CN109304205A - A kind of catalytic cracking catalyst and preparation method thereof improving coke selectivity - Google Patents
A kind of catalytic cracking catalyst and preparation method thereof improving coke selectivity Download PDFInfo
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- CN109304205A CN109304205A CN201710630437.7A CN201710630437A CN109304205A CN 109304205 A CN109304205 A CN 109304205A CN 201710630437 A CN201710630437 A CN 201710630437A CN 109304205 A CN109304205 A CN 109304205A
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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
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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
- B01J29/085—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
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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
- B01J29/80—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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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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
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The present invention provides a kind of catalytic cracking catalyst and preparation method thereof for improving coke selectivity, the catalyst includes 15-70wt% molecular sieve, 15-60wt% clay, 8-30wt% boehmite, 3-20wt% binder, phosphorus (in terms of P) 0.01-10wt%, magnesium (in terms of Mg) 0.01-5wt%.Preparation method is as follows: molecular sieve, expanding agent, clay, boehmite, phosphorus-containing compound and binder being mixed with beating, spray shaping；Above-mentioned preformed catalyst microballoon is roasted, is mixed with beating with magnesium-containing compound, ammonium salt, water, pH value is adjusted, heating is stirred, filtered, being dried to obtain catalytic cracking catalyst of the present invention.In the case where conversion ratio improves and heavy oil declines, the catalyst of the method for the present invention preparation has more excellent coke selectivity.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalysts and preparation method thereof, select more specifically to a kind of raising coke
Catalytic cracking catalyst of selecting property 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.
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 obtained by spraying, roasting, washing, drying values.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%, RE2O3 0.03-10%, aluminium oxide are 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
The catalytic cracking catalyst and its system that the object of the present invention is to provide a kind of coke yields is low, heavy oil conversion performance is strong
Preparation Method.
The present invention provides a kind of catalytic cracking catalyst preparation method for improving coke selectivity, this method includes that will divide
Sub- sieve, expanding agent, clay, boehmite, phosphorus-containing compound and binder are mixed with beating, and wherein the additional amount of expanding agent, which accounts for, urges
The 0.1-2% of agent slurries (butt), the additional amount (in terms of P) of phosphorus-containing compound account for the 0.01- of catalyst slurry (butt)
10%, carry out spray shaping；Above-mentioned molding catalyst microspheres are roasted into 60-180min at 300-600 DEG C, it then will be above-mentioned
Catalyst microspheres particle, magnesium-containing compound and ammonium salt and water are mixed with beating, and addition weight ratio is magnesium-containing compound (in terms of Mg): being urged
Catalyst particles (butt): ammonium salt: deionized water=0.001-0.05:1:0.01-0.1:2-5 adjusts pH value in 2.5-5.5, rises
Temperature is to 50-110 DEG C of stirring 15-60min；It filters, be dried to obtain catalytic cracking catalyst of the present invention.
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.
Expanding agent of the present invention is activated carbon, carbon nanotube, starch, sucrose, flour, polyethylene glycol, polystyrene
One or more of, preferably active carbon and polystyrene.
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.
In method provided by the present invention, in the catalyst microspheres particle-making step, it is mixed with beating in slurries described
Rare earth can also be added, to improve reactivity worth.
Rare earth of the present invention is selected from one of La, Ce, Pr, Nd or a combination thereof.
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.
In method provided by the invention, the ammonium salt is selected from ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate, ammonium nitrate, carbonic acid
It is one or several kinds of in ammonium, ammonium hydrogen carbonate, ammonium oxalate and ammonium phosphate.
In method provided by the invention, the implementation method can be used conventional method and implement, their specific reality
CN98117896.0, CN02103907.0 and CN200610112685.4 have detailed description to applying method in the patent, here
It is introduced into the present invention together by reference.
The present invention provides a kind of catalytic cracking catalyst for improving coke selectivity, which includes molecule
Sieve, clay, boehmite, phosphorus-containing compound, magnesium-containing compound and binder.In terms of catalyst butt quality, described is urged
Agent composition includes molecular sieve 15-70wt%, clay 15-60wt%, boehmite 8-30wt%, binder 3-20wt%,
Phosphorus-containing compound (in terms of P) 0.01-10wt%, magnesium-containing compound (in terms of Mg) 0.01-5wt%.The catalyst can also contain
There is the rare-earth oxide of 0-8wt%.
The present invention introduces expanding agent in catalyst pulping process and is conducive to improve the cellular structure of catalyst, while urging
Phosphorus-containing compound is added in agent slurries, it is first anti-with the strong acid center of phosphorus compound and molecular sieve in slurries and active matrix surface
It answers, weakens the acid strength of catalyst and increase with weak acid centric quantity, raising oil gas molecule connects with catalyst surface acid site
Probability is touched, improves the catalytic activity of catalyst external surface, while outer surface acid strength weakens, and reduces catalyst surface acid site
To the adsorption capacity of oil gas molecule, inhibit secondary response, reduces coke formation；Magnesium compound is then added in water-washing process to change
Property, since the strong acid in catalyst external surface and macropore has been weakened by phosphorus, the suction-operated of magnesium is weakened, accelerates magnesium ion
Diffusion reduces oil gas molecule in catalyst pores 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 road, improves the catalysis in catalyst duct
Activity improves the utilization rate in activated centre in catalyst duct；It, can will be in catalyst duct by the synergistic effect of phosphorus and magnesium
Outer acid site makes full use of, and significantly improves the catalytic activity and coke selectivity of catalyst.
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 are urged for Lanzhou Petrochemical
Disguise and sets feedstock oil, specific 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, full white-clay type catalyst are that Lanzhou Petrochemical Company is urged
The production of agent factory.
Poising agent is derived from Lanzhou Petrochemical Company oil plant.
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.
Diammonium hydrogen phosphate, magnesium chloride, ammonium phosphate, magnesium nitrate, phosphoric acid, magnesium sulfate, active carbon, polystyrene: analysis is pure, north
The production of capital chemical plant.
Embodiment 1
Catalyst microspheres preparation: by 660g boehmite, 991g kaolin, 216g Aluminum sol, 990gUSY molecular sieve,
Catalyst microspheres CB- is made in 2431g deionization, 2.1 grams of active carbons, 3 grams of diammonium hydrogen phosphates (in terms of phosphorus), homogeneous, spray shaping
1。
It takes 307 grams of catalyst microspheres CB-1 to roast 90 minutes at 450 DEG C, after being beaten with 1516 grams of deionized waters, is added
2.1 grams of magnesium chlorides (in terms of magnesium), 10 grams of ammonium chlorides are mixed with beating, and adjusting pH value is 3.9, are warming up to 85 DEG C and are stirred 40 minutes, filtering,
Obtain the invention patent catalyst C1 within dry 45 minutes at 120 DEG C.
Embodiment 2
Catalyst microspheres preparation: 0.3 gram of phosphoric acid (in terms of phosphorus), 570g boehmite, 503g kaolin, 225g aluminium is molten
Glue, 810gREY molecular sieve, 80g ZSM-5,28 grams of polystyrene, 5175g deionization and 67mL mixed in hydrochloric acid, homogeneous is spraying
It forms and catalyst microspheres CB-2 is made.
It takes 307 grams of catalyst microspheres CB-2 to roast 60 minutes at 600 DEG C, after being beaten with 620 grams of deionized waters, is added 15
Gram magnesium nitrate (in terms of magnesium), 3 grams of ammonium nitrate are mixed with beating, and adjusting pH value is 2.5, are warming up to 55 DEG C and are stirred 60 minutes, filtering, 80 DEG C
Lower drying obtains the invention patent catalyst C2 for 60 minutes.
Embodiment 3
Catalyst microspheres preparation: by 1095g boehmite, 728g kaolin, 1.5 grams of ammonium phosphate (in terms of phosphorus), 300 grams
Phosphoric acid (in terms of phosphorus), 365g galapectite, 1082g Aluminum sol, 26 grams of polystyrene, 353gREY molecular sieve, 358gREHY molecule
Catalyst microspheres CB-3 is made in sieve, the mixing of 352gDASY molecular sieve, 31g ZSM-5,5375g deionization, homogeneous, spray shaping.
It takes 303 grams of catalyst microspheres CB-3 to roast 180 minutes at 300 DEG C, after being beaten with 1200 grams of deionized waters, is added
30g ammonium chloride, 0.2 gram of magnesium sulfate (in terms of magnesium) and 0.1 gram of magnesium chloride (in terms of magnesium) are mixed with beating, and adjusting pH value is 3.4, are warming up to
110 DEG C are stirred 15 minutes, are filtered, are obtained the invention patent catalyst C3 within dry 30 minutes at 150 DEG C.
Embodiment 4
Catalyst microspheres preparation: by 776g boehmite, 1368g kaolin, 1005g Aluminum sol, 89 grams of ammonium phosphate (with
Phosphorus meter), 275g silica solution, 857gDASY molecular sieve, 102ml earth solution, 15 grams of polystyrene and 2 grams of active carbons, 4270g go
Catalyst microspheres CB-4 is made in the mixed in hydrochloric acid of ion and 71mL, homogeneous, spray shaping.
It takes 303 grams of catalyst microspheres CB-4 to roast 70 minutes at 500 DEG C, after being beaten with 1100 grams of deionized waters, is added 3
Gram magnesium sulfate (in terms of magnesium), 30 grams of ammonium chlorides and 10 grams of ammonium sulfate are mixed with beating, and adjusting pH value is 5.5, are warming up to 80 DEG C of stirrings 35
Minute, it filters, obtain catalyst C4 of the present invention within dry 45 minutes at 95 DEG C.
Comparative example 1
It is prepared according to patent CN1436835A providing method: macroporous aluminium oxide, 898 grams of hyperastable Y-type REs in 1056 grams are (dry
Base), 872 grams of kaolin, 560 grams of galapectites, 976 grams of Aluminum sols, 3257 grams of deionized waters be sufficiently mixed, stir 2 hours, army it
Spray drying forming afterwards.Thus obtained microsphere is roasted 0.5 hour at 450 DEG C.1000 grams of microballoon of roasting is gone, 10 kilograms of deionizations are added
Water and 0.225 kilogram of ammonium chloride, 75 DEG C agitator treating 20 minutes, after filtering be added ammonium phosphate (make catalyst phosphorus content 1.0
Weight %) and 10 kilograms of deionized waters, agitator treating 10 minutes at 75 DEG C, filtration drying obtain modified catalyst D1.
Comparative example 2
Catalyst microspheres preparation: by 660g boehmite, 991g kaolin, 216g Aluminum sol, 990gUSY molecular sieve,
2431g deionization, 2.1 grams of active carbons, 3 grams of diammonium hydrogen phosphates (in terms of phosphorus), 2.1 grams of magnesium chloride (in terms of magnesium) mixing, homogeneous, spray
Mist, which forms, is made catalyst microspheres DB-2.
It takes 307 grams of catalyst microspheres DB-1 to roast 90 minutes at 450 DEG C, is beaten with 1516 grams of deionized waters, be added 10
Gram ammonium chloride is mixed with beating, and adjusting pH value is 3.9, is warming up to 85 DEG C and is stirred 40 minutes, and filtering obtains at 120 DEG C for dry 45 minutes
Modified catalyst D2.
Comparative example 3
Catalyst microspheres preparation: by 660g boehmite, 991g kaolin, 216g Aluminum sol, 990gUSY molecular sieve,
Catalyst microspheres are made in 2431g deionization, 2.1 grams of magnesium chlorides (in terms of magnesium) and 2.1 grams of active carbon mixing, homogeneous, spray shaping
DB-3。
It takes 307 grams of catalyst microspheres DB-3 to roast 90 minutes at 450 DEG C, after being beaten with 1516 grams of deionized waters, is added 3
Gram diammonium hydrogen phosphate (in terms of phosphorus), 10 grams of ammonium chlorides are mixed with beating, and adjusting pH value is 3.9, are warming up to 85 DEG C and are stirred 40 minutes, mistake
It filters, obtain modified catalyst D3 within dry 45 minutes at 120 DEG C.
Embodiment 5
Catalyst microspheres preparation: by 660g boehmite, 1467g kaolin, 968g Aluminum sol, 11 grams of ammonium phosphate (with
Phosphorus meter), 7.7 grams of polystyrene, 777gDASY molecular sieve, 3 grams of active carbons, 71ml earth solution, 3500g deionization and 40mL
Catalyst microspheres CB-5 is made in mixed in hydrochloric acid, homogeneous, spray shaping.
It takes 303 grams of catalyst microspheres CB-5 to roast 67 minutes at 550 DEG C, after being beaten with 877 grams of deionized waters, is added 21
Gram magnesium sulfate (in terms of magnesium), 11 grams of ammonium nitrate are mixed with beating, and adjusting pH value is 4.7, are warming up to 75 DEG C and are stirred 55 minutes, filtering, 95
Obtain catalyst C5 of the present invention within dry 100 minutes at DEG C.
Embodiment 6
Catalyst microspheres preparation: 1.1 grams of phosphoric acid (in terms of phosphorus), 971g boehmite, 800g kaolin, 350g aluminium are molten
The mixed in hydrochloric acid of glue, 16 grams of polystyrene, 932gREY molecular sieve, 4500g deionization and 19mL, homogeneous, spray shaping are made and urge
Agent microballoon CB-6.
It takes 307 grams of catalyst microspheres CB-6 to roast 45 minutes at 475 DEG C, after being beaten with 1305 grams of deionized waters, is added
22 grams of magnesium nitrates (in terms of magnesium), 11 grams of ammonium chlorides are mixed with beating, and adjusting pH value is 3.7, are warming up to 65 DEG C and are stirred 70 minutes, filtering,
Obtain the invention patent catalyst C6 within dry 80 minutes at 75 DEG C.
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 | 3.48 | 3.55 | 3.46 | 3.33 | 3.43 | 3 | 3.51 | 3.49 | 3.33 |
| Liquefied gas | 13.7 | 13.84 | 13.53 | 14.77 | 13.87 | 13.26 | 13.73 | 13.86 | 12.4 |
| Gasoline | 41.9 | 42.57 | 41.52 | 40.5 | 42.78 | 43.39 | 40 | 40.48 | 38.11 |
| Diesel oil | 28.79 | 27.88 | 29.15 | 29.07 | 27.88 | 29.23 | 29.19 | 29.11 | 27.03 |
| Heavy oil | 4.98 | 4.93 | 5.31 | 5.52 | 4.87 | 4.46 | 5.84 | 6.02 | 12.11 |
| Coke | 7.15 | 7.23 | 7.03 | 6.81 | 7.17 | 6.66 | 7.73 | 7.04 | 7.02 |
| Conversion ratio | 66.23 | 67.19 | 65.54 | 65.41 | 67.25 | 66.31 | 64.97 | 64.87 | 60.86 |
| Total liquid yield | 84.39 | 84.29 | 84.2 | 84.34 | 84.53 | 85.88 | 82.92 | 83.45 | 77.54 |
From fixed bed evaluation result it is found that there is excellent heavy oil conversion performance using catalyst made of the method for the present invention
With good coke selectivity.After modified, heavy oil conversion performance reduces for comparative example D2 and comparative example D3 catalyst, this is because
Phosphorus and magnesium are introduced during catalyst modification simultaneously or introduces phosphorus after first introducing magnesium, magnesium ion radius is small and diffusional resistance is small, excellent
First and acidity of catalyst central reaction, covering part acid centre cause catalyst total acid content to reduce, reduce the cracking of catalyst
Performance.With 1 catalyst of comparative example (D1), compared with, conversion ratio improve and heavy oil decline in the case where, the method for the present invention preparation
Catalyst has more excellent coke selectivity.
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 (16)
1. a kind of catalytic cracking catalyst preparation method for improving coke selectivity, which is characterized in that the method includes dividing
Sub- sieve, expanding agent, clay, boehmite, phosphorus-containing compound and binder are mixed with beating, and wherein the additional amount of expanding agent accounts for dry
The 0.1-2% of base catalyst slurry, the additional amount of phosphorus-containing compound account for the 0.01-10% of stem-based catalyst slurries in terms of P, carry out
Spray shaping；Above-mentioned molding catalyst microspheres are roasted into 60-180min at 300-600 DEG C, it is then that above-mentioned catalyst is micro-
Ball particle, magnesium-containing compound and ammonium salt and water are mixed with beating, and it is the magnesium-containing compound in terms of Mg: stem-based catalyst that weight ratio, which is added,
Grain: ammonium salt: deionized water=0.001-0.05:1:0.01-0.1:2-5 adjusts pH value in 2.5-5.5, is warming up to 50-110 DEG C
Stir 15-60min；It filters, be dried to obtain catalytic cracking catalyst of the present invention.
2. 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.
3. preparation method according to claim 1, which is characterized in that the expanding agent is activated carbon, carbon nanotube, shallow lake
One or more of powder, sucrose, flour, polyethylene glycol, polystyrene.
4. preparation method according to claim 1 or 3, which is characterized in that the expanding agent is active carbon and polystyrene.
5. preparation method according to claim 1, which is characterized in that the clay be kaolin, bentonite, sepiolite,
One or more of galapectite, montmorillonite.
6. 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.
7. preparation method according to claim 1 or 6, which is characterized in that the boehmite is boehmite.
8. 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.
9. 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.
10. preparation method according to claim 1, which is characterized in that in the catalyst microspheres particle-making step,
Rare earth is added in described be mixed with beating in slurries.
11. preparation method according to claim 10, which is characterized in that the rare earth is in La, Ce, Pr, Nd
One kind or a combination thereof.
12. 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.
13. according to claim 1 or preparation method described in 12, which is characterized in that the magnesium-containing compound is magnesium chloride.
14. preparation method according to claim 1, which is characterized in that the ammonium salt is selected from ammonium chloride, ammonium sulfate, sulfuric acid
One of hydrogen ammonium, ammonium nitrate, ammonium carbonate, ammonium hydrogen carbonate, ammonium oxalate and ammonium phosphate are several.
15. a kind of catalytic cracking catalyst of the raising coke selectivity of the preparation of preparation method described in claim 1, feature exist
In the catalytic cracking catalyst includes molecular sieve, clay, boehmite, phosphorus-containing compound, magnesium-containing compound and bonding
Agent, in terms of catalyst butt quality, the catalyst composition includes molecular sieve 15-70wt%, and clay 15-60wt% intends thin
Diaspore 8-30wt%, binder 3-20wt%, the phosphorus-containing compound 0.01-10wt% in terms of P, the magnesium-containing compound in terms of Mg
0.01-5wt%.
16. catalyst according to claim 15, which is characterized in that the rare earth gold in the catalyst including 0-8wt%
Belong to oxide.
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