CN106927483B - Preparation method of modified Y-type molecular sieve - Google Patents

Preparation method of modified Y-type molecular sieve Download PDF

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CN106927483B
CN106927483B CN201511020519.7A CN201511020519A CN106927483B CN 106927483 B CN106927483 B CN 106927483B CN 201511020519 A CN201511020519 A CN 201511020519A CN 106927483 B CN106927483 B CN 106927483B
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molecular sieve
ammonium
preparation
iii
exchange
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CN106927483A (en
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高雄厚
孙书红
刘从华
张乐
郑云锋
黄校亮
张茵
王宝杰
潘志爽
石晓庆
姜健
王栋
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/24—Type Y
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70

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Abstract

A process for preparing modified Y-type molecular sieve includes such steps as exchanging NaY molecular sieve with ammonium salt, filtering, mixing with the compound containing IIIB element in periodic table, spray drying, hydrothermal calcining, exchanging with ammonium salt, adding precipitant or precipitant and filter aid, filtering and hydrothermal calcining. The IIIB element is not lost basically in the preparation process of the Y-type molecular sieve, exchange slurry is easy to filter, the molecular sieve yield is high, and the Y-type molecular sieve has excellent activity, hydrothermal stability and heavy metal pollution resistance.

Description

A kind of preparation method of Modified Zeolite Y
Technical field
The present invention relates to a kind of preparation methods of Modified Zeolite Y, more particularly to III B element in a kind of preparation process Substantially it does not lose, exchange slurries are easy filtering, molecular sieve high income, while having excellent activity, hydrothermal stability and anti-gold Belong to the preparation method of the Modified Zeolite Y of pollutant performance.
Background technique
Crude oil heaviness, in poor quality degree are increasingly sharpened, highly-efficient processing heavy oil, mix refining residual oil become oil refining enterprise improve plus Work ability, the urgent need for obtaining more high profit.Catalytic cracking is the most important technique of processing of heavy oil, since its heavy oil conversion is imitated Rate height, good product quality, non-hydrogen and the significant advantages such as operating pressure is low make it occupy act foot in refinery's processing heavy oil technique The status of weight is the main source of oil plant profit.According to statistics, whole world catalytic cracking unit shares 420 sets or so at present, Single set catalytic cracking unit is largest up to 10,000,000 tons/year, about 7.37 hundred million tons of total working ability, occupies the head of secondary operation Position.
Due to being easy to produce the macromolecular compound of coke in heavy oil and residual oil containing colloid, asphalitine etc., and contain Heavy metal nickel, vanadium etc. cause nickel content of vanadium on catalytic cracking equilibrium catalyst relatively common in 10000 μ g/g, and are up to The serious pollution of 15000 μ g/g is not also rare, and vanadium seriously destroys the activity in catalyst under catalytic cracking high temperature thermal and hydric environment The structure of component molecular sieve, causes catalyst activity to reduce, and catalytic cracking product distribution is made to be deteriorated.Therefore, it is necessary to develop to have The molecular sieve of excellent activity, hydrothermal stability and preventing from heavy metal pollution, to meet heavy oil, slag oil cracking to catalyst performance It is strict with.
In order to improve the activity and stability of molecular sieve, generally molecular sieve is changed using rare earth or phosphorus in the prior art Property processing, as Chinese patent CN1169717C discloses the method and product that a kind of Y zeolite is modified with rare earth ion, the party Method is raw material with NaY molecular sieve, is first exchanged through ammonium, then carries out hydro-thermal process, then with containing H+、NH4 +And RE3+Solution processing Afterwards, washed, dry, roasting, obtains modified molecular screen product.Chinese patent CN1111136C discloses a kind of phosphorous and rare earth Y type molecular sieve preparation method, be that NaY molecular sieve is first used into ammonium ion and rare earth ion exchanged, roasted, then with phosphatization Close the P of 1~10 weight % in object reaction bonded2O5, then roasted to obtain.Chinese patent CN1209288 C discloses one kind and contains The preparation method of the faujasite of phosphorus and rare earth is first once exchange instead with ammonium compounds and phosphorus compound by faujasite Then Ying Hou introduces earth solution in exchange slurries and further reacts, is filtered, washed, then roasted to obtain.Containing the boiling The catalyst activity stability of stone is good, and yield of gasoline is high, and coke yield is low, heavy oil cracking ability and resistance to heavy metal pollution By force.Chinese patent CN1026225 C discloses a kind of preparation method of rare-earth Y molecular sieve, is by NaY molecular sieve and rare earth ion After carrying out ion exchange in aqueous solution, filtering, filter cake is roasted to obtain in flowing water steam.Chinese patent CN1069553 C discloses a kind of method for preparing rare earth Y type molecular sieve, is that NaY molecular sieve and rare earth ion are carried out ion After exchange, filtering, filter cake is roasted again, and 1~40% of the product after roasting is recycled back into next group rare earth exchanged slurries The operation is continued the above, remaining is used to prepare catalyst as REY zeolite product, is so carried out continuously, and obtains Rare Earth Y Type molecular sieve.Chinese patent CN103058217 A discloses a kind of preparation method of Y molecular sieve containing rare earth, this method NaY Molecular sieve is raw material, is first exchanged through ammonium, then carries out hydro-thermal process, then with containing H+、NH4 +And RE3+It is molten with the mixing of organic solvent After liquid processing, mother liquor separation, filter cake roasting obtain modified molecular screen product.Chinese patent CN1159101 C discloses one kind and contains The preparation method of hyperastable Y-type RE zeolite, the overstable gamma zeolite and a kind of rare earth that sodium oxide content is 3~5 weight % by this method Polymer solution mixing, is made a kind of slurries, by obtained slurries in shear stress at least 10 kilograms per centimeters2Under conditions of be ground to It is 1 minute few, obtain modified molecular screen product.The zeolite of this method preparation has high hydrothermal stability, activity stability, anti-sodium And the ability of preventing from heavy metal pollution.
Existing Y type molecular sieve technology of preparing, solves the deficiency of molecular sieve some aspects, meets molecular sieve catalyst Demand in some aspects, but the prior art, after the rare earth ion exchanged of molecular sieve, general by filtering, filter cake is roasted Processing, molecular sieve can not all be exchanged to up by resulting in rare earth in this way, and a part of rare earth enters filtrate and is lost, rare earth Utilization rate is not high.The prior art just carries out hydrothermal calcine before rare earth exchanged, and molecular sieve structure is caused to destroy more, molecule Sieve activity decline.Rare earth is introduced in the solution after phosphorus exchange, and the sediment of phosphoric acid rare earth easy to form, phosphoric acid rare earth property is steady It is fixed, it is not easy to decompose in molecular sieve catalyst preparation or use process, is also not easy to react with heavy metal vanadium, makes rare earth The purpose that can not play the role of preferably molecular sieves stabilized structure, can not play good preventing from heavy metal pollution.Weight 1~40% of the molecular sieve product after roasting is recycled back into again the behaviour for continuing processing in next group rare earth exchanged slurries The problems such as making, complicated preparation of molecular sieve, energy waste and molecular sieve yield caused to reduce.It is used during system with molecular sieve for preparing is standby Organic solvent can bring new problem of environmental pollution.In addition, the Y molecular sieve containing rare earth has filtering hardly possible, make industrial life The continuity produced during producing is restricted, and reduces the production capacity of rare-earth-containing molecular sieve.Therefore, in order to meet molecular sieve to work Property, hydrothermal stability and resistance to heavy metal pollution requirement, meet molecular sieve preparation process clean with continuity requirement, Despite recent molecular sieve technology of preparing, but there is still a need for preparation process environmental protection, and the III B element utilization rate such as rare earth is high or does not damage It loses, while there is the molecular sieve new preparation technology of excellent activity, hydrothermal stability and preventing from heavy metal pollution.
Summary of the invention
The object of the invention is that avoiding the deficiency of above-mentioned technology, a kind of system with molecular sieve for preparing different from existing method is provided Preparation Method, the resulting Y type molecular sieve preparation process of the method for the present invention, the molecular sieve pulp containing III B element are easy filtering, III B member Element does not lose substantially, and molecular sieve technology of preparing is more environmentally-friendly, while resulting Y type molecular sieve has excellent activity, hydro-thermal steady Qualitative and preventing from heavy metal pollution performance.
In order to achieve the object of the present invention, the present invention provides a kind of preparation method of Modified Zeolite Y, it is characterised in that Preparation step includes: that NaY molecular sieve is first exchanged with ammonium ion, and the compound containing III B element in the periodic table of elements is mixed after filtering, It is not washed directly to carry out spray drying and hydrothermal calcine, it is then exchanged again with ammonium salt, and make to contain in the exchange slurries and can make III B element generates the anion of precipitating, carries out after filtering or without hydrothermal calcine.
Realize that the specific technical solution of the present invention can be with are as follows:
The preparation method of Modified Zeolite Y includes at least:
(1), NaY molecular sieve and ammonium salt are subjected to ion exchange, water and molecular sieve than 2~30, pH=2.8~6.5, It 5~100 DEG C of temperature, swap time 0.3~3.5 hour, filters, with water, containing III B element in the periodic table of elements after Washing of Filter Cake Compound mixing, content of III B element (in terms of oxide) in molecular sieve (in terms of butt) they are 0.5~20 weight %, without Washing is directly spray-dried, and is roasted；Molecular sieve sodium oxide content after roasting is 2~6 weight %；
(2), by the resulting molecular sieve of step (1), ammonium salt and water carry out ion exchange, and make the exchange slurries and or friendship Containing the anion that III B element can be made to generate precipitating in molecular sieve pulp after changing, water and molecular sieve are than 2~30, pH= 2.8~9.0, it 5~100 DEG C of temperature, swap time 0.3~3.5 hour, is carried out after filtering or without roasting.
In molecular sieve, the distribution of III B element is different in the periodic table of elements, and the influence to molecular sieve performance is different, Wherein, III B element on molecular sieve is exchanged in the form of an ion, can be entered in the small cage of molecular sieve during hydrothermal calcine, Molecular sieves stabilized crystal structure provides more acid activity centers.III B element existing in the form of independent phase, can trap Heavy metal vanadium forms stable vanadate, avoids vanadium from destroying the crystal structure of molecular sieve, has the function that preventing from heavy metal pollution.
Required in the present invention in step (2): for make to exchange slurries and or exchange after molecular sieve pulp in containing III can be made B element generate precipitating anion, be added precipitating reagent, as precipitating reagent can choose can provide III B element generate precipitating yin from The ammonium salt of son, specific one of such as ammonium carbonate, ammonium hydrogen carbonate, ammonium oxalate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate Or it is a variety of, it also can choose using other precipitating reagents for meeting above-mentioned requirements, specific such as ammonium hydroxide, oxalic acid, carbon dioxide, urea One of or it is a variety of.
The preparation method of modified molecular screen of the present invention, wherein it is anti-that the additional amount of the precipitating reagent meets precipitating The substance mol ratio answered.The oxalic acid, ammonium oxalate, ammonium carbonate, ammonium hydrogen carbonate, carbon dioxide, phosphoric acid, phosphoric acid hydrogen The additional amount of diammonium, ammonium dihydrogen phosphate, ammonium phosphate, urea etc. makes above-mentioned precipitating reagent depending on the additional amount of III B element compound : the weight ratio of the compound (oxide meter) of III B element is preferably 0.02~5: 1；The ammonium hydroxide additional amount regards molecule screening the pulp Depending on the pH value of liquid, it is maintained at molecular sieve pulp pH value in 6.0~9.0 ranges.Precipitating reagent can be in step (2) molecular sieve ammonium It is added in molecular sieve pulp before salt exchange, can also be added in molecular sieve pulp, be added after the exchange of step (2) molecular sieve ammonium salt It is preferably at least stirred after precipitating reagent 10 minutes, to guarantee that III B element dissociated in molecular sieve pulp precipitates.
The preparation method of modified molecular screen of the present invention by filter cake in rate-determining steps (1) and contains the periodic table of elements In the compound incorporation time of III B element, in mixed proportion and rate-determining steps (2) precipitating reagent additional amount, reach adjusting point The purpose of the distribution of III B element in son sieve, can be according to the reality to molecular sieve activity, stability and preventing from heavy metal pollution Need, adjust in the form of an ion and in the form of independent phase existing for III B element ratio.Filter cake with containing III B in the periodic table of elements The compound of element mixes, and in 5~100 DEG C of temperature stirrings at least more than half an hour, then is spray-dried, hydrothermal calcine, resulting In molecular sieve, III B element mainly exchanges on molecular sieve in the form of an ion, whipping temp it is more high be conducive to III B element with from Sub- form exchanges to molecular sieve up, wherein III B element that molecular sieve gets on is not exchanged on a small quantity, in subsequent hydrothermal calcine In the process, a part enters molecular sieve by migration of solid phases, plays the role of, another portion identical with III B element of ion exchange Divide and exist in the form of independent phase, can be used for trap heavy metals during catalytic cracking reaction.In step (2), the periodic table of elements In III B element there are anticommutings between ammonium salt, partially enter molecular sieve pulp in, be added containing can make III B element generate The anion of precipitating can make this III B element of part precipitating over a molecular sieve, in this way, both having made the sodium oxide content of molecular sieve into one Step reduces, and also avoids the loss of III B element, improves the utilization rate of III B element, the sediment of this III B element of part can rise To the effect of trap heavy metals during catalytic cracking reaction.
The preparation method of modified molecular screen of the present invention, wherein the ammonium salt in step (1) and step (2) is selected from sulfuric acid Ammonium, ammonium hydrogen sulfate, ammonium nitrate, ammonium chloride, ammonium carbonate, ammonium hydrogen carbonate, ammonium oxalate, ammonium citrate, ammonium dihydrogen citrate, citric acid One of hydrogen diammonium is a variety of, and ammonium salt is mainly used for exchanging the sodium on Y type molecular sieve, has the molecular sieve after exchange Surface acidity.
The preparation method of modified molecular screen of the present invention, wherein III B element is selected from scandium, yttrium, lanthanide rare One of element is a variety of.The lanthanide rare is lanthanum rich rare earth, cerium-rich rare earth, pure lanthanum or pure cerium.In step (1) Compound containing III B element be selected from the halide of water-soluble III B element, nitrate, sulfate, rich III B element chemical combination One of object is a variety of, be also possible to one of oxide, hydroxide, carbonate of III B element not soluble in water or It is a variety of, it can also the molten rear selection of acid.
III B element compound can be adjusted according to the actual needs to molecular sieve activity, stability and preventing from heavy metal pollution Ratio.NaY molecular sieve preferably by reducing grain graininess processing, is selected shearing, is sanded, in ball milling before spray drying One or more processing make molecular sieve median D (v, 0.5) less than 5 μm.
The preparation method of modified molecular screen of the present invention, wherein the roasting process, is that will contain the periodic table of elements In the molecular sieve of III B element carry out hydrothermal calcine under 10%~100% water vapour atmosphere, 450~700 DEG C of maturing temperature, roasting It burns the time 0.5~4 hour.In roasting process, there are dealuminzations and silicon migration, so that the Si-O-Al on framework of molecular sieve is by Si-O- Si is replaced, and since Si atom (diameter 0.082nm) is smaller than Al atom (diameter 0.1nm), bond distance shortens (Si-O bond distance 0.161nm, Al-O bond distance 0.174nm), structure cell is shunk, and molecular sieve structure stability improves.It is also adjoint simultaneously in roasting process Ion transfer, wherein in the periodic table of elements Ion transfer of III B element to II position S I and S in molecular sieve sodalite cage, Play the role of molecular sieves stabilized crystal structure and acid activity center is provided, the Na in sodalite cage+Ion then moves to supercage In, molecular sieve is detached from subsequent ion exchange process.Compared with simple high-temperature roasting, under 100% water vapour atmosphere Hydrothermal calcine is carried out, above-mentioned III B element ion and Na are more advantageous to+The migration of ion is more favorable to keep molecular sieve Crystal structure and structure cell are shunk.
Filter aid can be also added in step (2) in the preparation method of modified molecular screen of the present invention, and filter aid is selected from One of cationic polyacrylamide, anionic polyacrylamide, polyethyleneimine, aluminium polychloride are a variety of.It is added Amount is 0.01%~5% relative to molecular sieve butt.It can be before the exchange of step (2) molecular sieve ammonium salt, in exchange or after exchange It is added in molecular sieve pulp, is stirred after filter aid is added, preferably stir 2 minutes or more.Due to III B element ion modification There is filtering hardly possible in Y molecular sieve, be restricted the continuity produced in industrial processes, reduce containing III B element Molecular sieve production capacity, be added filter aid can effectively improve the rate of filtration of molecular sieve, thus ensure that production continuity and The raising of production capacity.
III B element (in terms of the oxide) content of Modified Zeolite Y of the present invention is 0.5~20 weight %, oxygen Change sodium content is 0.3~2 weight %.
Main advantages of the present invention and effect:
The present invention first exchanges NaY molecular sieve with ammonium ion, makes the sodium oxide content of NaY molecular sieve in 2~6 weight % ranges Interior, after filtering, filter cake mixes the compound containing III B element in the periodic table of elements, not washed directly to carry out spray drying and water Then thermal bake-out is exchanged with ammonium salt again, exchange and precipitating reagent or precipitating reagent and filter aid are added in slurries, is carried out after filtering or not Carry out hydrothermal calcine.This preparation of molecular sieve, the molecular sieve pulp containing III B element are easy filtering, and III B element is not damaged substantially It loses, molecular sieve preparation process is more environmentally-friendly, and III B element exists in the form of ion exchange and two kinds of independent phase in molecular sieve, point It does not play and improves molecular sieve activity, the purpose of stability and preventing from heavy metal performance.Molecular sieve of the present invention has excellent work simultaneously Property, hydrothermal stability and preventing from heavy metal pollution performance.
Specific embodiment
Illustrate the present invention with embodiment further below, but the present invention is not limited in these examples.
(1) analysis test method used in embodiment.
1. sodium oxide molybdena, rare earth oxide, yttria levels: being analyzed using X-fluorescence method.
2. the crystallinity of molecular sieve, lattice constant: being analyzed using X-ray diffraction method.
3. the determination of activity of catalyst: being carried out in the CSA-B type catalyst evaluation device of Huayang company production.Catalyst In advance under 800 DEG C, 100% water vapor conditions after aging 4h or 17h, huge port light diesel fuel is used to carry out determination of activity for raw material, 460 DEG C of reaction temperature, reaction time 70s, catalyst loading 5.0g, oil ratio 3.2.
(2) raw materials used specification in embodiment
1.NaY molecular sieve, kaolin (igloss 18.6%), Aluminum sol (salic 21.2 heavy %), rare earth chloride (RE2O3 288.7g/L), ammonium hydroxide (concentration 16%): it is industrial goods, picks up from Catalyst Factory of Lanzhou Petrochemical Company.
2. ammonium chloride, ammonium sulfate, ammonium nitrate, yttrium nitrate, lanthanum nitrate, cationic polyacrylamide, polyethyleneimine, yin from Sub- polyacrylamide, aluminium polychloride, ammonium carbonate: being chemical reagent.
3. hydrochloric acid: concentration 36%, chemical reagent.
Embodiment 1
(1) 1000g NaY molecular sieve (butt) is added in 7L deionized water, under stirring, 350g ammonium chloride is added, It is adjusted with hydrochloric acid and stirs 1h at 3.50,85 DEG C of slurry pH value, be filtered, washed later, gained filter cake and 250mL rare earth chloride, The mixing of 2.2L deionized water, stirs 0.5h, then spray drying carries out hydro-thermal in roaster under 100% water vapour atmosphere Roasting, 600 DEG C of maturing temperature, calcining time 2 hours.
(2) by the resulting molecular sieve of step (1), ammonium chloride and water according to molecular sieve (butt): ammonium salt: water=1:0.3:7 Weight ratio mixing, formed slurries, stir 1 hour under the conditions of 80 DEG C, pH=3.5, addition 1% (relative to molecular sieve butt) Cationic polyacrylamide stirs 5 minutes, adds ammonium carbonate, ammonium carbonate additional amount meets ammonium carbonate: III B element (oxide Meter) weight ratio=0.4, stir 10 minutes, be filtered, washed, filter cake roasts 2 hours under 600 DEG C, 100% water vapour atmosphere.
Obtain molecular sieve Z-1 of the present invention.
Embodiment 2
In addition to the molecular sieve pulp after ammonium salt exchange in 1 step of embodiment (2) is added without filter aid cation polypropylene Except amide, molecular sieve Z-2 of the present invention is made with embodiment 1 in other conditions.
Comparative example 1
According to existing patented technology, the comparison molecular sieve DZ-1 containing rare earth is made by ion-exchange process.
(1) 1000g NaY molecular sieve (butt) is added in 7L deionized water, under stirring, addition 350g ammonium chloride, 250mL rare earth chloride is adjusted with hydrochloric acid and stirs 1h at 3.50,85 DEG C of slurry pH value, is filtered, washed later, gained filter cake is roasting It burns and carries out hydrothermal calcine in furnace under 100% water vapour atmosphere, 600 DEG C of maturing temperature, calcining time 2 hours.
(2) the molecular sieve preparation condition in step (2) is the same as embodiment 1.
Comparison molecular sieve DZ-1 is made.
Comparative example 2
Other than the molecular sieve pulp after ammonium salt exchange in 1 step of embodiment (2) is added without precipitating reagent ammonium carbonate, Comparison molecular sieve DZ-2 is made with embodiment 1 in its condition.
Embodiment 3
(1) 1000g NaY molecular sieve (butt) is added in 10L deionized water, under stirring, 300g sulfuric acid is added Ammonium is adjusted with hydrochloric acid and stirs 1h at 3.45,90 DEG C of slurry pH value, is filtered, washed later, gained filter cake and 153g yttrium nitrate, The mixing of 2.4L deionized water, makes NaY molecular sieve (butt): compound (in terms of yttrium oxide) weight ratio 1:0.045 of yttrium, stirring 0.5h, spray drying, carries out hydrothermal calcine in roaster under 100% water vapour atmosphere, and 650 DEG C of maturing temperature, when roasting Between 1.5 hours.
(2) by the resulting molecular sieve of step (1), ammonium sulfate and water according to molecular sieve (butt): ammonium salt: water=1:0.3:5 Weight ratio mixing, formed slurries, stir 1 hour under the conditions of 90 DEG C, pH=3.5, be added 0.02% (relative to molecular sieve do Base) cationic polyacrylamide and ammonium oxalate, ammonium oxalate additional amount meet ammonium oxalate: the weight ratio of III B element (oxide meter) =1.2, it stirs 10 minutes, is filtered, washed, filter cake roasts 1.5 hours under 650 DEG C, 100% water vapour atmosphere.
Obtain molecular sieve Z-3 of the present invention.
Comparative example 3
According to existing patented technology, the comparison molecular sieve DZ-3 containing yttrium is made by ion-exchange process.
(1) 1000g NaY molecular sieve (butt) is added in 10L deionized water, under stirring, 300g sulfuric acid is added Ammonium, 153g yttrium nitrate make NaY molecular sieve (butt): compound (in terms of yttrium oxide) weight ratio 1:0.045 of yttrium uses hydrochloric acid It adjusts and stirs 1h at 3.45,90 DEG C of slurry pH value, be filtered, washed later, gained filter cake is in roaster in 100% water vapour gas Carry out hydrothermal calcine under atmosphere, 650 DEG C of maturing temperature, calcining time 1.5 hours.
(2) by the resulting molecular sieve of step (1), ammonium sulfate and water according to molecular sieve (butt): ammonium salt: water=1:0.3:5 Weight ratio mixing, formed slurries, stir 1 hour, be filtered, washed under the conditions of 90 DEG C, pH=3.5, filter cake 650 DEG C, It is roasted 1.5 hours under 100% water vapour atmosphere.
Embodiment 4
(1) 1000g NaY molecular sieve (butt) is added in 8L deionized water, under stirring, 350g ammonium chloride is added, It is adjusted with hydrochloric acid and stirs 1h at 4.20,80 DEG C of slurry pH value, be filtered, washed later, gained filter cake is gone with 425g lanthanum nitrate, 3.0L Ionized water mixing, makes NaY molecular sieve (butt): compound (in terms of lanthana) the weight ratio 1:0.16 of lanthanum, stirs at 80 DEG C 1h, spray drying, then carries out hydrothermal calcine in roaster under 60% water vapour atmosphere, and 580 DEG C of maturing temperature, when roasting Between 2.5 hours.
(2) by the resulting molecular sieve of step (1), ammonium nitrate and water according to molecular sieve (butt): ammonium salt: water=1:0.4:5 Weight ratio mixing, formed slurries, stir 2 hours under the conditions of 70 DEG C, pH=3.5, be added 0.8% (relative to molecular sieve do Base) anionic polyacrylamide, with the pH value of ammonium hydroxide adjusting molecular sieve pulp in 6.5~7.0 ranges, stirring 25 minutes, mistake Filter, washing, filter cake is in 200 DEG C of dryings.
Obtain molecular sieve Z-4 of the present invention.
Comparative example 4
According to existing patented technology, the comparison molecular sieve DZ-4 containing lanthanum is made by ion-exchange process.
(1) 1000g NaY molecular sieve (butt) is added in 8L deionized water, under stirring, addition 350g ammonium chloride, 425g lanthanum nitrate makes NaY molecular sieve (butt): compound (in terms of lanthana) weight ratio 1:0.16 of lanthanum is adjusted with hydrochloric acid 1h is stirred at 4.20,80 DEG C of slurry pH value, is filtered, washed later, gained filter cake is in roaster under 60% water vapour atmosphere Progress hydrothermal calcine, 650 DEG C of maturing temperature, calcining time 2.5 hours.
(2) by the resulting molecular sieve of step (1), ammonium nitrate and water according to molecular sieve (butt): ammonium salt: water=1:0.4:5 Weight ratio mixing, formed slurries, stir 2 hours, is filtered, washed under the conditions of 70 DEG C, pH=3.5, filter cake 200 DEG C do It is dry.
Embodiment 5
In addition to the molecular sieve pulp after ammonium salt exchange in 1 step of embodiment (2) is added without filter aid cation polypropylene Amide, but be added except 0.5% (relative to molecular sieve butt) polyethyleneimine, this hair is made with embodiment 1 in other conditions Bright molecular sieve Z-5.
Embodiment 6
In addition to the molecular sieve pulp after ammonium salt exchange in 1 step of embodiment (2) is added without filter aid cation polypropylene Amide, but be added except 0.3% (relative to molecular sieve butt) aluminium polychloride, this hair is made with embodiment 1 in other conditions Bright molecular sieve Z-6.
Molecular sieve Z-1~Z-6 using the Examples 1 to 6 preparation and molecular sieve DZ-1 using the preparation of comparative example 1~4~ DZ-4, physico-chemical property analysis test result are listed in Table 1 below.
The property of 1 Y type molecular sieve of table
Table 1 the result shows that, with using existing patented technology comparative example 1 prepare molecular sieve DZ-1 compared with, using implementation Molecular sieve Z-1 prepared by example 1, sodium oxide content, crystallinity, lattice constant are suitable with comparison molecular sieve DZ-1, but in molecular sieve In preparation process, the basic free of losses of rare earth, and the molecular sieve DZ-1 for using comparative example 1 to prepare, content of rare earth are lower than Z-1 molecular sieve 22.8%, a large amount of rare earth does not exchange to molecular sieve up in exchange process, is lost during the filtration process with filtrate, causes The utilization rate of rare earth is low, if environmental pollution can also be brought by not handling into the rare earth in filtrate.
Compared with the molecular sieve DZ-2 prepared using comparative example 2, the molecular sieve Z-1 prepared using embodiment 1, rare earth is contained Amount is 7.81%, is higher than comparison molecular sieve (content of rare earth 6.90%), illustrates to be conducive to make molecular sieve using rare-earth precipitation agent It exchanges the rare earth deposition dissociated in slurries over a molecular sieve, avoids rare earth from being lost with filtrate, to improve molecular sieve preparation process In rare earth utilization rate.
Compared with the molecular sieve Z-2 prepared using embodiment 2, the molecule of the preparation of the embodiment of the present invention 1,5,6 is respectively adopted Z-1, Z-5, Z-6 are sieved, property is suitable with molecular sieve Z-2, illustrates the performance that molecular sieve will not be significantly affected using filter aid.? It was found that, filter aid, which is added, significantly improves the rate of filtration of molecular sieve, the molecular sieve filtration time reduces by 20% or more, can It is related that cohesion and the sedimentation of sieve particle can be promoted with filter aid.
Compared with the molecular sieve DZ-3 prepared using comparative example 3, molecular sieve Z-3 prepared with embodiment 3, yttrium content are adopted It is 4.90%, is higher than comparison molecular sieve (yttrium content is 2.34%), illustrating to be more advantageous to using the method for the present invention hands over molecular sieve It changes the yttrium load to dissociate in slurries over a molecular sieve, yttrium is avoided to be lost with filtrate, to improve the standby yttrium in the process of system with molecular sieve for preparing Utilization rate.
Compared with the molecular sieve DZ-4 prepared using comparative example 4, the molecular sieve Z-4 prepared using embodiment 4, rare earth is contained Amount is 16.50%, is higher than comparison molecular sieve (content of rare earth 8.64%), illustrates to adopt even if in the case where content of rare earth height Still be more advantageous to the method for the present invention make molecular sieve exchange slurries in dissociate it is rare earth loaded over a molecular sieve, improve molecular sieve The utilization rate of rare earth in preparation process.
In order to investigate the cracking activity and hydrothermal stability of molecular sieve, the molecular sieve Z- of Examples 1 to 6 preparation is respectively adopted 1~Z-6 and using comparative example 1~4 prepare molecular sieve DZ-1~DZ-4, by the aluminium sol adhesive of 6% (in terms of aluminium oxide), 20% molecular sieve (butt meter), 74% kaolin (butt meter) and suitable deionized water are uniformly mixed, homogeneous, drying, Broken sieving, chooses the particle of 20~40 mesh, tests activity of the catalyst after 4h, 17h steam aging, test knot respectively Fruit is listed in table 2.
In order to investigate the resistance to heavy metal pollution of molecular sieve, the particle of above-mentioned 20~40 mesh is used into incipient impregnation Method impregnates 5000 μ g/g V (relative to catalyst granules) respectively, and the particle through pollution of vanadium is in 800 DEG C, 100% water vapour condition Lower processing 4h, the activity after testing pollution of vanadium catalyst 4h steam aging, test result are listed in table 2.
In table 2, the hydrothermal stability and an anti-huge sum of money of molecular sieve are characterized respectively with activity preservation rate R1 and activity preservation rate R2 Belong to pollution capacity.It defines respectively: activity preservation rate R1=17h steam aging activity/4h steam aging activity × 100%； Activity preservation rate R2=pollution of vanadium 4h steam aging activity/4h steam aging activity × 100%
Activity, hydrothermal stability and the preventing from heavy metal performance of 2 Y type molecular sieve of table
Table 2 the result shows that, with using comparative example 1 prepare molecular sieve DZ-1 compared with, with the embodiment of the present invention 1 prepare point Son sieve Z-1 is the catalyst of active component preparation, and 4h, 17h activity have been respectively increased 5 and 5 percentage points, activity preservation rate R1 2 percentage points are improved, illustrates that rare-earth-containing molecular sieve of the present invention has higher activity and hydrothermal stability；Its activity preservation rate R2 Higher than 4 percentage points of catalyst of the molecular sieve DZ-1 containing comparison, illustrate that catalyst of the present invention has better preventing from heavy metal pollution Performance.
It is to live with molecular sieve Z-1 prepared by the embodiment of the present invention 1 compared with the molecular sieve DZ-2 prepared using comparative example 2 Property component preparation catalyst, 4h, 17h activity has been respectively increased 2 and 2 percentage points, and activity preservation rate R1 improves 1 percentage Point, activity preservation rate R2 improve 5 percentage points, illustrate that rare-earth-containing molecular sieve of the present invention has higher activity and hydrothermally stable Property, there is better preventing from heavy metal performance.
Compared with the molecular sieve Z-2 prepared using embodiment 2, respectively with the molecular sieve of the preparation of the embodiment of the present invention 1,5,6 Z-1, Z-5, Z-6 are the catalyst of active component preparation, 4h, 17h activity and activity preservation rate R1, activity preservation rate R2 It is suitable with the catalyst of molecular sieve (Z-2) prepared containing embodiment 2, illustrate that catalyst will not be significantly affected using filter aid Performance.
It is to live with molecular sieve Z-3 prepared by the embodiment of the present invention 3 compared with the molecular sieve DZ-3 prepared using comparative example 3 Property component preparation catalyst, 4h, 17h activity has been respectively increased 7 and 6 percentage points, and activity preservation rate R1 improves 1 percentage Point, activity preservation rate R2 improve 13 percentage points, illustrate that molecular sieve containing yttrium of the invention has higher activity and hydrothermal stability, With better preventing from heavy metal performance.
It is to live with molecular sieve Z-4 prepared by the embodiment of the present invention 4 compared with the molecular sieve DZ-4 prepared using comparative example 4 Property component preparation catalyst, 4h, 17h activity has been respectively increased 4 and 3 percentage points, and activity preservation rate R1 improves 1 percentage Point, activity preservation rate R2 improve 18 percentage points, illustrate that rare-earth-containing molecular sieve of the present invention has higher activity and hydrothermally stable Property, there is better preventing from heavy metal performance.
The present invention makes the preventing from heavy metal performance improvement of molecular sieve using precipitating reagent, this makes to sink in molecular sieve with precipitating reagent is used The III B element content increase formed sediment is related, and the sediment of this independent phase is conducive to trap heavy metals vanadium, and it is old in hydro-thermal to reduce vanadium To the destruction of molecular sieve structure during change.

Claims (14)

1. a kind of preparation method of Modified Zeolite Y, which is characterized in that preparation step includes: that NaY molecular sieve first uses ammonium ion Exchange mixes the compound containing III B element in the periodic table of elements after filtering, not washed directly to carry out spray drying and hydro-thermal roasting It burns, is then exchanged again with ammonium salt, and make to filter laggard in the exchange slurries containing the anion that III B element can be made to generate precipitating It goes or without hydrothermal calcine.
2. preparation method according to claim 1, which is characterized in that the preparation method of Modified Zeolite Y includes at least:
(1), NaY molecular sieve and ammonium salt are subjected to ion exchange, water and molecular sieve are than 2~30, pH=2.8~6.5, temperature 5~100 DEG C, swap time 0.3~3.5 hour, filtering, after Washing of Filter Cake with water, the chemical combination containing III B element in the periodic table of elements Object mixing, in terms of III B element oxide, in the molecular sieve of butt meter content be 0.5~20 weight %, it is not washed directly into Row spray drying, hydrothermal calcine；Molecular sieve sodium oxide content after roasting is 2~6 weight %；
(2), by the resulting molecular sieve of step (1), ammonium salt and water carry out ion exchange, and make the exchange slurries and or exchange after Molecular sieve pulp in containing the anion that III B element can be made to generate precipitating, water and molecular sieve than 2~30, pH=2.8~ 9.0, it 5~100 DEG C of temperature, swap time 0.3~3.5 hour, is carried out after filtering or without roasting.
3. preparation method according to claim 2, which is characterized in that the ammonium salt in step (1) and step (2) is selected from sulfuric acid Ammonium, ammonium hydrogen sulfate, ammonium nitrate, ammonium chloride, ammonium carbonate, ammonium hydrogen carbonate, ammonium oxalate, ammonium citrate, ammonium dihydrogen citrate, citric acid One of hydrogen diammonium is a variety of.
4. preparation method according to claim 1 or 2, which is characterized in that it is dilute that III B element is selected from scandium, yttrium, group of the lanthanides One of earth elements are a variety of.
5. the preparation method according to claim 4, which is characterized in that the lanthanide rare is lanthanum rich rare earth, rich cerium is dilute Native, pure lanthanum or pure cerium.
6. preparation method according to claim 1, which is characterized in that in step (2): for make exchange slurries and or exchange Containing the anion that III B element can be made to generate precipitating in molecular sieve pulp afterwards, precipitating reagent is added；Precipitating reagent is that can provide III B Element generates one of the ammonium salt of anion of precipitating, ammonium hydroxide, oxalic acid, carbon dioxide, urea or a variety of.
7. preparation method according to claim 6, which is characterized in that ammonium salt is ammonium carbonate, ammonium hydrogen carbonate, ammonium oxalate, phosphorus One of sour hydrogen diammonium, ammonium dihydrogen phosphate, ammonium phosphate are a variety of.
8. preparation method according to claim 2, which is characterized in that the compound containing III B element in step (1) is selected from The halide of water-soluble III B element, nitrate, sulfate, rich III B element compound, III B element not soluble in water Oxide, hydroxide, carbonate are one such or a variety of.
9. preparation method according to claim 1 or 2, which is characterized in that the roasting is steamed in 10%~100% water It is carried out under vapour atmosphere, 450~700 DEG C of maturing temperature, calcining time 0.5~4 hour.
10. preparation method according to claim 2, which is characterized in that filter aid is added in step (2), filter aid is selected from One of cationic polyacrylamide, anionic polyacrylamide, polyethyleneimine, aluminium polychloride are a variety of；It is added Amount is 0.01%~5% relative to molecular sieve butt.
11. preparation method according to claim 6, which is characterized in that precipitating reagent in step (2): the III B member of oxide meter The weight ratio of plain compound is 0.02~5: 1.
12. preparation method according to claim 6, which is characterized in that precipitating reagent is ammonium hydroxide, and additional amount regards molecular sieve pulp PH value depending on, be maintained at molecular sieve pulp pH value in 6.0~9.0 ranges.
13. preparation method according to claim 1 or 2, which is characterized in that in terms of III B element oxide, the modification III B element content of Y type molecular sieve is 0.5~20 weight %, and sodium oxide content is 0.3~2 weight %.
14. preparation method according to claim 1 or 2, which is characterized in that NaY molecular sieve is before spray drying by drop Low grain graininess processing, selects one of shearing, sand milling, ball milling or a variety of processing, makes molecular sieve median D (v, 0.5) Less than 5 μm.
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