CN1951567A - A kaolin based compound molecule sieve and preparation method thereof - Google Patents
A kaolin based compound molecule sieve and preparation method thereof Download PDFInfo
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- CN1951567A CN1951567A CNA200510112999XA CN200510112999A CN1951567A CN 1951567 A CN1951567 A CN 1951567A CN A200510112999X A CNA200510112999X A CN A200510112999XA CN 200510112999 A CN200510112999 A CN 200510112999A CN 1951567 A CN1951567 A CN 1951567A
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Abstract
The invention relates to a caoline substrate composite molecule screen and relative preparation. Wherein, the invention is characterized in that: on the inner and outer surface of modified caoline micro ball which meets original position crystallization condition, there are Y molecule screen and ZSM-5 zeolite, while the relative content of Y molecule screen is 10-98%, and the ZSM-5 content is 2-90%. The invention leads Y zeolite and second molecule screen (ZSM-5 zeolite) into the inner and outer surface of micro ball, to improve the catalyst selectivity and improve the propone yield. And the invention expresses high thermal stability.
Description
Technical field
The present invention relates to a kind of kaolin based compound molecule sieve and preparation method thereof, this kaolin based compound molecule sieve can be used in the hydrocarbon conversion reactions such as catalytic cracking, hydrocracking, or is used as the catalyst of other chemical reaction, or uses as adsorbent.
Background technology
Early in the twentieth century Houdry company uses acid-treated clay catalyst to start after the catalytic cracking process, and the revolution first time of catalyst is to use unbodied aluminium oxide and silica.The more aluminium oxide at polyacid center and the use of silica are arranged, make the cracking activity of catalytic cracking process and selectivity surpass clay catalyst, but easily generate gas and coke.Revolution for the second time is applied to catalytic cracking catalyst along with zeolite and arrives.The main active component of at present industrial Cracking catalyst nearly all is the Y zeolite of various modifications.ZSM-5 adds in most of Cracking catalyst owing to it has good shape selectivity, improves the octane number and the liquid yield of gasoline, or increases the gas olefin yield.
Kaolin plays an important role in fluid cracking catalyst because its cheapness, anti-wear performance is good and certain pore passage structure can be provided.Kaolin microsphere is after high-temperature roasting is handled, method by in-situ crystallization, can in the duct (cave) of kaolin microsphere, grow y-type zeolite, through just having obtained in-situ crystallization FCC microspherical catalyst (material) after certain processing, this catalyst shows in FCC technology than the catalyst that uses the synthetic y-type zeolite of commonsense method and has more good effect.Therefore this in-situ crystallization catalyst or the preparation that is referred to as catalyst material cause insider's concern.
It is the method for the kaolin microsphere catalyst that contains faujasite of 50～80um that GB1271450 discloses the preparation particle size range, this method becomes metakaolin (being called for short soil partially) with kaolin microsphere in roasting below 704 ℃, again with the synthetic y-type zeolite of sodium metasilicate reaction, the degree of crystallinity of Y can reach 40%, avoid first synthesis of molecular sieve, added the complex process that clay prepares catalyst again.So-called kaolin in-situ crystallization (preparation y-type zeolite) technology that Here it is.
US3377006 discloses the technology with the synthetic y-type zeolite of special thin native partially powder.U.S. Pat P3367886,3367887,3506594,3647718,3657154,3663165,3932268 propose all to use the kaolin of roasting more than 900 ℃, and the silica alumina ratio of y-type zeolite is higher in the in-situ crystallization product of pointing out to prepare like this, but degree of crystallinity is lower than 30%.
In addition, EP369629 has proposed also adopt to improve that the high soil of fine powder increases mother liquor microballoon pore volume in the spray slurry, improve the method for the zeolite content in the microballoon with this, make crystallization product (being y-type zeolite) degree of crystallinity reach 70%, but the kaolin of ultra-fine powdery costs an arm and a leg, and in atomized microball, contain in a large number and passed through the kaolin of the bad adhesion of roasting, make the wear resistence variation of microballoon.
CN1139374A discloses the method for the improved fluid catalytic cracking zeolite catalyst of in-situ preparing, and this method comprises spray-drying hydrous kaolin, zirlite and is substantially free of the spinelle kaolin mixture of metakaolin; The microballoon that roasting generates make hydrous kaolin be transformed into metakaolin, and the zirlite hydrothermal transformation becomes transitional alumina; By the mixture of spinelle kaolin, transitional alumina and metakaolin microballoon of forming and the alkaline sodium silicate solution reaction that adds crystal seed, obtain containing the catalyst of y-type zeolite.
The kaolin that US4091007 has proposed with roasting is raw material, and kaolin provides the source of the aluminium more than 70% at least, adds a small amount of even whole silicon source, has synthesized the ZSM-5 molecular sieve by template agent 4-propyl bromide, and degree of crystallinity can reach 40%.
US3894931,3894933,3894934 disclosed data show, add the hydrothermally stable that a spot of (1～30%) ZSM-5 can improve catalyst in wide-aperture Y, X zeolite.
US4522705 discloses the clay in-situ crystallization and has generated ZSM-5, adds to and can improve the yield of liquid and the octane number of gasoline in the Y molecular sieve catalyst.
The relevant basic principle prompting of heterogeneous catalysis, the assembly of variety classes zeolite can overcome conventional binding agent to active, diluting effect optionally, improve the activity and the selectivity of zeolite; Eliminate binding agent obstruction and some unnecessary reactions, thereby the structure of control reaction relevant with binding agent and catalyst is beneficial to the conversion of hydro carbons to zeolite cavity.Based on understanding, two or more molecular sieves with difference or the different acidity of same structure are combined (as among crystal grain or sieve particle) to the oil-refining chemical detailed process; Perhaps the zeolite molecular sieve that will have identical topological structure makes up, and the mode by symbiosis or eutectic obtains bimolecular sieve material; Also the molecular sieve with different structure can be made up, obtaining corresponding bimolecular sieve nest is, bring into play the synergy between them, different being reflected in a certain zone (among a sieve particle) carried out, restrain some disadvantageous reaction, optimize the product result, heat transfer that will help reacting and mass transfer like this, this will be mixed more favourable than machinery.As core-shell type molecular sieve, promptly have the outside that a kind of molecular sieve (shell) is enclosed in another kind of molecular sieve (nuclear) and form a kind of new molecular screen material.
U.S. Pat 4,847,224, US 4,946, and 580 disclose to join by the nucleation gel that will contain zeolite A crystal seed and have helped in the synthetic fresh gel of zeolite B, and crystallization under the synthesis condition of zeolite B obtains containing the product of two kinds of zeolites of AB.Zeolite A, B have identical construction unit, and zeolite B is enclosed in the outside of zeolite A, have the effect of chemical bond between the two, and mechanical property also is improved.A comprises christianite and omega zeolite, and B comprises omega zeolite and modenite.They are used for the catalytic cracking result and show that yield of gasoline increases, and coke yield descends.
Tsang etc. have proposed a kind of synthetic method (U.S. Pat 5888921,1999 years) with hud typed structure double elements molecular sieve.The molecular sieve of making kernel is an aluminosilicate molecular sieves, comprises that faujasite, Y, L, A, modenite equal aperture are the zeolite of 5～7 , and the molecular sieve that is used for shell is phosphate aluminium molecular sieve (ALPO4, SAPO, MeAPO and MeAPSO's is a kind of).The mentality of designing of this bimolecular sieve is: shell acidity is weak (as ALPO-5), and kernel acidity is strong (ZSM-5).It uses as additive, and molecule bigger in the product of y-type zeolite is a little less than cracking on the shell ALPO-5, and isomerization is strong.But littler molecular energy enters kernel and the short chain isomerization takes place on strong acidic site.Its synthetic method is for to join the zeolite molecular sieve powder in the slurries of phosphoric acid, aluminium source, slaine and organic amine; stir 1-12h under the room temperature; put in the autoclave of inner liner polytetrafluoroethylene; 130-240 ℃ is reacted 12-18h down in baking oven; (530-570 ℃ of washing then, dry, roasting; N2 protection roasting 5-15h, roasting 1-3h in air then) obtain this bimolecular sieve catalyst.This bimolecular sieve is as the FCC additive, with ZSM-5 mutually specific energy improve the productive rate of C4, C5 alkene and gasoline yield loss little (U.S. Pat 5972205,1999 years)
People such as Joseph have synthesized contains at least a aluminium and phosphorus as the skeleton structure atom, has identical crystal framework structure, but composite molecular screen with different constituents, i.e. different phosphate aluminium molecular sieves of forming (European patent EP 0293937,1988 year) of outgrowth same bone shelf structure on a kind of phosphate aluminium molecular sieve.Because Y zeolite contains sodium ion, when synthesizing SAPO-37, sodium ion can not be arranged, to handle Y zeolite matrix when therefore on Y zeolite, growing SAPO-37, earlier exchange Na+ with ammonium salt, use TMACl (tetramethyl ammonium chloride) exchange then, use TMAOH (TMAH) exchange after the washing again, washing obtains TMAY.TMAY is joined in the gel of SAPO-37 that crystallization obtains composite molecular screen under the crystallization condition of SAPO-37.This composite molecular screen material has superior character, has better gasoline, gas, coke selectivity as Y-82/SAPO-37 than Y-82 (a kind of modified zeolite of Y-type product of Mobil company) or SAPO-37 in catalytic cracking, produces aromatic hydrocarbons still less.
It is the technology (Chinese patent ZL97103801.5,2000 years) of the synthetic ZSM-5 molecular sieve of raw material that people such as Zuo Lihua have invented with the NaY mother liquor.This method is that the mother liquor that removes by filter NaY at first makes the sial precipitation with acid, the spray-dried silicon aluminium microsphere of making of gained precipitation, and again that this silicon aluminium microsphere and NaOH, water and molecular sieve crystal seed is mixed, making mol ratio is SiO
2/ Al
2O
3=20～80, OH
-/ SiO
2=0.05～0.3, H
2O/SiO
2=2～10 reactant mixture obtains ZSM-5 type zeolite with the conventional method hydrothermal crystallizing again.Thereby effectively utilize the NaY mother liquor, reduced the synthetic cost of ZSM-5 molecular sieve, also improved the combined coefficient of single still unit volume.
A kind of preparation method (CN1435374A) of combined molecular sieve has been studied in the previous work of this seminar, the preparation method of a kind of combined molecular sieve that this invention provided is, reaction mixture gel with the synthetic first kind of micro porous molecular sieve of prior art preparation, carry out the phase I crystallization under certain condition, behind the crystallization certain hour, the template agent (perhaps crystal seed) that adds synthetic another kind of micro porous molecular sieve, and the suitable scope of acid-base value to of adjustment reactant mixture, carry out the hydrothermal crystallizing of second stage then at a certain temperature, behind the crystallization certain hour, obtain the combined molecular sieve of this micropore.Combinations thereof type molecular sieve or to be referred to as one of composite molecular screen typical case's representative be exactly ZSM-5/Y double elements composite molecular screen, it is by the synthetic NaY zeolite of first step elder generation crystallization, behind the crystallization certain hour, by adding template agent or the crystal seed of synthetic ZSM-5, again by adjusting the acid-base value of reactant mixture, afterwards, carry out the second step crystallization under suitable temperature, crystallization finishes after washing, drying obtain the ZSM-5/Y double elements composite molecular screen of Na type.Studies show that (catalysis journal, 2004, the 25th the 9th phase of volume, the 715th page to the 720th page) this material after proper method exchange and modification are handled, be used as the active component of catalytic cracking catalyst, during the heavy oil of catalytic cracking Xinjiang, compare with corresponding mechanical mixture molecular sieve catalyst, phosphorus modification composite molecular sieve catalyst has higher diesel oil selectivity, and its diesel yield has increased by 4.11 percentage points, and diesel and gasoline ratio has increased by 0.11.With the grand celebration wax oil is that the catalytic cracking experiment of raw material shows (chemistry of fuel journal, 2004, the 32nd the 6th phase of volume, the 745th page to the 749th page), use the catalytic cracking catalyst of ZSM-5/Y double elements composite molecular screen, shown than the catalyst that with ZSM-5 and Y mechanical impurity is active component and have the characteristics of high productivity of low carbon olefin hydrocarbon (ethene, propylene and butylene) as active component.Low-carbon alkene is compared with petrol and diesel oil has higher added value, is that petroleum refiner is desired.But foregoing invention application and disclosed document do not relate on kaolin, particularly kaolin microsphere (in) introduce the technology of (growth) two kinds of molecular sieve ZSM-5 and Y.
In sum, composite molecular screen and kaolin in-situ crystallization Y zeolite (or ZSM-5 zeolite) all are the catalysis materials with significant application value, obviously, by composite molecular screen technology and kaolin in-situ crystallization technology in conjunction with and the new catalytic material and the technology that produce will promote latest development such as catalytic cracking catalyst.Particularly Y and the two kinds of zeolites of ZSM-5 of existing outstanding representation in industrial catalyst all are incorporated on the kaolin, will produce new technology undoubtedly with practical value.But from disclosed document and Patent data, find not adopt the method for fractional crystallization, utilize kaolin (particularly at microballoon) in-situ crystallization synthetic faujasites and then will contain the technology that the further crystallization of the kaolinic mixed liquor of zeolite obtains containing the kaolin composite molecular screen of second kind of zeolite.
The kaolin microsphere catalyst that contains Y molecular sieve that generates by the in-situ crystallization method is also named catalytic cracking full clay catalyst, owing to present full clay catalyst is the kaolin microsphere after treated (as spray shaping, high-temperature roasting) to be carried out above-mentioned in-situ crystallization processing obtain.Therefore can not be with other molecular sieve component such as method adding ZSM-5 that are similar to the preparation such physics fusion of semi-synthetic or full synthesis catalytic Cracking catalyst (or being referred to as mechanical mixture) (about the notion of full white-clay type catalytic cracking catalyst, semi-synthetic catalytic cracking catalyst and full synthesis catalytic Cracking catalyst, can referring to: Chen Junwu, Cao Hanchang chief editor, " catalytic cracking process and engineering ", Sinopec publishing house, nineteen ninety-five version, the 3rd chapter, 204 pages and 230 pages; ).So technology provided by the present invention acquires a special sense for introduce second kind of molecular sieve (as ZSM-5) in full carclazyte catalytic cracking catalyst, can increase the productive rate of propylene, improves the octane number of gasoline.This technology is not seen open report as yet.
Summary of the invention
The purpose of this invention is to provide a kind of kaolin based compound molecule sieve and preparation method thereof, improve the shape selective catalysis performance of catalyst, improve product and distribute, make this kaolin based compound molecule sieve show high thermal stability simultaneously.
A kind of kaolin based compound molecule sieve that the present invention proposes is on the surfaces externally and internally of the modified kaolin microballoon that satisfies the in-situ crystallization condition, be distributed with Y molecular sieve and ZSM-5 zeolite, in relative crystallinity, wherein the relative amount of Y molecular sieve in two kinds of molecular sieves is 10～98%, and the relative amount of ZSM-5 zeolite in two kinds of molecular sieves is 2～90%.
More particularly, be on the modified kaolin microballoon that 600～1100 ℃ of following roastings obtained in 0.5～40 hour, to be distributed with Y molecular sieve and ZSM-5 zeolite simultaneously.The particle diameter of modified kaolin microballoon is generally at 20～140 microns.
A kind of kaolin based compound molecule sieve that the present invention proposes is to be matrix with the modified kaolin microballoon, adopt the method for in-situ crystallization, surfaces externally and internally synthetic (distribution) at modified kaolin has two kinds of different molecular sieves, and wherein a kind of is Y molecular sieve, and another kind is a ZSM-5 type zeolite.In relative crystallinity, the preferred relative amount of Y molecular sieve in two kinds of molecular sieves is 50～95%, and the relative amount of ZSM-5 zeolite in two kinds of molecular sieves is 5～50%.
The present invention also provides a kind of method of synthetic above-mentioned kaolin based compound molecule sieve, it promptly is the method for growing mixed molecular sieve on kaolin, adopt fractional crystallization, from the modified kaolin microballoon, under the condition of aluminium source, the existence of silicon source,, will contain the kaolin based compound molecule sieve that the further crystallization of the kaolinic mixed liquor of molecular sieve obtains containing second kind of molecular sieve then by in-situ crystallization, the synthetic a kind of molecular sieve of hydro-thermal.
The method of special recommendation of the present invention is to adopt the method for fractional crystallization, promptly utilizes kaolin in-situ crystallization to synthesize Y molecular sieve, and then will contain the kaolinic mixed liquor of Y molecular sieve obtains containing the ZSM-5 zeolite through further crystallization composite molecular screen.Concrete method can be that the kaolin microsphere with modification is a raw material, with the synthetic Y molecular sieve of directing agent method in-situ crystallization, be about to its reaction mixture gel and under 80～110 ℃, carry out the phase I crystallization, crystallization 8～68 hours, preferably 10～48 hours, then, add synthetic another kind of micro porous molecular sieve---the template agent or/and the crystal seed of ZSM-5 zeolite, and the acid-base value of adjustment reactant mixture is to pH=9.0～12.0, pH=9.5～11.5 preferably, carry out the hydrothermal crystallizing of second stage then under 120～240 ℃, crystallization time is 2～96 hours.Better condition is 140～200 ℃ of following crystallization 10～60 hours, and preferably 150～190 ℃ of following crystallization are 10～60 hours, obtain this composite molecular screen.
Certainly, above the template agent and the crystal seed of said second kind of molecular sieve, can also before the phase I crystallization or in the crystallization process, add, can obtain kaolin based compound molecule sieve of the present invention equally.
Need to prove among the present invention, the first crystallization stage can be adopted the method for the synthetic Y molecular sieve of kaolin in-situ crystallization, the preparation reaction mixture gel, under the condition of synthetic this molecular sieve, carry out crystallization then, product is without steps such as filter washings afterwards, but in same synthesis reactor, directly add the reagent of needs such as the template agent of synthetic second kind of molecular sieve or crystal seed, adjust to suitable acid-base value (also can adjust earlier acid-base value adds crystal seed again or/and the template agent), carry out the crystallization of second stage again.Form and/or, control two kinds of ratios that component is shared in the resulting composite molecular screen by the silicoaluminate of adjusting initial (the first crystallization stage) reaction mixture gel by adjusting reaction depth.Also can form and/or pass through and adjust reaction depth, control two kinds of ratios that component is shared in the resulting composite molecular screen by the silicoaluminate of adjusting the second crystallization elementary reaction mixture gel.
Said modified kaolin microballoon is meant the used modified kaolin microballoon of kaolin in-situ crystallization molecular sieve in the prior art among the present invention, be that common kaolin will pass through modification, make it have certain activity, the certain activity sial can be discharged, thereby in-situ crystallization conditions needed in the prior art can be satisfied.For example spray shaping, high-temperature roasting was 600～1100 ℃ of following roastings 0.5～40 hour.Preferably becoming modified kaolin (A) in 0.5～20 hour by 650～750 ℃ of roastings provides the aluminium source, and 900～1100 ℃ of following roastings became modified kaolin (B) in 0.5～20 hour provides the silicon source, then A and B is mixed use.Also can be preferred 750～1050 ℃ of following roastings 0.5～20 hour, only use a kind of kaolin through this temperature calcination process.Also can use technology in common knowledge in the disclosed technology, GB1271450 for example, US3377006, USP3367886,3367887,3506594,3647718,3657154,3663165,3932268, EP369629, CN1139374A, US4091007, the disclosed kaolin modification processing method of patent documentations such as US4522705.The particle diameter of kaolin microsphere adopt in-situ crystallization the particle diameter of general kaolin microsphere get final product.
Aluminium source among the present invention can also replenish as the aluminium source with the aluminum contained compound that adds again except that modified kaolin, as aluminum sulfate, and sodium aluminate, one or more in aluminium hydroxide, the boehmite etc.
Silicon source among the present invention also can replenish as the silicon source with the siliceous compound that adds again except that modified kaolin, as in sodium metasilicate, Ludox, silica gel, the white carbon etc. one or more.
Template agent among the present invention is: ethanol, isopropyl alcohol, NH
3Derivative, as primary amine (ethamine, n-propylamine, n-butylamine etc.), secondary amine (dipropylamine, dibutylamine etc.), quaternary ammonium salt (tetraethylammonium bromide, 4-propyl bromide, TBAB etc.) and other ammonium salt and composition thereof or their hydroxide.
Said crystal seed refers to ZSM-5 molecular sieve powder (its silica alumina ratio is 15～500 etc., perhaps pure silicon ZSM-5) among the present invention.Certainly except that synthesizing Y molecular sieve as the crystal seed in-situ crystallization with also passing through to add the Y molecular sieve powder the synthetic Y molecular sieve of directing agent method in-situ crystallization.
The resulting kaolin based compound molecule sieve of the present invention because contain composite molecular screen, as Y and ZSM-5 zeolite etc., by with after the conventional method modification, can be used for the hydro carbons catalytic conversion process, as catalytic cracking, hydrocracking etc.
Kaolin based compound molecule sieve provided by the present invention contains Y and two kinds of zeolites of ZSM-5.Compare with prior art, for example with the earlier synthetic NaY molecular sieve of use conventional method, adjust behind the reactant mixture pH more further the complex type molecular sieve of the synthetic ZSM-5 of hydrothermal crystallizing then and compare (Chinese invention patent ZL02100452.8, publication number: CN 1435374A), present technique has tangible difference and advance with it.One, the composite molecular screen material of gained of the present invention is actually the composite molecular screen material of one three constituent element, for example contains kaolin or kaolin microsphere (it can provide needed macropore of heavy oil molecules cracking and faintly acid), y-type zeolite and ZSM-5 zeolite (being abbreviated as Kaoline/Y/Z) in the material.And just double elements composite molecular screen material that top said technology (Chinese patent ZL02100452.8) obtains promptly only contains two kinds of micro porous molecular sieve components (as y-type zeolite molecular sieve and ZSM-5 zeolite molecular sieve, not containing the kaolin component) in the material; They are two years old, a key character of present technique is, the first step is by in-situ crystallization technology growth NaY zeolite on kaolin or kaolin microsphere, and the material that this in-situ crystallization technology obtains (kaolin/Y composite, or be referred to as kaolin/Y composite molecular screen, or be referred to as full carclazyte catalytic cracking catalyst, be abbreviated as Kaoline/Y), the existing proof as many pieces of patents in this specification front described (and this specification is NM) a host of facts is different from independent y-type zeolite, kaolin microsphere in-situ crystallization Y zeolite technology has obtained the wide industrial application in catalytic cracking industrial catalyst (being the usually said full clay catalyst of people), obtained good effect.And second step of the described three constituent element composite molecular screen materials of present technique is just on the basis of synthetic kaolin/Y composite, by adjusting relevant technologies parameter (as reactant mixture pH value, synthesis reaction temperature), proceed the second step hydrothermal crystallizing, zeolite such as regrowth ZSM-5 obtains three constituent element composite molecular screen material products (as Kaoline/Y/Z) at last on the basis of Kaoline/Y.The Kaoline/Y that kaolin in-situ crystallization generates be proved to be and generally Y zeolite compare and have special performance, so, the present invention is regrowth ZSM-5 zeolite on the basis of Kaoline/Y, can increase the type of the selecting catalytic action of the catalytic process of using this material undoubtedly, thereby improve selectivity relevant product.From Comparative Examples 2 listed experimental datas (table 1 and table 2) as can be seen, this material is compared with prior art, has advantage.
The present invention introduces y-type zeolite, ZSM-5 zeolite by the method for in-situ crystallization at modified kaolin microballoon surfaces externally and internally, has improved the shape selective catalysis performance of catalyst, has improved the product distribution.Simultaneously, kaolin based compound molecule sieve shows high thermal stability.
Description of drawings
Fig. 1 is the XRD spectra of the kaolin based compound molecule sieve of the embodiment of the invention 1 preparation;
Fig. 2 is the XRD spectra of the kaolin based compound molecule sieve of preparation in the embodiment of the invention 2;
Fig. 3 is the XRD spectra of the kaolin based compound molecule sieve of preparation in the embodiment of the invention 3;
Fig. 4 is the XRD spectra of the kaolin based compound molecule sieve of preparation in the embodiment of the invention 4, can find out all that from these X-ray diffraction spectrograms gained kaolin based compound molecule sieve material has the characteristic peak of NaY zeolite facies and the characteristic diffraction peak of ZSM-5 zeolite facies simultaneously;
Fig. 5 is the DTA differential thermal spectrogram of the embodiment of the invention 1 prepared kaolin based compound molecule sieve sample (Kaoline/Y/Z) and the kaolin Y molecular sieve sample (Kaoline/Y) that synthesized;
Fig. 6 is the photo of kaolin based compound molecule sieve when microscopically amplifies 100 times of preparation in the embodiment of the invention 1;
Fig. 7 is the photo of kaolin based compound molecule sieve when microscopically amplifies 400 times of preparation in the embodiment of the invention 1;
Stereoscan photograph when Fig. 8 amplifies 3000 times for the kaolin based compound molecule sieve of preparation in the embodiment of the invention 1 (demonstration be the pattern of a kaolin microsphere);
Stereoscan photograph when Fig. 9 amplifies 20000 times for the kaolin based compound molecule sieve of preparation in the embodiment of the invention 1 (demonstration be the pattern of kaolin microsphere) through two step crystallization rear surfaces;
Figure 10 is the stereoscan photograph when amplifying 5000 times with reference to the 1 prepared double elements composite molecular screen ZSM--5/Y (being Comparative Examples 2) of embodiment among the CN 1435374A;
Figure 11 is the stereoscan photograph when amplifying 25000 times with reference to the 1 prepared double elements composite molecular screen ZSM--5/Y of embodiment among the CN 1435374A;
Figure 12 is the stereoscan photograph (amplifying 1000 times) of the employed kaolin microsphere raw material of the embodiment of the invention;
Figure 13 is the stereoscan photograph after the microballoon that embodiment 1 prepared Kaoline/Y/ZSM-5 picks out the part particle integrity is pulverized;
After the microballoon that Figure 14 picks out the part particle integrity for embodiment 1 prepared Kaoline/Y/ZSM-5 is pulverized, to the sem photograph of the microcell element energy spectrum analysis at the inner different crystal form of resulting crushed particles position.
The specific embodiment
The invention will be further described below by embodiment.
1. the specifications of raw materials of using among the embodiment is:
(1), kaolin: industrial goods, the production of Suzhou kaolin company, spray shaping, 20～120 microns of particle diameters;
(2), waterglass: industrial goods;
(3), 18 water aluminum sulfate: industrial goods, or chemically pure reagent;
(4), tetraethylammonium bromide: industrial goods, or AR;
(5), 4-propyl bromide: industrial goods, or AR;
(6), phosphoric acid: industrial goods, or AR.
2. the physicochemical property of gained sample characterizes and evaluation method:
(1) thing of gained sample reaches relative crystallinity employing X-ray diffraction method (XRD) mutually and measure pipe pressure 40mV, tube current 35mA, CuK α radiation, sweep limits 2 θ=5～40 ° on SHIMADI-6000 type X-ray diffractometer.
The relative crystallinity of sample=(the characteristic peak peak area of the characteristic peak peak area/standard specimen of sample) * standard specimen degree of crystallinity
The zeolite of mentioning in the embodiment of the invention or specification or claims or the content of molecular sieve are all data represented with relative crystallinity.
(2) heat endurance of gained sample is measured with Universal V2.5H thermogravimetric analyzer, under air atmosphere, with 10 ℃/min temperature programming to 1200 ℃.Reflected the variation of molecular sieve heat in the temperature-rise period that is heated by differential thermal analysis, when molecular sieve structure caves in, become amorphously from crystalline phase that differential thermal is expressed as an exothermic peak.
(3) shape characteristic of gained sample is measured with light microscope and electron microscope (SEM).ESEM has spendable power spectrum, so that selected microcell is carried out elementary analysis.
(4) the catalytic cracking reaction evaluation experimental of gained sample is finished on the little anti-experimental provision of fixed bed.
Further the present invention will be described with embodiment and Comparative Examples below.
Embodiment 1
U.S. Pat 3,639,009, US3 are adopted in the preparation of directed agents, the method preparation for preparing the NaY directed agents that is proposed in 671,191.Concrete proportioning is as follows: 15SiO
2: Al
2O
3: 16Na
2O: 320H
2O (mol ratio).
15.60 gram waterglass are diluted with deionized water 21.70 grams, (w% refers to percentage by weight under agitation to add 50w% then successively, as follows) 18 water aluminum sulfate aqueous solution 1.31 grams, directed agents 8.0 grams of above-mentioned preparation, and 850 ℃ of roastings kaolin microsphere 3.33 grams after handling in 5 hours, stir the reactor of putting into 100 milliliters of inner liner polytetrafluoroethylenes after 10 minutes in 100 ℃ of crystallization 24 hours; After the cooling, add tetraethylammonium bromide 0.65 gram and TBAB 1.02 grams, stirred 10 minutes, transferring mixed serum pH value with the phosphoric acid solution of 30w% then is 10.15, stirs after 10 minutes and continues crystallization 24 hours in 165 ℃.After reaction finishes, product after filtration, washing, drying, XRD (as shown in Figure 1) test shows gained material has NaY characteristic peak and ZSM-5 characteristic peak simultaneously, illustrates and contains two kinds of zeolites in the gained material; Contain a large amount of kaolin microspheres in microphotograph (as Fig. 6, Fig. 7) the demonstration gained material, promptly kaolin microsphere is kept in two step crystallization process.Wherein NaY content (in relative crystallinity, down together) is 30%, and ZSM-5 content (in relative crystallinity, down together) is 9%.This kaolin based compound molecule sieve is referred to as Kaoline/Y/Z.
Embodiment 2
15.60 gram waterglass are diluted with deionized water 22.27 grams, under agitation add directed agents 8.0 grams among the embodiment 1 then successively, kaolin 3.73g after 850 ℃ of roastings were handled in 6 hours, the sulfuric acid 0.64g of 25.44w% stirs the reactor of putting into 100 milliliters of inner liner polytetrafluoroethylenes after 10 minutes in 100 ℃ of crystallization 24 hours; After the cooling, add tetraethylammonium bromide 0.65 gram and TBAB 1.02 grams, stirred 10 minutes, transferring mixed serum pH value with phosphoric acid solution then is 10.10, stirs after 10 minutes and continues crystallization 24 hours in 165 ℃.After reaction finished, product after filtration, washing, drying obtain the said material of the present invention.The XRD of this material (as shown in Figure 2) the analysis showed that to have ZSM-5 characteristic peak and NaY characteristic peak simultaneously, shows it is a kind of composite molecular screen material.
12.40 gram waterglass are diluted with deionized water 26.22 grams, under agitation add kaolin microsphere (B) 3.22 grams, 50w% 18 water aluminum sulfate aqueous solution 2.61 grams of 980 ℃ of following roastings after 3 hours then successively, directed agents 8.0 grams of above-mentioned preparation, 660 ℃ of roastings kaolin microsphere (A) 2.94 grams after 4 hours stir the reactor of putting into 100 milliliters of inner liner polytetrafluoroethylenes after 10 minutes in 100 ℃ of crystallization 24 hours; After the cooling, add tetraethylammonium bromide 0.65 gram and TBAB 1.02 grams, stirred 10 minutes, transferring mixed serum pH value with phosphoric acid solution then is 10.18, stirs after 10 minutes in 140 ℃ of continuation crystallization 15 hours, again 170 ℃ of continuation crystallization 8 hours.After reaction finishes, product after filtration, washing, drying, XRD (as shown in Figure 3) shows that the gained material has NaY characteristic peak and ZSM-5 characteristic peak simultaneously.Light microscope and sem observation the analysis showed that kaolin microsphere is kept in crystallization process.Show it is a kind of composite molecular screen material.Wherein NaY content is 43%, and ZSM-5 content is 17%.
15.60 gram waterglass are diluted with deionized water 23.39 grams, under agitation add 50w% 18 water aluminum sulfate aqueous solution 3.92 grams then successively, press directed agents 8.0 grams of embodiment 1 described preparation, kaolin 2.55 grams after 860 ℃ of roastings were handled in 4 hours stir the reactor of putting into 100 milliliters of inner liner polytetrafluoroethylenes after 10 minutes in 100 ℃ of crystallization 24 hours; After the cooling, add tetraethylammonium bromide 0.65 gram and TBAB 1.02 grams, stirred 10 minutes, transfer mixed serum pH value to 10.68 with phosphoric acid solution then, stir after 10 minutes and continued crystallization 24 hours in 165 ℃.After reaction finishes, product after filtration, washing, drying, XRD (as shown in Figure 4) test shows gained material has NaY characteristic peak and ZSM-5 characteristic peak simultaneously.Light microscope and sem observation the analysis showed that kaolin microsphere is kept in crystallization process.Show it is a kind of composite molecular screen material.Wherein NaY content is 20%, and ZSM-5 content is 25%.
9.44 gram waterglass are diluted with deionized water 26.37 grams, under agitation add successively then as said directed agents 8.0 grams among the embodiment one, kaolin (A) 3.73 grams, NaOH 1.02 grams of 700 ℃ of roastings after 3 hours, 1050 ℃ of following roastings kaolin (B) 9.70 grams after 2 hours stir the reactor of putting into 100 milliliters of inner liner polytetrafluoroethylenes after 10 minutes in 100 ℃ of crystallization 24 hours; Afterwards, add tetraethylammonium bromide 0.65g and TBAB 1.02 grams, stirred 10 minutes, transferring mixed serum pH value with phosphoric acid solution then is 10.20, stirs after 10 minutes and continues crystallization 24 hours in 160 ℃.After reaction finished, product after filtration, washing, drying obtain the said material of the present invention.The XRD analysis of this material shows to have ZSM-5 characteristic peak and NaY characteristic peak simultaneously.Show it is a kind of composite molecular screen material.Wherein NaY content is 40%, and ZSM-5 content is 15%.
Embodiment 6
8.95 gram waterglass are diluted with deionized water 25.37 grams, under agitation add successively then as said directed agents 7.6 grams among the embodiment 1, kaolin (A) 3.73 grams, NaOH 1.02 grams of 650 ℃ of roastings after 4 hours, 1100 ℃ of following roastings kaolin (B) 9.70 grams after 2 hours stir the reactor of putting into 100 milliliters of inner liner polytetrafluoroethylenes after 10 minutes in 100 ℃ of crystallization 24 hours; Afterwards, add silica alumina ratio (SiO
2/ Al
2O
3) be 50 ZSM-5 zeolite powder, 1.9 grams, stirred 10 minutes, transferring mixed serum pH value with sulfuric acid solution then is 10.30, stirs after 10 minutes in 165 ℃ of continuation crystallization 24 hours.After reaction finished, product after filtration, washing, drying obtain the said material of the present invention.The XRD analysis of this material shows to have ZSM-5 characteristic peak and NaY characteristic peak simultaneously.Show it is a kind of composite molecular screen material.Wherein NaY content is 35%, and ZSM-5 content is 8%.
Embodiment 7
13.0 gram waterglass and 2.5 gram Ludox are diluted with deionized water 24.0 grams, under agitation add 50w% 18 water aluminum sulfate aqueous solution 3.92 grams then successively, press directed agents 8.0 grams of embodiment 1 described preparation, kaolin 2.55 grams after 860 ℃ of roastings were handled in 4 hours stir the reactor of putting into 100 milliliters of inner liner polytetrafluoroethylenes after 10 minutes in 100 ℃ of crystallization 24 hours; After the cooling, add 4-propyl bromide 1.8 grams, stirred 10 minutes, transfer mixed serum pH value to 10.29 with phosphoric acid solution then, stir after 10 minutes and continued crystallization 24 hours in 165 ℃.After reaction finishes, product after filtration, washing, drying, XRD test shows gained material has NaY characteristic peak and ZSM-5 characteristic peak simultaneously.Light microscope and sem observation the analysis showed that kaolin microsphere is kept in crystallization process.Show it is a kind of composite molecular screen material.Wherein NaY content is 30%, and ZSM-5 content is 22%.
Comparative Examples 1
Finish and the kaolin microsphere in-situ crystallization Y zeolite (being referred to as Kaoline/Y) of preparation with first step crystallization according to embodiment 1, wherein NaY content is 40%.
Comparative Examples 2
With reference to the prepared double elements composite molecular screen material (being referred to as ZSM-5/Y) of embodiment among the open CN 1435374A of Chinese invention patent 1, wherein NaY content is 77.2%, and ZSM-5 content is 22.8%.
Preparation of catalysts
Respectively with embodiment 1 gained Kaoline/Y/Z, Comparative Examples 1 gained Kaoline/Y and Comparative Examples 2 gained ZSM-5/Y, hand over two roasting technologies (with molecular sieve (butt): La (NO by identical two
3)
36H
2O: NH
4NO
3: H
2O=5: 2.1: 1.5: 55 mass ratio and La (NO
3)
36H
2O, NH
4NO
3, H
2O is mixed, then at 80 ℃ of washing and filterings behind the exchange 2h down, 120 ℃ of oven dry 4h, be warming up to 540 ℃ with the speed of 4 ℃/min after roasting 2h; Then with the material (butt) after the exchange for the first time: La (NO
3)
36H
2O: NH
4NO
3: H
2O=5: 0.63: 1.31: 53 mass ratio mixes molecular sieve, La (NO
3)
36H
2O, NH
4NO
3, H
2O, exchange 1h down at 80 ℃, washing and filtering, dry 4h down for 120 ℃, after being warming up to 540 ℃ with the speed of 4 ℃/min roasting 2h handle make the rare earth hydrogen type catalyst (wherein ex situ REH-ZSM-5/Y Preparation of catalysts be with kaolin, molecular sieve REH-ZSM-5/Y, aluminium sol adhesive mix, dry, pulverize, and make in molecular sieve content and the REH-Kaoline/Y/Z catalyst molecular sieve content suitable, promptly the content of molecular sieve ZSM-5/Y is 40% in the catalyst.)。
Evaluating catalyst:
Respectively with above-mentioned three kinds of catalyst that obtain behind 800 ℃ of 100% steam treatment 4h, be charging with grand celebration heavy oil, the catalytic cracking experimental evaluation of carrying out with heavy oil microreactor the results are shown in table 1 and table 2.
The analysis of three kinds of catalyst crackates of table 1 relatively
| Project | Application Example 1 is used Comparative Examples 1 and is used the catalyst that the catalyst of the catalyst acquisition of Comparative Examples 2 acquisitions obtains |
| Product distribution/% | REH-Kaoline/Y/ZREH-Kaoline/Y REH-ZSM-5/Y Annotate |
| Loss+dry gas liquefied gas gasoline, diesel heavy oil coke | 2.84 2.77 2.81 22.75 16.49 22.25 47.47 48.73 46.8 11.86 14.38 11.58 8.58 8.93 8.88 6.5 8.7 7.68 |
| Total liquid is received (liquefied gas+gasoline+diesel oil), % | 82.08 79.6 80.63 |
| Conversion ratio, % | 79.56 76.69 79.54 |
| Liquefied gas/conversion ratio | 28.59％ 21.50％ 27.97％ |
| Coke/conversion ratio | 8.17％ 11.34％ 9.66％ |
Annotate: this Preparation of catalysts is that kaolin, REH-ZSM-5/Y (prepared double elements composite molecular screen makes after modification with reference to CN 1435374A), aluminium sol adhesive are mixed, dry again, pulverizing, behind 800 ℃ of 100% steam treatment 4h, form again, and make in molecular sieve content and the REH-Kaoline/Y/Z catalyst molecular sieve content suitable.
Table 1 data declaration, the REH-Kaoline/Y/Z catalyst towards heavy oil that application the present invention obtains has good cracking conversion capability, compare with the catalyst that contains REH-Kaoline/Y, conversion ratio (dry gas yied+liquefied gas yield+gasoline yield+coke yield) has improved 2.87%, and total liquid is received (liquefied gas+gasoline+diesel oil) has increased by 2.48 percentage points.And under the prerequisite that conversion ratio obviously increases, also has good coke selectivity, coke yield 2.2 units that descended, the coke yield of unit conversion rate has descended 3.17%, simultaneously, the octane number of the REH-Kaoline/Y/Z catalyst gained gasoline of use the present invention acquisition is compared with the octane number of the REH-Kaoline/Y catalyst gained gasoline that uses Comparative Examples 1 to obtain and has been improved 1.1 units; Compare with using the ZSM-5/Y composite molecular sieve catalyst that Comparative Examples 2 obtains, total liquid is received and has been increased by 1.45 units, and coke selectivity obviously improves, and coke yield has reduced by 1.18 percentage points, and the coke yield of unit conversion rate has descended 1.5%.
Table 2 uses the comparison of cracked gas composition analysis in the different catalysts products therefrom
| Catalyst | The catalyst that Application Example 1 obtains | Use the catalyst that Comparative Examples 1 obtains | Intensity of variation |
| REH-Kaoline/Y/Z | REH-Kaoline/Y | ||
| Gaseous species | The quality percentage composition (%) of gas comprises feed oil | ||
| The anti-butylene n-butene of methane ethane and ethylene propane propylene iso-butane normal butane isobutene maleic isopentane pentane | 1.05 0.98 1.43 3.36 7.55 6.62 1.73 0.96 0.90 0.94 0.68 3.55 0.31 | 0.30 0.28 0.77 4.89 4.00 8.85 1.99 0.47 0.40 0.49 0.39 3.96 0.37 | 0.75 0.70 0.66 -1.53 3.55 -2.23 -0.26 0.49 0.50 0.45 0.29 -0.41 -0.06 |
Cracked gas that table 2 is classified as is formed, and data are used technology gained Kaoline/Y/Z catalyst of the present invention as can be seen from table, and (Kaoline/Y) compares with Comparative Examples, and productivity of propylene has increased by 3.55 percentage points.The raw catelyst that uses the technology of the present invention and obtain is described, because the introducing of the 3rd component ZSM-5, can propylene enhancing.Propylene is very useful industrial chemicals, and its value is higher than gasoline, and this is that the refinery increases benefit and optimize the product distribution needed.
The above results is extraordinary because what increase is the liquid hydrocarbon of high added value, minimizing be unnecessary coke.The digital proof of table 1 and table 2, the Kaoline/Y/Z material of three constituent elements have obvious superior serviceability and the lower carbon number hydrocarbons selectivity than the ZSM-5/Y of the Kaoline/Y of two constituent elements and two constituent elements.The data of table 1 and table 2 illustrate that also the introducing of ZSM-5 shape selective catalysis component strengthens the shape selective catalysis usefulness of new material (catalyst Kaoline/Y/Z).
Molecular sieve differential thermal analysis contrast
Differential thermal analysis shows, according to conventional method (Comparative Examples 1 gained sample, or according to U.S. Pat 337700 and the synthetic sample of the disclosed method of US3639009.The lattice of the Y zeolite temperature of caving in is 930 ℃ among the prepared in-situ crystallization kaolin Y material Kaoline/Y of Comparative Examples 1, according to the lattice of Y among the embodiment of the invention 1 resulting kaolin based compound molecule sieve Kaoline/Y/ZSM-5 temperature of caving in is 954 ℃, as shown in Figure 5.Illustrate that Y zeolite has heat endurance preferably than Y zeolite among the Comparative Examples 1 gained Kaoline/Y in the gained material of the present invention.
The contrast of molecular sieve electronic microscope photos
Kaoline/Y/Z and Comparative Examples 2 prepared ZSM-5/Y with embodiment 1 gained are sample, characterize with same ESEM.Electromicroscopic photograph (as Fig. 8, Fig. 9) shows that three constituent element composite Kaoline/Y/Z of the present invention are microspheroidal.With ESEM with power spectrum the microcell results of elemental analyses that difform particle on the microballoon carries out is shown, the oarse-grained sial element of microsphere surface atomic ratio is much larger than short grained sial element atomic ratio among Fig. 9, again in conjunction with XRD analysis, illustrate that the microsphere surface bulky grain is a ZSM-5 crystal grain, and granule is the Y zeolite grain.As can be seen from Figure 8, Y and ZSM-5 zeolite growth are in the kaolin microsphere surface; For confirming also to grow in microsphere particle inside Y and ZSM-5 zeolite, we pick out the microballoon of part particle integrity, pulverize the back and take electromicroscopic photograph, and done sample microcell elementary analysis (as Figure 13,14) with the incidental power spectrum of Electronic Speculum in mortar.Photo shows, also exists two kinds of granule-morphologies of two kinds of particles and microsphere surface sizes of difformity and size consistent in microballoon inside; Power spectrum microcell elementary analysis data show that oarse-grained silica alumina ratio will be higher than granule.In conjunction with the experimental data of XRD material phase analysis, can prove that Y and ZSM-5 zeolite are distributed in the spheroid surfaces externally and internally again.And the electromicroscopic photograph (as Figure 10, Figure 11) of the prepared composite ZSM-5/Y of Comparative Examples 2 shows that it is the reunion shape, obviously has different patterns with products obtained therefrom of the present invention.Do not possess feature of the present invention, promptly do not have kaolin or kaolin microsphere.
Simultaneously, it is pointed out that and utilize Comparative Examples 2 prepared double elements molecular sieves can not use separately as industrial operable catalytic cracking catalyst, must be after ion-exchange treatment, could use in conjunction with after, the moulding with relevant matrix and binding agent.And proposed by the invention be three constituent element compounds of the technology preparation of kaolin raw material with the kaolin microsphere, after ion-exchange treatment, just can directly be used as industrial operable catalytic cracking catalyst.In addition, from Fig. 8,9 and Figure 12 more as can be seen, gained kaolin based compound molecule sieve product is obviously different with the pattern of employed kaolin microsphere raw material after the crystallization.
Claims (16)
1. kaolin based compound molecule sieve, it is characterized in that on the surfaces externally and internally of the modified kaolin microballoon that satisfies the in-situ crystallization condition, be distributed with Y molecular sieve and ZSM-5 zeolite, in relative crystallinity, wherein the relative amount of Y molecular sieve in two kinds of molecular sieves is 10～98%, and the relative amount of ZSM-5 zeolite in two kinds of molecular sieves is 2～90%.
2. kaolin based compound molecule sieve according to claim 1 is characterized in that being distributed with simultaneously Y molecular sieve and ZSM-5 zeolite on the modified kaolin microballoon that 600～1100 ℃ of following roastings obtained in 0.5～40 hour.
3. kaolin based compound molecule sieve according to claim 2 is characterized in that what the modified kaolin microballoon obtained 750～1050 ℃ of following roastings in 0.5～20 hour.
4. kaolin based compound molecule sieve according to claim 1, the particle diameter that it is characterized in that the modified kaolin microballoon is at 20～140 microns.
5. kaolin based compound molecule sieve according to claim 1 is characterized in that in relative crystallinity, and the relative amount of Y molecular sieve in two kinds of molecular sieves is 50～95% in the kaolin based compound molecule sieve.
6. kaolin based compound molecule sieve according to claim 1 is characterized in that in relative crystallinity, and the relative amount of ZSM-5 zeolite in two kinds of molecular sieves is 5～50% in the kaolin based compound molecule sieve.
7. the preparation method of the described kaolin based compound molecule sieve of claim 1, it is characterized in that adopting fractional crystallization, from the modified kaolin microballoon, under the condition of aluminium source, the existence of silicon source, by in-situ crystallization, the synthetic a kind of molecular sieve of hydro-thermal, will contain the kaolin based compound molecule sieve that the further crystallization of the kaolinic mixed liquor of molecular sieve obtains containing second kind of molecular sieve then.
8. the preparation method of kaolin based compound molecule sieve according to claim 7 is characterized in that aluminium source, silicon source are modified kaolin.
9. the preparation method of kaolin based compound molecule sieve according to claim 7, it is characterized in that becoming modified kaolin (A) in 0.5～20 hour by 650～750 ℃ of roastings provides the aluminium source, 900～1100 ℃ of following roastings became modified kaolin (B) in 0.5～20 hour provides the silicon source, and A and B mix use.
10. the preparation method of kaolin based compound molecule sieve according to claim 7 is characterized in that the aluminium source except that kaolin, also by aluminum sulfate, and sodium aluminate, one or more provide in aluminium hydroxide, the boehmite.
11. the preparation method of kaolin based compound molecule sieve according to claim 7, the silicon source that it is characterized in that molecular sieve is except that kaolin, also by one or more provide in sodium metasilicate, Ludox, silica gel, the white carbon.
12. the preparation method of kaolin based compound molecule sieve according to claim 7, it is characterized in that adopting the method for fractional crystallization, promptly utilize kaolin in-situ crystallization to synthesize Y molecular sieve, and then will contain the kaolinic mixed liquor of Y molecular sieve obtains containing the ZSM-5 zeolite through further crystallization composite molecular screen.
13. the preparation method of kaolin based compound molecule sieve according to claim 12, it is characterized in that with the modified kaolin microballoon be raw material, with the synthetic Y molecular sieve of directing agent method in-situ crystallization, its reaction mixture gel is carried out the phase I crystallization under 80～110 ℃, crystallization 8～68 hours, the template agent or/and the crystal seed that add synthetic ZSM-5 zeolite, and the acid-base value of adjustment reactant mixture is to pH=9.0～12.0, under 120～240 ℃, carry out the hydrothermal crystallizing of second stage then, crystallization 2～96 hours obtains this kaolin based compound molecule sieve.
14. the preparation method of composite molecular screen according to claim 13 is characterized in that the phase I crystallization, crystallization time is 10～48 hours.
15. the preparation method of kaolin based compound molecule sieve according to claim 13 is characterized in that the second crystallization stage crystallization temperature is 140～200 ℃.
16. the preparation method of kaolin based compound molecule sieve according to claim 13 is characterized in that the second crystallization stage acidity-basicity ph is adjusted to 9.5～11.5.
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| CN115044351A (en) * | 2022-06-29 | 2022-09-13 | 哈尔滨工业大学 | Molecular sieve/diatomite-based low-heat-conductivity composite shape-stabilized phase change material and preparation method thereof |
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