CN103785458A - Cracking assistant for improving low-carbon olefin concentration - Google Patents
Cracking assistant for improving low-carbon olefin concentration Download PDFInfo
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Abstract
The invention discloses a cracking assistant for improving the low-carbon olefin concentration. The cracking assistant comprises a phosphorus and transition metal-containing beta molecular sieve, a first-clay-containing phosphorus aluminum inorganic binder, other inorganic binder and second clay; the first-clay-containing phosphorus aluminum inorganic binder comprises 15-40 wt% by Al2O3 of an aluminum component, 45-80 wt % by P2O5 of a phosphorus component and 1-40 wt % by dry basis of first clay, the weight ratio of P to Al is 1-6; the phosphorus and transition metal-containing beta molecular sieve comprises 1-10wt% by P2O5 of phosphorus and 0.5-10 wt % by metallic oxide of a metal; and in the 27Al MAS NMR (Magic Angle Spinning Nuclear Magnetic Resonance) of the phosphorus and transition metal-containing beta molecular sieve, the ratio of resonance signal peak area at the chemical shift of 40+-3ppm to resonance signal peak area at the chemical shift of 54+-3ppm is greater than 1, and the percentage of the sun of the resonance signal peak area at the chemical shift of 0+-3ppm and the resonance signal peak area at the chemical shift of-12+-3ppm to the total peak area is less than 10%. The cracking assistant is used for catalytic cracking, and can improve ethylene concentrations in a catalytic cracking dry gas, and improve propylene and isobutylene concentration in a liquefied gas.
Description
Technical field
The present invention relates to a kind of cracking additive for producing low-carbon alkene by catalytically cracking.
Background technology
Low-carbon alkene alkene is important Organic Chemicals, and the whole world all increases year by year to the demand of low-carbon alkene.Fluid catalytic cracking is to produce one of important process of low-carbon alkene, and for most of catalytic cracking units, adding auxiliary agent is the effective technical way of increased low carbon olefine output.But prior art is to improving isobutylene concentration DeGrain in liquefied gas.Generate and reactive chemistry from FCC process isobutene, beta-molecular sieve is a kind of effectively active component.It is on the one hand in the process that removes its template, easily to make its structure suffer damage that beta-molecular sieve subject matter is in use embodied in, be on the other hand in course of reaction easily dealuminzation thereby activity stability poor.
In early stage patent, disclose some Cracking catalyst that contains β zeolite or auxiliary agents, can improve octane number, increased low carbon olefine output, liquefied gas, as patents such as US4740292, US4898846, US4911823 and WO95026533.What the β zeolite of using in these patents had emphasizes that, for low sodium h-type zeolite, what have emphasizes as high silica alumina ratio zeolite.The β of high silica alumina ratio can directly synthesize, and also can obtain by hydrothermal treatment consists or acid treatment.
US4837396 discloses a kind of catalyst, contains β zeolite and Y zeolite, and contains hydrothermal stability and the mechanical strength of metal ion type compound as stabilizing agent raising catalyst.This stabilizing agent can be [Al
2(OH)
5cl]
x, or Al
3zr (OH)
9cl
4.Stabilizing agent can be directly and the effect of β zeolite, also can in Kaolinite Preparation of Catalyst process, add.
US6355591 discloses a kind of assistant for calalytic cracking, the aluminum phosphate that contains 4-20%, and ZSM-5, β of 1-40% and composition thereof, the clay of 40-90%, can improve LPG output.The preparation method of aluminum phosphate is: SPA adds in deionized water and dilutes, and adds aluminium powder to dissolve, and wherein the mol ratio of Al and PO4 is 1:3, and pH is less than 2.0.The aluminum phosphate making is mixed with kaolin, then sneak into molecular sieve pulp, finally spraying is shaped.From Patent right requirement, this auxiliary agent is not containing other binding agent, other inorganic oxide except aluminum phosphate.In addition, in the embodiment of this patent, do not provide auxiliary agent preparation method and the performance containing β zeolite.
A kind of method of modifying of beta-molecular sieve is proposed in CN 1043450A, the method is that Na beta-molecular sieve is pumped to part framework aluminum with acid after roasting, then carrying out potassium exchange, to make zeolite potassium content be 0.5～2.5 heavy %, after drying, roasting, at room temperature soak 4～10 hours with microcosmic salt cushioning liquid including potassium hydrogen phosphate-potassium dihydrogen phosphate, hypophosphorous acid-potassium hypophosphite, phosphorous acid-potassium phosphite, nearly neutrality, take the circumstances into consideration washing or do not wash that to make on zeolite phosphorus content be 0.01～0.5 heavy %, then dry, roasting; Beta-molecular sieve after the method modification is applicable to as the hydrocarbon processing catalyst that relates to hydroisomerization reaction.
In CN 1179994A, proposed a kind of method of modifying of beta-molecular sieve, the method is less than 0.1 heavy % by Na beta-molecular sieve with ammonium ion exchange to the Na2O content on zeolite; Then the beta-molecular sieve of above-mentioned ammonium exchange is pumped to part framework aluminum with acid treatment, make its silica alumina ratio be greater than 50; Beta-molecular sieve after above-mentioned dealuminzation is mixed to post-drying with phosphoric acid or phosphate, and the amount that makes P2O5 on gained zeolite is 2～5 heavy %; Finally under water vapour atmosphere with 450～650 ℃ of hydrothermal calcines 0.5～4 hour.Can obtain higher alkene, the especially productive rate of isomeric olefine and lower coke yield by the beta-molecular sieve after the method modification when the cracking reaction for hydro carbons.
CN1872685A discloses a kind of phosphorous and transition metal, it is characterized in that the anhydrous chemical expression of this beta-molecular sieve, quality with oxide is counted (0～0.3) Na2O(0.5～10) Al2O3(1.3～10) P2O5(0.7～15) MxOy(70～97) SiO2, wherein, M is selected from the one in Fe, Co, Ni, Cu, Mn, Zn and Sn.This zeolite is applied in catalytic cracking, can be used as the active component of catalyst or auxiliary agent.
Still there is propylene and the not high enough problem of butylene concentration in liquefied gas in the auxiliary agent of existing employing β zeolite.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of cracking additive that improves catalytic cracking low-carbon alkene concentration and preparation method thereof, this auxiliary agent is containing beta-molecular sieve, be applied to catalytic cracking, can improve propylene, isobutylene concentration in ethylene concentration in catalytic cracked dry gas, liquefied gas, when vast scale adds auxiliary agent, not affect major catalyst heavy oil conversion performance simultaneously.
The invention provides a kind of assistant for calalytic cracking, take the butt weight of described auxiliary agent as benchmark, contain in the beta-molecular sieve of the phosphorous and transition metal of butt 10～75 heavy %, with the al composition containing in the phosphorus aluminium inorganic binder of the first clay (with Al
2o
3meter), phosphorus component is (with P
2o
5meter) and the first clay butt weight sum meter 3～30 heavy % containing the phosphorus aluminium inorganic binder of the first clay, in other inorganic binder of oxide 3～30 heavy % with in the second clay of butt 0～60 heavy %; Wherein, take the described phosphorus aluminium inorganic binder butt weight containing the first clay as benchmark, the described phosphorus aluminium inorganic binder containing the first clay comprises with Al
2o
3meter 15～40 % by weight al compositions, with P
2o
5count the phosphorus component of 45～80 % by weight and the first clay in butt 1～40 % by weight, and its P/Al weight ratio is 1.0～6.0; The beta-molecular sieve of described phosphorous and transition metal, with P
2o
5meter phosphorus content accounts for 1 ~ 10 % by weight, accounts for 0.5 ~ 10 % by weight in metal oxide tenor,, this molecular sieve
27in Al MAS NMR, chemical shift is that 40 ± 3ppm resonance signal peak area and chemical shift are that the ratio of 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, and the chemical shift percentage that to be 0 ± 3ppm and chemical shift account for total peak area for the resonance signal peak area sum of-12ppm ± 3ppm is less than or equal to 10%.
The present invention also provides a kind of preparation method of assistant for calalytic cracking, comprises the beta-molecular sieve of phosphorous and transition metal, mixes containing phosphorus aluminium inorganic binder, other inorganic binder of the first clay, adds or do not add the second clay, making beating, and spraying is dry; Wherein, the described phosphorus aluminium compound inorganic binder containing the first clay, in butt, contains with Al
2o
3meter 15～40 % by weight alumina component, with P
2o
5meter 45～80 % by weight phosphorus component and in butt 1～40 % by weight clay, its P/Al weight ratio is that 1.0～6.0, pH is 1.0～3.5, this binding agent solid content is 15～60 % by weight; The beta-molecular sieve of described phosphorous and transition metal, phosphorous and transition metal, with P
2o
5meter phosphorus content accounts for 1 ~ 10 % by weight, accounts for 0.5 ~ 10 % by weight, this molecular sieve in metal oxide tenor
27in Al MAS NMR, chemical shift is that 40 ± 3ppm resonance signal peak area and chemical shift are that the ratio of 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, and the chemical shift percentage that to be 0 ± 3ppm and chemical shift account for total peak area for the resonance signal peak area sum of-12ppm ± 3ppm is less than or equal to 10%.
Described phosphorous and preparation method transition metal beta-molecular sieve comprises former beta-molecular sieve powder in the temperature range of 200 ℃ to 800 ℃, after at least two non-overlapping temperature ranges are from low to high processed with removed template method, dealuminzation, then carry out phosphorus and metal-modified step.More specifically, comprise the steps:
(1) sodium type beta-molecular sieve is made to the Na on molecular sieve through ammonium exchange
2o content is less than 0.2 heavy %;
(2) molecular sieve step (1) being obtained after drying, is processed at least 0.5 hour under 200-400 ℃ of temperature range, then under 500-800 ℃ of temperature range, processes at least 0.5 hour removed template method being warmed up in 2 hours at the most; ;
(3) at temperature 25-100 ℃, the product obtaining by dealumination agent solution treatment steps (2);
(4) introduce phosphorus-containing compound and metallic compound molecular sieve is carried out to modification;
(5) calcination process at least 0.5 hour at 400-800 ℃
The first described clay is one or more in kaolin, sepiolite, concave convex rod, tired de-soil, imvite and diatomite.
The second described clay is selected from one or more that well known to a person skilled in the art in clay, for example be selected from one or more in kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, tired de-stone, diatomite, galapectite, saponite, boron-moisten soil and hydrotalcite, be preferably one or more the mixture in kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone.
Cracking additive provided by the invention, also contains other inorganic binder except described phosphorus aluminium inorganic binder argillaceous.Described other inorganic binder is selected from one or more in the inorganic oxide that is customarily used in assistant for calalytic cracking or catalyst substrates and binder component, for example boehmite, aluminium colloidal sol, phosphorus aluminium glue, silicon-aluminum sol, waterglass be at the mixture of interior one or more, wherein preferred one or more of boehmite, aluminium colloidal sol, phosphorus aluminium glue.
In catalyst aid provided by the present invention, can also contain with P
2o
5the phosphorus additive of meter 0～15 heavy %, the compound that described phosphorus additive is selected from phosphorus comprises one or more in inorganic compound and the organic compound of phosphorus, can be soluble in water, also can be to be insoluble in water or water-fast phosphorus compound, for example, be selected from one or more in oxide, phosphoric acid, phosphate, phosphite, hypophosphites, subphosphate, acid phosphate and the phosphorous organic compound of phosphorus.Preferred phosphorus compound is one or more in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, aluminum phosphate and phosphorus aluminium colloidal sol.In the catalyst obtaining, phosphorus additive exists with the form of phosphorus compound (as the oxide of phosphorus, phosphate, phosphite, subphosphate, acid phosphate).When containing in auxiliary agent except described containing other the phosphorous binding agent the phosphorus aluminium inorganic binder of the first clay for example when phosphorus aluminium colloidal sol, the phosphorus of other described inorganic phosphor-contained binding agent introducing is considered as phosphorus additive.The total content of the phosphorus that phosphorus additive is introduced is no more than 15 % by weight.Described phosphorus additive may reside in any position that may exist of auxiliary agent, as may reside in the inside, duct of zeolite, the surface of zeolite, may reside in described host material, can also be present in the surface and described host material of inside, duct, zeolite of zeolite simultaneously.Described phosphorus additive do not comprise phosphorous and transition metal and containing the phosphorus relating in the phosphorus aluminium inorganic binder of the first clay.
Assistant for calalytic cracking provided by the invention, there is good anti-wear performance and Catalytic Cracking Performance, for heavy oil catalytic cracking reaction, can increase RFCC liquefied gas yield, improve significantly propylene in catalytic cracking liquefied gas and isobutene low-carbon alkene concentration, improve the ethylene concentration in dry gas, the productive rate of ethene, propylene and isobutene is high, coke selectively low, improve the octane number of gasoline, and in the time that vast scale adds auxiliary agent, do not affect the heavy oil conversion performance of major catalyst.Compared with existing auxiliary agent, there is higher heavy oil transformation activity, higher ethene, propylene and selective isobutene, in dry gas in ethene, liquefied gas propylene and isobutylene concentration higher, having better coke and dry gas selective, is also to have higher liquid to receive unexpectedly.For example, industrial MLC-500 poising agent is 16h at 480 ℃, weight (hourly) space velocity (WHSV)
-1, react under the oil ratio condition that is 5, liquefied gas yield is 15.31 % by weight, and heavy oil yield is 15.78 % by weight, and it is 76.69 % by weight that liquid is received, productivity of propylene is 4.76 % by weight, isobutene productive rate is 1.36 % by weight, and ethylene yield is 0.42 % by weight, and in liquefied gas, density of propylene is 31.09 % by weight, isobutylene concentration is 8.88 % by weight, ethene in dry gas is 28.57 % by weight, and coke selectivity is 9.34 % by weight, and octane number is 90.1.And 50 % by weight that contain provided by the invention are phosphorous and transition metal, 12 % by weight kaolin, 24 % by weight are containing the phosphorus aluminium inorganic binder of the first clay, 8 % by weight boehmites, the auxiliary agent of 6 % by weight aluminium colloidal sols, after mixing with above-mentioned MLC-500 poising agent with the weight ratio of 10:90, under similarity condition, react, liquefied gas yield is 17.98 % by weight, heavy oil yield is 14.11 % by weight, it is 78.12 % by weight that liquid is received, productivity of propylene is 6.04 % by weight, , isobutene productive rate is 2.26 % by weight, ethylene yield is 0.48 % by weight, in liquefied gas, density of propylene is 33.37 % by weight, in liquefied gas, isobutylene concentration is 12.57 % by weight, ethene in dry gas is 31.37 % by weight, coke selectivity is 9.24 % by weight, octane number is 90.8.
The specific embodiment
Assistant for calalytic cracking provided by the present invention, clay, other inorganic binder of 5～25 heavy % and the phosphorus additive of 0～10 heavy % of phosphorous and transition metal, 10～45 heavy % of the described phosphorus aluminium inorganic binder that contains the first clay that preferably includes 8～25 heavy %, 20～60 heavy %.
In the content of wherein said phosphorus additive, do not comprise phosphorous and transition metal and containing the phosphorus amount relating in the phosphorus aluminium inorganic binder of the first clay.Described phosphorous and transition metal is phosphorous and transition metal, with P
2o
5meter phosphorus content accounts for 1 ~ 10 % by weight, accounts for 0.5 ~ 10 % by weight in metal oxide tenor, and silica alumina ratio is not less than 30(molecule mol ratio), this molecular sieve
27in Al MAS NMR, chemical shift is that 40 ± 3ppm resonance signal peak area and chemical shift are that the ratio of 54ppm ± 3ppm resonance signal peak area is greater than 1, and the chemical shift percentage that to be 0 ± 3ppm and chemical shift account for total peak area for the resonance signal peak area sum of-12ppm ± 3ppm is less than 10%.Transition metal in the beta-molecular sieve of described phosphorous and transition metal is preferably selected from one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn.
Under preferable case, described the first clay containing in the phosphorus aluminium inorganic binder of the first clay comprises tired de-soil, and more preferably the first described clay is rectorite.Take butt weight as benchmark, the described phosphorus aluminium compound binding agent containing the first clay contains with Al
2o
3the al composition of meter 15～35 % by weight, with P
2o
5count the phosphorus component of 50～75 % by weight and the first clay in butt 8～35 % by weight, and not chloride, and it is 1.0～3.5 that its P/Al weight ratio is preferably 2.0～5.0, pH.
In the preparation method of assistant for calalytic cracking provided by the invention, the described phosphorus aluminium inorganic binder containing the first clay, take its butt weight as benchmark, contains with Al
2o
3meter 15～40 % by weight al compositions, with P
2o
5count the phosphorus component of 45～80 % by weight and the first clay in butt 1～40 % by weight, its P/Al weight ratio is that 1.0～6.0, pH is 1.0～3.5, and this binding agent solid content is 15～60 % by weight.The described phosphorus aluminium compound inorganic binder preparation method containing the first clay comprises:
(1) alumina source, the first clay and water making beating are dispersed into the slurries that solid content is 8～45 % by weight; Described alumina source is can be by the aluminium hydroxide of sour peptization and/or aluminium oxide, in the first clay of butt and with Al
2o
3the weight ratio of the alumina source of meter is 1～40:15～40;
(2) stir in the lower slurries that obtain toward step (1) and add SPA according to the part by weight of P/Al=1～6; In wherein said P/Al, P is the weight of the phosphorus in simple substance in phosphoric acid, and Al is the weight in the aluminium of simple substance in alumina source;
(3) slurries that step (2) obtained react 15～90 minutes at 50～99 ℃ of temperature.
Wherein, the consumption of alumina source, SPA and the first clay, makes the obtained phosphorus aluminium inorganic binder containing the first clay, take its butt weight as benchmark, comprises: 15～40 % by weight preferably 15～35 % by weight are derived from the Al of described alumina source
2o
3, 45～80 % by weight are 50～75 % by weight P preferably
2o
5, 1～40 % by weight is the first clay of 8～35 % by weight preferably; Described P/Al weight ratio is preferably 1.2～6.0, and more preferably 2～5.Alumina source is one or more in p-aluminium oxide, x-aluminium oxide, η-aluminium oxide, gama-alumina, k-aluminium oxide, δ-aluminium oxide, θ-aluminium oxide, gibbsite, surge aluminium stone, promise diaspore, diaspore, boehmite and boehmite, and described al composition is derived from described alumina source.The first described clay is one or more in kaolin, sepiolite, concave convex rod, tired de-soil, imvite and diatomite, is preferably rectorite.Its concentration of described SPA is 60 ~ 98 % by weight, more preferably 75 ~ 90 % by weight.The charging rate of phosphoric acid be preferably 0.01-0.10Kg phosphoric acid/minute/Kg alumina source, more preferably 0.03-0.07Kg phosphoric acid/minute/Kg alumina source.
The inorganic binder of described phosphorous aluminium compound is due to the introducing of clay, mass transfer, the heat transfer of storeroom not only in preparation process, are improved, the adhesive cures of having avoided the inhomogeneous local moment vigorous reaction heat release overtemperature of material to cause, can regulate more neatly the pH value of binding agent, obtain the binding agent of high solids content, and do not need high temperature depolymerization, the step such as concentrated, preparation method is simple.The adhesive property of the binding agent obtaining is with not introduce phosphorus al binder prepared by clay mitigation suitable; And the method introduces clay, especially there is the tired de-soil of layer structure, improve the heavy oil conversion performance of carbon monoxide-olefin polymeric, the auxiliary agent that makes to obtain has better selective.
Phosphorous and transition metal beta-molecular sieve of the present invention, with P
2o
5meter phosphorus content accounts for the heavy % of 1-10, account for the heavy % of 0.5-10 in metal oxide tenor, it is characterized in that this molecular sieve
27in Al MAS NMR, chemical shift is that 40 ± 3ppm resonance signal peak area and chemical shift are that the ratio of 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, and the chemical shift percentage that to be 0 ± 3ppm and chemical shift account for total peak area for the resonance signal peak area sum of-12ppm ± 3ppm is for being less than or equal to 10%.Phosphorous and the transition metal beta-molecular sieve non-framework aluminum of described modification is few, and phosphorus and framework aluminum coordination is simultaneously abundant, and framework aluminum is adequately protected, and has excellent hydrothermal stability and better product selectivity.
Phosphorous and transition metal beta-molecular sieve of the present invention, with P
2o
5meter phosphorus content accounts for the heavy % of 1-10, preferably accounts for the heavy % of 1-8, accounts for the heavy % of 0.5-10, preferably accounts for the heavy % of 0.5-5 in metal oxide tenor.Said metal is one or more in Fe, Co, Ni, Cu, Mn, Zn and Sn preferably.
Phosphorous and transition metal beta-molecular sieve of the present invention, its
27in Al MAS NMR, chemical shift is the four-coordination framework aluminum species that 54 ± 3ppm resonance signal characterizes, chemical shift be 40 ± 3ppm resonance signal characterize be and the framework aluminum species of phosphorus coordination, what chemical shift was that 0 ± 3ppm resonance signal characterizes is hexa-coordinate non-framework aluminum species, and chemical shift for what-12 ± 3ppm resonance signal characterized is and the non-framework aluminum species of phosphorus coordination.Phosphorous and the transition metal beta-molecular sieve of modification provided by the invention, this molecular sieve
27in Al MASNMR, chemical shift is that 40 ± 3ppm resonance signal peak area and chemical shift are that the ratio of 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, is preferably greater than or equal to 2, for example, be a value of 2-5; The chemical shift percentage that to be 0 ± 3ppm and chemical shift account for total peak area for the resonance signal peak area sum of-12ppm ± 3ppm for being less than 10%, be preferably and be less than 6%, be for example a value in 1-4%.
Described in provided by the invention, state phosphorous and preparation method transition metal molecular sieve, it is characterized in that comprising by former beta-molecular sieve powder in the temperature range of 200 ℃ to 800 ℃, after at least two non-overlapping temperature ranges are from low to high processed with removed template method, dealuminzation, then carry out phosphorus and metal-modified step.Preferred step comprises:
(1) sodium type beta-molecular sieve is made to the Na on molecular sieve through ammonium exchange
2o content is less than 0.2 heavy %;
(2) molecular sieve step (1) being obtained after drying, is processed at least 0.5 hour under 200-400 ℃ of temperature range, then under 500-800 ℃ of temperature range, processes at least 0.5 hour removed template method being warmed up in 2 hours at the most;
(3) at temperature 25-100 ℃, the product obtaining by the dealumination agent solution treatment steps (2) of weight concentration 1-20%;
(4) introduce phosphorus-containing compound and metallic compound molecular sieve is carried out to modification;
(5) calcination process at least 0.5 hour at 400-800 ℃.
Preparation method provided by the invention, compared with the modifying process of existing beta-molecular sieve, the main distinction is that method of modifying of the present invention is that former beta-molecular sieve powder (containing the sodium type beta-molecular sieve of organic formwork agent) is processed with after roasting removed template method through non-overlapping temperature range stage by stage from low to high, β zeolite is carried out to dealumination treatment by chemical method, then carry out the modification of phosphorus and transition metal.
In phosphorous and transition metal beta-molecular sieve preparation method of the present invention, in said step (1), said sodium type beta-molecular sieve (Na beta-molecular sieve) is the sodium type beta-molecular sieve (as USP3,308,069, CNZL00107486.5) of conventional crystallization gained.In usually said sodium type beta-molecular sieve, sodium content is counted the heavy % of 4-6 with sodium oxide molybdena.Said ammonium exchanges to reduce the process of sodium content, preferably according to molecular sieve: ammonium salt: H
2o=1:(0.1-1): the exchange at least 0.5 hour at room temperature to 100 ℃ of weight ratio (5-10), the preferred process of filtering after 0.5-2 hour, such ammonium exchange process can repeat 1-4 time, so that the Na on molecular sieve
2o content is less than 0.2 heavy %.Said ammonium salt can be conventional inorganic ammonium salt, can be selected from one of ammonium chloride, ammonium sulfate or ammonium nitrate or their mixture.
In phosphorous and transition metal beta-molecular sieve preparation method of the present invention, said step (2) is the molecular sieve that adopts low temperature to obtain to the different temperatures interval treatment step (1) of high temperature, the process of removed template method.Said processing is in the interval of 200 ℃ to 800 ℃, in at least two non-overlapping temperature ranges from low to high, carry out, said low temperature range is 200-400 ℃, preferred 300-350 ℃, and said high temperature range is 500-800 ℃, preferred 500-600 ℃.For example, said processing is by Na after the exchange of step (1) ammonium
2the molecular sieve that O content is less than 0.2 heavy % after dry first 200-400 ℃, preferred calcination process at least 0.5 hour at 300-350 ℃, preferably 1-12 hour, then 2 hours at the most, be preferably warmed up to 500-800 ℃, preferred calcination process at least 0.5 hour under 500-600 ℃ of temperature range, preferably 1-8 hour in 1 hour.In step (2), also can, before above-mentioned said two temperature ranges are processed, first at least process 1 hour fully to remove moisture at 120-180 ℃.
In phosphorous and transition metal beta-molecular sieve preparation method of the present invention, said step (3) is at temperature 25-100 ℃, the process of the product obtaining by dealumination agent solution treatment steps (2).In step (2), the consumption of dealumination agent is to add by required dealuminzation degree experience, is 1-6 hour conventionally with the dealumination agent solution-treated time, and dealumination agent solution preferred weight concentration is preferably 1-20%.Said dealumination agent is selected from organic acid (comprising ethylenediamine tetra-acetic acid, oxalic acid, citric acid, sulfosalicylic acid), inorganic acid (comprising fluosilicic acid, hydrochloric acid, sulfuric acid, nitric acid), organic and inorganic salts (comprising ammonium oxalate, ammonium fluoride, ammonium fluosilicate, ammonium fluoroborate), and chemical dealuminization process can once or several times be carried out.
In phosphorous and transition metal beta-molecular sieve preparation method provided by the invention, introduce phosphorus-containing compound and metallic compound carries out modification to the product of step (3) in step (4).Said phosphorus-containing compound is selected from one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) or ammonium phosphate or its mixture.Said metallic compound is selected from the water soluble salt of metal, and the water soluble salt of said metal is selected from sulfate, nitrate, chlorate.Said metal is selected from one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn.The water soluble salt of said metal exemplifies but is not limited to ferric sulfate, cobaltous sulfate, nickelous sulfate, copper sulphate, manganese sulfate, zinc sulfate, STANNOUS SULPHATE CRYSTALLINE, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, manganese nitrate, zinc nitrate, nitric acid tin, iron chloride, cobalt chloride, nickel chloride, copper chloride, manganese chloride, zinc chloride, stannic chloride etc.
The said modifying process of step (4) can adopt the mode of dipping or ion-exchange to carry out.Wherein said dipping can adopt again following a, b, tri-kinds of modes of c:
A. the phosphorus-containing compound aqueous solution of the molecular sieve after dealuminzation and amount of calculation is evenly dried in room temperature to a 95 ℃ making beating, under 400-800 ℃ of condition after roasting, then mix, dry in room temperature to 95 ℃ with the compound water solution containing one of Fe, Co, Ni, Cu, Mn, Zn, Sn of amount of calculation.
B. the phosphorus-containing compound aqueous solution of the molecular sieve after dealuminzation and amount of calculation is evenly dried in room temperature to a 95 ℃ making beating, mix oven dry with the compound water solution containing one of Fe, Co, Ni, Cu, Mn, Zn, Sn of amount of calculation in room temperature to 95 ℃ again, wherein also can be by the reversed order of the above-mentioned two kinds of solution of dipping.
C. the molecular sieve after dealuminzation is mixed to post-drying with the phosphorus-containing compound of amount of calculation and the mixed aqueous solution of the compound of one of Fe, Co, Ni, Cu, Mn, Zn, Sn in room temperature to 95 ℃.
In the time that the said modifying process of step (4) carries out in the mode of ion-exchange, normally the phosphorus-containing compound aqueous solution of the molecular sieve after dealuminzation and amount of calculation is evenly dried in room temperature to a 95 ℃ making beating, under 400-800 ℃ of condition after roasting, again with the compound water solution containing one of Fe, Co, Ni, Cu, Mn, Zn, Sn of amount of calculation by 1:(5-20) solid-to-liquid ratio mix after, filter after 2-3 hour 80-95 ℃ of stirring, can repeated exchanged repeatedly, after exchange, gained samples with water is washed repeatedly, dries.
In phosphorous and transition metal beta-molecular sieve preparation method provided by the invention, step (5) is phosphorus that step (4) is obtained and metal-modified beta-molecular sieve product at 400-800 ℃, preferably calcination process at least 0.5 hour at 500-600 ℃, preferred 0.5-8 hour.Wherein said calcination process process can adopt dry roasting also can adopt wet roasting, and said wet roasting is preferably at 1-100%, more preferably carry out under 100% steam atmosphere.
The preparation method of assistant for calalytic cracking provided by the invention, described by phosphorus aluminium inorganic binder phosphorous and transition metal, that contain the first clay, other inorganic binder mixing, making beating, its reinforced order does not have specific (special) requirements, for example, can will mix (can omit relevant addition step when not containing the second clay time) making beating with the second clay containing the phosphorus aluminium inorganic binder of the first clay, other inorganic binder (can omit relevant addition step when not containing other inorganic binder time), phosphorous and transition metal.
Assistant for calalytic cracking preparation method provided by the invention, also comprises the spray-dired step of the slurries that described making beating is obtained.Spray-dired method is known for those skilled in the art, and the present invention does not have specific (special) requirements.
In the time containing phosphorus additive in auxiliary agent, one of its introducing mode of described phosphorus additive is following method or the combination of several method, but is not limited to these methods:
1, before spray drying forming, in slurries, add phosphorus compound;
2, be incorporated in auxiliary agent by other inorganic binder, when containing phosphorus aluminium colloidal sol in inorganic oxide binder, after roasting, in auxiliary agent, both brought phosphorus into, phosphorus aluminium colloidal sol can play again the effect of host material and binding agent, and this part phosphorus also belongs to phosphorus additive of the present invention;
3, after auxiliary agent spray drying forming through dipping or chemisorbed phosphorus compound, through Separation of Solid and Liquid (if necessary), dry and roasting process introducing, wherein said dry temperature is room temperature to 400 ℃, preferably 100～300 ℃, the temperature of roasting is 400～700 ℃, be preferably 450～650 ℃, roasting time is 0.5～100 hour, is preferably 0.5～10 hour.
Cracking additive provided by the invention is applicable to hydrocarbon oil catalytic cracking.During for catalytic cracking process, can in catalyst cracker, add separately, after also can mixing with Cracking catalyst, use.Generally, auxiliary agent provided by the invention accounts for 1～30 heavy % of FCC catalyst and catalyst mixture total amount provided by the invention, be preferably 3～20 heavy %, described hydrocarbon ils is selected from various petroleum distillates, as crude oil, reduced crude, decompression residuum, normal pressure wax oil, decompressed wax oil, straight-run gas oil, propane is light/one or more in heavily de-oiling, wax tailings and coal liquefaction products.Described hydrocarbon ils can contain the beavy metal impurity such as nickel, vanadium and sulphur, nitrogen impurity, can be up to 3.0 % by weight as the content of sulphur, and the content of nitrogen can be up to 2.0 % by weight, and the content of the metal impurities such as vanadium, nickel is up to 3000ppm.
Cracking additive provided by the invention is for catalytic cracking process, and cracking hydrocarbon oil condition is conventional catalytic cracking condition.In general, this cracking hydrocarbon oil condition comprises that reaction temperature is 400～600 ℃, is preferably 450～550 ℃, and weight (hourly) space velocity (WHSV) is 10～120 hours
-1, be preferably 10～80 hours
-1, oil ratio (weight ratio) is 1～20, is preferably 3～15.Cracking additive provided by the invention can be used for existing various catalyst cracker, for example fixed bed reactors, fluidized-bed reactor, riser reactor, multi-reaction-area reactor.
The following examples will be further described the present invention, but not thereby limit the present invention.
Part material used is as follows: boehmite is Shandong Aluminium Industrial Corp's manufacture product, the heavy % of solid content 60; Aluminium colloidal sol is the industrial products that catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, Al
2o
3content is 21.5 heavy %; Waterglass is the industrial products that catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, SiO
2the heavy % of content 28.9, Na
2o content 8.9%; Kaolin is the special kaolin of Cracking catalyst that Kaolin of Suzhou company produces, the heavy % of solid content 78; Tired de-soil: Hebei Zhongxiang Mingliu Rectorite Development Co., Ltd., quartz sand <3.5 % by weight, Al
2o
339.0 % by weight, Fe
2o
32.0 % by weight, Na
2o 0.03 % by weight, solid content 77 % by weight.SB aluminium hydrate powder: German Condex company produces, Al
2o
3content 75 % by weight; Gamma oxidation aluminium powder: German Condex company produces, Al
2o
3content 95 % by weight.Hydrochloric acid: chemical pure, concentration 36～38 % by weight, Beijing Chemical Plant produces.
Embodiment 1～9 preparation the present invention molecular sieve used; Comparative example 1～2 preparation contrast molecular sieve.
27alMAS NMR peak area ratio is in table 1.In each embodiment and comparative example, in each beta-molecular sieve sample, Na
2o, Fe
2o
3, Co
2o
3, NiO, CuO, Mn
2o
3, ZnO, SnO
2, Al
2o
3, SiO
2, P
2o
5content for x-ray fluorescence method measure (referring to " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publish),
27al MAS NMR adopts Bruker Avance III500MHz NMR to test, and formant spectrogram carries out adopting integration method to calculate each peak area after swarming matching.
Embodiment 1
By β zeolite, (Na β, Shandong catalyst plant is produced, SiO
2/ Al
2o
3=25, the heavy % of sodium oxide content 4.5, lower with) use NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample, 350 ℃ of calcination process 2 hours, is then warming up to 4 hours removed template methods of 550 ℃ of calcination process for 40 minutes; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of solid content 10 heavy %, adds oxalic acid 20g in stirring, is warming up to 80 ℃ and stirs 1h, and filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar to such an extent that solid content is the molecular sieve pulp of 40 heavy %, by 6.8gH
3pO
4(concentration 85%) and 3.2gCu (NO
3)
23H
2o is dissolved in 30g water, dries with molecular sieve pulp hybrid infusion; Gained sample is in 550 ℃ of calcination process 2 hours, i.e. modified beta molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.1Na
2o1.9Al
2o
34.0P
2o
51.0CuO93.0SiO
2.
27al MASNMR peak area ratio is listed in table 1.
Embodiment 2
By β zeolite NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample, 150 ℃ of calcination process 2 hours, is then warming up to 350 ℃ of calcination process 2 hours for 30 minutes, then, within 30 minutes, is warming up to 4 hours removed template methods of 500 ℃ of calcination process; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of solid content 10 heavy %, adds fluosilicic acid 10g in stirring, is warming up to 60 ℃ and stirs 1h, and filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar to such an extent that solid content is the molecular sieve pulp of 40 heavy %, by 11.8gH
3pO
4(concentration 85%) and 6.3gCuCl
2be dissolved in 90g water, dry with filter cake hybrid infusion; Gained sample is in 550 ℃ of calcination process 2 hours, i.e. modified beta molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.1Na
2o3.5Al
2o
36.9P
2o
53.5CuO86.0SiO
2.
27al MASNMR peak area ratio is listed in table 1.
Embodiment 3
By β zeolite NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample, 350 ℃ of calcination process 2 hours, is then warming up to 4 hours removed template methods of 600 ℃ of calcination process for 50 minutes; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of solid content 10 heavy %, adds ammonium fluosilicate 15g in stirring, is warming up to 60 ℃ and stirs 1h, and filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar to such an extent that solid content is the molecular sieve pulp of 40 heavy %; By 4.2gNH
4h
2pO
4be dissolved in 60g water, dry with filter cake hybrid infusion, through 550 ℃ of calcination process 2 hours; Cu (the NO that is 5% in the ratio of solid-to-liquid ratio 5:1 and concentration by above-mentioned sample
3)
2solution exchanges 2 hours at 80-90 ℃, filters, then exchanges several times, until reach aim parameter, then in 550 ℃ of calcination process 2 hours, i.e. modified beta molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.03Na
2o1.7Al
2o
32.5P
2o
52.1CuO93.7SiO
2.
27al MASNMR peak area ratio is listed in table 1.
Embodiment 4
By β zeolite NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample, 300 ℃ of calcination process 2 hours, is then warming up to 4 hours removed template methods of 550 ℃ of calcination process for 60 minutes; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of solid content 10 heavy %, adds ammonium oxalate 25g in stirring, is warming up to 60 ℃ and stirs 1h, and filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar to such an extent that solid content is the molecular sieve pulp of 40 heavy %; By 6.9gH
3pO
4(concentration 85%) and 8.1gFe (NO
3)
39H
2o is dissolved in 90g water, dries with filter cake hybrid infusion; Gained sample is in 550 ℃ of calcination process 2 hours, i.e. modified beta molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.1Na
2o2.8Al
2o
34.1P
2o
51.5Fe
2o
391.5SiO
2.
27al MASNMR peak area ratio is listed in table 1.
Embodiment 5
By β zeolite NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample, 350 ℃ of calcination process 2 hours, is then warming up to 4 hours removed template methods of 550 ℃ of calcination process for 40 minutes; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of solid content 10 heavy %, adds fluosilicic acid 10g in stirring, is warming up to 60 ℃ and stirs 1h, and filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar to such an extent that solid content is the molecular sieve pulp of 40 heavy %; By 9.3gH
3pO
4(concentration 85%) and 33.6gCo (NO
3) 6H
2o is dissolved in 90g water, dries with filter cake hybrid infusion; Gained sample is at 550 ℃, calcination process 2 hours, i.e. modified beta molecular sieve provided by the invention under 100% steam atmosphere.
Elementary analytical chemistry consists of 0.1Na
2o2.4Al
2o
35.4P
2o
59.6Co
2o
382.5SiO
2.
27al MASNMR peak area ratio is listed in table 1.
Embodiment 6
By β zeolite NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample, 350 ℃ of calcination process 2 hours, is then warming up to 4 hours removed template methods of 550 ℃ of calcination process for 40 minutes; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of solid content 10 heavy %, adds fluosilicic acid 10g in stirring, is warming up to 60 ℃ and stirs 1h, and filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar to such an extent that solid content is the molecular sieve pulp of 40 heavy %; By 6.0gH
3pO
4(concentration 85%) and 6.3gNi (NO
3)
26H
2o is dissolved in 90g water, dries with filter cake hybrid infusion; Gained sample is in 550 ℃ of calcination process 2 hours, i.e. modified beta molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.08Na
2o1.9Al
2o
34.3P
2o
51.8NiO91.9SiO
2.
27al MASNMR peak area ratio is listed in table 1.
Embodiment 7
By β zeolite NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample, 350 ℃ of calcination process 2 hours, is then warming up to 4 hours removed template methods of 550 ℃ of calcination process for 40 minutes; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of solid content 10 heavy %, adds fluosilicic acid 10g in stirring, is warming up to 60 ℃ and stirs 1h, and filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar to such an extent that solid content is the molecular sieve pulp of 40 heavy %; By 6.0gH
3pO
4(concentration 85%) and 35.4gMn (NO
3)
2be dissolved in 90g water, dry with filter cake hybrid infusion; Gained sample is in 550 ℃ of calcination process 2 hours, i.e. modified beta molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.09Na
2o1.6Al
2o
33.8P
2o
56.4Mn
2o
388.1SiO
2.
27alMAS NMR peak area ratio is listed in table 1.
Embodiment 8
By β zeolite NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample, 350 ℃ of calcination process 2 hours, is then warming up to 4 hours removed template methods of 550 ℃ of calcination process for 40 minutes; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of solid content 10 heavy %, adds oxalic acid 30g in stirring, is warming up to 60 ℃ and stirs 1h, and filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar to such an extent that solid content is the molecular sieve pulp of 40 heavy %; By 2.1gH
3pO
4(concentration 85%) and 5.9gZn (NO
3)
26H
2o is dissolved in 90g water, dries with filter cake hybrid infusion; Gained sample is in 550 ℃ of calcination process 2 hours, i.e. modified beta molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.15Na
2o1.2Al
2o
31.5P
2o
51.6ZnO95.9SiO
2.
27al MASNMR peak area ratio is listed in table 1.
Embodiment 9
By β zeolite NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample, 350 ℃ of calcination process 2 hours, is then warming up to 4 hours removed template methods of 550 ℃ of calcination process for 40 minutes; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of solid content 10 heavy %, adds fluosilicic acid 10g in stirring, is warming up to 60 ℃ and stirs 1h, and filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar to such an extent that solid content is the molecular sieve pulp of 40 heavy %; Add 6.0gH
3pO
4(concentration 85%) and 3.7gSnCl
45H
2o is dissolved in 90g water, dries with filter cake hybrid infusion; Gained sample is in 550 ℃ of calcination process 2 hours, i.e. modified beta molecular sieve provided by the invention.
Elementary analytical chemistry consists of 0.11Na
2o2.9Al
2o
34.1P
2o
51.7SnO
291.2SiO
2.
27al MASNMR peak area ratio is listed in table 1.
Comparative example 1
The explanation of this comparative example is prepared phosphorous and beta-molecular sieve transition metal according to the method for CN1872685A.
By 100g(butt) Na β zeolite (with embodiment 1 Na β zeolite used) uses NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Add 6.9gH
3pO
4(concentration 85%) and 8.1gFe (NO
3)
39H
2o is dissolved in 90g water, dries with filter cake hybrid infusion; Gained sample, 550 ℃ of calcination process 2 hours, obtains contrasting zeolite, is designated as B1.Elementary analytical chemistry consists of 0.1Na
2o6.0Al
2o
34.1P
2o
51.5Fe
2o
388.3SiO
2.
27al MAS NMR peak area ratio is listed in table 1.
Comparative example 2
Beta-molecular sieve, according to the method processing of embodiment 4, but was not taken out to aluminium processing before phosphorus modification, obtain comparative example 2 molecular sieves.Elementary analytical chemistry consists of 0.1Na
2o6.4Al
2o
33.9P
2o
51.4Fe
2o
388.1SiO
2.
27al MAS NMR peak area ratio is listed in table 1.
Comparative example 3
By β zeolite NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample is at 4 hours removed template methods of 550 ℃ of calcination process; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of solid content 10 heavy %, adds oxalic acid 20g in stirring, is warming up to 80 ℃ and stirs 1h, and filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar to such an extent that solid content is the molecular sieve pulp of 40 heavy %, by 6.8gH
3pO
4(concentration 85%) and 3.2gCu (NO
3)
23H
2o is dissolved in 30g water, dries with molecular sieve pulp hybrid infusion; Gained sample, 550 ℃ of calcination process 2 hours, obtains the modified beta molecular sieve of contrast.
Elementary analytical chemistry consists of 0.1Na
2o1.7Al
2o
34.1P
2o
51.1CuO93.2SiO
2.
27al MASNMR peak area ratio is listed in table 1.
Comparative example 4
By β zeolite NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample is at 4 hours removed template methods of 550 ℃ of calcination process; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of solid content 10 heavy %, adds fluosilicic acid 10g in stirring, is warming up to 60 ℃ and stirs 1h, and filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar to such an extent that solid content is the molecular sieve pulp of 40 heavy %; Add 6.0gH
3pO
4(concentration 85%) and 3.2gCu (NO
3)
23H
2o, 2.6gZn (NO
3)
26H
2o is dissolved in 90g water, dries with filter cake hybrid infusion; Gained sample, 550 ℃ of calcination process 2 hours, obtains the modified beta molecular sieve of contrast.
Elementary analytical chemistry consists of 0.11Na
2o2.5Al
2o
34.1P
2o
51.0CuO0.7ZnO91.6SiO
2.
27al MAS NMR peak area ratio is listed in table 1.
Table 1
Embodiment 10～13 preparation the present invention phosphorus aluminium inorganic binder argillaceous used, formula and composition are in table 2.
Embodiment 10
This example is prepared phosphorus aluminium inorganic binder argillaceous of the present invention.
0.74 kilogram of boehmite (is contained to Al
2o
30.45 kilogram), 0.39 kilogram of tired de-soil (0.30 kilogram of butt) and 1.6 kilograms of decationizing water making beating 30 minutes, under stirring, in slurries, add 2.03 kilograms of SPAs (mass concentration 85%), phosphoric acid add speed be 0.04Kg phosphoric acid/minute/Kg alumina source, be warming up to 70 ℃, then at this temperature, react 45 minutes, make the inorganic binder of phosphorous aluminium compound.Material proportion is in table 2.
Embodiment 11～13
The all phosphorus aluminium inorganic binders containing the first clay of example 8～10 preparation the present invention.Material proportion is in table 2.
Comparative example 5
This comparative example is prepared comparative example of the present invention phosphorus aluminium glue used (phosphorus aluminium colloidal sol).
Phosphorus aluminium glue preparation: by 0.66 kilogram of boehmite (0.44 kilogram of butt) and 1.75 kilograms of decationizing water making beating 30 minutes, under stirring, in slurries, add 2.6 kilograms of SPAs (chemical pure, the heavy % of phosphoric acid 85), be warming up to 70 ℃, then at this temperature, react 45 minutes, obtain phosphorus aluminium glue (phosphorus aluminium inorganic binder).Material proportion is in table 2.
Embodiment 14～22 preparation auxiliary agent provided by the present invention.Auxiliary formula is in table 3, and preparation process is described below:
Table 2
Embodiment 14
Get molecular sieve-4 A
1, kaolin and boehmite, add decationized Y sieve water and and aluminium colloidal sol making beating 120 minutes, obtain the slurries of solid content 30 % by weight, add hydrochloric acid to regulate the pH value 3.0 of slurries, then continue making beating 45 minutes, then the phosphorus aluminium inorganic binder argillaceous that adds embodiment 11 to prepare, stir after 30 minutes, by dry the slurries spraying obtaining, obtain microballoon, by microballoon roasting 1 hour at 500 ℃, make ZJ
1, its proportioning is in table 3.
Embodiment 15
Get molecular sieve-4 A
2, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, adding hydrochloric acid to regulate the pH value of slurries is 3.0, continue making beating 45 minutes, then toward the phosphorus aluminium inorganic binder argillaceous that wherein adds embodiment 10 to prepare.The slurries that obtain, 500 ℃ of dry gas inlet temperatures, are sprayed under the condition that exhaust temperature is 180 ℃ dry, obtain average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 ℃.
Get thus obtained microsphere product, add ammonium dibasic phosphate aqueous solution, be warming up to 60 ℃ under stirring, react after 20 minutes at this temperature, by slurries vacuum filtration, dry, then roasting 2 hours at 500 ℃, makes auxiliary agent ZJ
2.Auxiliary agent proportioning is in table 3.
Embodiment 16
Get molecular sieve-4 A
3with boehmite, kaolin, diatomite, add decationized Y sieve water and waterglass making beating 120 minutes, obtain the slurries of solid content 35 % by weight, add hydrochloric acid to make the pH value 3 of slurries, then pull an oar 45 minutes, to the phosphorus aluminium inorganic binder argillaceous that adds embodiment 12 to prepare in mixed serum, stir 30 minutes, by dry the slurries spraying obtaining, obtain microballoon, by microballoon roasting 1 hour at 500 ℃, obtain auxiliary agent ZJ
3, its proportioning is in table 3.
Embodiment 17
Get molecular sieve-4 A
4with boehmite, kaolin, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 38 % by weight, add hydrochloric acid to make the pH value 3.0 of slurries, then pull an oar 45 minutes, then the phosphorus al binder providing toward the phosphorus aluminium inorganic binder argillaceous that adds in mixed serum embodiment 13 to prepare and comparative example 3, stirs 30 minutes.The slurries that obtain, 500 ℃ of dry air inlet temperatures, are sprayed under the condition that exhaust temperature is 180 ℃ dry, obtain average particulate diameter and be the microballoon of 65 microns, by microballoon roasting 1 hour at 500 ℃, obtain auxiliary agent ZJ
4, its proportioning is in table 3.
Embodiment 18
Get molecular sieve-4 A
5with boehmite, kaolin, add decationized Y sieve water making beating 120 minutes, obtain the slurries of solid content 30 % by weight, adding hydrochloric acid to regulate the pH value of slurries is 3, then pull an oar 45 minutes, then, toward the phosphorus al binder argillaceous that adds embodiment 10 to prepare in slurries, stir 30 minutes.By dry the slurries spraying obtaining, obtain microballoon.By microballoon roasting 1 hour at 500 ℃, obtain auxiliary agent ZJ
5, auxiliary agent proportioning is in table 3.
Embodiment 19
Get molecular sieve-4 A
6, kaolin, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, adding hydrochloric acid to regulate the pH value of slurries is 3, continues making beating 45 minutes, then the phosphorus al binder argillaceous that adds embodiment 11 to prepare, and after diammonium hydrogen phosphate solid stirs, by dry the slurries spraying obtaining, obtain microballoon, by microballoon roasting 1 hour at 400 ℃, make auxiliary agent ZJ
6.Proportioning is in table 3.
Embodiment 20
Get molecular sieve-4 A
7with boehmite, kaolin, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, regulating the pH value of slurries with hydrochloric acid is 3.0, then continues making beating 45 minutes, the phosphorus al binder argillaceous that adds embodiment 12 to prepare, stir 30 minutes, by dry the slurries spraying obtaining, obtain microballoon, by microballoon roasting 1 hour at 500 ℃, make auxiliary agent ZJ
7.Auxiliary agent proportioning is in table 3.
Embodiment 21
Get molecular sieve-4 A
8, kaolin soil and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, adding hydrochloric acid to make the pH value of slurries is 3, continues making beating 30 minutes, the phosphorus al binder argillaceous that adds embodiment 12 to prepare, pull an oar again 30 minutes, then, by dry the slurries spraying obtaining, obtain, by microballoon roasting 1 hour at 500 ℃, make auxiliary agent ZJ
8.Auxiliary agent proportioning is in table 3.
Embodiment 22
Get molecular sieve-4 A
9, kaolin soil and boehmite, add decationized Y sieve water making beating 120 minutes, obtain the slurries of solid content 30 % by weight, adding hydrochloric acid to make the pH value of slurries is 3, continues making beating 30 minutes, the phosphorus al binder argillaceous that adds embodiment 13 to prepare, pull an oar again 30 minutes, then, by dry the slurries spraying obtaining, obtain, by microballoon roasting 1 hour at 500 ℃, make auxiliary agent ZJ
8.Auxiliary agent proportioning is in table 3.
Comparative example 6
Get A
4, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, under stirring, adding concentration is the hydrochloric acid of 36 % by weight, and the pH value that makes slurries is 3.0, then pulls an oar 45 minutes, by dry the slurries spraying obtaining, obtain average particulate diameter and be the microballoon of 65 microns, by microballoon roasting 1 hour at 500 ℃, make reference auxiliary agent DB
1.Reference auxiliary agent proportioning is in table 4.
Comparative example 7
Get A
4, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, under stirring, add hydrochloric acid, by the pH value 3.0 of hydrochloric acid content control slurries, mixture was continued to making beating after 45 minutes, the phosphorus al binder that adds comparative example 2 to make, then stir 30 minutes, by the slurries that obtain 500 ℃ of inlet temperatures, under the condition that exhaust temperature is 180 ℃, spray dry, obtain average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 ℃, make reference auxiliary agent DB
2.Reference auxiliary agent proportioning is in table 4.
Comparative example 8-10
Prepare auxiliary agent by the method for embodiment 17, be not both and use molecular sieve B
1-B
4replace A
4, make reference auxiliary agent DB
3– DB
6.Reference auxiliary agent proportioning is in table 4.
Comparative example 11
By the method for comparative example 4 is prepared to auxiliary agent, be not both and use molecular sieve B
2replace A
4, make reference auxiliary agent DB
4.Reference auxiliary agent proportioning is in table 4.
Embodiment 23
The auxiliary agent that getting embodiment 14-22 provides carries out intensity index (being abrasion index) to be measured, and wherein assay method carries out according to RIPP strength test standard method (by straight tube intensity meter mensuration), records respectively its intensity index A.I., the results are shown in table 5.
Comparative example 12
The auxiliary agent that getting comparative example 6-11 provides carries out intensity index (being abrasion index) to be measured, and wherein assay method carries out according to RIPP strength test standard method (by straight tube intensity meter mensuration), records respectively its intensity index A.I., the results are shown in table 5.The contrast auxiliary agent DB that comparative example 6, ratio 11 provide
1, DB
6intensity cannot meet catalytic cracking process requirement, does not make performance evaluation.
Embodiment 24～28
The following examples, take fixed fluidized-bed reactor as example, illustrate the cracking reaction effect of cracking additive provided by the invention.
Respectively by 30 grams of ZJ
1-ZJ
8under 800 ℃, 100% steam atmosphere condition, carry out the burin-in process of 12 hours.Get the ZJ through burin-in process of different amounts
1-ZJ
8mix respectively from the industrial FCC equilibrium catalyst (the FCC equilibrium catalyst that the industrial trade mark is MLC-500, main character is in table 6) of different amounts.Catalyst mixture is packed in the reactor of small fixed flowing bed-tion reacting device, feedstock oil oil shown in his-and-hers watches 7 carries out catalytic cracking (feedstock oil character is in table 7).Table 8 and table 9 have provided used catalyst mixture weight composition, reaction condition and reaction result.
Comparative example 13～17
Comparative example below, take fixed fluidized-bed reactor as example, illustrates the situation that uses reference auxiliary agent.
By the method in embodiment 19, same feedstock oil is carried out to catalytic cracking, different is that used catalyst is respectively 100% industrial FCC equilibrium catalyst, DB
2～DB
5mixture with industrial FCC equilibrium catalyst.Table 8 has provided used catalyst mixture weight composition, reaction condition and reaction result.
Can find out from table 8 and table 9, compared with the auxiliary agent of preparing with existing method, catalyst aid provided by the invention, have higher catalytic cracking liquefied gas yield, the productive rate of ethene, propylene and isobutene is higher, and propylene, isobutylene concentration in catalytic cracking liquefied gas are higher, ethylene concentration in dry gas is higher, heavy oil conversion performance is higher, and coke and dry gas selective better is also to have higher liquid to receive unexpectedly.
Table 3
Table 4
Table 5
Table 6
Table 7
Table 8
Table 9
Claims (18)
1. improve an assistant for calalytic cracking for low-carbon alkene concentration, contain in the beta-molecular sieve of the phosphorous and transition metal of butt 10～75 heavy %, in al composition, phosphorus component and the first clay butt weight sum 3～30 heavy % containing the phosphorus aluminium inorganic binder of the first clay, in other inorganic binder of oxide 3～30 heavy % with in the second clay of butt 0～60 heavy %; Wherein, take the described phosphorus aluminium inorganic binder butt weight containing the first clay as benchmark, the described phosphorus aluminium inorganic binder containing the first clay comprises with Al
2o
3meter 15～40 % by weight al compositions, with P
2o
5count the phosphorus component of 45～80 % by weight and the first clay in butt 1～40 % by weight, and its P/Al weight ratio is 1～6; The beta-molecular sieve of described phosphorous and transition metal, with P
2o
5meter phosphorus content accounts for the heavy % of 1-10, account for the heavy % of 0.5-10 in metal oxide tenor, it is characterized in that this molecular sieve
27in Al MAS NMR, chemical shift is that 40 ± 3ppm resonance signal peak area and chemical shift are that the ratio of 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, and the chemical shift percentage that to be 0 ± 3ppm and chemical shift account for total peak area for the resonance signal peak area sum of-12ppm ± 3ppm is for being less than or equal to 10%.
2. according to auxiliary agent claimed in claim 1, it is characterized in that, the beta-molecular sieve of described phosphorous and transition metal, with P
2o
5meter phosphorus content preferably accounts for 1 ~ 8 heavy %, preferably accounts for 0.5 ~ 5 heavy %, this molecular sieve in metal oxide tenor
27in Al MAS NMR, chemical shift is that 40 ± 3ppm resonance signal peak area and chemical shift are that the ratio of 54ppm ± 3ppm resonance signal peak area is more than or equal to 2, and the chemical shift percentage that to be 0 ± 3ppm and chemical shift account for total peak area for the resonance signal peak area sum of-12ppm ± 3ppm is less than or equal to 6%.
3. according to auxiliary agent claimed in claim 1, it is characterized in that, this auxiliary agent comprises the second clay, other inorganic binder of 5～25 heavy % and the phosphorus additive of 0～15 heavy % of described phosphorous and transition metal, 10～45 heavy % containing the phosphorus aluminium inorganic binder of the first clay, 20～60 heavy % of 8～25 heavy %.
4. according to auxiliary agent claimed in claim 1, it is characterized in that, the first described clay is one or more in kaolin, sepiolite, concave convex rod, tired de-soil, imvite and diatomite; Described the second clay is selected from kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone the mixture of one or more; Other described inorganic matter binding agent is selected from one or more mixture of boehmite, aluminium colloidal sol, silicon-aluminum sol, waterglass and phosphorus aluminium colloidal sol.
5. a preparation method for assistant for calalytic cracking, comprises the beta-molecular sieve of phosphorous and transition metal, mixes containing phosphorus aluminium inorganic binder, other inorganic binder of the first clay, adds or do not add the second clay, making beating, and spraying is dry; Wherein, the described phosphorus aluminium compound inorganic binder containing the first clay, take its butt weight as benchmark, contains with Al
2o
3meter 15～40 % by weight al compositions, with P
2o
5meter 45～80 % by weight phosphorus component and in butt 1～40 % by weight clay, its P/Al weight ratio is that 1～6, pH value is 1～3.5, this binding agent solid content is 15～60 % by weight; The beta-molecular sieve of described phosphorous and transition metal, with P
2o
5meter phosphorus content accounts for 1 ~ 10 % by weight, accounts for 0.5 ~ 10 % by weight, this molecular sieve in metal oxide tenor
27in Al MAS NMR, chemical shift is that 40 ± 3ppm resonance signal peak area and chemical shift are that the ratio of 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, and the chemical shift percentage that to be 0 ± 3ppm and chemical shift account for total peak area for the resonance signal peak area sum of-12ppm ± 3ppm is less than or equal to 10%.
6. in accordance with the method for claim 5, it is characterized in that, the described phosphorus aluminium inorganic binder preparation method containing the first clay comprises:
(1) alumina source, the first clay and water making beating are dispersed into the slurries that solid content is 8～45 % by weight; Described alumina source is can be by the aluminium hydroxide of sour peptization and/or aluminium oxide, in the first clay of butt and with Al
2o
3the weight ratio of the alumina source of meter is 1～40:15～40;
(2) stir in the lower slurries that obtain toward step (1) and add SPA according to the part by weight of P/Al=1～6;
(3) slurries that step (2) obtained react 15～90 minutes at 50～99 ℃ of temperature.
7. in accordance with the method for claim 5, it is characterized in that the described phosphorus aluminium inorganic binder containing the first clay, take its butt weight as benchmark, comprises 15～35 % by weight and be derived from the Al of described alumina source
2o
3, 50～75 % by weight P
2o
5with the first clay of 8～35 % by weight, described P/Al weight ratio is 2～5.
8. according to the method described in claim 6 or 7, it is characterized in that, described alumina source is one or more in p-aluminium oxide, x-aluminium oxide, η-aluminium oxide, gama-alumina, k-aluminium oxide, δ-aluminium oxide, θ-aluminium oxide, gibbsite, surge aluminium stone, promise diaspore, diaspore, boehmite and boehmite; The first described clay is one or more in kaolin, sepiolite, concave convex rod, tired de-soil, imvite and diatomite, and the temperature described in step (3) is 65 ~ 90 ℃.
9. in accordance with the method for claim 5, it is characterized in that, the preparation method of the beta-molecular sieve of described phosphorous and transition metal comprises former beta-molecular sieve powder in the temperature range of 200 ℃ to 800 ℃, after at least two mutual non-overlapping temperature ranges are from low to high processed with removed template method, dealuminzation, then carry out phosphorus and metal-modified step.
10. in accordance with the method for claim 5, it is characterized in that, described phosphorous and transition metal beta-molecular sieve preparation method comprises:
(1) sodium type beta-molecular sieve is made to the Na on molecular sieve through ammonium exchange
2o content is less than 0.2 heavy %;
(2) molecular sieve step (1) being obtained after drying, is processed at least 0.5 hour under 200-400 ℃ of temperature range, then under 500-800 ℃ of temperature range, processes at least 0.5 hour removed template method being warmed up in 2 hours at the most;
(3) at temperature 25-100 ℃, the product obtaining by dealumination agent solution treatment steps (2);
(4) introduce phosphorus-containing compound and metallic compound molecular sieve is carried out to modification;
(5) calcination process at least 0.5 hour at 400-800 ℃.
11. in accordance with the method for claim 10, wherein, said ammonium exchange is according to molecular sieve: ammonium salt: H
2o=1:(0.1-1): the process that exchange was filtered after at least 0.5 hour at room temperature to 100 ℃ of weight ratio (5-10), this process is at least carried out once; Said ammonium salt is preferably selected from one of ammonium chloride, ammonium sulfate or ammonium nitrate or their mixture.
12. in accordance with the method for claim 10, it is characterized in that in step (2) before, the product of step (1) at least being processed 1 hour at 120-180 ℃.
13. in accordance with the method for claim 10, wherein, said dealumination agent is selected from organic acid, inorganic acid, organic salt or inorganic salts; Said dealumination agent, its weight concentration is 1-20%; Said step (3) is carried out once or is carried out several times.
14. in accordance with the method for claim 13, wherein, said organic acid is selected from ethylenediamine tetra-acetic acid, oxalic acid, citric acid or sulfosalicylic acid, said inorganic acid is selected from fluosilicic acid, hydrochloric acid, sulfuric acid or nitric acid, and said organic salt is selected from ammonium oxalate, ammonium fluoride, ammonium fluosilicate or ammonium fluoroborate.
15. in accordance with the method for claim 10, and wherein, said phosphorus-containing compound is selected from one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) or ammonium phosphate or its mixture; Said metallic compound is selected from one or more in the compound of Fe, Co, Ni, Cu, Mn, Zn and Sn.
16. according to the method described in claim 10 or 15, wherein, and the water soluble salt that said metallic compound is metal.
17. in accordance with the method for claim 16, and wherein, the water soluble salt of said metal is selected from the one in the sulfate of metal, nitrate or chlorate.
18. in accordance with the method for claim 10, and wherein, the said calcination process process of step (5) is roasting under steam atmosphere.
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| CN107971006A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of assistant for calalytic cracking of propylene enhancing and preparation method thereof |
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