CN101745413B - Catalytic cracking catalyst and preparation method thereof - Google Patents
Catalytic cracking catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN101745413B CN101745413B CN2008102400376A CN200810240037A CN101745413B CN 101745413 B CN101745413 B CN 101745413B CN 2008102400376 A CN2008102400376 A CN 2008102400376A CN 200810240037 A CN200810240037 A CN 200810240037A CN 101745413 B CN101745413 B CN 101745413B
- Authority
- CN
- China
- Prior art keywords
- clay
- zeolite
- catalytic cracking
- preparation
- cracking catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a catalytic cracking catalyst and a preparation method thereof. Based on 100 percent mass of the catalyst, the catalyst comprises 1 to 50 percent of modified clay, 0 to 40 percent of unmodified clay, 10 to 60 percent of zeolite, 5 to 30 percent of binder, 0.1 to 35 percent of alumina, 0.1 to 8 percent of phosphorus compound based on simple-substance phosphorus, and 0.1 to 6percent of rare earth compounds based on RE2O3, wherein the modified clay is clay roasted for 0.3 to 10 hours at 800 to 1,100 DEG C; based on 100 percent mass of the modified clay, the modified clay contains 0.1 to 3.0 percent of P, 0.1 to 4.0 percent of RE2O3, 0.1 to 1.5 percent of Na2O; and the modified clay has the pore volume of 0.1 to 0.5 mL/g, the specific surface are of 50 to 400 m<2>/g and the average particle size of 0.5 to 15 mu m. The catalytic cracking catalyst can increase propylene yield and the propylene concentration in liquefied gas and effectively reduce the yield of heavy oil.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalyst and preparation method thereof, more specifically, is a kind of heavy oil transformation Catalysts and its preparation method that is applicable to the producing more propylene of catalytic cracking process.
Background technology
Along with the petrochemical industry industrial expansion, catalytic cracking process is not only the important means that light-end products are provided, and also provides the important production technology of basic chemical raw materials such as low-carbon alkene, especially propylene simultaneously.The process program of petrochemical process production propylene has multiple, such as metathesis reaction technology, butylene disproportionation reaction (CN1618512, CN1618515), dehydrogenating propane technology (as CN1073893), preparing propylene from methanol technology and the catalytic cracking process etc. of traditional light-end products steam splitting process, ethene and butylene.Analysis-by-synthesis is produced propylene by catalytic cracking process and is had distinguishing features such as small investment, adaptability to raw material is wide, cost is low and more and more receive publicity.In catalytic cracking reaction technology, reach producing more propylene and have that the device change is little by changing catalyst performance, the technical advantage of economically feasible, instant effect.To this, developed dissimilar molecular sieve modified and catalyst preparation technology both at home and abroad, and obtained certain application.
The research of external oil refining catalyst and manufacturer are devoted for years to the research that improves the FCC catalyst performance in employing shape-selective molecular sieve ZSM-5, to improve the productivity of propylene of FCC apparatus.The FCC catalyst A pex catalyst series that more typical product has Grace Davison company to develop to have the propylene enhancing function, productivity of propylene can reach more than 15%, propylene enhancing auxiliary agent Olefins Max, addition 3～4% o'clock, propylene increases by 0.9 percentage point; The catalyst A FX of the propylene enhancing of Albemarle company exploitation, K series of products can amplitude peak improve productivity of propylene; The Select Z propylene enhancing auxiliary agent of BASF AG's exploitation can not dilute the active productivity of propylene that increases of major catalyst, and the propylene enhancing Penta series auxiliary agent that other also has the exploitation of Intercat company also has certain propylene enhancing effect.
USP5318696 has proposed a kind of hydrocarbon conversion process process of the catalyst of forming based on large pore molecular sieve and low silica-alumina ratio ZSM molecular sieve, can produce high-knock rating gasoline, and producing more propylene.
USP5997728 discloses a large amount of methods of selecting the shape auxiliary agent of using in the heavy charge catalytic cracking process.Auxiliary agent is made up of the ZSM-5 molecular sieve that adds 12～40% in the [amorphous.Auxiliary dosage at least 10% can significantly improve low-carbon alkene, especially the productive rate of propylene.
USP5110776 discloses the preparation method with the phosphorous modified ZSM-5 molecular sieve catalyst.Said phosphorus modifying process is that molecular sieve is dispersed in the phosphorus-containing compound aqueous solution of pH value 2～6, mixes spray drying forming then with matrix.The catalyst of preparation does not increase dry gas and coke yield when improving octane number.
USP5171921 discloses a kind of ZSM-5 molecular sieve of phosphorus modification.The silica alumina ratio 20～60 of this molecular sieve adopts the phosphorus compound dipping after 500～700 ℃ of steam treatment are used for C
3～C
20The hydrocarbon conversion forms C
2～C
5During alkene, improved reactivity.
C has been proposed among the EP0109059A1
4～C
12Alkene is converted into the technology of propylene.The catalyst that uses contains silica alumina ratio less than 300 ZSM-5 molecular sieve, 400～600 ℃ of reaction temperatures, and air speed was greater than 50 hours
-1Because the ZSM-5 that adopts does not pass through modification, the selectivity of propylene is lower.
USP5236880 discloses the catalyst that comprises MFI or MEL structure molecular screen, adopt metal-modified based on the VIII family of Ni, heat and hydrothermal treatment consists under the control temperature of harshness, modified metal is able at surface enrichment.The catalyst that has added modified molecular screen is used for can increasing C when alkane transforms
5～C
12Octane number and C
3～C
4Olefins yield.
Domestic research institution is is also researching and developing aspect the catalytic cracking process producing more propylene.The propylene enhancing auxiliary agent MP031 of Beijing Shi Keyuan of China Petrochemical Industry exploitation, application shows that the productive rate of liquefied gas has improved 0.4 percentage point, productivity of propylene improves 0.6 percentage point; The LP1 auxiliary agent of Luoyang Petrochemical engineering company of China Petrochemical Industry exploitation can make the productivity of propylene of catalytic cracking improve 1～2.5 percentage point accounting for catalyst inventory 5～8% o'clock; Lanzhou Petrochemical Company research institute has also successfully developed propylene enhancing FCC catalyst LCC-1 and auxiliary agent LCC-A, has shown the propylene enhancing function certain.
CN1034223 discloses a kind of catalyst for cracking that is used to produce low-carbon alkene, is by 0～70% clay, and 5～99% inorganic oxide and 1～50% zeolite are formed.Zeolite wherein is the mixture of five-membered ring silica-rich zeolite of the phosphorous and rare earth of 1～25% heavy REY or Y-type high-Si zeolite and 75～100%.Can effectively improve C
2=～C
4=productive rate.
CN1147420A discloses a kind of phosphorous and rare earth and has had the molecular sieve of MFI structure, and this molecular sieve has excellent hydrothermal activity stability and good selectivity of light olefin when being used for the hydro carbons pyrolytic conversion.
CN1057408A discloses a kind of catalyst for cracking of silica-rich zeolite, and said silica-rich zeolite contains ZSM-5, β zeolite or the modenite of 0.01～3.0 heavy % phosphorus, 0.01～1.0 heavy % iron or 0.01～10 heavy aluminium, has shown higher catalytic pyrolysis activity.
CN1465527A discloses a kind of MFI structure molecular screen of phosphorous and transition metal, and said transition metal is a kind of among Fe, Co, the Ni.This molecular sieve is applied to the catalytic cracking process of hydro carbons, can increase substantially C
2～C
4The productive rate of alkene and selectivity.
CN1796496 discloses a kind of cracking additive that improves density of propylene, this auxiliary agent by butt by the inorganic oxide binder of the clay of the modified zsm-5 zeolite of 10～65 heavy %, 0～60 heavy %, 15～60 heavy %, 0.5～15 heavy % be selected from the VIIIB family metal one or more metallic addition and the phosphorus additives of 2～25 heavy % form, wherein, said modified zsm-5 zeolite is through phosphorus and be selected from the metal-modified of one of Fe, Co or Ni, its anhydrous chemical expression is counted (0～0.3) Na with oxide
2O (0.5～5) Al
2O
3(1.3～10) P
2O
5(0.7～15) M
xO
y(70～97) SiO
2, x represents the atomicity of M, and y represents to satisfy the required number of M oxidation state, and said metallic addition and phosphorus additive all are in oxide.This cracking additive is applied in the catalytic cracking process of petroleum hydrocarbon, when increasing the catalytic cracking liquefied gas yield and improving the catalytically cracked gasoline octane number, can improve the density of propylene in the liquefied gas significantly.
CN1854254A discloses a kind of preparation method who produces the Cracking catalyst of premium-type gasoline and producing more propylene.Comprise that phosphorous clay slurry, phosphorus containing molecular sieve slurries, rare earth compound and binding agent with preparation mix, spray drying forming, said molecular sieve are y-type zeolite and the modified molecular screen with MFI structure.The catalyst of preparation can be produced the low high isoparaffin gasoline of alkene, producing more propylene, iso-butane simultaneously.
CN1872415 discloses a kind of assistant for calalytic cracking preparation method of the ZSM-5 of containing zeolite, it is characterized in that the ZSM-5 zeolite is crystallization growth on 840-1100 ℃ of roasting kaolin, through ion-exchange, washing, drying and/or calcination process, be prepared into the fluid catalytic cracking auxiliary agent then, to improve the reactivity worth of auxiliary agent, has the function of propylene enhancing.
As can be seen, various molecular sieve auxiliary agent of the prior art and catalyst are used for catalytic cracking process, all can reach the purpose of producing more propylene to a certain extent, but can not realize the efficient conversion of heavy oil in propylene enhancing, this is the remarkable shortcoming of prior art.As everyone knows, the efficient conversion that realizes heavy charge is the essential requirement of catalytic cracking process, along with general heaviness of feedstock oil in the world wide and poor qualityization are on the rise, Cracking catalyst that the exploitation performance is more superior and preparation method thereof, realize the efficient conversion of producing more propylene and heavy oil simultaneously, thereby the overall economic efficiency that improves oil refining enterprise seems very urgent.
Summary of the invention
On the basis of existing technology, the catalytic cracking catalyst and preparation method thereof that the purpose of this invention is to provide a kind of producing more propylene.Catalytic cracking catalyst disclosed by the invention can improve density of propylene in productivity of propylene and the liquefied gas, and effectively reduces the heavy oil productive rate, increases the purpose product yield of cracking reaction.
The invention discloses a kind of catalytic cracking catalyst, is benchmark with catalyst quality 100%, comprises modified clay 1～50%, preferred 5～40%; Unmodified clay 0～40%, preferred 5～35%; Zeolite molecular sieve 10～60%, preferred 15～50%; Binding agent 5～30%, preferred 5～20%; Add aluminium oxide 0.1～35%, preferred 0.5～30%; Phosphorus compound (in elemental phosphorous) 0.1～8%, preferred 0.5～5%; Rare earth compound is (with RE
2O
3Meter) 0.1～6%, preferred 0.1～4%; Wherein modified clay is through 800～1100 ℃, and the clay after the roasting in 0.3～10 hour in modified clay quality 100%, contains P 0.1～3.0%, RE
2O
30.1～4.0%, Na
2O 0.1～1.5%, modified clay pore volume 0.1～0.5mL/g, specific surface 50～400m
2/ g, average grain diameter 0.5～15 μ m.
Unmodified clay of the present invention is the untreated clay of relative modified clay.
Catalytic cracking catalyst of the present invention, zeolite molecular sieve are one or more in y-type zeolite, ZSM zeolite, β zeolite, MCM zeolite, L zeolite, aluminum phosphate zeolite, the omega zeolite.
Catalytic cracking catalyst of the present invention, the preferred Y zeolite of zeolite molecular sieve or Y zeolite and other zeolite mixtures, other zeolites wherein are one or more in ZSM zeolite, β zeolite, the MCM zeolite.
Catalytic cracking catalyst of the present invention, one or more among the preferred REY of Y zeolite, REHY, P-REY, USY, the REUSY.
Catalytic cracking catalyst of the present invention, the preferred ZSM-5 of ZSM zeolite.
Catalytic cracking catalyst of the present invention, the preferred MCM-22 of MCM zeolite.
Catalytic cracking catalyst of the present invention, clay are selected from one or more in kaolin, halloysite, imvite, sepiolite, diatomite, bentonite, the crosslinked lamellar clay.
Catalytic cracking catalyst of the present invention, binding agent are one or more in aluminium colloidal sol, Ludox, sial complex sol, silica-alumina gel, aluminum phosphate colloidal sol, the phosphaljel.
Catalytic cracking catalyst of the present invention, adding aluminium oxide is boehmite, α-Al
2O
3, η-Al
2O
3, γ-Al
2O
3In one or more.
Modified clay in the catalytic cracking catalyst of the present invention, in modified clay quality 100%, its P content preferred 0.5～2.0%.
Modified clay in the catalytic cracking catalyst of the present invention, in modified clay quality 100%, its RE
2O
3Content preferred 0.5～3.0%.
Modified clay in the catalytic cracking catalyst of the present invention, preferred 1～10 μ m of its average grain diameter.
Catalytic cracking catalyst of the present invention, must contain modified clay, modified clay has certain central hole structure and reactivity, has adopted the composite modified treatment technology of phosphorus and rare earth, as the carrier of catalytic cracking catalyst, increased cracking activity to heavy oil molecules.
The present invention also provides the preparation method of catalytic cracking catalyst, and concrete steps are as follows:
(1) preparation of modified clay
Clay was 800～1100 ℃ of roastings 0.3～10 hour; Clay after the roasting and deionized water are mixed, add concentration and be 0.5～15 mole of hydroxide ion/liter inorganic alkali solution, at 50～100 ℃, reacted 0.1～5 hour, obtain clay slurry, wherein, deionized water and clay (butt) weight ratio is 1.5～10, inorganic alkali solution and clay (butt) weight ratio is 0.5～8, inorganic base be in NaOH, waterglass, ammoniacal liquor, the sodium metaaluminate one or more; Clay slurry is filtered, wash with inorganic acid solution, introduce phosphorus and rare earth then, filter drying at 30～100 ℃.
The introducing mode of phosphorus and rare earth can adopt the precipitation method, exchange process or infusion process, as long as can reach the content requirement of phosphorus and rare earth in the product.The present invention recommends to adopt the mode of dipping to introduce phosphorus and rare earth.
The concrete preparation process that the present invention recommended is:
(a) average grain diameter be 0.5～15 μ m clay 800～1100 ℃ of roastings 0.3～10 hour, preferred 0.5～7 hour.
Preferred 1～10 μ m of the average grain diameter of clay.
Clay can be one or more in kaolin, galapectite, imvite, sepiolite, diatomite, bentonite, the lamellar clay, preferred kaolin and/or galapectite.
Among the preparation method of modified clay disclosed in this invention, should select average grain diameter for use is the clay of 0.5～15 μ m.This is because adopt the less clay of particle diameter in modifying process, can react more fully with alkaline matter, improves modification efficiency.And clay as the matrix components of catalytic cracking catalyst, can have good dispersive property in catalyst preparation process after modification, improves the catalyst reaction performance.
(b) clay after the roasting and deionized water are mixed, add concentration and be 0.5～15 mole of hydroxide ion/liter inorganic alkali solution, at 50～100 ℃, reacted preferred 0.5～3 hour 0.1～5 hour, obtain clay slurry, wherein, deionized water and clay (butt) weight ratio is 1.5～10, preferred 3～8, inorganic alkali solution and clay (butt) weight ratio is 0.5～8, inorganic base be in NaOH, waterglass, ammoniacal liquor, the sodium metaaluminate one or more.
Preferred ammoniacal liquor of inorganic base and/or waterglass.
(c) clay slurry is filtered, at 30～100 ℃, with concentration be 0.1～2.0 moles of hydrogen ion/liter inorganic acid solution wash, inorganic acid solution and clay (butt) weight ratio is 3～30.
Inorganic acid can be one or more in sulfuric acid, hydrochloric acid, the nitric acid.
(d) dipping phosphorus and rare earth: clay after the pickling and deionized water making beating, adding phosphorus compound, earth solution handled 0.5～3 hour in 30～100 ℃ under stirring, this phosphorus compound is inorganic phosphate or solubility inorganic phosphate, in the substance weight ratio, phosphorus compound is in the quality of contained P elements, P/ clay (butt) is 0.001～0.03, and is preferred 0.005～0.02, and rare earth is with RE
2O
3The quality meter, RE
2O
3/ clay (butt) is 0.001～0.04, preferred 0.005～0.03.Deionized water and clay (butt) weight ratio is 10～20.
Phosphorus compound can be one or more in phosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, aluminum phosphate, sodium dihydrogen phosphate, sodium hydrogen phosphate, the pyrophosphoric acid.
Rare earth can be a mixed chlorinated rare earth, one or more in the mixeding acid rare-earth.
At last, more after filtration, drying, get final product the finished product modified clay.
(2) preparation of composite interstitial substance slurries
Modified clay, deionized water are mixed, under stirring, add unmodified clay and deionized water, continue to add adding the alumina component stirring reaction 0.1～3 hour, add binding agent, mix, make the composite interstitial substance slurries.
(3) preparation of composite zeolite molecular sieve slurries
Zeolite molecular sieve and deionized water are mixed, add phosphorus compound and rare earth compound, stirring reaction 0.5～2 hour makes the composite molecular screen slurries.
(4) composite interstitial substance slurries, composite zeolite molecular sieve slurries are mixed the back spray-drying, obtain catalytic cracking catalyst of the present invention.
The specific embodiment
The present invention will be further described for the following examples, but the present invention is not restricted to these embodiment.
(1) used analysis test method in the embodiment of the invention.
| Project | Method | Standard No. |
| P，m％ | Phosphorus molybdenum colorimetric method | Q/SYLS?0586-2002 |
| Na 2O，m％ | Flame spectrometry | Q/SYLS?0568-2002 |
| RE 2O 3，m％ | Colorimetric method | Q/SYLS?0580-2002 |
| Specific surface, m 2/g | The thermal desorption chromatography | Q/SYLS?0600-2002 |
| Pore volume, mL/g | The water droplet method | Q/SYLS?0521-2002 |
| Micro-activity, m% | Miniature fixed bed reaction | Q/SYLS?0589-2002 |
| Reaction selectivity | Fixed fluidized bed reaction | Q/SYLS?0641-2002 |
| Granularity | The laser particle analyzer method | Q/SYLS?0519-2002 |
(2) raw materials used specification among the embodiment
1. kaolin: China Kaolin Co., Ltd, kaolinite 85%, igloss 15.1%; Galapectite: Zhuzhou galapectite, galapectite 87%, igloss 14.8%.
2. ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), sodium dihydrogen phosphate, solid is industrial goods; Hydrochloric acid, concentration 30%; Nitric acid, concentration 40%; Phosphoric acid, concentration 80%; Phosphorous acid, chemical pure; Ammoniacal liquor, chemical pure.
3. rare earth chloride contains rare earth oxide 250 grams per liters; Nitric acid rare earth contains rare earth oxide 248 grams per liters, is industrial goods.
4. boehmite, igloss 40%; γ-Al
2O
3, igloss 10%; Aluminium colloidal sol, salic 23.0 heavy %; Ludox, silicon oxide-containing 23.6 heavy % are industrial certified products.
5.REY, REHY, P-REY, USY, REUSY molecular sieve be qualified industrial goods, Catalyst Factory of Lanzhou Petrochemical Company production; The β zeolite, China University Of Petroleum Beijing provides; The MCM-22 molecular sieve, the Dalian Chemistry and Physics Institute provides; High silica ZSM-5, silica alumina ratio 300, Fudan University in Shanghai production; Low silica ZSM-5, silica alumina ratio 38, Nankai University produces.
The preparation of modified clay:
Embodiment 1
1590g is restrained kaolin 950 ℃ of roastings 1 hour in Muffle furnace, the cooling back mixes with 4000 ml deionized water, add 10 moles of hydroxide ions/liter sodium hydroxide solution 1670 gram, under the stirring, be warming up to 92 ℃, stirring reaction 2 hours, filter then, with 12000 milliliters 75 ℃ 0.3 mol sulfuric acid scrubbing,, add 80% phosphatase 11,0 gram again with the making beating of 12000 ml deionized water, 80 milliliters of re chlorides, stirred 0.5 hour down at 60 ℃, filtration, drying make modified kaolin N-1.Modified kaolin N-1 character is listed in the table 1.
Embodiment 2
1200g is restrained galapectite 1050 ℃ of roastings 0.5 hour in Muffle furnace, the cooling back mixes with 5000 ml deionized water, add 5 moles of hydroxide ions/liter sodium hydroxide solution 3200 gram and 1 mole of hydroxide ion/liter waterglass 1360 restrain, under the stirring, be warming up to 75 ℃, stirring reaction 3 hours, filter then, with 15000 milliliters 75 ℃ 0.7 mol salt acid elution,, add ammonium phosphate 50 grams again with the making beating of 20000 ml deionized water, 25 milliliters of rare earth nitrate solutions, stirred 2 hours down at 40 ℃, filter, drying makes modification galapectite N-2.Modification galapectite N-2 character is listed in the table 1.
Embodiment 3
3120g is restrained kaolin 850 ℃ of roastings 3 hours in Muffle furnace, the cooling back mixes with 18000 ml deionized water, add 14 moles of hydroxide ions/liter sodium hydroxide solution 4100 gram and 1 mole of hydroxide ion/liter sodium metaaluminate 2000 restrain, under the stirring, be warming up to 70 ℃, stirring reaction 1 hour, filter then, with 40000 milliliters 50 ℃ 0.3 mol sulfuric acid scrubbing,, add phosphorous acid 35 grams again with the making beating of 30000 ml deionized water, 318 milliliters of re chlorides, stirred 1 hour down at 80 ℃, filter, drying makes modified kaolin N-3.Modified kaolin N-3 character is listed in the table 1.
Embodiment 4
1200g is restrained kaolin 1050 ℃ of roastings 0.5 hour in Muffle furnace, cooling back and 10 moles of hydroxide ions/liter waterglass 5500 grams and 1 mole of hydroxide ion/liter ammoniacal liquor 2400 grams mix, under the stirring, be warming up to 75 ℃, stirring reaction 3 hours, filter then, 0.7 mol salt acid elution with 6000 milliliters 75 ℃, pull an oar with 20000 ml deionized water again, add ammonium dihydrogen phosphate (ADP) 40 grams and diammonium hydrogen phosphate 10 grams, 36 milliliters of rare earth nitrate solutions stirred 3 hours down at 40 ℃, filtration, drying make modified kaolin N-4.Modified kaolin N-4 character is listed in the table 1.
The preparation of catalytic cracking catalyst:
Embodiment 5
Modified kaolin N-1 among the 1590 gram embodiment 1 is added 3800 ml deionized water, under agitation add kaolin 1590 gram and 4100 ml deionized water, add 3350 gram boehmites, sustained response 0.5 hour, add aluminium colloidal sol 4350 grams, mix, obtain the composite interstitial substance slurries.
In butt, get 3400 gram REUSY and 600 gram high silica ZSM-5s, add 8500 gram deionized waters, stir, add 400 gram phosphoric acid, mix, add 750 milliliters of mixed chlorinated rare earth solution again, stirred 2 hours, make the composite molecular screen slurries.
Above-mentioned two strands of slurries are fully mixed, and spray drying forming, washing, drying through conventional promptly get catalyst cracking particles I-1 of the present invention, and the main composition of I-1 is listed in the table 2.
Embodiment 6
Modification galapectite N-2 among the 1200 gram embodiment 2 is added 3700 ml deionized water, under agitation add kaolin 3120 gram and 10400 ml deionized water, add 4190 gram boehmites, sustained response 0.2 hour, add Ludox 2175 grams, mix, obtain the composite interstitial substance slurries.
In butt, get 2750 gram REHY, 200 gram high silica ZSM-5s, 150 gram β zeolites, add 4700 gram deionized waters, stir, add 200 gram diammonium hydrogen phosphates, mix, add 1800 milliliters of mixed chlorinated rare earth solution again, stirred 1 hour, make the composite molecular screen slurries.
Above-mentioned two strands of slurries are fully mixed, and spray drying forming, washing, drying through conventional promptly get catalyst cracking particles I-2 of the present invention, and the main composition of I-2 is listed in the table 2.
Embodiment 7
Modified kaolin N-3 among modification galapectite N-2 among the 1200 gram embodiment 2 and the 3120 gram embodiment 3 is added 14000 ml deionized water, add 5000 gram boehmites, sustained response 1.5 hours adds Ludox 3250 grams, mix, obtain the composite interstitial substance slurries.
In butt, get 2050 gram USY, 650 gram MCM-22 zeolites, add 4200 gram deionized waters, stir, add 3000 gram sodium dihydrogen phosphates, mix, add 400 milliliters of mixeding acid rare-earth solution again, stirred 1.5 hours, make the composite molecular screen slurries.
Above-mentioned two strands of slurries are fully mixed, and spray drying forming, washing, drying through conventional promptly get catalyst cracking particles I-3 of the present invention, and the main composition of I-3 is listed in the table 2.
Embodiment 8
Modified kaolin N-3 among the 3120 gram embodiment 3 is added 6500 ml deionized water, under agitation add galapectite 1800 gram and 7000 ml deionized water, add 2300 gram boehmites and 210 gram γ-Al
2O
3, sustained response 1 hour adds aluminium colloidal sol 5000 grams, mixes, and obtains the composite interstitial substance slurries.
In butt, get 3350 gram P-REY and add 5700 gram deionized waters, stir, add 1780 gram ammonium phosphate, mix, add 90 milliliters of mixeding acid rare-earth solution again, stirred 0.5 hour, make the composite molecular screen slurries.
Above-mentioned two strands of slurries are fully mixed, and spray drying forming, washing, drying through conventional promptly get catalyst cracking particles I-4 of the present invention, and the main composition of I-4 is listed in the table 2.
Embodiment 9
Modified kaolin N-4 among the 1200 gram embodiment 4 is added 4100 ml deionized water, under agitation add galapectite 3120 gram and 10400 ml deionized water, add 850 gram boehmites, sustained response 3 hours, add aluminium colloidal sol 6500 grams, mix, obtain the composite interstitial substance slurries.
In butt, get 2000 gram REHY, 800 gram REY, 100 gram high silica ZSM-5s, 100 gram MCM-22 zeolites, add 4700 gram deionized waters, stir, add 50 gram diammonium hydrogen phosphates, 50 gram sodium dihydrogen phosphates, mix, add 1250 milliliters of mixed chlorinated rare earth solution again, stirred 1 hour, and made the composite molecular screen slurries.
Above-mentioned two strands of slurries are fully mixed, and spray drying forming, washing, drying through conventional promptly get catalyst cracking particles I-5 of the present invention, and the main composition of I-5 is listed in the table 2.
Embodiment 10
Modified kaolin N-3 among the 2750 gram embodiment 3 is added 8000 ml deionized water, under agitation add kaolin 350 gram and 2500 ml deionized water, add 160 gram boehmites, sustained response 2.5 hours, add aluminium colloidal sol 8700 grams, mix, obtain the composite interstitial substance slurries.
In butt, get 3000 gram REUSY, 1200 gram P-REY, 500 gram β zeolites, 600 gram MCM-22 zeolites, add 7700 gram deionized waters, stir, add 1060 gram diammonium hydrogen phosphates, mix, add 840 milliliters of mixed chlorinated rare earth solution again, stirred 0.5 hour, and made the composite molecular screen slurries.
Above-mentioned two strands of slurries are fully mixed, and spray drying forming, washing, drying through conventional promptly get catalyst cracking particles I-6 of the present invention, and the main composition of I-6 is listed in the table 2.
Embodiment 11
Modified kaolin N-4 among the 450 gram embodiment 4 is added 1200 ml deionized water, under agitation add kaolin 4050 gram and 11000 ml deionized water, add 800 gram γ-Al
2O
3, sustained response 1.5 hours adds Ludox 11000 grams, mixes, and obtains the composite interstitial substance slurries.
In butt, get 1900 gram USY, add 2800 gram deionized waters, stir, add 2800 gram phosphoric acid, mix, add 1550 milliliters of mixeding acid rare-earth solution again, stirred 2 hours, make the composite molecular screen slurries.
Above-mentioned two strands of slurries are fully mixed, and spray drying forming, washing, drying through conventional promptly get catalyst cracking particles I-7 of the present invention, and the main composition of I-7 is listed in the table 2.
Embodiment 12
Modified kaolin N-1 among the 1350 gram embodiment 1 is added 2200 ml deionized water, under agitation add galapectite 2350 gram and 5500 ml deionized water, add 3600 gram γ-Al
2O
3, sustained response 0.5 hour adds Ludox 8800 grams, mixes, and obtains the composite interstitial substance slurries.
In butt, get 500 gram P-REY, 50 gram USY, 500 gram MCM-22 zeolites, add 1800 gram deionized waters, stir, add 800 gram ammonium dihydrogen phosphate (ADP)s, 980 gram diammonium hydrogen phosphates, mix, add 2260 milliliters of mixeding acid rare-earth solution again, stirred 1.5 hours, and made the composite molecular screen slurries.
Above-mentioned two strands of slurries are fully mixed, and spray drying forming, washing, drying through conventional promptly get catalyst cracking particles I-8 of the present invention, and the main composition of I-8 is listed in the table 2.
Comparative Examples 1
According to the method among the embodiment 5, use unmodified clay to prepare comparative catalyst B-1.
3180 gram kaolin are added 8000 ml deionized water, add 3350 gram boehmites, sustained response 0.5 hour adds aluminium colloidal sol 4350 grams, mixes, and obtains the composite interstitial substance slurries.
In butt, get 3400 gram REUSY and 600 gram high silica ZSM-5s, add 8500 gram deionized waters, stir, add 400 gram phosphoric acid, mix, add 750 milliliters of mixed chlorinated rare earth solution again, stirred 2 hours, make the composite molecular screen slurries.
Above-mentioned two strands of slurries are fully mixed, and spray drying forming, washing, drying through conventional promptly get catalyst cracking particles B-1, and the main composition of B-1 is listed in the table 2.
Comparative Examples 2
According to the method among the embodiment 7, use unmodified clay to prepare comparative catalyst B-2.
1200 gram galapectites and 3120 gram kaolin are added 14000 ml deionized water, add 5000 gram boehmites, sustained response 1.5 hours adds Ludox 3250 grams, mixes, and obtains the composite interstitial substance slurries.
In butt, get 2050 gram USY, 650 gram MCM-22 zeolites, add 4200 gram deionized waters, stir, add 700 gram sodium dihydrogen phosphates, mix, add 400 milliliters of mixeding acid rare-earth solution again, stirred 1.5 hours, make the composite molecular screen slurries.
Above-mentioned two strands of slurries are fully mixed, and spray drying forming, washing, drying through conventional promptly get catalyst cracking particles B-2, and the main composition of B-2 is listed in the table 2.
Comparative Examples 3
According to the method among the embodiment 9, use unmodified clay to prepare comparative catalyst B-3.
With 4320 gram galapectite and 10400 ml deionized water, add 850 gram boehmites, sustained response 3 hours adds aluminium colloidal sol 6500 grams, mixes, and obtains the composite interstitial substance slurries.
In butt, get 2000 gram REHY, 800 gram REY, 100 gram high silica ZSM-5s, 100 gram MCM-22 zeolites, add 4700 gram deionized waters, stir, add 50 gram diammonium hydrogen phosphates, 50 gram sodium dihydrogen phosphates, mix, add 1250 milliliters of mixed chlorinated rare earth solution again, stirred 1 hour, and made the composite molecular screen slurries.
Above-mentioned two strands of slurries are fully mixed, and spray drying forming, washing, drying through conventional promptly get catalyst cracking particles B-3, and the main composition of B-3 is listed in the table 2.
Comparative Examples 4
Method according to patent CN1854254 embodiment 2 prepares comparative catalyst B-4, compares with embodiment 5 methods.
In the slurries with 3180 gram kaolin adding 4000 gram deionized waters and the 352 ammonium dihydrogen phosphate (ADP)s formation that restrain, stir and obtained kaolin slurry in 1.5 hours.
Get boehmite 3350 grams, aluminium colloidal sol 4350 grams, deionized water 3900 grams and 280 milliliters of hydrochloric acid (analyzing pure) mix stirring 1.5 hours, obtain the binding agent slurries.
Get 3400 gram REY zeolites, low silica ZSM-5 zeolite of 600 grams and 100 gram phosphoric acid and 8500 gram deionized waters mix, and add 10 milliliters of ammoniacal liquor again, make molecular sieve pulp.
Above-mentioned three strands of slurries and 750 milliliters of re chlorides are mixed, pass through conventional spray shaping, wash and be drying to obtain catalytic cracking catalyst B-4, the main composition of B-4 is listed in the table 2.
Embodiment 13
On small fixed flowing bed-tion reacting device, feedstock oil is that Xinjiang is mixed and to be urged material, and catalyst sample was handled 10 hours under 800 ℃, 100% water vapor conditions in advance, catalyst loading amount 150 grams, and oil ratio 5.0,500 ℃ of reaction temperatures, weight space velocity is 16 hours
-1, the reactivity worth of catalyst I of the present invention-1～I-8 and comparative catalyst B-1～B-4 is compared evaluation, the density of propylene data are listed in the table 3 in the product cloth of cracking reaction and productivity of propylene and the liquefied gas.
The character of table 1 modified clay
| Sample | N-1 | N-2 | N-3 | N-4 |
| P，％ | 1.9 | 1.0 | 0.5 | 1.3 |
| RE 2O 3，％ | 1.5 | 0.6 | 3.0 | 0.9 |
| Na 2O，％ | 1.0 | 1.2 | 0.5 | 1.1 |
| Specific surface, m 2/g | 201 | 195 | 185 | 214 |
| Pore volume, mL/g | 0.30 | 0.28 | 0.27 | 0.32 |
| Micro-activity, % | 28 | 26 | 26 | 27 |
Table 3 catalyst of the present invention and comparative catalyst's evaluation result
| Catalyst | I-1 | I-2 | I-3 | I-4 | I-5 | I-6 | I-7 | I-8 | Contrast B-1 | Contrast B-2 | Contrast B-3 | Contrast B-4 |
| Dry gas % | 1.85 | 1.93 | 2.08 | 2.02 | 1.89 | 2.22 | 1.83 | 1.82 | 1.83 | 1.84 | 1.91 | 1.78 |
| Liquefied gas % | 22.09 | 23.29 | 22.59 | 21.98 | 20.73 | 24.22 | 20.58 | 21.45 | 22.57 | 22.15 | 21.03 | 21.25 |
| Gasoline % | 52.15 | 50.06 | 51.47 | 51.35 | 52.89 | 49.70 | 53.46 | 52.55 | 51.04 | 52.08 | 52.24 | 51.72 |
| Diesel oil % | 13.75 | 14.33 | 14.18 | 14.45 | 14.41 | 13.97 | 14.05 | 13.89 | 13.10 | 13.45 | 14.17 | 13.76 |
| Heavy oil % | 3.88 | 4.08 | 3.47 | 3.86 | 4.13 | 3.44 | 4.35 | 4.28 | 4.85 | 4.55 | 4.81 | 5.05 |
| Coke % | 6.05 | 5.65 | 6.10 | 6.17 | 5.47 | 6.29 | 5.45 | 5.50 | 5.75 | 5.79 | 5.71 | 5.71 |
| Conversion ratio % | 82.37 | 81.59 | 82.35 | 81.69 | 81.46 | 82.59 | 81.60 | 81.83 | 82.05 | 82.00 | 81.02 | 81.19 |
| Total liquid is received % | 87.99 | 87.68 | 88.24 | 87.78 | 88.03 | 87.89 | 88.09 | 87.89 | 86.71 | 87.68 | 87.44 | 86.73 |
| Propylene % | 8.75 | 8.90 | 8.45 | 8.26 | 8.05 | 9.65 | 8.05 | 8.27 | 8.01 | 7.82 | 7.59 | 7.42 |
| Density of propylene %* | 39.6 | 38.2 | 37.4 | 37.6 | 38.8 | 39.8 | 39.1 | 38.6 | 35.5 | 35.3 | 36.1 | 34.9 |
| Gasoline RON | 93.0 | 93.5 | 93.2 | 93.2 | 93.6 | 94.5 | 93.8 | 94.0 | 93.5 | 93.5 | 94.0 | 93.1 |
*Density of propylene is defined as: productivity of propylene/liquefied gas yield * 100%
By table 2 data as can be seen, on fixed fluidized bed reaction unit, compare with the comparative catalyst, adopt catalytic cracking catalyst disclosed in this invention to have high productivity of propylene and low heavy oil productive rate, and have higher density of propylene, shown that fully catalyst of the present invention has the response characteristic of high productivity of propylene and low heavy oil productive rate.
Claims (16)
1. a catalytic cracking catalyst is characterized in that with catalyst quality 100% be benchmark, comprises modified clay 1～50%; Unmodified clay 0～40%; Zeolite molecular sieve 10～60%; Binding agent 5～30%; Add aluminium oxide 0.1～35%; In elemental phosphorous, phosphorus compound 0.1～8%; With RE
2O
3Meter, rare earth compound 0.1～6%; Wherein modified clay is through 800～1100 ℃, and the clay after the roasting in 0.3～10 hour in modified clay quality 100%, contains P0.1～3.0%, RE
2O
30.1～4.0%, Na
2O 0.1～1.5%, modified clay pore volume 0.1～0.5mL/g, specific surface 50～400m
2/ g, average grain diameter 0.5～15 μ m.
2. catalytic cracking catalyst according to claim 1 is characterized in that modified clay 5～40%; Unmodified clay 5～35%; Zeolite molecular sieve 15～50%; Binding agent 5～20%; Add aluminium oxide 0.5～30%; In elemental phosphorous, phosphorus compound 0.5～5%; With RE
2O
3Meter, rare earth compound 0.1～4%.
3. catalytic cracking catalyst according to claim 1 is characterized in that zeolite molecular sieve is one or more in y-type zeolite, ZSM zeolite, β zeolite, MCM zeolite, L zeolite, aluminum phosphate zeolite, the omega zeolite.
4. catalytic cracking catalyst according to claim 3 is characterized in that zeolite molecular sieve is Y zeolite or Y zeolite and other zeolite mixtures, and other zeolites wherein are one or more in ZSM zeolite, β zeolite, the MCM zeolite.
5. catalytic cracking catalyst according to claim 3 is characterized in that the Y zeolite is one or more among REY, REHY, P-REY, USY, the REUSY; ZSM zeolite is ZSM-5; The MCM zeolite is MCM-22.
6. catalytic cracking catalyst according to claim 1 is characterized in that clay is selected from one or more in kaolin, halloysite, imvite, sepiolite, diatomite, bentonite, the crosslinked lamellar clay.
7. catalytic cracking catalyst according to claim 1 is characterized in that binding agent is one or more in aluminium colloidal sol, Ludox, sial complex sol, silica-alumina gel, aluminum phosphate colloidal sol, the phosphaljel.
8. catalytic cracking catalyst according to claim 1, it is characterized in that adding aluminium oxide is boehmite, α-Al
2O
3, η-Al
2O
3, γ-Al
2O
3In one or more.
9. catalytic cracking catalyst according to claim 1 is characterized in that modified clay wherein, in modified clay quality 100%, and its P content 0.5～2.0%; RE
2O
3Content 0.5～3.0%.
10. the preparation method of the described catalytic cracking catalyst of claim 1 is characterized in that the concrete preparation process of this catalytic cracking catalyst is:
(1) preparation of modified clay
Clay was 800～1100 ℃ of roastings 0.3～10 hour; Clay after the roasting and deionized water are mixed, add concentration and be 0.5～15 mole of hydroxide ion/liter inorganic alkali solution, at 50～100 ℃, reacted 0.1～5 hour, obtain clay slurry, wherein, deionized water and clay butt weight ratio are 1.5～10, inorganic alkali solution and clay butt weight ratio are 0.5～8, inorganic base be in NaOH, waterglass, ammoniacal liquor, the sodium metaaluminate one or more; Clay slurry is filtered, wash with inorganic acid solution, introduce phosphorus and rare earth in the mode of dipping then, filter drying at 30～100 ℃;
(2) preparation of composite interstitial substance slurries
Modified clay, deionized water are mixed, under stirring, add unmodified clay and deionized water, continue to add adding the alumina component stirring reaction 0.1～3 hour, add binding agent, mix, make the composite interstitial substance slurries;
(3) preparation of composite zeolite molecular sieve slurries
Zeolite molecular sieve and deionized water are mixed, add phosphorus compound and rare earth compound, stirring reaction 0.5～2 hour makes the composite molecular screen slurries;
(4) composite interstitial substance slurries, composite zeolite molecular sieve slurries are mixed the back spray-drying, make catalytic cracking catalyst.
11. the preparation method of catalytic cracking catalyst according to claim 10 is characterized in that in the preparation of modified clay, inorganic acid solution concentration be 0.1～2.0 moles of hydrogen ion/liter, inorganic acid solution/clay (weight) is 3～30.
12. the preparation method of catalytic cracking catalyst according to claim 10, it is characterized in that in the preparation of modified clay, the actual conditions of introducing phosphorus and rare earth in the mode of dipping is: clay after the pickling and deionized water making beating, add phosphorus compound, earth solution was handled 0.5～3 hour in 30～100 ℃ under stirring, this phosphorus compound is inorganic phosphate or solubility inorganic phosphate, in the substance weight ratio, phosphorus compound is in the quality of contained P elements, P/ clay butt is 0.001～0.03, and rare earth is with RE
2O
3The quality meter, RE
2O
3/ clay butt is 0.001～0.04, and deionized water/clay butt is 10～20.
13. the preparation method of catalytic cracking catalyst according to claim 10 is characterized in that in the preparation of modified clay that inorganic base is ammoniacal liquor and/or waterglass.
14. the preparation method of catalytic cracking catalyst according to claim 10 is characterized in that in the preparation of modified clay that inorganic acid is one or more in sulfuric acid, hydrochloric acid, the nitric acid.
15. the preparation method of catalytic cracking catalyst according to claim 10, it is characterized in that in the preparation of modified clay that the form of one or more in P employing adding phosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, aluminum phosphate, sodium dihydrogen phosphate, sodium hydrogen phosphate, the pyrophosphoric acid is introduced.
16. the preparation method of catalytic cracking catalyst according to claim 10 is characterized in that in the preparation of modified clay, rare earth adopts mixed chlorinated rare earth, one or more in the mixeding acid rare-earth.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102400376A CN101745413B (en) | 2008-12-17 | 2008-12-17 | Catalytic cracking catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102400376A CN101745413B (en) | 2008-12-17 | 2008-12-17 | Catalytic cracking catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101745413A CN101745413A (en) | 2010-06-23 |
| CN101745413B true CN101745413B (en) | 2011-12-07 |
Family
ID=42473404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102400376A Active CN101745413B (en) | 2008-12-17 | 2008-12-17 | Catalytic cracking catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101745413B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108160099B (en) * | 2016-12-07 | 2020-09-04 | 中国石油天然气股份有限公司 | Heavy oil catalytic cracking catalyst |
| CN110813367A (en) * | 2019-11-20 | 2020-02-21 | 延安大学 | Phosphorus and rare earth synergistically modified ZSM-5 and method for increasing propylene yield through catalytic cracking of ZSM-5 |
| CN114425413B (en) * | 2020-09-21 | 2023-07-11 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent for increasing concentration of butene in liquefied gas and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388221A (en) * | 2001-05-30 | 2003-01-01 | 中国石油化工股份有限公司 | Catalytic cracking assistant for reducing olefine content in gasoline |
| CN1796494A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Method for cracking hydrocarbon oil |
| CN1796496A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Cracking auxiliary agent for raising density of propylene |
-
2008
- 2008-12-17 CN CN2008102400376A patent/CN101745413B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388221A (en) * | 2001-05-30 | 2003-01-01 | 中国石油化工股份有限公司 | Catalytic cracking assistant for reducing olefine content in gasoline |
| CN1796494A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Method for cracking hydrocarbon oil |
| CN1796496A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Cracking auxiliary agent for raising density of propylene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101745413A (en) | 2010-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101745412B (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN101134905B (en) | Method for improving solid content of catalytic cracking catalyst slurry | |
| CN103447063B (en) | Heavy oil Efficient Conversion catalytic cracking catalyst and preparation method thereof | |
| AU2012351265B2 (en) | High light received heavy oil catalytic cracking catalyst and preparation method therefor | |
| CN101837301B (en) | Catalytic cracking propylene catalyst with yield increase and preparation method | |
| CN101134906B (en) | Method for improving solid content of catalytic cracking catalyst slurry | |
| CN100395312C (en) | Method for catalytic cracking petroleum hydrocarbons | |
| CN101108734B (en) | Beta type molecular sieve and method of manufacturing the same | |
| CN101537365B (en) | Modified method for improving hydrothermal stability of molecular sieve in FCC catalyst with high efficiency | |
| CN101767027A (en) | Preparation method of cracking catalyst containing ultrastable molecular sieve | |
| CN102049290B (en) | RFCC high octane gasoline additive and preparation method thereof | |
| CN103157507A (en) | Heavy oil catalytic cracking catalyst and preparation method thereof | |
| CN101767028A (en) | Preparation method of fluid catalytic cracking catalyst | |
| CN103301870B (en) | The preparation method of assisted catalyst for catalyzing cracking | |
| CN102371171B (en) | Catalytic cracking fluidized bed catalyst synthesized in situ | |
| CN102134082A (en) | Preparation method of ZSM-5 molecular sieve | |
| CN100395029C (en) | Production of liquefied gas cracking catalyst with gasoline olefin content decreasement | |
| CN101745413B (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN1209288C (en) | Modified octahedral zeolite and hydrocarbon cracking catalyst containing the octahedral zeolite | |
| CN1267533C (en) | Catalytic and thermal cracking catalyst for increasing production of ethane and propylene | |
| CN1104955C (en) | Once-exchanging once-calcining phosphoreted Y-zeolite cracking catalyst and preparing method thereof | |
| CN101590432B (en) | Modified clay and preparation method thereof | |
| CN1307098C (en) | Method for preparing rare-earth ultrastable Y-type zeolite | |
| CN102372552A (en) | Catalytic pyrolysis method for producing ethene and propylene | |
| CN102166533B (en) | Composite modified molecular sieve improving activity and hydrothermal stability and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |