CN109304212A - A kind of catalytic cracking catalyst and preparation method thereof - Google Patents
A kind of catalytic cracking catalyst and preparation method thereof Download PDFInfo
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- CN109304212A CN109304212A CN201710632183.2A CN201710632183A CN109304212A CN 109304212 A CN109304212 A CN 109304212A CN 201710632183 A CN201710632183 A CN 201710632183A CN 109304212 A CN109304212 A CN 109304212A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Abstract
The present invention provides a kind of catalytic cracking catalyst and preparation method thereof, the catalyst includes 15-60wt% molecular sieve, 15-60wt% clay, 10-30wt% boehmite, 5-20wt% binder, 0.1-5wt% phosphorus-containing compound (in terms of P), 0.1-3wt% magnesium-containing compound (in terms of Mg), can also contain 0-5wt% rare earth oxide.Preparation method is as follows: (1) shaping of catalyst: molecular sieve, clay, boehmite, phosphorus-containing compound and binder being mixed with beating；Then magnesium-containing compound is added to be mixed with beating, heating stirring, carries out spray shaping, preformed catalyst is made in roasting；(2) catalyst modification: above-mentioned preformed catalyst, ammonium salt, phosphorus-containing compound and water are mixed with beating, and adjust pH, temperature reaction, and catalytic cracking catalyst of the present invention is made in filtration drying.Catalyst provided by the invention has the characteristics that coke yield is low, total liquid yield (the sum of liquefied gas, gasoline and diesel oil) is high.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalyst and preparation method thereof, more specifically to a kind of phosphorus, magnesium-modified
Catalytic cracking catalyst and preparation method thereof.
Background technique
Fluid catalytic cracking technology (FCC) becomes mink cell focus because investment is relatively fewer, adaptability to raw material is strong, easy to operate
The important means of secondary operation.With high-quality in world wide, light crude oil resource increasingly exhausted and coking production ability
Improve, oil refining enterprise is enhancing efficiency by relying on tapping internal latent power, mixed in catalytic cracking unit refining large scale crude oil with poor quality, as residual oil, wax tailings,
Deasphalted oil etc..Since inferior feedstock oil crackability can be poor, carbon deposition quantity on FCC catalyst is caused to increase, coke, which is adsorbed in, urges
It is not easy to be desorbed on agent acid centre, seriously affects catalyst heavy oil conversion performance and product distribution.
For petroleum refining industry, high heavy oil conversion rate and low coking yield are that catalytic cracking unit production chases after always
The target asked.People make catalytic cracking catalyst adapt to the requirement of above-mentioned target by the performance of improvement matrix and molecular sieve.
CN1255530A, US5164073 use natural material such as concave convex rod, palygorskite, diatom with larger pore volume
Soil etc. is used as catalyst substrates material；The preparation process of EP0550271A1, US5051385, US5997729 in aluminium-based catalyst
Middle that siliceous material is added, such as waterglass generates unformed macropore alumina silicate to improve heavy oil cracking ability.
Patent CN1436835A disclose a kind of catalytic cracking contain in catalyst and preparation method thereof, catalyst in it is big
Porous aluminum oxide 5-60%, zeolite 5-60%, binder 5-40%, clay 5-85%, the average Kong Zhi of the middle macroporous aluminium oxide
Diameter is not less than 3 nanometers, and the preparation method of the catalytic cracking catalyst is by zeolite and middle macroporous aluminium oxide, binder, clay
After mixing, it is made by spraying, roasting, washing, drying.It is compared with conventional catalyst, the catalyst heavy oil conversion performance
Enhancing, gasoline and coke selectivity are obviously improved.
Patent CN106179458A provides a kind of catalytic cracking catalyst, wherein with the catalytic cracking catalyst
On the basis of total weight, the catalytic cracking catalyst contain the cracking activity constituent element of 1-60%, 1-50% mesoporous active materials,
The clay of 1-70% and the binder of 1-70%, the mesoporous active materials have boehmite crystal phase structure.The invention is special
Benefit is used cooperatively by specific cracking activity constituent element, specific mesoporous active materials and clay and binder, increases catalysis
The content of Cracking catalyst mesoporous is conducive to the diffusion and cracking of heavy oil macromolecular.
Patent CN101767029A discloses a kind of catalyst for cracking heavy oil and its application, and the catalyst contains the boiling of Y type
Stone and modified rectorite, preparation method include: that rectorite, auxiliary agent, water and acid-mixed are closed, and obtain modified rectorite, then will
Modified rectorite and y-type zeolite be mixed with beating, is spray-dried and obtains catalyst；Wherein the auxiliary agent be selected from La, Co, Zn, Cu and
One or more of compound of Ti, the y-type zeolite include a kind of silica alumina ratio be 6-15, lattice constant 2.440-
The ratio that the pore volume for the second hole that 2.458nm, zeolite mesoporous diameter are 80-1000 angstroms accounts for total second hole pore volume is 30%-
60% modification ultrastable.The catalyst heavy oil conversion performance is strong, and coke selectivity is good.
In the composition of FCC catalyst, Y type molecular sieve has decisive impact the combined reaction performance of catalyst,
Therefore be modified to Y type molecular sieve is to improve one of catalytic cracking catalyst reactivity worth means the most effective.Closely
Nian Lai, the acidity sieved both at home and abroad by regulatory molecule control cracking reaction, reduce the condensation reaction of precursors of coke, improvement is urged
The coke selectivity of agent.
NaY molecular sieve is pre-payed with ammonium sulfate and shifts to Na in zeolite by EP3971832O be 1-5% (weight), then with it is phosphorous
Compound combination drying roasting be prepared into phosphorous super-stable Y molecular sieves, improve catalyst cracking activity and gasoline selection
Property.
CN1279130A discloses a kind of preparation method of P Modification super-stable Y molecular sieves, and this method includes will be with oxidation
The weight of object, the phosphorus containing 0.5-5%, 0.5~6% Na2O, lattice constant are 2.460~2.475nm
P-NH4NaY molecular sieve 450~700 DEG C hydrothermal calcine 0.5-4 hours under 100% water vapour atmosphere in roaster；It will roasting
Product after burning carries out the reaction of liquid phase aluminium-eliminating and silicon-replenishing；Then it filters, washs.Cracking catalyst containing the molecular sieve is being used for hydrocarbon
Yield of light oil is high when class cracking reaction, and coke yield is low, and heavy oil conversion performance is high.
CN103506153A discloses a kind of catalytic cracking catalyst for reducing coke yield and producing gasoline, containing with dry
The Modified Zeolite Y of base meter 10-50%, the specific Y type molecular sieve containing rare earth no more than 30%, 10-70% clay and with
The inorganic oxide binder of oxide meter 10-40%；The Modified Zeolite Y lattice constant is 2.420-2440nm,
By weight percentage, P 0.05-6%, RE2O3For 0.03-10%, aluminium oxide is less than less than 22% than hydroxyl nest concentration
0.35mmol/g.Catalytic cracking catalyst provided by the invention can reduce green coke, improve heavy oil utilization rate.
CN1624079A discloses a kind of hydrocarbon cracking catalyzer containing modcfied faujasite, wherein the method for modifying of zeolite
Reacted first to swap faujasite with phosphorus compound and ammonium compounds, water and weight zeolite than 2~25, pH2.0~
6.5, temperature is 10~150 DEG C, and swap time is 0.l~4 hour, then introduces earth solution in exchange slurries, when reaction
Between be 1~60 minute, further react, through being filtered, washed, by phosphorus and rare earth modified zeolite at 250~800 DEG C, l~
0.l~3.5 hour are roasted under 100% steam and are obtained.Using the lattice constant of the modified zeolite of this method of modifying preparation
2.440~2.465nm, 2.0~6.5 weight % of sodium oxide molybdena, 0.01~3 weight % of phosphorus content, 0.1~15 weight of rare earth oxide
Measure %.Catalyst activity stability containing the molecular sieve is good, and coke yield is low, heavy oil cracking ability and resistance to heavy metal pollution
By force.
CN101537366A reports a kind of modified molecular screen that can improve coking behavior, it is characterised in that the molecular sieve by
NaY molecular sieve hands over the preparation method of two roastings to obtain through two, and (1) handles NaY molecular sieve, treatment conditions with phosphorous ammonium salt solution exchange
Are as follows: system temperature be 40~100 DEG C, solution handle the time be 0.5~3 hour, pH=3.0~6.0, phosphorous exchange solution with divide
The weight ratio of son sieve is that the weight ratio of 3~20, P/ molecular sieve is 0.05~6.0%, filters, washs after exchange；(2) hydro-thermal is carried out
It handles, 450~750 DEG C of temperature, is roasted 0.5~4 hour under 1~100% water vapour；(3) with containing RE3+Ammonium salt solution exchange processing
Sample after one roasting, treatment conditions are as follows: system temperature is 40~100 DEG C, and the solution processing time is 0.5~3 hour, pH=3.0~
8.5, contain RE3+The weight ratio for exchanging solution and molecular sieve is 3~20, RE2O3The weight ratio of/molecular sieve is preferably 0.05~
6.5%, it filters, washs after exchange；(4) hydro-thermal process is carried out again, and treatment conditions are (2) with first time hydro-thermal process
Condition.The molecular sieve have more to middle macropore pore volume and good stability, while reducing catalyst coke yield,
Heavy oil pyrolysis ability further increases.
CN102019195A discloses a kind of catalytic cracking catalyst containing modified Y molecular sieve, which contains 2~45 weights
Measure % modified Y molecular sieve, modified Y molecular sieve, which refers to swap by Y type molecular sieve with earth solution, react, water and divide
Son sieve weight ratio 2~30, pH=2.5~7.0, temperature are 0~100 DEG C, swap time 0.1~3.5 hour, are then starched in exchange
The predecessor of phosphorus is introduced in liquid, the reaction time 1~70 minute, by being filtered, washed, filter cake was at 180~650 DEG C, 5~100%
It roasts 0.5~6 hour and obtains under steam；2.450~2.479 sodium rice of molecular sieve lattice constant, 2.0~6.0 weight of sodium oxide molybdena
Measure %, 0.01~2.5 weight % of phosphorus, 11~23 weight % of rare earth oxide.Catalyst containing above-mentioned modified molecular screen has strong
Heavy oil conversion performance and good coke selectivity.
Patent CN101284243A discloses a kind of Cracking catalyst, described containing rare earth superstable Y-type molecular sieve and matrix
Matrix includes silica binder, and the rare earth superstable Y-type molecular sieve is obtained by method comprising the following steps: by superstable gamma-type
Zeolite and equivalent concentration are temperature range of the acid solution of 0.01N-2N with the ratio of solvent and solute weight ratio 4-20 at 20 DEG C -100 DEG C
Lower mixing, washing, filtering after stirring -300 minutes 10 minutes, adds rare-earth salt solution and carries out rare earth ion exchanged, after exchange
Washing, filtering, drying.Catalyst of the present invention is used for heavy oil catalytic cracking, and high conversion rate, gasoline yield is high, and coke yield is low.
It can be seen that the middle macropore ratio for improving host material from above-mentioned patent, improve the diffusion velocity of oil gas molecule, it can
To improve the heavy oil conversion performance and coke selectivity of catalyst, but improve limited extent；And all draw to molecular sieve modified
Enter single P elements or single magnesium elements are modified.When with solution containing phosphate modified molecular screen, Phosphate hydrolysis generates phosphoric acid,
Again due to the influence of the size and steric configuration of phosphoric acid molecules, phosphoric acid cannot be introduced into the strong acid inside molecular sieve aperture and in duct
Center reacts, and [such as Shen Zhihong, Pan Huifang, Xu Chunsheng phosphorus is to catalyst and cracking of hydrocarbon surface acidity and anti-charcoal performance
Influence, University of Petroleum's journal (natural science edition), 1994,18 (2): 86-99], therefore be unable to improve acid centre in duct
Coke selectivity；Magnesium ion radius is small, can migrate to the aperture of molecular sieve.But due to duct diffusional resistance, in magnesium ion
The acid site in molecular sieve outer surface and macropore is inevitably covered into duct transition process, and molecular sieve acid amount is caused to subtract
It is few, eventually lose heavy oil conversion performance.Therefore, above-mentioned patent can not solve aperture coke selectivity and heavy oil conversion simultaneously
Contradiction.
Summary of the invention
That the object of the present invention is to provide a kind of coke yields is low, heavy oil conversion performance is strong, total liquid yield (liquefied gas, gasoline and
The sum of diesel oil) high catalytic cracking catalyst and preparation method thereof.
The present invention provides a kind of preparation methods of catalytic cracking catalyst, this method comprises: (1) shaping of catalyst: will
Molecular sieve, clay, boehmite, phosphorus-containing compound and binder are mixed with beating 30-180 minutes, are obtained catalyst slurry, are urged
Rare earth compound and inorganic acid can also be added in agent slurries, above-mentioned material is added order and is not particularly limited；Then it is added
Magnesium-containing compound is mixed with beating, and is warming up to 50-100 DEG C of constant temperature 30-90 minutes, is carried out spray shaping, is roasted obtained shaped catalyst
Agent；(2) catalyst modification: above-mentioned preformed catalyst, ammonium salt, phosphorus-containing compound and water are mixed with beating, and additional proportion is molding
Catalyst (butt): ammonium salt: phosphorus-containing compound (in terms of phosphorus): water=1:0.03-0.1:0.0005-0.03:3-5, adjusting pH is
3.0-5.0, is warming up to 60-100 DEG C of reaction 30-90 minutes, and catalytic cracking catalyst of the present invention is made in filtration drying.
Molecular sieve of the present invention be NaY, NaX pass through modified various molecular sieves, as REY, REX, REHY, USY,
The Y type molecular sieve of REUSY and various high silica alumina ratios, X-type molecular sieve, ZSM type molecular sieve, one or more of beta-molecular sieve.
Clay of the present invention is that kaolin, bentonite, sepiolite, galapectite, montmorillonite etc. can be used as catalyst
The various clays of component.
Boehmite of the present invention can for one of boehmite, three boehmites, bayerite or
A combination thereof, preferably boehmite.
Phosphorus-containing compound of the present invention be selected from orthophosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate,
It is one or several kinds of in aluminum phosphate and pyrophosphoric acid.
Binder of the present invention is silica-alumina gel, in sial complex sol, Aluminum sol, aluminium chloride, silica solution
Or mixtures thereof one kind.
Rare earth compound of the present invention is a kind of in rare earth chloride, nitric acid rare earth, rare earth oxide and sulfuric acid rare earth
Or it is several.Wherein the rare earth is preferably lanthanum and/or cerium.
Inorganic acid of the present invention is selected from the one or more of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, preferably hydrochloric acid.
Magnesium-containing compound of the present invention is a kind of or several in magnesium chloride, magnesium nitrate, hydroxy chloride magnesium and magnesium sulfate
Kind, preferably magnesium chloride.
Ammonium salt of the present invention is selected from ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate, ammonium nitrate, ammonium carbonate, ammonium hydrogen carbonate, grass
It is one or several kinds of in sour ammonium and ammonium phosphate.
Implementation method of the present invention can be used conventional method and implement, their specific implementation method is in the patent
CN98117896.0, CN02103907.0 and CN200610112685.4 have detailed description, introduce the present invention together here
In by reference.
The present invention provides a kind of catalytic cracking catalyst, which contains molecular sieve, clay, intends thin water aluminium
Stone, phosphorus-containing compound, magnesium-containing compound and binder.In terms of catalyst butt quality, the catalyst group becomes molecular sieve
15-60wt%, clay 15-60wt%, boehmite 10-30wt%, binder 5-20wt%, phosphorus-containing compound (in terms of P)
0.1-5wt%, magnesium-containing compound (in terms of Mg) 0.1-3wt%, can also contain rare earth oxide 0-5wt%.
The present invention introduces phosphorus-containing compound in catalyst pulping process, first with molecular sieve and work in phosphorus compound and slurries
Property stromal surface strong acid center reaction, make catalyst acid strength weaken and weak acid centric quantity increase, improve oil gas molecule
With the contact probability in catalyst surface acid site, the catalytic activity of catalyst external surface is improved, while outer surface acid strength weakens,
Reduce catalyst surface acid site to the adsorption capacity of oil gas molecule, inhibits secondary response, reduce coke formation；Then it is added
Magnesium compound is modified, since the strong acid in catalyst external surface and macropore has been weakened by phosphorus, weakens to the suction-operated of magnesium, adds
The diffusion of fast magnesium ion reduces oil gas molecule so that magnesium ion is easier to migrate to its strong acid center of modulation in catalyst pores
The oil gas molecule and the contact probability in acid site in duct outside strong Adsorption Effect hole in catalyst duct, improves catalyst pores
Catalytic activity in road improves the utilization rate in activated centre in catalyst duct；Phosphorous chemical combination is added during catalyst modification
Object and ammonium salt reduce the sodium content in catalyst, improve the activity and stability of catalyst, further improve the heavy oil of catalyst
Conversion capability；By the synergistic effect of phosphorus and magnesium, the acid site inside and outside catalyst duct can be made full use of, significantly improve and urge
The heavy oil conversion performance and coke selectivity of agent, to improve total liquid yield (liquefied gas, gasoline and the diesel oil of catalytic cracking process
The sum of).
Specific embodiment
Following example is to features of the present invention further instruction, but protection scope of the present invention is not by these examples
Limitation.
(1) evaluation method used in example
Catalytic cracking reaction selective evaluation: catalyst cracking reaction is carried out in small fixed flowing bed (FFB) device
Selective evaluation.Catalyst first passes through 800 DEG C in advance, handles 10h under the conditions of 100% water vapour.Reaction raw materials oil nature such as table 1,
500~535 DEG C of reaction temperature, 12~15h of air speed-1, oil ratio 5.
1 raw material oil nature of table
(2) places of origin of raw materials used in example and specification
Kaolin: China Kaolin Co., Ltd, kaolinite 86 are % heavy.
Galapectite: the positive mining industry Co., Ltd in Nanning four, galapectite 95 are % heavy.
Aluminum sol: Catalyst Factory of Lanzhou Petrochemical Company, Al2O3Content 24.56 is % heavy, and Al/Cl molar ratio is 1.24.
USY zeolite, REHY zeolite, REY zeolite, DASY, ZSM-5 are Catalyst Factory of Lanzhou Petrochemical Company production.
Boehmite: alumina content is 75.4 heavy %, the production of Shandong Alumina factory.
Hydrochloric acid, nitric acid: industrial goods.
Ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium carbonate, ammonium hydrogen carbonate, ammonium hydroxide: industrial goods.
Silica solution: Dalian Inst of Chemicophysics, Chinese Academy of Sciences's production, SiO2Content 27.0 is % heavy, with salt acid for adjusting pH
Value is 2.5.
Lanthanum chloride, cerous nitrate, diammonium hydrogen phosphate, magnesium chloride, ammonium phosphate, magnesium nitrate, phosphoric acid, magnesium sulfate: pure, Beijing is analyzed
Chemical plant production.
Embodiment 1
Shaping of catalyst: 660g boehmite, 991g kaolin, 540g Aluminum sol, 990gUSY are added in a kettle
Molecular sieve, 2431g deionization, 3 grams of diammonium hydrogen phosphates (in terms of phosphorus) are stirred 60 minutes, and it is mixed that 5.5 grams of magnesium chlorides (in terms of magnesium) are added
Mashing is closed, 60 DEG C is warming up to and mixes 60 minutes, spray shaping, 500 DEG C of roastings, 20 minutes obtained preformed catalyst CD1.
Catalyst modification: be added in a kettle 2478 grams of above-mentioned preformed catalyst CD1,10 kilograms of water, 21 grams of phosphoric acid (with
Phosphorus meter) and 125 grams of ammonium chlorides, adjusting PH is 4.1, is warming up to 90 DEG C, is stirred 65 minutes, filtration drying obtains catalyst of the present invention
C1。
Embodiment 2
Shaping of catalyst: in a kettle be added 1.7 grams of phosphoric acid (in terms of phosphorus), 1810gREY molecular sieve, 190g ZSM-5,
5175g deionization stirs 10 minutes, and the salt of 464g boehmite, 593g kaolin, 1744g Aluminum sol and 67mL is then added
Acid stirs 180 minutes, and 100 grams of magnesium nitrate (in terms of magnesium) mixing are added, is warming up to 100 DEG C, stirs 30 minutes, spray shaping,
600 DEG C of roastings, 60 minutes obtained preformed catalyst CD2.
Catalyst modification: 3397 grams of above-mentioned preformed catalyst CD2,10 kilograms of water, 1.8 grams of ammonium phosphate are added in a kettle
(in terms of phosphorus) and 102 grams of ammonium nitrate, adjusting pH is 3.1, is warming up to 60 DEG C, is stirred 90 minutes, filtration drying obtains the present invention and urges
Agent C2.
Embodiment 3
Shaping of catalyst: 1333g boehmite, 728g kaolin, 75 grams of ammonium phosphate are added in a kettle (with phosphorus
Meter), 1.7 grams of phosphoric acid (in terms of phosphorus), 365g galapectite, 353gREY molecular sieve, 358gREHY molecular sieve, 352gDASY molecular sieve,
31g ZSM-5,5375g deionization and 1082g Aluminum sol stir 30 minutes, and 0.2 gram of magnesium sulfate (in terms of magnesium) and 0.15 gram is added
Magnesium chloride (in terms of magnesium) is warming up to 50 DEG C, stirs 90 minutes, spray shaping, 400 DEG C of roastings, 90 minutes obtained preformed catalysts
CD3。
Catalyst modification: 3430 grams of above-mentioned preformed catalyst CD3,17 kilograms of water, 58 grams of ammonium phosphate are added in a kettle
(in terms of phosphorus), 42 grams of phosphoric acid (in terms of phosphorus), 173 grams of ammonium sulfate and 172 grams of ammonium nitrate, adjusting PH is 4.9, is warming up to 100 DEG C, stirs
It mixes 30 minutes, filtration drying obtains catalyst C3 of the present invention.
Embodiment 4
Shaping of catalyst: in a kettle be added 9 grams of ammonium phosphate (in terms of phosphorus), 275g silica solution, 710gDASY molecular sieve,
235 grams of lanthanum chlorides, 4270g deionization are beaten 35 minutes, and 776g boehmite, 3255g kaolin and 1005g aluminium is then added
Colloidal sol stirs 10 minutes, and 35 grams of magnesium sulfate (in terms of magnesium) are added and are mixed with beating, and is warming up to 75 DEG C, stirs 70 minutes, spray shaping,
350 DEG C of roastings, 80 minutes obtained preformed catalyst CD4.
Catalyst modification: 4736 grams of above-mentioned preformed catalyst CD4,17 kilograms of water, 10 grams of phosphoric acid hydrogen are added in a kettle
Ammonium (in terms of phosphorus) and 189 grams of ammonium nitrate, adjusting pH is 3.5, is warming up to 80 DEG C, is stirred 40 minutes, filtration drying obtains the present invention
Catalyst C4.
Embodiment 5
Shaping of catalyst: 12 grams of diammonium hydrogen phosphates (in terms of phosphorus), 987gDASY molecular sieve, 71 grams of nitre are added in a kettle
Sour cerium, 5124g deionization be beaten 35 minutes, then be added 877g boehmite stir 15 minutes, be added 1127g kaolin and
2600g Aluminum sol is beaten 20 minutes, and the mashing of 74 grams of magnesium nitrates (in terms of magnesium) is added, is warming up to 71 DEG C, stirs 60 minutes, it is spraying at
Type, 400 DEG C of roastings, 55 minutes obtained preformed catalyst CD5.
Catalyst modification: 3351 grams of above-mentioned preformed catalyst CD5,15 kilograms of water, 31 grams of phosphoric acid hydrogen are added in a kettle
Ammonium (in terms of phosphorus) and 107 grams of ammonium chlorides, adjusting pH is 4.3, is warming up to 67 DEG C, is stirred 55 minutes, filtration drying obtains the present invention
Catalyst C5.
Embodiment 6
Shaping of catalyst: being added 1150gREY, 300gDASY molecular sieve in a kettle and the mixing of 2100g deionized water is beaten
Then 16 grams of ammonium phosphate (in terms of phosphorus) and 13 grams of phosphoric acid (in terms of phosphorus) are added in slurry, stir 23 minutes, and 1091g is added and intends thin water aluminium
Stone, 911g kaolin and 771g Aluminum sol stir 40 minutes, and 5 grams of magnesium chlorides (in terms of magnesium) are added, and are warming up to 60 DEG C, stir 40 points
Clock, spray shaping, 500 DEG C of roastings, 35 minutes obtained preformed catalyst CD6.
Catalyst modification: 3278 grams of above-mentioned preformed catalyst CD6,15 kilograms of water, 44 grams of di(2-ethylhexyl)phosphates are added in a kettle
Hydrogen ammonium (in terms of phosphorus) and 78 grams of ammonium sulfate, adjusting pH is 3.7, is warming up to 58 DEG C, is stirred 64 minutes, filtration drying obtains the present invention
Catalyst C6.
Comparative example 1
It is prepared according to patent CN101284243A providing method:
990gUSY molecular sieve (butt) is taken, being added to stirring in 10 liters of 0.2N oxalic acid aqueous solutions is uniformly mixed it, heating
It keeps 1 as a child filtering to 95 DEG C, be washed with water, take out filter cake, be placed in 2 liters of decationized Y sieve water, it is molten that 71.2 grams of rare earths are added
Liquid, stirring are warming up to 92 DEG C and are kept for 1 hour, are then filtered, washed, filter cake is boiled in 120 DEG C of dryings to get rare earth superstable Y-type
Stone sample, is denoted as A.
Silica solution preparation: the water glass solution and 1 liter of acid aluminum sulfate solution for being 155g/l by 1 liter of silica concentration
(free acid concentration 148g/l, alumina content 20g/l) introduces flash mixer reaction simultaneously, obtains silica solution.
The preparation of kaolin and silica solution slurries: being added 991g kaolin in the silica solution of above-mentioned preparation, is beaten 1 hour
Obtain kaolin and silica solution slurries.
The preparation of the mixed serum of boehmite and molecular sieve: by the boehmite of 660g and 1320 grams of deionized waters
Mixing is beaten 30 minutes, 25 milliliters of hydrochloric acid is then added, then is beaten 2 hours, and 990 grams of A molecular sieve pulps, mashing is then added
30 minutes, obtain the mixed serum of boehmite and molecular sieve.
The preparation of catalyst: by the boehmite of the kaolin of above-mentioned preparation and silica solution slurries and above-mentioned preparation and divide
The mixed serum mixing of son sieve, is beaten 10 minutes, obtains catalyst slurry, then in 180 DEG C of the at a temperature of slurries that will obtain
Spray drying forming obtains the solid particle that diameter is 20-120 microns, is washed with deionized to no sodium ion and is detected,
It is dried after filtering in 150 DEG C, obtains catalyst D1.
Comparative example 2
Shaping of catalyst: 660g boehmite, 991g kaolin, 540g Aluminum sol, 990gUSY are added in a kettle
Molecular sieve, 2431g deionization, 3 grams of diammonium hydrogen phosphates (in terms of phosphorus) and 5.5 grams of magnesium chlorides (in terms of magnesium) are mixed with beating, stirring 60
Minute, it is warming up to 60 DEG C and stirs 60 minutes, spray shaping, 500 DEG C of roastings, 20 minutes obtained preformed catalyst DD2.
Catalyst modification: be added in a kettle 2478 grams of above-mentioned preformed catalyst DD2,10 kilograms of water, 21 grams of phosphoric acid (with
Phosphorus meter) and 125 grams of ammonium chlorides, adjusting pH is 4.1, is warming up to 90 DEG C, is stirred 65 minutes, filtration drying obtains catalyst of the present invention
D2。
Comparative example 3
Shaping of catalyst: 660g boehmite, 991g kaolin, 540g Aluminum sol, 990gUSY are added in a kettle
Molecular sieve, 2431g deionization, 5.5 grams of magnesium chlorides (in terms of magnesium) are stirred 60 minutes, and it is mixed that 3 grams of diammonium hydrogen phosphates (in terms of phosphorus) are added
Mashing is closed, 60 DEG C is warming up to and mixes 60 minutes, spray shaping, 500 DEG C of roastings, 20 minutes obtained preformed catalyst DD3.
Catalyst modification: be added in a kettle 2478 grams of above-mentioned preformed catalyst DD3,10 kilograms of water, 21 grams of phosphoric acid (with
Phosphorus meter) and 125 grams of ammonium chlorides, adjusting pH is 4.1, is warming up to 90 DEG C, is stirred 65 minutes, filtration drying obtains catalyst of the present invention
D3。
The catalyst reaction performance evaluation result of embodiment 1-6 and comparative example 1-3 preparation is listed in Table 2 below.
The catalyst fixed bed evaluation result of table 2
| Catalyst | C1 | C2 | C3 | C4 | C5 | C6 | D1 | D2 | D3 |
| Dry gas | 3.39 | 3.45 | 3.34 | 3.21 | 3.17 | 3.06 | 3.45 | 3.34 | 3.19 |
| Liquefied gas | 13.67 | 13.66 | 13.43 | 14.79 | 13.51 | 14.66 | 13.78 | 13.72 | 12.82 |
| Gasoline | 43.11 | 43.78 | 42.82 | 41.7 | 43.07 | 42.18 | 42.14 | 41.61 | 39.34 |
| Diesel oil | 27.52 | 26.76 | 27.92 | 27.79 | 27.99 | 27.87 | 27.52 | 28 | 25.4 |
| Heavy oil | 5.13 | 5.11 | 5.45 | 5.71 | 5.37 | 5.49 | 6.02 | 6.24 | 12.33 |
| Coke | 7.18 | 7.24 | 7.04 | 6.8 | 6.89 | 6.74 | 7.09 | 7.09 | 6.92 |
| Conversion ratio | 67.35 | 68.13 | 66.63 | 66.5 | 66.64 | 66.64 | 66.46 | 65.76 | 62.27 |
| Total liquid yield | 84.3 | 84.2 | 84.17 | 84.28 | 84.57 | 84.71 | 83.44 | 83.33 | 77.56 |
From fixed bed evaluation result it is found that being had using catalyst made of the modified molecular sieve of the method for the present invention excellent
Heavy oil conversion performance and good coke selectivity.After modified, heavy oil conversion performance drops for comparative example D2 and comparative example D3 catalyst
It is low, this is because introduce phosphorus and magnesium simultaneously during catalyst modification or introduce phosphorus after first introducing magnesium, magnesium ion radius it is small and
Diffusional resistance is small, preferentially with acidity of catalyst central reaction, covering part acid centre, cause catalyst total acid content reduce, drop
The cracking performance of low catalyst.Compared with 1 catalyst of comparative example (D1), in the case where conversion ratio improves and heavy oil declines, this
The catalyst of inventive method preparation has more excellent coke selectivity and higher total liquid yield.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (17)
1. a kind of catalytic cracking catalyst preparation method, which is characterized in that the described method includes: (1) shaping of catalyst: by molecule
Sieve, clay, boehmite, phosphorus-containing compound and binder are mixed with beating 30-180 minutes, obtain catalyst slurry；Then plus
Enter magnesium-containing compound to be mixed with beating, be warming up to 50-100 DEG C of constant temperature 30-90 minutes, carries out spray shaping, roasting is made molding and urges
Agent；(2) catalyst modification: above-mentioned preformed catalyst, ammonium salt, phosphorus-containing compound and water are mixed with beating, and additional proportion is dry
Base molded catalyst: ammonium salt: the phosphorus-containing compound in terms of phosphorus: water=1:0.03-0.1:0.0005-0.03:3-5, adjusting pH is
3.0-5.0, is warming up to 60-100 DEG C of reaction 30-90 minutes, and catalytic cracking catalyst of the present invention is made in filtration drying.
2. preparation method according to claim 1, which is characterized in that be added in catalyst slurry described in step (1) dilute
Earth compounds and inorganic acid.
3. preparation method according to claim 1, which is characterized in that the molecular sieve is NaY, NaX by modified
Various molecular sieves, Y type molecular sieve, X-type molecular sieve selected from REY, REX, REHY, USY, REUSY and various high silica alumina ratios,
ZSM type molecular sieve, one or more of beta-molecular sieve.
4. preparation method according to claim 1, which is characterized in that the clay is kaolin, bentonite, Hai Pao
One or more of stone, galapectite, montmorillonite.
5. preparation method according to claim 1, which is characterized in that the boehmite is boehmite, three water
One of softening aluminium stone, bayerite or a combination thereof.
6. preparation method described in one of -5 according to claim 1, which is characterized in that the boehmite is the soft aluminium of a water
Stone.
7. preparation method according to claim 1, which is characterized in that the phosphorus-containing compound be selected from orthophosphoric acid, phosphorous acid,
One of ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, aluminum phosphate and pyrophosphoric acid are several.
8. preparation method according to claim 1, which is characterized in that the binder is silica-alumina gel, sial is compound molten
Or mixtures thereof one of glue, Aluminum sol, aluminium chloride, silica solution.
9. preparation method according to claim 2, which is characterized in that the rare earth compound is selected from rare earth chloride, nitre
One or more of acid rare earth, rare earth oxide and sulfuric acid rare earth.
10. the preparation method according to claim 2 or 9, which is characterized in that the rare earth is lanthanum and/or cerium.
11. preparation method according to claim 2, which is characterized in that the inorganic acid be selected from hydrochloric acid, nitric acid, phosphoric acid,
One or more of sulfuric acid.
12. the preparation method according to claim 2 or 11, which is characterized in that the inorganic acid is hydrochloric acid.
13. preparation method according to claim 1, which is characterized in that the magnesium-containing compound is selected from magnesium chloride, nitric acid
One or more of magnesium, hydroxy chloride magnesium and magnesium sulfate.
14. according to claim 1 or preparation method described in 13, which is characterized in that the magnesium-containing compound is magnesium chloride.
15. preparation method according to claim 1, which is characterized in that the ammonium salt is selected from ammonium chloride, ammonium sulfate, sulphur
One of sour hydrogen ammonium, ammonium nitrate, ammonium carbonate, ammonium hydrogen carbonate, ammonium oxalate and ammonium phosphate are several.
16. a kind of catalytic cracking catalyst of preparation method preparation as claimed in claim 1 or 2, which is characterized in that the catalysis is split
Change catalyst and contains molecular sieve, clay, boehmite, phosphorus-containing compound, magnesium-containing compound and binder；With catalyst butt
Quality meter, the catalyst group become molecular sieve 15-60wt%, clay 15-60wt%, boehmite 10-30wt%, glue
Tie agent 5-20wt%, the phosphorus-containing compound 0.1-5wt% in terms of P, the magnesium-containing compound 0.1-3wt% in terms of Mg.
17. catalyst according to claim 16, which is characterized in that the oxidation in the catalyst including 0-5wt% is dilute
Soil.
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| CN112717961A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Filter residue and preparation method thereof, and catalytic cracking catalyst and preparation method thereof |
| CN115582141A (en) * | 2021-07-06 | 2023-01-10 | 中国石油天然气股份有限公司 | Catalyst for oil slurry cracking and coke gasification and preparation method thereof |
| CN116212940A (en) * | 2023-03-06 | 2023-06-06 | 青岛惠城环保科技集团股份有限公司 | Preparation method of catalytic cracking catalyst with excellent coke and dry gas selectivity |
| CN116265106A (en) * | 2021-12-17 | 2023-06-20 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst for high yield of low carbon olefin |
| CN116265107A (en) * | 2021-12-17 | 2023-06-20 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst for producing diesel oil in large quantity |
| CN116265109A (en) * | 2021-12-17 | 2023-06-20 | 中国石油天然气股份有限公司 | Preparation method of heavy oil efficient conversion catalyst |
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| CN116265107A (en) * | 2021-12-17 | 2023-06-20 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst for producing diesel oil in large quantity |
| CN116265109A (en) * | 2021-12-17 | 2023-06-20 | 中国石油天然气股份有限公司 | Preparation method of heavy oil efficient conversion catalyst |
| CN116328819A (en) * | 2021-12-17 | 2023-06-27 | 中国石油天然气股份有限公司 | Preparation method of low-coke catalytic cracking catalyst |
| CN116212940A (en) * | 2023-03-06 | 2023-06-06 | 青岛惠城环保科技集团股份有限公司 | Preparation method of catalytic cracking catalyst with excellent coke and dry gas selectivity |
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