CN102029177B - Cracking catalyst and preparation method thereof - Google Patents
Cracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a cracking catalyst, which comprises: raw materials and water are mixed to prepare a slurry solution by utilizing the catalyst containing a Y type molecular sieve and a silicon vector; the slurry solution is dried to obtain a catalyst precursor; the catalyst precursor is baked; and a contact reaction is carried out on the catalyst precursor and an acidic ammonium salt solution. The preparation method of the cracking catalyst can enhance the crystallization retaining degree of the Y type molecular sieve in the catalyst and the stability of the catalyst. The catalyst prepared by utilizing the method is used for the catalytic cracking of heavy oil and has the advantages of strong conversion capability of the heavy oil, high yield of gasoline, and low sulphur content in the gasoline.
Description
Technical field
The present invention relates to a kind of hydrocarbon oil catalytic cracking Catalysts and its preparation method that contains super-stable Y molecular sieves.
Background technology
The super-stable Y molecular sieves of high silica alumina ratio, good hydrothermal stability, mesopore is more, is used for RFCC and has higher heavy oil transformation rate, is the main active component of existing catalyst for heavy oil catalytic cracking.The method of producing super-stable Y molecular sieves in the industry mainly is hydro-thermal method (for example CN1005405C, a CN1065844A disclosed method); This method is carried out dealuminzation to molecular sieve under high-temperature water vapor atmosphere; To improve the silica alumina ratio of molecular sieve; Yet owing to there is not extraneous silicon source to fill up the room that dealuminzation produces, this method can make crystal structure produce defective, and apparent in view decline can take place molecular sieve crystallinity.
CN1629258A discloses a kind of preparation method who contains the Cracking catalyst of rare earth superstable Y-type molecular sieve; It is characterized in that this method be with NaY molecular sieve and the ammonium salt aqueous solution that contains 6-94 weight % ammonium salt normal pressure with contact more than twice or twice with the weight ratio of molecular sieve 0.1-24 according to ammonium salt to the condition of the boiling temperature that is not more than ammonium salt aqueous solution greater than 90 ℃, make Na in the molecular sieve
2O content is reduced to below the 1.5 weight %, uses rare-earth salts content to contact with molecular sieve down at 70 ℃-95 ℃ as the aqueous solution of 2-10 weight % then, makes rare earth in the molecular sieve with RE
2O
3Count 0.5-18 weight %, mix with carrier again, drying.
CN1098130A discloses a kind of catalytic cracking catalyst that contains the composite aluminum base binding agent, and oxide, the 5-40m% that is selected from elements such as Sn, Ti, Mg by clay, the composite aluminum base binding agent of 5-40m%, the 0-5m% of 20-80m% is selected from faujasite that lattice constant is 2.432-2.472nm, ZSM-5 zeolite, β zeolite and composition thereof and forms.Its preparation method is that clay is mixed making beating with deionized water, adds hcl acidifying, adds boehmite, aluminium colloidal sol, zeolite molecular sieve making beating, promptly gets product through drying, washing or roasting.
The production of cracking catalyst that more than contains super-stable Y molecular sieves; The preparation super-stable Y molecular sieves mixes making beating, drying and moulding with super-stable Y molecular sieves then with carrier earlier, and flow process is complicated; And because the molecular sieve heap is than little; Particle is thin, and recovery difficult is big, usually causes the synthetic yield of molecular sieve not high.
Summary of the invention
The technical problem that the present invention will solve provides a kind of new Cracking catalyst and preparation method thereof.
The present invention provides a kind of preparation method of Cracking catalyst, and this method comprises:
The catalyst raw material and the water that (1) will comprise Y zeolite, silicon carrier are mixed with slurries, then slurry dried are obtained catalyst precarsor; The content of sodium oxide molybdena is 2～14 weight % in the wherein said Y property molecular sieve;
(2) catalyst precarsor that obtains of step (1) is under 350-550 ℃, water vapour atmosphere roasting 0.25-3 hour;
(3) catalyst precarsor after step (2) roasting being contacted with ammonium salt solution, is to react 10-60 minute under 2.5-5.0, temperature are 60-95 ℃ in the pH value, filters then, washs; Catalyst precarsor: H wherein
2O=1: 10-20 (weight ratio), ammonium concentration are 3-15 weight %;
(4) with step (3) products therefrom in 450-750 ℃ of roasting 0.5-4 hour.
(5) product that step (4) is obtained contacts with ammonium salt solution, in 60-95 ℃ of down reaction 10-60 minute, filters then, washs, drying; Catalyst: H wherein
2O=1: 10-20 (weight ratio), ammonium concentration are 1-6 weight %, and slurry pH value is 2.5-5.0.
The present invention also provides a kind of Cracking catalyst, it is characterized in that, said catalyst is prepared by production of cracking catalyst provided by the invention.
Production of cracking catalyst provided by the invention will comprise that earlier Y molecular sieve mixes making beating with the raw material of silicon carrier, and will be dry then; Preparation Cracking catalyst precursor; Again it is handled under water vapour atmosphere, and exchange processing, obtain containing the catalyst of ultra-steady Y molecular sieve; Carrier holds the high-temperature tolerance that body can be protected molecular sieve as heat, and silicon wherein helps improving the silica alumina ratio of molecular sieve, makes molecular sieve keep higher degree of crystallinity, improves the structural stability of molecular sieve and the heat and the hydrothermal stability of catalyst; Especially in molecular sieve, contain under the situation of desulfurization metal component, can reduce the broken ring of the introducing of desulfurization metal component, make it have higher crystallization reservation degree, improve the structural stability and the hydrothermal stability of catalyst molecular sieve structure.In addition since sieve particle less, pile lower, in the conventional Hydrothermal Preparation ultra-steady Y molecular sieve process; Molecular sieve reclaims difficulty, and cost recovery is higher, and the molecular sieve yield is lower; And in the inventive method molecular sieve is mixed with carrier, carries out super stabilizing again after the moulding; Help reducing the loss of molecular sieve in the super stabilizing process, reduce cost recovery, improve the yield of molecular sieve.Method for preparing catalyst provided by the invention can improve the pore volume of catalyst, in the catalyst the relative crystallization of Y zeolite keep Du Keda 75-95%, lattice constant can less than
, Na
2O content is less than 1%, and when also containing the transition metal component in the used molecular sieve raw material, molecular sieve still can keep higher degree of crystallinity.
Catalyst provided by the invention; The existing Cracking catalyst that contains super-stable Y molecular sieves has higher hydrothermal stability and the stronger big molecule cracking of heavy oil ability; Be used for RFCC, can improve yield of gasoline, yield of light oil and yield of liquefied gas, improve the heavy oil transformation rate; In particular for the hydrocarbon oil containing surphur cracking, can reduce the sulfur content in the cracking gasoline significantly.
The specific embodiment
In the production of cracking catalyst provided by the invention, Na in the described Y zeolite of step (1)
2O content is 2～14 weight %, preferred 3～10 weight %; The silica alumina ratio of Y molecular sieve is 4.5-8, is preferably 5-8.Can also contain other ion beyond the Na in the described Y molecular sieve; Described other ion can be one or more in rare earth, ammonium, H, Li, Mg, Ca, Zr, V, Ni, Cd, In, Sn, Hg, Tl, Pb, Bi, B and Al (the non-framework of molecular sieve aluminium) ion, and preferred Y molecular sieve is NaY, HY, NH
4In Y, REY, REHY, RENH4Y, VHY, REUSY, DASY, the USY molecular sieve one or more.In the time of other metal ion of containing in the molecular sieve beyond the Na, in oxide, the content of this other metal ion is no more than 12 weight %.When containing rare earth in the said Y property molecular sieve, the content of rare earth preferably is no more than 12 weight %, and the content of other metal ion beyond 2～8 weight % more preferably, sodium and rare earth preferably is no more than 2 weight %.
In the production of cracking catalyst provided by the invention, the described catalyst raw material of step (1) comprises silicon carrier, is benchmark with the weight of prepared catalyst, and the content that is derived from the silica of silicon carrier is 15-65 weight %.Described silicon carrier is that catalytic cracking catalyst prepares one or more in the siliceous carrier of being habitually practised, for example one or more in the precursor of the precursor of clay, silica, silica, amorphous aluminum silicide, amorphous aluminum silicide.Wherein, said clay is selected from Cracking catalyst clay commonly used for example kaolin, halloysite, imvite, diatomite, tired in the soil one or more, the preferred kaolin of taking off; The precursor of said amorphous aluminum silicide can be selected from the mixture of silicon-aluminum sol, Ludox and aluminium colloidal sol, in the silica-alumina gel one or more; The precursor of said silica can be selected from one or more in Ludox, silicon gel and the waterglass, is preferably Ludox.Said Ludox can be acid, neutral, alkaline silicon, and the introducing amount of Ludox makes the content that is derived from the silica of Ludox in the catalyst that obtains be no more than 15 weight %, is preferably 1-15 weight %.Preferred described silicon carrier comprises clay, is benchmark with the weight of catalyst, and the content of clay is that 10-80 weight % is preferably 20-50 weight %.
In the production of cracking catalyst provided by the invention; The described catalyst raw material of step (1) can also comprise non-silicon inorganic oxide carrier; Said non-silicon inorganic oxide carrier is selected from Cracking catalyst inorganic oxide commonly used or in its precursor one or more, for example one or more in aluminium oxide, titanium oxide, zirconia and their precursor.Described aluminium oxide can be the aluminium oxide of various crystal formations, for example one or more in γ, β, α, the η κ aluminium oxide; The precursor of said aluminium oxide can be one or more in the hydrated alumina, for example boehmite and/or aluminium colloidal sol.With the catalyst total amount is benchmark, and the content of carrier in the said catalyst (comprising silicon carrier and non-silicon carrier) is no more than 80 weight %, is preferably 10-70 weight %, and wherein, the content of non-silicon inorganic oxide carrier is no more than 40 weight %.。
Under the preferable case; Comprise in the inorganic oxide carrier (binding agent) of making the Cracking catalyst binding agent commonly used one or more in the described raw material of step (1); Described binding agent is one or more in al binder, silicon bonding and the sial binding agent for example; Described al binder is one or more in the precursor of aluminium oxide and aluminium oxide, and described aluminium oxide precursor is boehmite and/or aluminium colloidal sol for example.Described silicon bonding is Ludox, silicon gel, waterglass for example, and preferred Ludox can be neutral, alkaline or acid Ludox.Described sial binding agent is Alusil for example.With the catalyst total amount is benchmark, and in oxide, the content of binding agent is 1-25 weight %, is preferably 5-15 weight %.
In the production of cracking catalyst provided by the invention; The consumption of Y zeolite and carrier is the conventional amount used of raw material described in the existing Cracking catalyst preparation in the step (1); Preferably, in catalyst butt weight, the consumption amount of making of carrier and Y zeolite makes the carrier that contains the preferred 55-75 weight of 50-80 weight % in the resulting catalyst; The Y zeolite of the preferred 25-45 weight of 20-50 weight % %, the silica content that is derived from carrier in the catalyst are 15-65 weight %.
In the production of cracking catalyst provided by the present invention, can also comprise in the described raw material of step (1) and select the type molecular sieve that said shape-selective molecular sieve is ZSM-5, ZRP, beta-molecular sieve for example; Preferably ZSM-5 and/or ZRP molecular sieve, its silica alumina ratio is preferably 20-500.Weight with catalyst is benchmark, and the said content of selecting the type molecular sieve is no more than 50 weight %, preferably is no more than 30 weight %.
In the production of cracking catalyst provided by the invention, in the step (1), the solid content that raw material is mixed the slurries of making beating formation with water is 10-50 weight %, is preferably 15-30 weight %; With the condition of slurry dried is that catalytic cracking catalyst prepares drying condition commonly used in the process, and in general, baking temperature is 100-350 ℃, is preferably 200-300 ℃.Said drying can be used oven dry, forced air drying or spray-dired method, the method for preferably spray drying.
In the production of cracking catalyst provided by the invention, with the catalyst precarsor roasting, it is 350-575 ℃ that temperature is watered in roasting to step (2), is preferably 350-500 ℃ under water vapour atmosphere; Roasting time is 0.25-3.5 hour, preferred 0.5-2 hour.Preferably the butt weight with catalyst precarsor is benchmark, and the water content in the roasting procatalyst precursor is 10-25 weight %, more preferably 10-20 weight %; Water content in the control catalyst helps improving the degree of crystallinity of molecular sieve, if water content is lower in the catalyst precarsor, can catalyst precarsor be mixed the water content that increases in the catalyst precarsor with distilled water or deionized water.
Among the cracking agent preparation method provided by the present invention, in the step (3) catalyst precarsor after the roasting and deionized water, ammonium salt are mixed, and the pH value of regulating resulting slurries is 2.5-5.0, then 60-95 ℃ of reaction 10-60 minute down; Said slurry pH value is preferably 2.8-4.5, and reaction temperature is preferably 80-95 ℃, and the reaction time is preferably 15-60 minute; Wherein, catalyst: H
2O=1: 10-20 (weight ratio), ammonium salt mix ammonium ion in the solution that forms with water concentration is 3-15 weight %, and the concentration of ammonium ion is preferably 5-10 weight %.Filter the reaction back, and with catalyst and solution separating, the catalyst that obtains after the separation washs.The pH value of slurries can adopt ammoniacal liquor or acid to regulate, and said acid is hydrochloric acid, sulfuric acid, nitric acid for example.
In the production of cracking catalyst provided by the present invention; Product roasting in inert gas, air or water vapour atmosphere that step (4) obtains step (3); Wherein said water vapour atmosphere can be the water vapour that feeds water vapour or catalyst self generation; Sintering temperature is 450-750 ℃, is preferably 500-700 ℃; Roasting time is 0.5-4 hour, is preferably 1-4 hour.
Among the Cracking catalyst agent preparation method provided by the present invention; Catalyst precarsor and water, the ammonium salt of step (5) after with step (4) roasting mixes; In the pH value is under 2.5-5.0,60-95 ℃, reacts 10-60 minute, filters then, washs, drying obtains catalyst; Preferably, reaction temperature is 80-95 ℃, and the reaction time is 15-45 minute, and the pH value is 2.8-3.5; Catalyst: H wherein
2O=1: 10-1: 20 (weight ratios), the concentration of ammonium ion is 1-6 weight % in the solution that ammonium salt and water form, and is preferably 2-5 weight %.Said ammonium salt is ammonium sulfate, ammonium chloride or ammonium nitrate; The pH value of slurries is regulated and can be adopted ammoniacal liquor or acid to regulate, and said acid is hydrochloric acid, sulfuric acid, nitric acid for example.Said drying can adopt existing dry technologies such as pneumatic conveying drying, oven dry, and the present invention does not have specific (special) requirements.
In the production of cracking catalyst provided by the present invention, the washing described in step (3) and (5) can be adopted existing method, for example can spend deionised water; Said washing can be carried out one or many, and preferred said washing makes that no acid group detects in the washing water after washing.
In the production of cracking catalyst provided by the present invention; Can also comprise the step of introducing adjuvant component; Said adjuvant component can be introduced in the process of step (1) preparation slurries; Also can be after step (1), step (5) increases a step that catalyst precarsor is contacted with adjuvant component before.Said adjuvant component is rare earth compound for example, is benchmark with the weight of catalyst, and the content of the rare earth element of said catalyst is no more than 5 weight % (with RE
2O
3Meter), wherein said rare earth element is to be master's mixed rare-earth elements with lanthanum and/or cerium, and wherein the content of lanthanum and/or cerium is more than the 50 weight % of total rare earth element amount, more than the preferred 60 weight %.The preferred soluble-salt of introducing rare earth.
Method for preparing catalyst provided by the invention, the relative crystallinity reservation degree of Y zeolite is not less than 75% in the resulting catalyst, the lattice constant that is generally 75-95%, molecular sieve less than
, Na
2O content is less than 1%, and when containing rare earth in the molecular sieve raw material, the content of rare earth of molecular sieve is constant basically in the catalyst.
In the Cracking catalyst provided by the invention, be benchmark with the butt weight of catalyst, contain the carrier of 50-80 weight %, the Y zeolite of 20-50 weight % contains or does not contain shape-selective molecular sieve; The silica content that wherein is derived from carrier is 15-65 weight %, and the content of selecting the type molecular sieve is not no more than 30 weight %.Preferred said catalyst contains the Y zeolite of 20-50 weight %, the clay of 20～50 weight %, in the binding agent of oxide 1～25 weight %.
In the catalyst cracking method provided by the invention, described catalytic cracking condition is the conventional reaction condition of general cracking hydrocarbon process, and for example reaction temperature is 400-600 ℃, is preferably 450-550 ℃, weight (hourly) space velocity (WHSV) 5-30 hour
-1, be preferably 8-25 hour
-1, oil ratio (weight ratio of catalyst and feedstock oil) is 1-10, preferred 2-7.
Catalyst cracking method provided by the invention is applicable to the heavy oil hydrocarbon oil catalytic cracking, especially is applicable to the hydrocarbon oil containing surphur catalytic cracking.Said heavy oil is for example: reduced crude, decompression residuum, vacuum gas oil (VGO), AGO (atmospheric gas oil), propane deasphalting oil.
Following embodiment will be described further the present invention, but these embodiment can not be interpreted as qualification of the present invention.Said relative crystallinity is that the products molecule sieve is compared resulting degree of crystallinity with the NaY raw material (defining its degree of crystallinity is 100%) among the embodiment 1 among the present invention; The assay method of this relative crystallinity is referring to " petrochemical industry analytical method (RIPP test method) " (volume such as Yang Cuiding; Science Press, nineteen ninety publishes) in RIPP 146-90 standard method.
Embodiment 1-5
These embodiment explain the preparation of catalyst precarsor provided by the invention.
In raw materials used, molecular sieve is catalyst Shandong branch company of China Petrochemical Industry and produces, and wherein, the lattice constant of NaY molecular sieve is 2.473 nanometers, and sodium oxide content 14 weight %, solid content are 79.48 weight %, degree of crystallinity 100%; REHY molecular sieve lattice constant is 2.470 nanometers, sodium oxide content 3.8 weight %, and rare earth oxide content 6.5 weight %, solid content are 78.4 weight %, degree of crystallinity 86%; V-REHY molecular sieve lattice constant is 2.469 nanometers, sodium oxide content 3.8 weight %, and rare earth oxide content 6.5 weight %, vanadium (in simple substance) content is 1.0 weight %, solid content is 77.9 weight %, degree of crystallinity 77%.Kaolin is China Kaolin Co., Ltd's industrial products, and its solid content is 84 weight %; Boehmite is that Shandong Aluminum Plant produces, and its alumina content is 35 weight %; Aluminium colloidal sol is that catalyst Shandong branch company of China Petrochemical Industry produces, and its alumina content is 21 weight %.Ludox is produced by the Beijing Chemical Plant, and its silica content is 25 weight %, and pH value is 7.2.The consumption of the various raw materials of each embodiment is seen table 1.
The preparation process of catalyst precarsor is following:
(1) take by weighing quantitative boehmite and quantitative water mixes, under agitation add quantitative concentration and be 36% concentrated hydrochloric acid (chemical pure, the Beijing Chemical Plant produces), hydrochloric acid (HCl) and boehmite are (with Al
2O
3Meter) mol ratio is 0.14, the gained mixture is warming up to 70 ℃ wore out 1.5 hours, and the boehmite that obtains wearing out, its alumina content are 12 weight %.
(2) with quantitative Y zeolite, quantitative aluminium colloidal sol or Ludox, kaolin, above-mentioned aging boehmite and deionized water mix, and it is 28 weight % that the consumption of water makes the slurry solid content that obtains, and spray-drying obtains catalyst precarsor.
Table 1 has been listed the consumption of used aluminium colloidal sol, boehmite, Ludox, kaolin and Y zeolite and the kind of used Y zeolite.Table 2 has provided the weight of catalyst CM-1～CM-5 and has formed.Y zeolite, binding agent and kaolinic content during catalyst is formed are got by calculating.The content of rare earth oxide adopts x-ray fluorescence spectrometry.
Table 1
Table 2
| The embodiment numbering | The catalyst precarsor numbering | Y zeolite | Kaolin | Boehmite | Aluminium colloidal sol | Ludox |
| Embodiment 1 | CM-1 | 25％ | 45％ | 20％ | 10％ | 0 |
| Embodiment 2 | CM-2 | 35％ | 35％ | 18％ | 0％ | 12％ |
| Embodiment 3 | CM-3 | 45％ | 30％ | 15％ | 4％ | 6％ |
| Embodiment 4 | CM-4 | 40％ | 32％ | 20％ | 8 | 0 |
| Embodiment 5 | CM-5 | 45％ | 30％ | 15％ | 4％ | 6％ |
Embodiment 6～7
In 100 gram (dry basis) catalyst precarsor CM-1, CM-2, add deionized water respectively; Making the water content in the catalyst precarsor is 15 weight % (the butt weight with catalyst precarsor is benchmark); At 450 ℃; Roasting is 1.5 hours in 100% water vapour atmosphere, then with 2 liters of ammonium concentrations (NH that is 6 weight %
4)
2SO
4Aqueous solution; Carried out ion-exchange 45 minutes in 90 ℃, replenish hydrochloric acid in the exchange process, keeping slurry pH value is 4.0; Filter then; Spend that sulfate radical-free detects in the water after deionised water filter cake to the washing, with this wet cake 750 ℃ of roastings 2 hours, again with 2 liters of ammonium concentrations (NH that is 3 weight %
4)
2SO
4The aqueous solution carried out ion-exchange 30 minutes in 85 ℃; Using hydrochloric acid control slurry pH value in the exchange process is 3.5, filters, and spends that sulfate radical-free detects in the water after deionised water filter cake to the washing; Promptly obtain the ultra steady catalyst of molecular sieve original position of the present invention after the drying, be designated as CM-1a and CM-2a.Table 3 has provided the lattice constant of Y zeolite, relative crystallinity and specific area among the CM-1a-CM-2a.
Embodiment 8～9
(the butt weight with CM-3 is benchmark at 110 gram catalyst precarsor CM-3; Water content 9 weight %), (the butt weight with CM-4 is benchmark to CM-4; Water content 9.5 weight %) add 10 gram deionized waters in respectively, (the NH that roasting was 4 weight % with 2 liters of ammonium concentrations after 1 hour in 400 ℃ of water vapour atmospheres
4)
2SO
4The aqueous solution carried out ion-exchange 60 minutes in 90 ℃, replenished hydrochloric acid in the exchange process, made slurry pH value remain 4.0, filtered, with 10 times of deionized water washing leaching cakes to catalyst weight.With this wet cake 650 ℃ of roastings 4 hours, again with 2 liters of ammonium concentrations (NH that is 2 weight %
4)
2SO
4The aqueous solution carried out ion-exchange 40 minutes in 90 ℃, replenished hydrochloric acid in the exchange process, and making slurry pH value is 3.5; Filter; With 10 times of deionized water washing leaching cakes to catalyst weight, promptly obtain the ultra steady catalyst of molecular sieve original position of the present invention after the drying, be designated as CM-3a and CM-4a.Table 3 has provided the lattice constant of Y zeolite among CM-3a and the CM-4a, relative crystallinity and specific area.
Embodiment 10
With 100 gram (dry basis) catalyst CM-5 (with butt CM-5 weight is benchmark, water content 10 weight %), (NH that roasting was 8 weight % with 2 liters of ammonium concentrations after 3 hours in 350 ℃ of water vapour atmospheres
4)
2SO
4The aqueous solution carried out ion-exchange 45 minutes in 85 ℃, and replenishing hydrochloric acid control slurry pH value in the exchange process is 4.0, filters, and spent that no acid group detects in the water after deionised water filter cake to the washing.With this wet cake 525 ℃ of roastings 4 hours, again with 2 liters of ammonium concentrations (NH that is 5 weight %
4)
2SO
4The aqueous solution carried out ion-exchange 30 minutes in 95 ℃, replenished hydrochloric acid in the exchange process, and the control slurry pH value is 3.5; Filter; Spend the deionised water filter cake to the washing after water in no acid group detect, promptly obtain the ultra steady catalyst of molecular sieve original position of the present invention after the drying, be designated as CM-5a.Table 3 has provided the lattice constant of Y zeolite, relative crystallinity and specific area among the CM-5a.
Wherein, the content of sodium oxide molybdena during molecular sieve is formed, the content of aluminium oxide and the content of silica all adopt x-ray fluorescence spectrometry; Lattice constant and relative crystallinity adopt X-ray diffraction method to measure; Specific surface and pore volume adopt N
2Absorption (BET) method is measured.The framework si-al ratio of molecular sieve is got by computes:
Silica alumina ratio=192/ [1124 * (a
0-2.42383)] a wherein
0Be lattice constant, nm.
Table 3:
| The embodiment numbering | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 |
| The catalyst numbering | CM-1a | CM-2a | CM-3a | CM-4a | CM-5a |
| The molecular sieve lattice constant, nm | 2.449 | 2.450 | 2.457 | 2.455 | 2.455 |
| The molecular sieve relative crystallinity, % | 75 | 79 | 85 | 83 | 75 |
| The framework of molecular sieve silica alumina ratio | 6.79 | 6.53 | 5.15 | 5.48 | 5.48 |
| Specific area, m 2/g | 198 | 238 | 276 | 254 | 224 |
| Total pore volume, ml/g | 0.145 | 0.193 | 0.229 | 0.216 | 0.206 |
| Micro pore volume, ml/g | 0.078 | 0.106 | 0.130 | 0.114 | 0.104 |
| Catalyst chemical is formed, weight % | |||||
| Na 2O | 0.21 | 0.27 | 0.19 | 0.15 | 0.14 |
| RE 2O 3 | 0 | 0 | 2.8 | 2.6 | 2.6 |
| V 2O 5 | 0 | 0 | 0 | 0 | 0.45 |
Comparative Examples 1
This Comparative Examples is explained conventional super-stable Y molecular sieves Preparation of catalysts and effect thereof.
Utilize the NaY molecular sieve of embodiment 1 to prepare the USY molecular sieve according to existing method: NaY molecular sieve and 2 liters of (NH that concentration is 6 weight % that embodiment 1 is used
4)
2SO
4Aqueous solution; Carried out ion-exchange 45 minutes in 90 ℃, replenish hydrochloric acid in the exchange process, keeping slurry pH value is 4.0; Filter then; Spend that no acid group detects in the water after deionised water filter cake to the washing, with the roasting 2 hours in 750 ℃ of this wet cake, again with 2 liters of concentration (NH that is 3 weight %
4)
2SO
4The aqueous solution carried out ion-exchange 30 minutes in 85 ℃, and using hydrochloric acid control slurry pH value in the exchange process is 3.5, filters; Washing, drying, roasting 2 hours in 750 ℃, water vapour atmosphere then; Promptly obtain the USY molecular sieve; The framework si-al ratio of this molecular sieve is 7.06, and lattice constant is 2.448 nanometers, and degree of crystallinity is 69%.
Replace the NaY molecular sieve among the embodiment 1 with prepared USY molecular sieve, prepare catalyst, be designated as D1 according to the method for embodiment 1.
Comparative Examples 2
Press embodiment 4 preparation catalyst, difference is, uses the super stable molecular sieve DASY6.0 that contains rare earth to replace REHY.The silica alumina ratio of DASY6.0 is 5.48, and lattice constant is 2.455 nanometers, and content of rare earth is 6.0 weight %, and degree of crystallinity is 70%, and catalyst Shandong branch company of China Petrochemical Industry produces.Catalyst is designated as D2.
Table 4
| The catalyst numbering | D1 | D2 |
| The molecular sieve lattice constant, nm | 2.448 | 2.455 |
| The molecular sieve relative crystallinity, % | 69 | 70 |
| The framework of molecular sieve silica alumina ratio | 7.06 | 5.48 |
| Specific surface | ||
| Total pore volume, ml/g | 0.127 | 0.178 |
| Micro pore volume, ml/g | 0.069 | 0.095 |
| Chemical composition, weight % | ||
| Na 2O | 0.14 | 0.15 |
| RE 2O 3 | 0 | 2.62 |
Embodiment 11～15
These embodiment explain catalyst catalytic performance provided by the invention.
With boiling range is that 235～335 ℃ light diesel fuel is a reaction raw materials, and to through 800 ℃, the catalyst CM-1a～CM-5a of 100% steam aging 4 hours or 17 hours carries out the light oil microactivity evaluation on micro-reactor continuously.Catalyst loading amount 5.0 grams, 460 ℃ of reaction temperatures, air speed 16 hours
-1, the agent weight of oil is than 3.2.Evaluation result is listed in the table 5.
Comparative Examples 3-4
Method by embodiment 11-15 is estimated catalyst D1, the D2 for preparing among the Comparative Examples 1-2, and the result sees table 5.
Table 5
| The embodiment numbering | The catalyst numbering | Micro-activity, 800 ℃/4h | Micro-activity, 800 ℃/17h |
| Embodiment 11 | CM-1a | 66 | 45 |
| Embodiment 12 | CM-2a | 72 | 50 |
| Embodiment 13 | CM-3a | 80 | 56 |
| Embodiment 14 | CM-4a | 75 | 53 |
| Embodiment 15 | CM-5a | 74 | 51 |
| Comparative Examples 3 | D-1 | 62 | 40 |
| Comparative Examples 4 | D-2 | 73 | 49 |
Comparative Examples 5
Method according to embodiment 5 prepares catalyst; (lattice constant is 2.455 nanometers to the V-REUSY that different is with equivalent, sodium oxide content 0.15 weight %, rare earth oxide content 6.5 weight %; V element content 1 weight %; Solid content is 92 weight %) replace V-REHY wherein, the degree of crystallinity that prepared catalyst is fresh dose is that 70%, 17 hour 100% steam aging post crystallization degree is 30%; Its micro-activity is respectively 35.And the degree of crystallinity of the catalyst of embodiment 10 preparations after wearing out in 17 hours is 55%.
Embodiment 13
Following embodiment explains the catalytic performance of catalyst provided by the invention and comparative catalyst's catalytic performance.
Resulting catalyst CM-1a and D1 in 800 ℃, 100% water vapour atmosphere aging 4 hours down, are estimated on ACE.Feedstock oil character is seen table 6.Catalyst loading amount 9.0 grams, 460 ℃ of reaction temperatures, evaluation result is listed in the table 7.Product adopts gc analysis.
Embodiment 14
Resulting catalyst CM-4a and D2 in aging 4 hours of 800 ℃, 100% water vapour atmosphere, are estimated on ACE.Feedstock oil character is seen table 6.Catalyst loading amount 9.0 grams, 500 ℃ of reaction temperatures, evaluation result is listed in the table 8.Product adopts gc analysis.
Visible by table 7 and table 8, compare with the catalyst of existing method preparation, the Cracking catalyst of the inventive method preparation, heavy oil conversion performance is higher, and yield of liquefied gas, yield of light oil, yield of gasoline improve, and sulfur in gasoline content reduces, and the productive rate of dry gas reduces.
Table 6
| Project | Index |
| Density (20 ℃), g/cm 3 | 0.9044 |
| Kinematic viscosity, mm 2/s | |
| 50℃ | 57.69 |
| 100℃ | 9.96 |
| Freezing point, ℃ | 40.0 |
| Carbon residue, weight % | 2.97 |
| Molecular weight (actual measurement) | 390 |
| C 7Insoluble matter | 0.37 |
| C, weight % | 85.98 |
| H, weight % | 12.86 |
| S, weight % | 0.55 |
| Alkali nitrogen, ppm | 1000 |
| Boiling range, ℃ | |
| Initial boiling point | 243 |
| 5％ | 294 |
| 10％ | 316 |
| 30％ | 395 |
| 50％ | 429 |
| 70％ | 473 |
Table 7
| Catalyst | CM-1a | D1 |
| Reaction temperature, ℃ | 460 | 460 |
| Oil ratio | 6 | 6 |
| Air speed, hour -1 | 16 | 16 |
| Material balance, weight % | ||
| ?H 2～C 2 | 1.1 | 1.02 |
| Liquefied gas | 18.43 | 17.98 |
| ?C 5+ gasoline | 48.25 | 45.86 |
| Diesel oil | 21.47 | 22.67 |
| Heavy oil | 8.78 | 10.34 |
| Coke | 1.97 | 2.13 |
| Content of sulfur in gasoline, ppm (weight) | 479 | 895 |
Table 8
| Catalyst | CM-4a | D2 |
| Reaction temperature, ℃ | 500 | 500 |
| Oil ratio | 6 | 6 |
| Air speed, hour -1 | 16 | 16 |
| Material balance, weight % | ||
| H 2～C 2 | 1.5 | 1.36 |
| Liquefied gas | 21.99 | 21.06 |
| C 5+ gasoline | 52.62 | 47.29 |
| Diesel oil | 17.48 | 19.44 |
| Heavy oil | 2.41 | 6.96 |
| Coke | 4 | 3.89 |
| Content of sulfur in gasoline, ppm | 287 | 604 |
Claims (12)
1. the preparation method of a Cracking catalyst may further comprise the steps:
The mixed raw material that (1) will comprise Y zeolite and silicon carrier is equipped with slurries, then slurry dried is obtained catalyst precarsor; The content of sodium oxide molybdena is 2～14 weight % in the wherein said Y zeolite;
(2) catalyst precarsor that step (1) is obtained under 350-575 ℃, water vapour atmosphere roasting 0.25-3 hour;
(3) product with step (2) contacts with ammonium salt solution, is to react 10-60 minute under 2.5-5.0, temperature are 60-95 ℃ in the pH value, filters then, washs; Catalyst: H wherein
2O=1: 10-20, ammonium concentration are 3-15 weight %;
(4) with step (3) products therefrom in 450-750 ℃ of following roasting 0.5-4 hour;
(5) step (4) products therefrom being contacted with ammonium salt solution, is to react 10-60 minute under 2.5-5.0, temperature are 60-95 ℃ in the pH value, filters then, washs; Catalyst: H wherein
2O=1: 10-20, ammonium concentration are 1-6 weight %.
2. according to the described method of claim 1, it is characterized in that described Y zeolite comprises one or more in rare earth, ammonium, H, Li, Mg, Ca, Zr, V, Ni, Cd, In, Sn, Hg, Tl, Pb, Bi, B and the Al ion.
3. according to the described method of claim 1, it is characterized in that described Y zeolite is NaY, HY, NH
4Y, REY, REHY, RENH
4In Y, the VHY molecular sieve one or more.
4. according to claim 1,2 or 3 described methods, it is characterized in that sodium oxide content is 3～10 weight % in the described Y zeolite.
5. according to the described method of claim 1, it is characterized in that said silicon carrier comprises one or more in the precursor of clay, silica, silica precursor, amorphous aluminum silicide, amorphous aluminum silicide.
6. according to claim 1 or 5 described methods, it is characterized in that said silicon carrier comprises clay, described clay is that kaolin, imvite, diatomite and tired takes off one or more in the soil.
7. according to claim 1 or 5 described methods, it is characterized in that in the step (2), the water content of roasting procatalyst precursor is 10-25 weight %, the temperature of roasting is 350-500 ℃; Roasting time is 0.5-3.5 hour.
8. according to the described method of claim 1, it is characterized in that in the step (3), ammonium concentration is 5-10 weight %, the pH value is 2.8-4.5, and temperature is 80-95 ℃, and the reaction time is 15-60 minute.
9. according to the described method of claim 1, it is characterized in that in the step (4), sintering temperature is 500-700 ℃, roasting time is 1-4 hour;
10. according to the described method of claim 1, it is characterized in that ammonium concentration is 2-5 weight % in the step (5), slurry pH value is 2.8-3.5, and temperature is 80-95 ℃, and the reaction time is 15-45 minute.
11., it is characterized in that described kaolin is halloysite according to the described method of claim 6.
12. a catalytic cracking catalyst is characterized in that, said catalyst is by each described method preparation of claim 1-10.
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| RU2802819C2 (en) * | 2018-06-29 | 2023-09-04 | Чайна Петролеум Энд Кемикал Корпорейшн | Modified y-type molecular sieves, catalytic cracking catalyst containing them, catalyst production and application of sieves |
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| CN1205981A (en) * | 1997-07-17 | 1999-01-27 | 中国石油化工总公司 | Preparation of fine-grain superstable Y-molecular sieve |
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| RU2802819C2 (en) * | 2018-06-29 | 2023-09-04 | Чайна Петролеум Энд Кемикал Корпорейшн | Modified y-type molecular sieves, catalytic cracking catalyst containing them, catalyst production and application of sieves |
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