist of 45 weight % kaolin, 30 weight % molecular sieves, 25 weight %SiO
2Binding agent.RE in the catalyst
2O
3Content is 2.6%.Its performance sees Table 1.
Comparative Examples 1
Under 35 ℃ the room temperature, (catalyst Shandong branch company of China Petrochemical Industry produces, SiO with the 7.1kg sodium silicate
2Content 20 weight %, modulus 3.2) mix with 9.1kg decationized Y sieve water, adding concentration is the sulfuric acid solution 1.2kg of 20 weight % in stirring down then, obtains SiO
2Concentration 8.2 weight %, the silica sol composition of pH value 10.78.
Add 3.1kg kaolin (China Kaolin Co., Ltd produces, solid content 84 weight %) in 4.3kg decationized Y sieve water, making beating makes kaolin slurry.
(catalyst Shandong branch company produces, solid content 91.7 weight %, RE in the molecular sieve to add 1.9kg REY molecular sieve in 3.0kg decationized Y sieve water
2O
3Content 15 weight %), making beating obtains molecular sieve pulp.
Above-mentioned silica sol composition, kaolin slurry, molecular sieve pulp are mixed, stir, obtain catalyst slurry,, obtain the micro-spherical catalyst particle this slurries spray-drying.
With catalyst granules, ammonium sulfate and deionized water according to catalyst: (NH
4)
2SO
4: H
2The weight ratio of O=1:0.8:20 is mixed, and stirs, and regulating the slurries pH value is 3.7, is warming up to 70 ℃, and stirs 60 minutes, filter, filter cake with 10 times to the drip washing of catalyst butt weight deionized water, oven dry.
Under 550 ℃,, obtain catalyst DB-1 to gained oven dry filter cake roasting 2 hours.Catalyst DB-1 consists of 45 weight % kaolin, 30 weight % molecular sieves, 25 weight %SiO
2Binding agent.Catalyst middle rare earth content is 2.7%.Its performance sees Table 1.
Embodiment 3
Under 26 ℃ the room temperature, (catalyst Shandong branch company of China Petrochemical Industry produces, SiO with the 7.2kg sodium silicate
2Content 20 weight %, modulus 3.2) mix with 6.3kg decationized Y sieve water, following in stirring then to wherein adding the sulfuric acid solution 0.8kg that concentration is 30 weight %, obtain SiO
2Concentration 10.1 weight %, the silica sol composition of pH value 10.87.
Add 3.5kg kaolin (China Kaolin Co., Ltd produces, solid content 84 weight %) in 4.9kg decationized Y sieve water, making beating obtains kaolin slurry.
Add 1.8kgNaY molecular sieve (catalyst Shandong branch company produces, and solid content 78.2%, sodium oxide content are 13.7%) in 2.9kg decationized Y sieve water, making beating obtains molecular sieve pulp.
Above-mentioned silica sol composition, kaolin slurry, molecular sieve pulp are mixed, and making beating obtains catalyst slurry, with this slurries spray-drying, obtains the micro-spherical catalyst particle, then with catalyst granules and ammonium chloride and deionized water according to catalyst: NH
4Cl:H
2The weight ratio of O=1:1:15 mixes, and the pH value of regulating slurries is 3.8, is warming up to 80 ℃, stirred 50 minutes, and filtration then, filter cake is with 10 times of deionized water drip washing, oven dry to catalyst weight.
Under 560 ℃, to dried filter cake roasting 3 hours, then with itself and ammonium chloride and deionized water according to catalyst: NH
4Cl:H
2The weight ratio of O=1:1:15 mixes, and is warming up to 70 ℃, and washing exchange 60 minutes is filtered, and filter cake obtains catalyst C with 10 times of deionized water drip washing, oven dry to catalyst weight.Catalyst C consists of 51 weight % kaolin, 24 weight % molecular sieves, 25 weight %SiO
2Binding agent.Its performance sees Table 1.
Comparative Examples 2
Method according to embodiment 3 prepares catalyst granules, and (catalyst Shandong branch company of China Petrochemical Industry produces the HY molecular sieve that different is in order to butt meter equivalent, sodium oxide content 4.5 weight %.) replacement NaY molecular sieve wherein.Then with catalyst granules and ammonium chloride and deionized water according to catalyst: NH
4Cl:H
2The weight ratio of O=1:1:15 mixes, and the pH value of regulating slurries is 3.8, is warming up to 70 ℃, stirred 60 minutes, and filtered then, filter cake is with 10 times of deionized water drip washing, oven dry to catalyst weight, under 560 ℃, to dried filter cake roasting 3 hours.Obtain catalyst DB-2.
Embodiment 4
Under 26 ℃ the room temperature, (catalyst Shandong branch company of China Petrochemical Industry produces, SiO with the 7.2kg sodium silicate
2Content 20 weight %, modulus 3.2) mix with 6.3kg decationized Y sieve water, adding concentration in above-mentioned water glass solution then under stirring is the sulfuric acid solution 0.8kg of 30 weight %, obtains SiO
2Concentration 10.1 weight %, the silica sol composition of pH value 10.87.
Add 2.8kg kaolin (China Kaolin Co., Ltd produces, solid content 84 weight %) in 3.9kg decationized Y sieve water, making beating obtains kaolin slurry.
Add 1.8kgNaY molecular sieve (catalyst Shandong branch company produces, and solid content 78.2%, sodium oxide content are 13.7%) in 2.9kg decationized Y sieve water, making beating obtains molecular sieve pulp.
Above-mentioned silica sol composition, kaolin slurry, molecular sieve pulp are mixed, stir adding boehmite 1.8kg (Shandong Aluminum Plant produces, solid content 33%) down, making beating obtains catalyst slurry, with this slurries spray-drying, obtains the micro-spherical catalyst particle.
With resulting micro-spherical catalyst particle and ammonium sulfate and deionized water according to catalyst: (NH
4)
2SO
4: H
2The weight ratio of O=1:1.2:20 is mixed, and stirs, and regulating the slurries pH value is 3.8, is warming up to 70 ℃, and stirs 60 minutes, filter, filter cake with 10 times to the drip washing of catalyst butt weight deionized water, oven dry.
Under 520 ℃, to gained oven dry filter cake roasting 2.5 hours.With catalyst and ammonium sulfate and water according to catalyst: (NH
4)
2SO
4: H
2The weight ratio of O=1:1.5:20 is mixed, and stirs, and is warming up to 70 ℃, and washing exchange 60 minutes is filtered, and filter cake obtains catalyst D with 10 times of deionized water drip washing, oven dry to catalyst weight.Catalyst D consists of 41 weight % kaolin, 24 weight % molecular sieves, 25 weight %SiO
2Binding agent, 10 weight % alumina hosts.Its performance sees Table 1.
Embodiment 5
(catalyst Shandong branch company produces, SiO with the 7.2kg sodium silicate under the room temperature
2Concentration 28.8 weight %, modulus 3.0) mix with 8.9kg decationized Y sieve water, under agitation to wherein adding 25 weight % sulfuric acid 1.3kg, obtain SiO then
2Concentration 11.9 weight %, the silica sol composition of pH value 11.03.
Add 3.1kg imvite (southization Red Hill bentonite Co., Ltd produces, and solid content is 78.6 weight %) in 4.0kg decationized Y sieve water, making beating obtains montmorillonite slurry.
Add 3.1kgNaY molecular sieve (catalyst Shandong branch company produces, and solid content 78.2%, sodium oxide content are 13.7%) in 4.9kg decationized Y sieve water, making beating obtains molecular sieve pulp.
Above-mentioned silica sol composition, montmorillonite slurry, molecular sieve pulp are mixed, stir, obtain catalyst slurry,, obtain the micro-spherical catalyst particle this slurries spray-drying, then with catalyst granules and ammonium phosphate and water according to catalyst: (NH
4)
3PO
4: H
2The weight ratio of O=1:1.5:20 is mixed, and stirs, and the slurries pH value is 10.1, is warming up to 95 ℃, and washing exchange 30 minutes is filtered, and filter cake is with 15 times of deionized water drip washing, oven dry to catalyst weight.
With dried filter cake 550 ℃ of following roastings 2 hours, then with ammonium phosphate and water according to catalyst: (NH
4)
3PO
4: H
2The weight ratio of O=1:1.5:20 mixes, and stirs, and is warming up to 85 ℃, and washing exchange 80 minutes is filtered, filter cake with 10 times to the drip washing of catalyst weight deionized water, oven dry, obtain catalyst E.Catalyst E consists of 35 weight % imvites, 35 weight % molecular sieves, 30 weight %SiO
2Binding agent.Its performance sees Table 1.
Embodiment 6
(catalyst Shandong branch company produces, SiO with the 6.0kg sodium silicate
2Concentration 28.8 weight %, modulus 3.0) mix with 5.7kg decationized Y sieve water, following in stirring then to the salpeter solution 2.1kg that wherein adds concentration 6 weight %, obtain SiO
2The silica sol composition of concentration 12.5 weight %, pH value 11.07.
Add 0.8kg kaolin (China Kaolin Co., Ltd produces, solid content 84 weight %) in 1.1kg decationized Y sieve water, making beating makes kaolin slurry.
Add 2.5kg NaY molecular sieve (catalyst Shandong branch company produces, and solid content 78.2%, sodium oxide content are 13.7%) in 4.0kg decationized Y sieve water, making beating obtains molecular sieve pulp.
Above-mentioned silica sol composition, kaolin slurry, molecular sieve pulp are mixed, stir, obtain catalyst slurry,, obtain the micro-spherical catalyst particle this slurries spray-drying, then with catalyst granules and ammonium sulfate and deionized water according to catalyst: (NH
4)
2SO
4: H
2The weight ratio of O=1:1.8:20 is mixed, and stirs, and the slurries pH value is 10.3, is warming up to 90 ℃, and stirs 60 minutes, filters, and filter cake is with 12 times of deionized water drip washing, oven dry to catalyst weight.
Under 580 ℃, to gained filter cake roasting 2 hours.Then with catalyst and ammonium sulfate and water according to catalyst: (NH
4)
2SO
4: H
2The weight ratio of O=1:1.8:25 is mixed, and stirs, and is warming up to 90 ℃, and washing exchange 60 minutes is filtered, and filter cake obtains catalyst F with 15 times of deionized water drip washing, oven dry to catalyst weight.Catalyst F consists of 15 weight % kaolin, 45 weight % molecular sieves, 40 weight %SiO
2Binding agent.Its performance sees Table 1.
Embodiment 7
Under the room temperature, (catalyst Shandong branch company of China Petrochemical Industry produces, SiO to get the 6.5kg sodium silicate
2Content 28.8 weight %, modulus 3.4) mix with 4.3kg decationized Y sieve water, following in stirring then to the hydrochloric acid solution 1.6kg that wherein adds concentration 10 weight %, obtain SiO
2Concentration 15 weight %, the silica sol composition of pH value 11.3.
Add 2.5kg halloysite (China Kaolin Co., Ltd produces, solid content 74.0 weight %) at above-mentioned Ludox, making beating makes kaolin slurry.
Add 3.1kg NaY molecular sieve (catalyst Shandong branch company produces, solid content 78.2%) in 3.6kg decationized Y sieve water, making beating obtains molecular sieve pulp.
Above-mentioned silica sol composition, kaolin slurry, molecular sieve pulp are mixed, stir, obtain the pH value and be 11.12 dissolved colloidal state catalyst slurry, with this slurries spray-drying, obtain the micro-spherical catalyst particle then.
With the micro-spherical catalyst particle that obtains and ammonium sulfate and deionized water according to catalyst: (NH
4)
2SO
4: the weight ratio of H2O=1:2:25 is mixed, and stirs, and the slurries pH value is 10.4, is warming up to 65 ℃, and stirs 80 minutes, filters, and filter cake is with 12 times of deionized water drip washing, oven dry to catalyst weight.
Under 530 ℃, to gained filter cake roasting 4 hours.With catalyst and ammonium sulfate and water according to catalyst: (NH
4)
2SO
4: H
2The weight ratio of O=1:2:25 is mixed, and stirs, and is warming up to 80 ℃, and washing exchange 60 minutes is filtered, and filter cake obtains catalyst G with 12 times of deionized water drip washing, oven dry to catalyst weight.Catalyst G consists of 30 weight % kaolin, 40 weight % molecular sieves, 30 weight %SiO
2Binding agent.Its performance sees Table 1.
Table 1
| Example number | The catalyst numbering | Apparent bulk density/g.ml -1 | Weeper volume/ml.g -1 | Abrasion index %h | Sodium oxide molybdena/weight % |
| Embodiment 1 | A | 0.63 | 0.48 | 2.4 | 0.24 |
| Embodiment 2 | B | 0.59 | 0.51 | 2.1 | 0.21 |
| Comparative Examples 1 | DB-1 | 0.61 | 0.50 | 2.0 | 0.15 |
| Embodiment 3 | C | 0.66 | 0.47 | 2.2 | 0.25 |
| Embodiment 4 | D | 0.50 | 0.61 | 1.6 | 0.29 |
| Embodiment 5 | E | 0.56 | 0.54 | 1.8 | 0.30 |
| Embodiment 6 | F | 0.53 | 0.57 | 1.9 | 0.34 |
| Embodiment 7 | G | 0.58 | 0.53 | 2.5 | 0.32 |
| Embodiment 18 | K | 0.64 | 0.49 | 2.1 | 0.24 |
By table 1 as seen, the catalyst of the inventive method preparation has bigger pore volume and lower bulk density.
Embodiment 8～14
In order to investigate the reactivity worth of catalyst, respectively to above-mentioned catalyst A, B, C, DB-1, D, E, F, G at 800 ℃, burin-in process 8h under 100% water vapor conditions carries out ACE (fixed fluidized bed) then and estimates, employed feedstock oil is decompressed wax oil, and character sees Table 2.The reaction condition of catalyst and the results are shown in Table 3.
Comparative Examples 3～4
Investigate the cracking reaction performance of catalyst DB-1, DB-2 according to the method for embodiment 8.The results are shown in Table 3.
Table 2
| Project | Data | Project | Data |
| Density (20 ℃)/gcm -3 | 0.9044 | Condensation point/℃ | 40 |
| Index of refraction (20 ℃) | 1.5217 | Aniline point/℃ | 95.8 |
| Viscosity (100 ℃)/mm 2·s -1 | 9.96 | Boiling range/℃ | |
| Carbon residue, % | 3 | Initial boiling point | 243 |
| Element is formed (ω), % | 5％ | 294 | |
| C | 85.98 | 10％ | 316 |
| H | 12.86 | 30％ | 395 |
| S | 0.55 | 50％ | 429 |
| N | 0.18 | 70％ | 473 |
Table 3
| Example number | Embodiment 8 | Embodiment 9 | Comparative Examples 3 | Comparative Examples 4 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 18 | Comparative Examples 5 |
| Catalyst | A | B | DB-1 | DB-2 | C | D | E | F | G | K | DB-3 |
| Reaction temperature | 500 | 500 | 500 | 500 | 500 | 500 | 500 | 500 | 500 | 500 | 500 |
| Oil ratio, wt/wt | 7.03 | ?5 | ?5 | 7.03 | 7.03 | 7.03 | 7.03 | 7.03 | 7.03 | 7.03 | 7.03 |
| Gas, wt% | 12.6 | 14.2 | 14.4 | 11.5 | 11.3 | 12.4 | 13.5 | 13.9 | 13.1 | 11.2 | 11.1 |
| Coke, wt% | 4.9 | 6.1 | 6.2 | 4.8 | 4.7 | 4.8 | 5.3 | 5.5 | 5.2 | 4.7 | 4.7 |
| Gasoline, wt% | 48.6 | 53.2 | 53.4 | 48.9 | 49.2 | 50.9 | 51.3 | 52.1 | 50.4 | 50.8 | 47.8 |
| Diesel oil, wt% | 18.6 | 15.6 | 14.8 | 19.5 | 19.7 | 18.4 | 17.1 | 16.6 | 17.6 | 18.4 | 20.6 |
| Heavy oil, wt% | 15.3 | 10.9 | 11.2 | 15.3 | 15.1 | 13.5 | 12.8 | 11.9 | 13.7 | 14.9 | 15.8 |
| Conversion ratio, wt% | 66.1 | 73.5 | 74 | 65.2 | 65.2 | 68.1 | 70.1 | 71.5 | 68.7 | 66.7 | 63.6 |
Embodiment 15
Catalyst E that embodiment 5 is obtained and mixed chlorinated rare earth, water are according to NaY (in butt): Re
2O
3: H
2The weight ratio of O=1:0.3:10 is mixed, and exchanges 30 minutes down at 75 ℃, and drying obtains catalyst H then, and the content of rare earth among the catalyst H is 2.8 weight %.
Embodiment 16
Under 40 ℃, (catalyst Shandong branch company of China Petrochemical Industry produces, SiO with the 13.5kg sodium silicate
2Content 4 weight %, modulus 2.8) adding concentration is the sulfuric acid solution 0.7kg of 30 weight % in stirring down, obtains SiO
2Concentration 3.8 weight %, the silica sol composition of pH value 10.87.This silica sol composition is placed not gelling in 48 hours.
Embodiment 17
Under 15 ℃, (catalyst Shandong branch company of China Petrochemical Industry produces, SiO with the 13.5kg sodium silicate
2Content 20 weight %, modulus 3.2) adding concentration is the sulfuric acid solution 1.5kg of 8 weight % in stirring down, obtains SiO
2Concentration 18 weight %, the silica sol composition of pH value 11.3.This silica sol composition is placed not gelling in 48 hours.
Embodiment 18
Method according to embodiment 3 prepares catalyst, and different is, the catalyst microballoon that spray-drying is obtained is with after sulphur ammonium, water mix, and the pH value of regulating slurries with ammoniacal liquor is 10.Obtain catalyst and be designated as K, according to the method for embodiment 8 catalyst K is estimated then, the results are shown in Table 3.
Comparative Examples 5
Getting temperature is 18 ℃ of concentration, 25 weight % sulfuric acid solution 3.5kg, and (catalyst Shandong branch company produces, and contains SiO with the 7.2kg sodium silicate
2Concentration 20%, modulus 3.2) mixes with 7.3kg decationized Y sieve water and dilute, be cooled to 18 ℃, stir then in the above-mentioned sulfuric acid weak solution of the slow adding of the sodium silicate that will dilute down, obtain SiO
2Concentration 8 weight %, the pH value is 1.55 Ludox.
Add 3.4kg kaolin (China Kaolin Co., Ltd produces, solid content 84 weight %) in 4.8kg decationized Y sieve water, making beating obtains kaolin slurry.Kaolin slurry is mixed stirring with the Ludox slurries.
Add 1.36kg HY molecular sieve (butt, catalyst Shandong branch company produces, with Comparative Examples 2) in 2.3kg decationized Y sieve water, making beating is 3.5 with the watery hydrochloric acid adjust pH.
Molecular sieve pulp is joined in above-mentioned Ludox-kaolin slurry, stir, obtain the pH value and be 2.90 dissolved colloidal state catalyst slurry,, obtain the micro-spherical catalyst particle this slurries spray-drying, then catalyst granules is washed with sulphur aqueous ammonium and deionized water, oven dry obtains catalyst, is numbered DB-3, it consists of 51 weight % kaolin, 24 weight % molecular sieves, 25 weight %SiO
2Binding agent, pore volume are 0.34ml.g
-1, heap is than being 0.69g.ml
-1Method according to embodiment 8 is estimated, and the results are shown in Table 3.
By the data of table 3 as seen, catalyst provided by the invention has higher conversion ratio and stronger heavy oil cracking ability, has the good characteristics of coke selectivity simultaneously.Catalyst adds alumina host, and slurry oil reduces in the crackate, illustrates that the matrix activity of catalyst is improved, and heavy oil cracking ability is enhanced.Catalyst of the present invention use the NaY molecular sieve prepare catalyst exchange again and use exchange in advance the molecular sieve preparation catalyst performance quite or omit, performance is better than the Cracking catalyst for preparing with acidic silicasol.
Claims (10)
1. the preparation method of a catalytic cracking catalyst comprises a kind of alkaline silica sol composition is mixed, pulls an oar with the NaY molecular sieve, then the step of spray-drying, ion-exchange, drying; Contain 0.9～7 weight %M in the described alkaline silica sol composition
2O, 3～20 weight %SiO
2, the acid group of 0.5～7 weight % and the water of aequum, the pH value of alkaline silica sol composition is 10～11.5, wherein M is an alkali metal.
2. in accordance with the method for claim 1, it is characterized in that the pH value of described silica sol composition is 10.2～11.3, SiO in the silica sol composition
2Content be 5～20%, the content of acid group is 0.8～5 weight %, M
2O content is 1.5～6 weight %.
3. in accordance with the method for claim 2, it is characterized in that SiO in the described silica sol composition
2Content be 5～15%, the content of acid group is 1～4 weight %, M
2O content is 1.5～5 weight %.
4. according to claim 1,2 or 3 described methods, it is characterized in that the pH value of described silica sol composition is 10.8～11.2.
5. according to claim 1,2 or 3 described methods, it is characterized in that described acid group is Cl
-, NO
3 -, SO
4 2-Or PO
4 3-Described M is Na.
6. in accordance with the method for claim 1, it is characterized in that described ion-exchange may further comprise the steps: catalyst granules that spray-drying is obtained and inorganic ammonium salt, H
2O is according to catalyst: inorganic ammonium salt: H
2O=1: (0.5～2): the weight ratio of (5～30) is mixed, and regulating its pH value is 9～11, in 60～95 ℃ of maintenances 30～80 minutes down, filters then, washs, drying, 520～650 ℃ of following roastings 2～4 hours; Then according to catalyst: inorganic ammonium salt: H
2O=1: (0.5～2): the catalyst granules of the weight ratio of (5～30) after with roasting mixes with inorganic ammonium salt, stirs 20～80 minutes in 60～95 ℃.
7. an alkaline silica sol composition is characterized in that, the pH value of described alkaline silica sol composition is 10～11.5; Weight with alkaline silica sol composition is benchmark, contains 0.9～7 weight %M in the described alkaline silica sol composition
2O, 3～20 weight %SiO
2, the acid group of 0.5～7 weight % and the water of aequum; Described M is an alkali metal.
8. according to the described alkaline silica sol composition of claim 7, it is characterized in that the pH value of described silica sol composition is 10.2～11.3, SiO in the silica sol composition
2Content be 5～20%, the content of acid group is 0.8～5 weight %, M
2O content is 1.5～6 weight %, and described acid group is Cl
-, NO
3 -, PO
4 3-Or SO
4 2-Described M is Na.
9. according to claim 7 or 8 described alkaline silica sol compositions, it is characterized in that SiO in the described alkaline silica sol composition
2Content be 5～20%, the content of acid group is 0.8～5 weight %, M
2O content is 1.5～6 weight %, and the pH value is 10.8～11.2.
10. according to the described alkaline silica sol composition of claim 7, it is characterized in that the temperature of described alkaline silica sol composition is 0～60 ℃.
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