CN103785458B - A kind of cracking additive improving low-carbon olefin concentration - Google Patents
A kind of cracking additive improving low-carbon olefin concentration Download PDFInfo
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- CN103785458B CN103785458B CN201210419340.9A CN201210419340A CN103785458B CN 103785458 B CN103785458 B CN 103785458B CN 201210419340 A CN201210419340 A CN 201210419340A CN 103785458 B CN103785458 B CN 103785458B
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Abstract
Improve a cracking additive for low-carbon olefin concentration, containing phosphorous and transition metal, containing the first clay phosphorus aluminium inorganic binder, other inorganic binder and the second clay; Wherein, the described phosphorus aluminium inorganic binder containing the first clay comprises with Al
2o
3count 15 ~ 40 % by weight al compositions, with P
2o
5the phosphorus component of meter 45 ~ 80 % by weight and in the first clay of 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 1 ~ 10 heavy %, accounts for 0.5 ~ 10 heavy % with metal oxide tenor, this molecular sieve
27al? MAS? in NMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 54ppm ± 3ppm resonance signal peak area is greater than 1, and the percentage that the resonance signal peak area sum of chemical shift to be 0 ± 3ppm and chemical shift be-12ppm ± 3ppm accounts for total peak area is less than 10%.This auxiliary agent is applied to catalytic cracking, can improve propylene, isobutylene concentration in ethylene concentration in catalytic cracked dry gas, 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 demand of the whole world to low-carbon alkene all increases year by year.Fluid catalytic cracking is one of important process of producing low-carbon alkene, for most of catalytic cracking unit, adds the effective technical way that auxiliary agent is increased low carbon olefine output.But prior art is to isobutylene concentration DeGrain in raising liquefied gas.Generate and reactive chemistry from FCC process isobutene, beta-molecular sieve is a kind of effective active component.It is on the one hand in the process removing its template, easily 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 easy dealuminzation thus activity stability is poor.
Disclose some Cracking catalyst containing β zeolite or auxiliary agents in early stage patent, can improve octane number, increased low carbon olefine output, liquefied gas, as patents such as US4740292, US4898846, US4911823 and WO95026533.What the β zeolite 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 be obtained by hydrothermal treatment consists or acid treatment.
US4837396 discloses a kind of catalyst, containing β zeolite and Y zeolite, and improves hydrothermal stability and the mechanical strength of catalyst as stabilizing agent containing metal ion type compound.This stabilizing agent can be [Al
2(OH)
5cl]
x, or Al
3zr (OH)
9cl
4.Stabilizing agent can directly and the effect of β zeolite, also can add in Kaolinite Preparation of Catalyst process.
US6355591 discloses a kind of assistant for calalytic cracking, the aluminum phosphate containing 4-20%, ZSM-5, β of 1-40% and composition thereof, and the clay of 40-90% can improve LPG output.The preparation method of aluminum phosphate is: SPA adds deionizing dilution with water, and add aluminium powder and dissolve, wherein the mol ratio of Al and PO4 is that 1:3, pH are less than 2.0.Obtained aluminum phosphate is mixed with kaolin, then is mixed into molecular sieve pulp, shaping of finally spraying.From Patent right requirement, this auxiliary agent is not containing other binding agent, other inorganic oxide except aluminum phosphate.In addition, the auxiliary agent preparation method containing β zeolite and performance is not provided in the embodiment of this patent.
A kind of method of modifying of beta-molecular sieve is proposed in CN1043450A, the method is that Na beta-molecular sieve is pumped part framework aluminum with acid after roasting, then carrying out potassium exchange makes zeolite potassium content be 0.5 ~ 2.5 heavy %, after drying, roasting with comprise potassium hydrogen phosphate-potassium dihydrogen phosphate, hypophosphorous acid-potassium hypophosphite, phosphorous acid-potassium phosphite, the microcosmic salt cushioning liquid of weakly acidic pH at room temperature soaks 4 ~ 10 hours, take the circumstances into consideration washing or do not wash to make phosphorus content on zeolite be 0.01 ~ 0.5 heavy %, then dry, roasting; The hydrocarbon processing catalyst as relating to hydroisomerization reaction is applicable to through the beta-molecular sieve that the method is modified.
Propose a kind of method of modifying of beta-molecular sieve in CN1179994A, Na beta-molecular sieve ammonium ion exchange to the Na2O content on zeolite is less than 0.1 heavy % by the method; Then the beta-molecular sieve acid treatment that above-mentioned ammonium exchanges is pumped part framework aluminum, make its silica alumina ratio be greater than 50; Beta-molecular sieve after above-mentioned dealuminzation is mixed post-drying with phosphoric acid or phosphate, makes the amount of P2O5 on gained zeolite be 2 ~ 5 heavy %; Last under water vapour atmosphere with 450 ~ 650 DEG C of hydrothermal calcines 0.5 ~ 4 hour.Higher alkene can be obtained when the cracking reaction for hydro carbons, especially the productive rate of isomeric olefine and lower coke yield by the modified beta-molecular sieve of the method.
CN1872685A discloses a kind of phosphorous and transition metal, it is characterized in that the anhydrous chemical expression of this beta-molecular sieve, (0 ~ 0.3) Na2O(0.5 ~ 10 are counted with the quality of oxide) 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 as the active component of catalyst or auxiliary agent.
Still there is the not high enough problem of propylene and butene 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 and a kind ofly improves cracking additive of catalytic cracking low-carbon olefin concentration and preparation method thereof, this auxiliary agent is containing beta-molecular sieve, be applied to catalytic cracking, propylene, isobutylene concentration in ethylene concentration in catalytic cracked dry gas, liquefied gas can be improved, when vast scale adds auxiliary agent, do not affect major catalyst heavy oil conversion performance simultaneously.
The invention provides a kind of assistant for calalytic cracking, with the butt weight of described auxiliary agent for benchmark, containing in the beta-molecular sieve of the phosphorous and transition metal of the heavy % of butt 10 ~ 75, with contain the first clay phosphorus aluminium inorganic binder in al composition (with Al
2o
3meter), phosphorus component is (with P
2o
5meter) and the heavy % of the first clay butt weight sum meter 3 ~ 30 containing the phosphorus aluminium inorganic binder of the first clay, in other inorganic binder of the heavy % of oxide basis 3 ~ 30 with second clay of the heavy % of butt 0 ~ 60; Wherein, with the described phosphorus aluminium inorganic binder butt weight containing the first clay for benchmark, the described phosphorus aluminium inorganic binder containing the first clay comprises with Al
2o
3count 15 ~ 40 % by weight al compositions, with P
2o
5the phosphorus component of meter 45 ~ 80 % by weight and in the first clay of 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 with metal oxide tenor, this molecular sieve
27in AlMASNMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, and the percentage that the resonance signal peak area sum of chemical shift to be 0 ± 3ppm and chemical shift be-12ppm ± 3ppm accounts for total peak area 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, the phosphorus aluminium inorganic binder containing the first clay, the mixing of other inorganic binder, adds or do not add the second clay, making beating, spraying dry; Wherein, the described phosphorus aluminium compound inorganic binder containing the first clay, in butt, contains with Al
2o
3count 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 1.0 ~ 6.0, pH is 1.0 ~ 3.5, and 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 with metal oxide tenor, this molecular sieve
27in AlMASNMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, and the percentage that the resonance signal peak area sum of chemical shift to be 0 ± 3ppm and chemical shift be-12ppm ± 3ppm accounts for total peak area is less than or equal to 10%.
Described phosphorous and preparation method that is transition metal beta-molecular sieve comprises former for beta-molecular sieve powder in the temperature range of 200 DEG C to 800 DEG C, through the non-overlapping temperature range process of at least two from low to high with after removed template method, dealuminzation, then carry out phosphorus and metal-modified step.More specifically, comprise the steps:
(1) sodium form beta-molecular sieve is exchanged the Na made on molecular sieve through ammonium
2o content is less than 0.2 heavy %;
(2) molecular sieve step (1) obtained after drying, processes at least 0.5 hour under 200-400 DEG C of temperature range, then under being warmed up to 500-800 DEG C of temperature range in 2 hours at the most, processes at least 0.5 hour removed template method; ;
(3) at temperature 25-100 DEG C, the product obtained by dealumination agent solution treatment steps (2);
(4) introducing phosphorus-containing compound and metallic compound carry out modification to molecular sieve;
(5) calcination process at least 0.5 hour at 400-800 DEG C
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, such as 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 the mixture of one or more in kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone.
Cracking additive provided by the invention, also containing other inorganic binder except described phosphorus aluminium inorganic binder argillaceous.Other inorganic binder described is selected from one or more in the inorganic oxide being customarily used in assistant for calalytic cracking or catalyst substrates and binder component, such as boehmite, Alumina gel, phosphorus aluminium glue, silicon-aluminum sol, waterglass are at the interior mixture of one or more, wherein preferably boehmite, Alumina gel, phosphorus aluminium glue one or more.
Can also contain with P in catalyst aid provided by the present invention
2o
5the phosphorus additive of the heavy % of meter 0 ~ 15, the compound that described phosphorus additive is selected from phosphorus comprises one or more in the inorganic compound of phosphorus and organic compound, can be soluble in water, also can be insoluble in water or water-fast phosphorus compound, such as, be selected from one or more in the oxide of phosphorus, phosphoric acid, phosphate, phosphite, hypophosphites, subphosphate, acid phosphate and phosphorous organic compound.Preferred phosphorus compound is one or more in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, aluminum phosphate and phosphorus Alumina gel.In the catalyst obtained, phosphorus additive exists with the form of phosphorus compound (oxide, phosphate, phosphite, subphosphate, acid phosphate as phosphorus).When containing other the phosphorous binding agent such as phosphorus Alumina gel except the described phosphorus aluminium inorganic binder containing the first clay in auxiliary agent, the phosphorus that other described inorganic phosphor-contained binding agent is introduced 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, duct as may reside in zeolite is inner, the surface of zeolite, may reside in described host material, can also be present in the inside, duct of zeolite, the surface of zeolite and described host material simultaneously.Described phosphorus additive does not comprise phosphorous and transition metal and contains the phosphorus related 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, RFCC liquefied gas yield can be increased, improve the propylene in catalytic cracking liquefied gas and the concentration of isobutene low-carbon alkene, the ethylene concentration improved in dry gas significantly, the productive rate of ethene, propylene and isobutene is high, coke selective low, improve the octane number of gasoline, and do not affect the heavy oil conversion performance of major catalyst when vast scale adds auxiliary agent.Compared with existing auxiliary agent, there is higher heavy oil transformation active, higher ethene, propylene and selective isobutene, in dry gas in ethene, liquefied gas propylene and isobutylene concentration higher, there is better coke and dry gas selectivity, surprisingly also there is higher liquid and receive.Such as, industrial MLC-500 poising agent 480 DEG C, weight (hourly) space velocity (WHSV) is 16h
-1, oil ratio is react under the condition of 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 the 50 % by weight phosphorous and transition metal of containing provided by the invention, 12 % by weight kaolin, 24 % by weight containing the phosphorus aluminium inorganic binder of the first clay, 8 % by weight boehmites, the auxiliary agent of 6 % by weight Alumina gel, after mixing with above-mentioned MLC-500 poising agent with the weight ratio of 10:90, react under similarity condition, 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.
Detailed description of the invention
Assistant for calalytic cracking provided by the present invention, preferably include 8 ~ 25 heavy % described contain the first clay phosphorus aluminium inorganic binder, phosphorous and transition metal, the clay of 10 ~ 45 heavy %, other inorganic binder of 5 ~ 25 heavy % of 20 ~ 60 heavy % and the phosphorus additive of 0 ~ 10 heavy %.
Do not comprise phosphorous and transition metal in the content of wherein said phosphorus additive and contain the phosphorus amount related 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, and account for 0.5 ~ 10 % by weight with metal oxide tenor, silica alumina ratio is not less than 30(molecule mol ratio), this molecular sieve
27in AlMASNMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 54ppm ± 3ppm resonance signal peak area is greater than 1, and the percentage that the resonance signal peak area sum of chemical shift to be 0 ± 3ppm and chemical shift be-12ppm ± 3ppm accounts for total peak area is less than 10%.Transition metal in the beta-molecular sieve of described phosphorous and transition metal be preferably selected from Fe, Co, Ni, Cu, Mn, Zn, Sn one or more.
Under preferable case, described comprises tired de-soil containing the first clay in the phosphorus aluminium inorganic binder of the first clay, and the first more preferably described clay is rectorite.With butt weight for 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
5the phosphorus component of meter 50 ~ 75 % by weight and in the first clay of butt 8 ~ 35 % by weight, and chloride, it is not 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, with its butt weight for benchmark, contains with Al
2o
3count 15 ~ 40 % by weight al compositions, with P
2o
5meter 45 ~ 80 % by weight phosphorus component and in the first clay of butt 1 ~ 40 % by weight, its P/Al weight ratio is 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 are pulled an oar be dispersed into the slurries that solid content is 8 ~ 45 % by weight; Described alumina source is can by the aluminium hydroxide of sour peptization and/or aluminium oxide, in the first clay of butt with Al
2o
3the weight ratio of the alumina source of meter is 1 ~ 40:15 ~ 40;
(2) stirring is descended in the slurries obtained toward step (1) and is added SPA according to the part by weight of P/Al=1 ~ 6; In wherein said P/Al P be in phosphoric acid in the weight of the phosphorus of simple substance, Al is in the weight of the aluminium of simple substance in alumina source;
(3) slurries that step (2) obtains are reacted 15 ~ 90 minutes at 50 ~ 99 DEG C of temperature.
Wherein, the consumption of alumina source, SPA and the first clay, makes the obtained phosphorus aluminium inorganic binder containing the first clay, with its butt weight for benchmark, comprises: 15 ~ 40 % by weight preferred 15 ~ 35 % by weight Al being derived from described alumina source
2o
3, 45 ~ 80 % by weight preferred 50 ~ 75 % by weight P
2o
5, 1 ~ 40 % by weight preferably 8 ~ 35 % by weight the first clay; Described P/Al weight ratio is preferably 1.2 ~ 6.0, is 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, is more preferably 75 ~ 90 % by weight.The charging rate of phosphoric acid be preferably 0.01-0.10Kg phosphoric acid/minute/Kg alumina source, be 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, in preparation process, not only improve mass transfer, the heat transfer of storeroom, avoid the adhesive cures that material uneven local moment vigorous reaction heat release overtemperature causes, the pH value of binding agent can be regulated more neatly, obtain the binding agent of high solids content, and not needing high temperature depolymerization, the step such as concentrated, preparation method is simple.The adhesive property of the binding agent obtained 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 obtained is had 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 with metal oxide tenor, it is characterized in that this molecular sieve
27in AlMASNMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, and chemical shift is 0 ± 3ppm and chemical shift is that the resonance signal peak area sum of-12ppm ± 3ppm accounts for the percentage of total peak area 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 fully, framework aluminum is adequately protected in phosphorus and framework aluminum coordination simultaneously, 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 with metal oxide tenor, preferably accounts for the heavy % of 0.5-5.One or more preferably in Fe, Co, Ni, Cu, Mn, Zn and Sn of said metal.
Phosphorous and transition metal beta-molecular sieve of the present invention, its
27in AlMASNMR, chemical shift is the four-coordination framework aluminum species that 54 ± 3ppm resonance signal characterizes, chemical shift be 40 ± 3ppm resonance signal characterize be the framework aluminum species with phosphorus coordination, chemical shift be 0 ± 3ppm resonance signal characterize be hexa-coordinate non-framework aluminum species, chemical shift be-12 ± 3ppm resonance signal sign be the non-framework aluminum species with phosphorus coordination.Phosphorous and the transition metal beta-molecular sieve of modification provided by the invention, this molecular sieve
27in AlMASNMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, is preferably greater than or equal to 2, such as, be a value of 2-5; The resonance signal peak area sum of chemical shift to be 0 ± 3ppm and chemical shift be-12ppm ± 3ppm accounts for the percentage of total peak area for being less than 10%, being preferably less than 6%, such as, be a value in 1-4%.
Preparation method that is phosphorous and transition metal molecules sieve is stated described in provided by the invention, it is characterized in that comprising by former for beta-molecular sieve powder in the temperature range of 200 DEG C to 800 DEG C, through the non-overlapping temperature range process of at least two from low to high with after removed template method, dealuminzation, then carry out phosphorus and metal-modified step.Preferred step comprises:
(1) sodium form beta-molecular sieve is exchanged the Na made on molecular sieve through ammonium
2o content is less than 0.2 heavy %;
(2) molecular sieve step (1) obtained after drying, processes at least 0.5 hour under 200-400 DEG C of temperature range, then under being warmed up to 500-800 DEG C of temperature range in 2 hours at the most, processes at least 0.5 hour removed template method;
(3) at temperature 25-100 DEG C, the product obtained by the dealumination agent solution treatment steps (2) of weight concentration 1-20%;
(4) introducing phosphorus-containing compound and metallic compound carry out modification to molecular sieve;
(5) calcination process at least 0.5 hour at 400-800 DEG C.
Preparation method provided by the invention, compared with the modifying process of existing beta-molecular sieve, the main distinction be method of modifying of the present invention be by former for beta-molecular sieve powder (the sodium form beta-molecular sieve containing organic formwork agent) after non-overlapping temperature range stage by stage process is from low to high with roasting removed template method, chemically dealumination treatment is carried out to β zeolite, then carry out the modification of phosphorus and transition metal.
Of the present invention phosphorous with in transition metal beta-molecular sieve preparation method, in said step (1), said sodium form beta-molecular sieve (Na beta-molecular sieve) is the sodium form beta-molecular sieve (as USP3,308,069, CNZL00107486.5) of conventional crystallization gained.In usually said sodium form beta-molecular sieve, sodium content counts the heavy % of 4-6 with sodium oxide molybdena.Said ammonium exchanges with the process reducing sodium content, preferably according to molecular sieve: ammonium salt: H
2o=1:(0.1-1): the process that the weight ratio of (5-10) exchanges at least 0.5 hour, preferably filters after 0.5-2 hour at room temperature to 100 DEG C, such ammonium exchange process can repeat 1-4 time, to make the Na on molecular sieve
2o content is less than 0.2 heavy %.Said ammonium salt for conventional inorganic ammonium salt, can be selected from ammonium chloride, one of 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) be adopt low temperature to obtain to different temperatures interval treatment step (1) of high temperature molecular sieve, removed template method process.Said process is in the interval of 200 DEG C to 800 DEG C, carry out in the non-overlapping temperature range of at least two from low to high, said low temperature range is 200-400 DEG C, preferred 300-350 DEG C, and said high temperature range is 500-800 DEG C, preferred 500-600 DEG C.Such as, said process is Na after being exchanged by step (1) ammonium
2the molecular sieve that O content is less than 0.2 heavy % first calcination process at least 0.5 hour at 200-400 DEG C, preferably 300-350 DEG C after the drying, preferred 1-12 hour, then in 2 hours at the most, preferably 1 hour, 500-800 DEG C, preferred calcination process at least 0.5 hour under 500-600 DEG C of temperature range is warmed up to, preferred 1-8 hour.In step (2), also before above-mentioned said two temperature range process, first at least can process 1 hour fully to remove moisture at 120-180 DEG C.
Of the present invention phosphorous with in transition metal beta-molecular sieve preparation method, said step (3) is at temperature 25-100 DEG C, the process of the product obtained by dealumination agent solution treatment steps (2).In step (2), the consumption of dealumination agent adds by required degree of dealumination experience, and usual is 1-6 hour 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.
Provided by the invention phosphorous with in transition metal beta-molecular sieve preparation method, carry out modification in step (4) introducing phosphorus-containing compound and the product of metallic compound to step (3).Said phosphorus-containing compound is selected from phosphoric acid, ammonium hydrogen phosphate, one of 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 be selected from Fe, Co, Ni, Cu, Mn, Zn, Sn one or more.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.
Step (4) said modifying process can adopt the mode of dipping or ion-exchange to carry out.Wherein said dipping can adopt again following a, b, c tri-kinds of modes:
A. the phosphorus-containing compound aqueous solution of the molecular sieve after dealuminzation and amount of calculation is pulled an oar in room temperature to 95 DEG C and evenly dry, under 400-800 DEG C of condition after roasting, then mix with the compound water solution containing one of Fe, Co, Ni, Cu, Mn, Zn, Sn of amount of calculation in room temperature to 95 DEG C, dry.
B. the phosphorus-containing compound aqueous solution of the molecular sieve after dealuminzation and amount of calculation is pulled an oar in room temperature to 95 DEG C and evenly dry, oven dry is mixed in room temperature to 95 DEG C again with the compound water solution containing one of Fe, Co, Ni, Cu, Mn, Zn, Sn of amount of calculation, wherein also can by the reversed order of the above-mentioned two kinds of solution of dipping.
C. the molecular sieve after dealuminzation is mixed post-drying with the mixed aqueous solution of the compound of one of Fe, Co, Ni, Cu, Mn, Zn, Sn in room temperature to 95 DEG C with the phosphorus-containing compound of amount of calculation.
When step (4) said modifying process 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 pulled an oar in room temperature to 95 DEG C and evenly dry, under 400-800 DEG C of condition after roasting, again with amount of calculation containing the compound water solution of one of Fe, Co, Ni, Cu, Mn, Zn, Sn by 1:(5-20) solid-to-liquid ratio mix after, filter after stirring 2-3 hour at 80-95 DEG C, can repeated exchanged repeatedly, after exchanging, the washing of gained samples with water repeatedly, is dried.
Provided by the invention phosphorous with in transition metal beta-molecular sieve preparation method, step (5) is the phosphorus and metal-modified beta-molecular sieve product calcination process at least 0.5 hour, the preferably 0.5-8 hour at 400-800 DEG C, preferably 500-600 DEG C that step (4) are obtained.Wherein said calcination process process can adopt dry roasting also can adopt wet roasting, and said wet roasting is preferably carried out under 1-100%, more preferably 100% steam atmosphere.
The preparation method of assistant for calalytic cracking provided by the invention, described by phosphorous and transition metal, the phosphorus aluminium inorganic binder containing the first clay, the mixing of other inorganic binder, making beating, its reinforced order does not have particular/special requirement, such as can by containing the phosphorus aluminium inorganic binder of the first clay, other inorganic binder (when then not omitting relevant addition step containing when other inorganic binder), phosphorous and transition metal with the second clay mixing (when then not omitting relevant addition step containing when the second clay) making beating.
Assistant for calalytic cracking preparation method provided by the invention, also comprises the spray-dired step of the slurries described making beating obtained.Spray-dired method is known for those skilled in the art, and the present invention does not have particular/special requirement.
When containing phosphorus additive in auxiliary agent, its incorporation way of described phosphorus additive is the combination of one of following method or several method, but is not limited to these methods:
1, phosphorus compound is added going in slurries of spray drying forming;
2, be incorporated in auxiliary agent by other inorganic binder, time in such as inorganic oxide binder containing phosphorus Alumina gel, both brought phosphorus in auxiliary agent after roasting, phosphorus Alumina gel 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 the temperature of said drying is room temperature to 400 DEG C, preferably 100 ~ 300 DEG C, the temperature of roasting is 400 ~ 700 DEG C, be preferably 450 ~ 650 DEG C, 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 add in catalyst cracker separately, use after also can mixing with Cracking catalyst.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 distillate, as crude oil, reduced crude, decompression residuum, normal pressure wax oil, decompressed wax oil, straight-run gas oil, propane is light/heavily de-oiling, one or more in wax tailings and coal liquefaction products.Described hydrocarbon ils can contain the beavy metal impurity such as nickel, vanadium and sulphur, nitrogen impurity, and the content as sulphur can up to 3.0 % by weight, and the content of nitrogen can 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 used in catalytic cracking process, and cracking hydrocarbon oil condition is conventional catalytic cracking condition.In general, it is 400 ~ 600 DEG C that this cracking hydrocarbon oil condition comprises reaction temperature, and be preferably 450 ~ 550 DEG C, 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, such as 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; Alumina gel 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
2content 28.9 heavy %, 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
2o0.03 % 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 prepares the present invention's molecular sieve used; Comparative example 1 ~ 2 prepares contrast molecular sieve.
27alMASNMR 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 with x-ray fluorescence method measure (see " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publish),
27alMASNMR adopts BrukerAvanceIII500MHz NMR to test, and formant spectrogram adopts integration method to calculate each peak area after carrying out 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 same) use NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample, 350 DEG C of calcination process 2 hours, is then warming up to 550 DEG C of calcination process, 4 hours removed template methods for 40 minutes; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of the heavy % of solid content 10, adds oxalic acid 20g in stirring, and be warming up to 80 DEG C and stir 1h, filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar solid content is 40 molecular sieve pulps weighing %, 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 DEG C 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.
27alMASNMR peak area ratio lists in table 1.
Embodiment 2
By β zeolite NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample, 150 DEG C of calcination process 2 hours, is then warming up to 350 DEG C of calcination process 2 hours for 30 minutes, then, within 30 minutes, is warming up to 500 DEG C of calcination process, 4 hours removed template methods; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of the heavy % of solid content 10, adds fluosilicic acid 10g in stirring, and be warming up to 60 DEG C and stir 1h, filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar solid content is 40 molecular sieve pulps weighing %, by 11.8gH
3pO
4(concentration 85%) and 6.3gCuCl
2be dissolved in 90g water, dry with filter cake hybrid infusion; Gained sample 550 DEG C 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.
27alMASNMR peak area ratio lists in table 1.
Embodiment 3
By β zeolite NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample, 350 DEG C of calcination process 2 hours, is then warming up to 600 DEG C of calcination process, 4 hours removed template methods for 50 minutes; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of the heavy % of solid content 10, adds ammonium fluosilicate 15g in stirring, and be warming up to 60 DEG C and stir 1h, filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar solid content is 40 molecular sieve pulps weighing %; By 4.2gNH
4h
2pO
4be dissolved in 60g water, dry with filter cake hybrid infusion, through 550 DEG C of calcination process 2 hours; Be the Cu (NO of 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 DEG C, filters, then exchanges several times, until reach aim parameter, then 550 DEG C of calcination process 2 hours, i.e. and 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.
27alMASNMR peak area ratio lists in table 1.
Embodiment 4
By β zeolite NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample, 300 DEG C of calcination process 2 hours, is then warming up to 550 DEG C of calcination process, 4 hours removed template methods for 60 minutes; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of the heavy % of solid content 10, adds ammonium oxalate 25g in stirring, and be warming up to 60 DEG C and stir 1h, filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar solid content is 40 molecular sieve pulps weighing %; 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 550 DEG C 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.
27alMASNMR peak area ratio lists in table 1.
Embodiment 5
By β zeolite NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample, 350 DEG C of calcination process 2 hours, is then warming up to 550 DEG C of calcination process, 4 hours removed template methods for 40 minutes; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of the heavy % of solid content 10, adds fluosilicic acid 10g in stirring, and be warming up to 60 DEG C and stir 1h, filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar solid content is 40 molecular sieve pulps weighing %; 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 at 550 DEG C, 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.
27alMASNMR peak area ratio lists in table 1.
Embodiment 6
By β zeolite NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample, 350 DEG C of calcination process 2 hours, is then warming up to 550 DEG C of calcination process, 4 hours removed template methods for 40 minutes; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of the heavy % of solid content 10, adds fluosilicic acid 10g in stirring, and be warming up to 60 DEG C and stir 1h, filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar solid content is 40 molecular sieve pulps weighing %; 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 550 DEG C 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.
27alMASNMR peak area ratio lists in table 1.
Embodiment 7
By β zeolite NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample, 350 DEG C of calcination process 2 hours, is then warming up to 550 DEG C of calcination process, 4 hours removed template methods for 40 minutes; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of the heavy % of solid content 10, adds fluosilicic acid 10g in stirring, and be warming up to 60 DEG C and stir 1h, filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar solid content is 40 molecular sieve pulps weighing %; 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 550 DEG C 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.
27alMASNMR peak area ratio lists in table 1.
Embodiment 8
By β zeolite NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample, 350 DEG C of calcination process 2 hours, is then warming up to 550 DEG C of calcination process, 4 hours removed template methods for 40 minutes; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of the heavy % of solid content 10, adds oxalic acid 30g in stirring, and be warming up to 60 DEG C and stir 1h, filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar solid content is 40 molecular sieve pulps weighing %; 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 550 DEG C 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.
27alMASNMR peak area ratio lists in table 1.
Embodiment 9
By β zeolite NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample, 350 DEG C of calcination process 2 hours, is then warming up to 550 DEG C of calcination process, 4 hours removed template methods for 40 minutes; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of the heavy % of solid content 10, adds fluosilicic acid 10g in stirring, and be warming up to 60 DEG C and stir 1h, filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar solid content is 40 molecular sieve pulps weighing %; 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 550 DEG C 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.
27alMASNMR peak area ratio lists in table 1.
Comparative example 1
The explanation of this comparative example prepares phosphorous and beta-molecular sieve that is transition metal according to the method for CN1872685A.
By 100g(butt) Na β zeolite (with the Na β zeolite that embodiment 1 is used) uses NH
4cl solution exchanges washing 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 DEG C of calcination process 2 hours, namely 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.
27alMASNMR peak area ratio lists in table 1.
Comparative example 2
By the method process of beta-molecular sieve according to embodiment 4, but do not carry out taking out aluminium process before P Modification, obtain comparative example 2 molecular sieve.Elementary analytical chemistry consists of 0.1Na
2o6.4Al
2o
33.9P
2o
51.4Fe
2o
388.1SiO
2.
27alMASNMR peak area ratio lists in table 1.
Comparative example 3
By β zeolite NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample is at 550 DEG C of calcination process, 4 hours removed template methods; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of the heavy % of solid content 10, adds oxalic acid 20g in stirring, and be warming up to 80 DEG C and stir 1h, filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar solid content is 40 molecular sieve pulps weighing %, 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 DEG C 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.
27alMASNMR peak area ratio lists in table 1.
Comparative example 4
By β zeolite NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample is at 550 DEG C of calcination process, 4 hours removed template methods; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of the heavy % of solid content 10, adds fluosilicic acid 10g in stirring, and be warming up to 60 DEG C and stir 1h, filtered water is washed till filtrate neutrality; Filter cake is added water and pulls an oar solid content is 40 molecular sieve pulps weighing %; 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 DEG C 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.
27alMASNMR peak area ratio lists in table 1.
Table 1
Embodiment 10 ~ 13 prepares the present invention's phosphorus aluminium inorganic binder argillaceous used, and formula and composition are in table 2.
Embodiment 10
This example prepares phosphorus aluminium inorganic binder argillaceous of the present invention.
By 0.74 kilogram of boehmite (containing Al
2o
30.45 kilogram), 0.39 kilogram of tired de-soil (butt 0.30 kilogram) pulls an oar 30 minutes with 1.6 kilograms of decationizing water, in slurries, 2.03 kilograms of SPAs (mass concentration 85%) are added under stirring, phosphoric acid add speed be 0.04Kg phosphoric acid/minute/Kg alumina source, be warming up to 70 DEG C, then react 45 minutes at this temperature, i.e. the inorganic binder of obtained phosphorous aluminium compound.Material proportion is in table 2.
Embodiment 11 ~ 13
Example 8 ~ 10 prepares all phosphorus aluminium inorganic binders containing the first clay of the present invention.Material proportion is in table 2.
Comparative example 5
This comparative example prepares comparative example of the present invention phosphorus aluminium glue used (phosphorus Alumina gel).
Prepared by phosphorus aluminium glue: 0.66 kilogram of boehmite (butt 0.44 kilogram) and 1.75 kilograms of decationizing water are pulled an oar 30 minutes, in slurries, 2.6 kilograms of SPAs (chemical pure is added under stirring, the heavy % of phosphoric acid 85), be warming up to 70 DEG C, then react 45 minutes at this temperature, obtain phosphorus aluminium glue (phosphorus aluminium inorganic binder).Material proportion is in table 2.
Embodiment 14 ~ 22 prepares 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 Alumina gel pull an oar 120 minutes, obtain the slurries of solid content 30 % by weight, add the pH value 3.0 that hydrochloric acid regulates slurries, then continue making beating 45 minutes, then phosphorus aluminium inorganic binder argillaceous prepared by embodiment 11 is added, stir after 30 minutes, by the slurries spraying dry obtained, obtain microballoon, by microballoon roasting 1 hour at 500 DEG C, obtained 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 Alumina gel is pulled an oar 120 minutes, obtain the slurries of solid content 30 % by weight, add hydrochloric acid and regulate the pH value of slurries to be 3.0, continue making beating 45 minutes, then toward the phosphorus aluminium inorganic binder argillaceous wherein adding embodiment 10 preparation.By the slurries that obtain dry gas inlet temperature 500 DEG C, carry out spraying dry under the condition that exhaust temperature is 180 DEG C, obtain the microballoon that average particulate diameter is 65 microns.By microballoon roasting 1 hour at 500 DEG C.
Get thus obtained microsphere product, add ammonium dibasic phosphate aqueous solution, under stirring, be warming up to 60 DEG C, react after 20 minutes at this temperature, by slurries vacuum filtration, drying, then roasting 2 hours at 500 DEG C, obtained 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 is pulled an oar 120 minutes, obtain the slurries of solid content 35 % by weight, add the pH value 3 that hydrochloric acid makes slurries, then pull an oar 45 minutes, phosphorus aluminium inorganic binder argillaceous prepared by embodiment 12 is added in mixed serum, stir 30 minutes, by the slurries spraying dry obtained, obtain microballoon, by microballoon roasting 1 hour at 500 DEG C, 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 Alumina gel is pulled an oar 120 minutes, obtain the slurries of solid content 38 % by weight, add the pH value 3.0 that hydrochloric acid makes slurries, then pull an oar 45 minutes, then phosphorus aluminium inorganic binder argillaceous and the phosphorus al binder that provides of comparative example 3 prepared by embodiment 13 are provided in mixed serum, stir 30 minutes.By the slurries that obtain dry air inlet temperature 500 DEG C, carry out spraying dry under the condition that exhaust temperature is 180 DEG C, obtain the microballoon that average particulate diameter is 65 microns, by microballoon roasting 1 hour at 500 DEG C, 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 and pull an oar 120 minutes, obtain the slurries of solid content 30 % by weight, adding hydrochloric acid regulates the pH value of slurries to be 3, then pull an oar 45 minutes, in slurries, then add phosphorus al binder argillaceous prepared by embodiment 10, stir 30 minutes.By the slurries spraying dry obtained, obtain microballoon.By microballoon roasting 1 hour at 500 DEG C, 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 Alumina gel is pulled an oar 120 minutes, obtain the slurries of solid content 30 % by weight, add hydrochloric acid and regulate the pH value of slurries to be 3, continue making beating 45 minutes, then phosphorus al binder argillaceous prepared by embodiment 11 is added, and after diammonium hydrogen phosphate solid stirs, by the slurries spraying dry obtained, obtain microballoon, by microballoon roasting 1 hour at 400 DEG C, obtained 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 Alumina gel is pulled an oar 120 minutes, obtain the slurries of solid content 30 % by weight, the pH value regulating slurries with hydrochloric acid is 3.0, then continues making beating 45 minutes, add phosphorus al binder argillaceous prepared by embodiment 12, stir 30 minutes, by the slurries spraying dry obtained, obtain microballoon, by microballoon roasting 1 hour at 500 DEG C, obtained 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 Alumina gel is pulled an oar 120 minutes, obtain the slurries of solid content 30 % by weight, add hydrochloric acid and make the pH value of slurries be 3, continue making beating 30 minutes, add phosphorus al binder argillaceous prepared by embodiment 12, pull an oar 30 minutes, the slurries spraying dry then will obtained, obtains again, by microballoon roasting 1 hour at 500 DEG C, obtained 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 to pull an oar 120 minutes, obtain the slurries of solid content 30 % by weight, add hydrochloric acid and make the pH value of slurries be 3, continue making beating 30 minutes, add phosphorus al binder argillaceous prepared by embodiment 13, pull an oar 30 minutes, the slurries spraying dry then will obtained, obtains again, by microballoon roasting 1 hour at 500 DEG C, obtained 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 Alumina gel is pulled an oar 120 minutes, obtain the slurries of solid content 30 % by weight, add the hydrochloric acid that concentration is 36 % by weight under stirring, make the pH value of slurries be 3.0, then pull an oar 45 minutes, by the slurries spraying dry obtained, obtain the microballoon that average particulate diameter is 65 microns, by microballoon roasting 1 hour at 500 DEG C, obtained 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 Alumina gel is pulled an oar 120 minutes, obtain the slurries of solid content 30 % by weight, under stirring, add hydrochloric acid, controlled the pH value 3.0 of slurries by hydrochloric acid content, mixture is continued making beating after 45 minutes, add the phosphorus al binder that comparative example 2 is obtained, then stir 30 minutes, by the slurries that obtain inlet temperature 500 DEG C, carry out spraying dry under the condition that exhaust temperature is 180 DEG C, obtain the microballoon that average particulate diameter is 65 microns.By microballoon roasting 1 hour at 500 DEG C, obtained 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, obtained reference auxiliary agent DB
3– DB
6.Reference auxiliary agent proportioning is in table 4.
Comparative example 11
Prepare auxiliary agent by the method for comparative example 4, be not both and use molecular sieve B
2replace A
4, obtained reference auxiliary agent DB
4.Reference auxiliary agent proportioning is in table 4.
Embodiment 23
The auxiliary agent that Example 14-22 provides carries out intensity index (i.e. abrasion index) and measures, and wherein assay method carries out according to RIPP strength test standard method (measuring with straight tube intensity meter), records its intensity index A.I. respectively, the results are shown in table 5.
Comparative example 12
The auxiliary agent that getting comparative example 6-11 provides carries out intensity index (i.e. abrasion index) and measures, and wherein assay method carries out according to RIPP strength test standard method (measuring with straight tube intensity meter), records its intensity index A.I. respectively, 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, for fixed fluidized-bed reactor, illustrate the cracking reaction effect of cracking additive provided by the invention.
Respectively by 30 grams of ZJ
1-ZJ
8800 DEG C, carry out the burin-in process of 12 hours under 100% steam atmosphere condition.Get the ZJ through burin-in process of different amount
1-ZJ
8mix respectively from the industrial FCC equilibrium catalyst (the industrial trade mark is the FCC equilibrium catalyst of MLC-500, and main character is in table 6) of different amount.Loaded by catalyst mixture 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 give used catalyst mixture weight composition, reaction condition and reaction result.
Comparative example 13 ~ 17
Comparative example below, for fixed fluidized-bed reactor, illustrates the situation using reference auxiliary agent.
By the method in embodiment 19, catalytic cracking is carried out to same feedstock oil, be respectively 100% industrial FCC equilibrium catalyst, DB unlike used catalyst
2~ DB
5with the mixture of industrial FCC equilibrium catalyst.Table 8 gives used catalyst mixture weight composition, reaction condition and reaction result.
As can be seen from table 8 and table 9, compared with the auxiliary agent prepared 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 the propylene in catalytic cracking liquefied gas, isobutylene concentration are higher, ethylene concentration in dry gas is higher, heavy oil conversion performance is higher, coke and dry gas better selective, surprisingly also has higher liquid and receives.
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 olefin concentration, contain in the beta-molecular sieve of the phosphorous and transition metal of the heavy % of butt 10 ~ 75, in the phosphorus aluminium inorganic binder containing the first clay of al composition, phosphorus component and the heavy % of the first clay butt weight sum 3 ~ 30, in other inorganic binder of the heavy % of oxide basis 3 ~ 30 with second clay of the heavy % of butt 0 ~ 60; Wherein, with the described phosphorus aluminium inorganic binder butt weight containing the first clay for benchmark, the described phosphorus aluminium inorganic binder containing the first clay comprises with Al
2o
3count 15 ~ 40 % by weight al compositions, with P
2o
5the phosphorus component of meter 45 ~ 80 % by weight and in the first clay of 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 with metal oxide tenor, it is characterized in that this molecular sieve
27in AlMASNMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, and chemical shift is 0 ± 3ppm and chemical shift is that the resonance signal peak area sum of-12ppm ± 3ppm accounts for the percentage of total peak area for being less than or equal to 10%;
The described phosphorus aluminium inorganic binder preparation method containing the first clay comprises:
(1) alumina source, the first clay and water are pulled an oar be dispersed into the slurries that solid content is 8-45 % by weight; Described alumina source is can by the aluminium hydroxide of sour peptization and/or aluminium oxide, in the first clay of butt with Al
2o
3the weight ratio of the alumina source of meter is 1-40:15-40;
(2) stirring is descended in the slurries obtained toward step (1) and is added SPA according to the part by weight of P/Al=1-6;
(3) slurries that step (2) obtains are reacted 15-90 minute at 50-99 DEG C of temperature.
2. according to auxiliary agent according to claim 1, it is characterized in that, the beta-molecular sieve of described phosphorous and transition metal, with P
2o
5meter phosphorus content accounts for 1 ~ 8 heavy %, accounts for 0.5 ~ 5 heavy % with metal oxide tenor, this molecular sieve
27in AlMASNMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 54ppm ± 3ppm resonance signal peak area is more than or equal to 2, and the percentage that the resonance signal peak area sum of chemical shift to be 0 ± 3ppm and chemical shift be-12ppm ± 3ppm accounts for total peak area is less than or equal to 6%.
3. according to auxiliary agent according to claim 1, it is characterized in that, this auxiliary agent comprises the phosphorus additive containing the phosphorus aluminium inorganic binder of the first clay, the beta-molecular sieve of the described phosphorous and transition metal of 20 ~ 60 heavy %, second clay of 10 ~ 45 heavy %, other inorganic binder of 5 ~ 25 heavy % and 0 ~ 15 heavy % of 8 ~ 25 heavy %.
4. according to auxiliary agent according to 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 second clay to be selected from kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone one or more mixture; Other described inorganic matter binding agent is selected from the mixture of one or more of boehmite, Alumina gel, silicon-aluminum sol, waterglass and phosphorus Alumina gel.
5. described in a claim 1, improve the preparation method of the assistant for calalytic cracking of low-carbon olefin concentration, comprise the beta-molecular sieve of phosphorous and transition metal, the phosphorus aluminium inorganic binder containing the first clay, the mixing of other inorganic binder, add or do not add the second clay, making beating, spraying dry; Wherein, the described phosphorus aluminium inorganic binder containing the first clay, in its butt weight for benchmark, contains with Al
2o
3count 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 1 ~ 6, and pH value is 1 ~ 3.5, and 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 with metal oxide tenor, this molecular sieve
27in AlMASNMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, and the percentage that the resonance signal peak area sum of chemical shift to be 0 ± 3ppm and chemical shift be-12ppm ± 3ppm accounts for total peak area 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 are pulled an oar be dispersed into the slurries that solid content is 8 ~ 45 % by weight; Described alumina source is can by the aluminium hydroxide of sour peptization and/or aluminium oxide, in the first clay of butt with Al
2o
3the weight ratio of the alumina source of meter is 1 ~ 40:15 ~ 40;
(2) stirring is descended in the slurries obtained toward step (1) and is added SPA according to the part by weight of P/Al=1 ~ 6;
(3) slurries that step (2) obtains are reacted 15 ~ 90 minutes at 50 ~ 99 DEG C of temperature.
7. in accordance with the method for claim 6, it is characterized in that, the described phosphorus aluminium inorganic binder containing the first clay, with its butt weight for benchmark, comprises the Al that 15 ~ 35 % by weight are derived from described alumina source
2o
3, 50 ~ 75 % by weight P
2o
5with 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 ρ-aluminium oxide, χ-aluminium oxide, η-aluminium oxide, gama-alumina, κ-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 DEG C.
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 for beta-molecular sieve powder in the temperature range of 200 DEG C to 800 DEG C, through the mutual non-overlapping temperature range process of at least two from low to high with after 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 beta-molecular sieve preparation method that is transition metal comprises:
(1) sodium form beta-molecular sieve is exchanged the Na made on molecular sieve through ammonium
2o content is less than 0.2 heavy %;
(2) molecular sieve step (1) obtained after drying, processes at least 0.5 hour under 200-400 DEG C of temperature range, then under being warmed up to 500-800 DEG C of temperature range in 2 hours at the most, processes at least 0.5 hour removed template method;
(3) at temperature 25-100 DEG C, the product obtained by dealumination agent solution treatment steps (2);
(4) introducing phosphorus-containing compound and metallic compound carry out modification to molecular sieve;
(5) calcination process at least 0.5 hour at 400-800 DEG C.
11. in accordance with the method for claim 10, wherein, said ammonium exchanges is according to molecular sieve: ammonium salt: H
2o=1:(0.1-1): the process that the weight ratio of (5-10) is filtered exchange at least 0.5 hour at room temperature to 100 DEG C after, this process is at least carried out once; Said ammonium salt is selected from ammonium chloride, one of ammonium sulfate or ammonium nitrate or their mixture.
12. in accordance with the method for claim 10, it is characterized in that before step (2), and the product of step (1) is at least processed 1 hour at 120-180 DEG C.
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, said organic salt is ammonium oxalate, and said inorganic salts are selected from 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 phosphoric acid, ammonium hydrogen phosphate, one of ammonium dihydrogen phosphate (ADP) or ammonium phosphate or its mixture; Said metallic compound be selected from the compound of Fe, Co, Ni, Cu, Mn, Zn and Sn one or more.
16. according to the method described in claim 10 or 15, and wherein, said metallic compound is the water soluble salt of 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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| CN107970999B (en) * | 2016-10-21 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of assistant for calalytic cracking and preparation method thereof containing phosphorous Beta molecular sieve |
| CN107970996B (en) * | 2016-10-21 | 2020-03-24 | 中国石油化工股份有限公司 | Phosphorus-containing and metal-loaded IMF structure-containing molecular sieve and preparation method thereof |
| CN107970982B (en) * | 2016-10-21 | 2019-10-25 | 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 |
| CN107971006B (en) * | 2016-10-21 | 2019-10-25 | 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 |
| CN107971001B (en) * | 2016-10-21 | 2019-11-15 | 中国石油化工股份有限公司 | It is a kind of to contain the assistant for calalytic cracking and preparation method thereof for being rich in mesoporous Beta molecular sieve |
| CN107971029B (en) * | 2016-10-21 | 2019-11-15 | 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 |
| CN114471676B (en) * | 2020-10-28 | 2023-03-10 | 中国石油化工股份有限公司 | Cracking auxiliary agent |
| CN115624986A (en) * | 2020-06-24 | 2023-01-20 | 中国石油化工股份有限公司 | Phosphorus and metal-containing core-shell type molecular sieve and synthesis method thereof |
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