CN1299857A - Petroleum hydrocarbon cracking catalyst and its preparation - Google Patents
Petroleum hydrocarbon cracking catalyst and its preparation Download PDFInfo
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- CN1299857A CN1299857A CN 99125942 CN99125942A CN1299857A CN 1299857 A CN1299857 A CN 1299857A CN 99125942 CN99125942 CN 99125942 CN 99125942 A CN99125942 A CN 99125942A CN 1299857 A CN1299857 A CN 1299857A
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Abstract
The present invention relates to a petroleum cracking catalyst containg waste slag produced by catalyst plant and its preparation method. It is characterized by that the waste slag discharged by catalyst plant can be subtitued for a part of carrier filler in cracking catalyst for example natural clay or full-synthetic carrier to eliminate the waste slag diacharged by catalyst plant completely, reduce environmental pollution and cost of catalyst.
Description
The present invention relates to catalyst for cracking petroleum hydrocarbons and preparation method thereof, what also relate to silicon-aluminum containing class waste residue utilizes method again.
Catalyst for cracking petroleum hydrocarbons is the catalyzer of consumption maximum, and its development has been experienced acidic white earth catalyzer, sial bead and microballoon cracking catalyst and at present widely usedly has been main active component and is the microballoon cracking or the catalyst for cracking of weighting material with natural or synthesizing Si-Al material with various modified Y zeolites.Existing cracking catalyst carrier mainly is divided into two major types: (1) adopts natural mineral such as kaolin, dust trachelospermum jasminoide or sepiolite to make weighting agent, add mineral acid or aluminium colloidal sol is made the semi-synthetic carrier that adhesive preparation becomes with aluminium (and/or silicon) oxide compound, and is a lot of with the article of the catalyzer patent of this class carrier application and report; (2) with the full synthesis carrier of aluminium reactant salts such as silicon source such as water glass and Tai-Ace S 150 or sodium aluminate preparation, the catalyzer with this class preparing carriers a lot (the Hou Xianglin chief editor, Sinopec press publishes for " Chinese oil Refining Technologies ", P481) in early days.At present to use maximum be natural kaolin to the weighting material in the hydrocarbon cracking catalyzer, and with the molten pseudo-boehmite of acid or aluminium colloidal sol, silicon sol etc. as binding agent.
Catalyst plant particularly has the catalyzer manufactory of cracking catalyst kind, all produces a large amount of solid slags every year, wherein mainly is Si0
2, Al
2O
3, RE
2O
3, Na
2O and Fe
2O
3Deng composition, and contain Cl
-, SO4
=, F
-, Ca
++, Mg
++, F
-, P, As, Pb etc., the water content of waste residue generally surpasses 50%, its physical aspect mainly is made up of zeolites such as Y, silicon (aluminium) glue, aluminum oxide, kaolin and a small amount of clay of the cracking agent particle of various brands, various ion exchange form, has become the blowdown rich and influential family of petrochemical industry.
The technology that relates to controlling waste residue in the prior art and utilize is more, as adopting physical methods such as shaping, briquetting, as CN87103419, CN1051523A with waste residue as material of construction and filler.From waste residue, extract the technology of useful component for another example, from the waste residue that contains rare earth, extract rare earth such as CN1044635A, but can not be all effective to various components, can not complete digestion fall waste residue, even increase the amount of waste residue owing to treating processes.It is more for the main waste residue of forming, technology that liquid waste disposal technique particularly is prepared into zeolites to relate to silicon, aluminium, and mainly contain: JP5155611 will contain SiO
2And Al
2O
3Inorganic or organic waste fusion and be added to the alkali of equivalent at least such as sodium hydroxide in boil and be used to prepare zeolite, waste residue is SiO preferably
2/ Al
2O
3=2～4 sludge or its incineration ash; JP5221628, JP6256012, JP6239612 are also similar substantially; This method is not suitable for the catalyst plant waste residue, because very big catalyst plant waste residue elder generation fusion obviously is uneconomic for water content.EP451112A will be less than 300 microns sial waste material with about 20% H
2SO
4Solvent and solute weight ratio 1.3～6 and 150～230 ℃ of following processing 0.25～0.75 hour, be cooled to 60～150 ℃ then, use alkali such as sodium-hydroxide treatment again, and in every liter, add 0.2～0.5 the gram flocculation agent, time obtain silicon-aluminium glue body in pH3.5～4.5, a ℃ following reaction obtains zeolite in pH=8～13 and 60～200 for hydro-oxidation sodium and water, and zeolite type depends on the mixture composition.J5514412 adds flocculation agent and adjusts the basicity crystallization with silicate and sodium-hydroxide treatment aluminum oxide sludge to go out zeolite again, and characteristics are earlier with acid or alkaline purification and add flocculation agent.What difference was little with it is that USP4310496 dissolves the silicon-dioxide formation alkalimetal silicate that contains useless cigarette ash with alkali hydroxide soln down at 60～110 ℃, isolate to be regardless of with gac or oxygenant and separate component, at room temperature with the alkali metal aluminate reaction and stir 8～48 hours crystallization down at 70～100 ℃ and obtain Y zeolite.USP4784980 adopts sodium hydroxide and sodium aluminate and solid spent catalyst to carry out long-time two-stage reaction to remove part metals vanadium and nickel and to form zeolite A or P with useless Preparation of Catalyst A type zeolite.USP4055622 prepares A type zeolite with aluminium making residue, and its waste residue is actual only as the aluminium source.Known to the inventor, with form and composition all the wet waste residue of catalyst plant sial class of more complicated still do not appear in the newspapers as the method for preparing cracking or catalyst for cracking of the partially filled thing of preparation cracking catalyst carrier, the improvement technology that the complete digestion of catalyst plant waste residue is fallen is not reported yet.
The purpose of this invention is to provide a kind of catalyst of cracking petroleum that contains the catalyst plant waste residue and preparation method thereof, fall catalyst plant with complete digestion and efflux waste residue, reduce the pollution of environment and the cost of reduction catalyzer.
The basic ideas of the inventive method are that the waste residue that effluxes with catalyst plant replaces a part of carrier weighting material such as natural clay or full synthesis carrier in the cracking catalyst, and other of catalyzer formed according to actual needs and determined flexibly by prior art.
Catalyst for cracking petroleum hydrocarbons provided by the present invention by butt weight by 10-50 weight %, the Y zeolite of preferred 15-40 weight %, 0-15 weight %, the shape-selective molecular sieve that comprises ZSM-5 zeolite or β zeolite of preferred 0-10 weight %, 5～25 weight %, the catalyst plant waste residue of the siliceous and/or aluminium of preferred 10-20 weight %, and the carrier of its surplus is formed.
Said Y zeolite in the catalyzer provided by the present invention, said shape-selective molecular sieve and said carrier determine that according to prior art the present invention has no particular limits it according to the practical use of said catalyzer; For example Y zeolite can be super steady Y (USY), hyperastable Y-type RE (REUSY), Rare Earth Y (REY), rare earth HY (REHY) etc.; The ZSM-5 molecular sieve can be that silica alumina ratio is the ZSM-5 molecular sieve of 20-1000; The β zeolite can be that silica alumina ratio is the β zeolite of 20-500.Wherein said carrier can be full synthesis carrier or semi-synthetic carrier, but preferably contains the semi-synthetic carrier of natural clay and aluminum oxide and/or silicon oxide.
The preparation method of catalyst for cracking petroleum hydrocarbons provided by the present invention specifically comprises: with solid content is 10～70 weight %, the catalyst plant waste residue of the siliceous and/or aluminium of preferred 15～50 weight % join according in the Preparation of Catalyst slurries that contain molecular sieve and carrier of the method for prior art preparation to replace a part of carrier wherein; Thorough mixing evenly after, with gained slurry mixture spraying drying according to a conventional method; In the end in the gained slurry mixture, the add-on of said waste residue is counted 5～25 weight % of whole catalyzer butt gross weight by butt weight, be preferably 10-20 weight %: the add-on of said molecular sieve is counted 10～50 weight % of whole catalyzer butt gross weight by butt weight, is preferably 15-40 weight %; All the other are the add-on of said carrier; The solid content of last gained slurries is determined according to prior art, is generally 15-50 weight %.When said carrier was full synthesis carrier, this carrier had adhesive property (promptly can not add other binding agent); When said carrier is semi-synthetic carrier, said carrier is for example for example pseudo-boehmite, aluminium colloidal sol, the mixture of silicon sol of sour peptization of kaolin, polynite, dust trachelospermum jasminoide or sepiolite and binding agent of natural clay, wherein the add-on of binding agent is counted the 10-35 weight % of whole catalyzer butt gross weight by butt weight, is preferably 15-25 weight %.
Said waste residue siliceous and/or aluminium is the waste residue that effluxes of catalyst plant catalyst plant that the catalyst of cracking petroleum kind is particularly arranged in the Catalysts and its preparation method provided by the present invention, and its butt is formed SiO in (referring to the composition through gained resistates after 800 ℃ of roastings in 2 hours)
2And Al
2O
3Total content should be more than or equal to 50 heavy %, preferably more than or equal to 70 heavy %, more preferably more than or equal to 80 heavy %; Said waste residue can contain rare earth, also can contain iron, calcium, magnesium and Cl
-, SO4
=, F
-Deng impurity; The water content of said waste residue has no particular limits, but preferably solid content weighs % more than or equal to 5; This waste residue mainly by the cracking catalyst particle of various brands, various ion exchange form (as Na
+, H
+, NH
4 +And rare earth ion) comprise that Y zeolite is (as NaY, REY, HY, REHY, NH
4Y, USY, REUSY etc.) and the ZSM-5 zeolite form in clay-type substance such as interior molecular sieve, silica gel or alumino silica gel, aluminum oxide and kaolin, metakaolins.This waste residue can also can directly add the water making beating without grinding through processing such as grindings when being used to prepare catalyzer.
To account for the ratio that whole catalyzer forms be 10～25% to said waste residue in the Catalysts and its preparation method provided by the present invention, is generally about 15%, can complete digestion fall the waste residue that is produced in the whole Catalyst Production process.Because for catalyst plant, the waste residue that is produced and its catalyst yield have corresponding relation.
The advantage of method provided by the present invention is under the situation that does not change existing cracking catalysis agent producing process and equipment substantially, the waste residue that catalyst plant produced is fallen in digestion, improve environment, and save starting material such as kaolin, dust trachelospermum jasminoide or synthesizing Si-Al class material significantly, waste residue can replace 10～25% kaolin or synthesizing Si-Al class material, prepared cracking catalyst tear strength is suitable with prior art products obtained therefrom quality, and little index alive is higher than prior art products.Because the waste material that cracking catalyst is produced in producing is the overwhelming majority who accounts for the catalyst plant waste material, the amount of waste residue and the output of cracking catalyst have corresponding relation, as long as determine to prepare the incorporation of waste residue in the catalyzer process, just can realize not having the running balance of waste sludge discharge, guarantee to save starting material under the prerequisite that product quality does not descend significantly simultaneously.
The following examples will the present invention is further illustrated.
In each embodiment, the catalyst abrasion assessment of indices is according to " petrochemical complex analytical procedure (RIPP test method) " (volume such as Yang Cuiding, Science Press publishes, nineteen ninety version) in the RIPP29-90 standard method carry out, the little assessment of indices alive of catalyzer carries out (the same) by the RIPP92-90 standard method, the chemical constitution of catalyzer presses RIPP134-90 and (the same) measured in the RIPP111-90 standard method, and the specific surface of zeolite and pore volume are pressed the GB/T5816-1995 standard method and measured.Percentage composition in this specification sheets all is a weight percentage.
Embodiment 1
Get the 1103g waste residue and (take between the catalyst plant integrated car of Chang Ling Na
2O=10.5%, SiO
2=54.8%, Al
2O
3=16.1%, RE
2O
3=1.28%, SO
4==7.85%, Cl-=1.50%, solid content 13.6%, proportion 1.015) ammoniumsulphate soln of grinding back adding 1.25% is 5440 milliliters, stir after 0.5 hour under 90 ℃ and filter (sample after the filtration is 0.44% by its sodium oxide content of butt), filter cake after the filtration and 421 gram kaolin (the Suzhou machine selects 2#, solid content 71%, down together), 952 are restrained aluminium colloidal sols (production of Chang Ling catalyst plant, Al
2O
3Content 21%, down together), with 389 gram SRY molecular sieve (Chang Ling catalyst plant commerical prods, contents on dry basis 90%, together following) and 2450 ml deionized water mixing making beating is evenly, then with its spray drying forming according to a conventional method, with the catalyzer after the moulding with 10 liters of 0.35% Secondary ammonium phosphate (Beijing chemical reagent factory) solution 60 ℃ of following agitator treatings 15 minutes, wash once again after the filtration, to reduce the sodium content of catalyzer, after the drying, the tear strength index that records this catalyzer is 1.8, and little index alive is 65.
Comparative Examples 1
The explanation of this Comparative Examples does not contain the preparation and the effect of the cracking catalyst of catalyst plant waste residue.
With 1816 gram kaolin, 952 gram aluminium colloidal sols, 389 gram SRY molecular sieves and 3300 ml deionized water are mixed making beating evenly, then with its spray drying forming according to a conventional method, with the catalyzer after the moulding with 8 liters of 0.35% Secondary ammonium phosphate (Beijing chemical reagent factory) solution 60 ℃ of following agitator treatings 15 minutes, after the filtration again washing once, to reduce the sodium content of catalyzer, after the drying, obtain the comparative catalyst, the tear strength index that records this catalyzer is 1.7, and little index alive is 60.
Embodiment 2
The 855g waste residue (is taken between the catalyst plant integrated car of Chang Ling Na
2O=6.6%, SiO
2=84.2%, Al
2O
3=0.2, RE
2O
3=2.99%, Fe
2O
3=0.15%, SO
4==0.47%, Cl
-=2.0%, solid content 11.7%) and 652 gram kaolin, 279 gram pseudo-boehmite (Shandong Aluminum Plant's commerical prod, Al
2O
3Content 67%), 42 gram hydrochloric acid (Beijing chemical reagent factories, concentration 36%, down together), the making beating of 2000 ml deionized water mixes, 60 ℃ of following ageings restrained the REUSY zeolite slurries to slurries PH＞2.8 backs and 1000 in 4 hours and (take from the Chang Ling molecular sieve workshop of Catalyst Factory, solid content 25%, mix down together), then with its spray drying forming according to a conventional method, with the catalyzer after the moulding with 8 liters of 0.35% Secondary ammonium phosphate (Beijing chemical reagent factory) solution 60 ℃ of following agitator treatings 15 minutes, wash once again after the filtration, with the sodium content of reduction catalyzer, after the drying, the tear strength index that records this catalyzer is 1.5, and little index alive is 75.
Comparative Examples 2
Repeat the step of embodiment 2, different is not add said waste residue, and kaolinic add-on is 792 grams, and the add-on of other raw material is identical with operation steps.It is 74 that last gained catalyzer records its little index alive, and the tear strength index is 1.6.
Embodiment 3
The catalyzer of the present invention and the preparation thereof of full synthesis carrier used in the present embodiment explanation.
(the Zhou village catalyst plant contains SiO at 675 gram water glass
2124 grams per liters, modulus 3.3) adds 400 gram water in and mix stirring 10 minutes, be 30% hydrochloric acid soln to wherein adding 50 ml concns then, stir the hydrochloric acid soln that adds 9 milliliters of these concentration after 10 minutes again, stir, aging after 1.5 hours, regulating its PH with hydrochloric acid soln is 3.0～3.5, adding 176 gram concentration then is 28% aluminum chloride (chemical plant, Kingsoft) solution, after mixing, add 74 ml concns and be 16% ammoniacal liquor (Beijing Chemical Plant) solution, after mixing, (take from the Zhou village catalyst plant, Na to wherein adding 396 gram waste residues
2O=6.74%, SiO
2=68.4%, Al
2O
3=18.4, RE
2O
3=2.6%, Fe
2O
3=0.2%, Ca=0.1%, Mg=0.05%, Pb=0.0074%, As=0.017%, F=0.0057%, solid content 13.6%) also making beating mixes, add 176 gram REY zeolite slurries (Zhou village catalyst plant, contents on dry basis 25%) and stirring at last, with its spray drying forming according to a conventional method, is that 3.5% ammoniumsulphate soln is at twice 60 ℃ of washings 15 minutes down with the catalyzer after the moulding with 20 liters of concentration, behind the filtration drying, the index little alive that records catalyzer is 73, and the tear strength index is 2.0.
Comparative Examples 3
Repeat the step of embodiment 3, different is not add said waste residue, and the add-on of REY zeolite slurry is 129 grams, and the add-on of other raw material is identical with operation steps.It is 71 that last gained catalyzer records its little index alive, and the tear strength index is 2.0.
Embodiment 4
At 2365 gram solid contents is that to add 2370 gram solid contents in 25.9% the SRY molecular sieve pulp be 26.0% REUSY slurries and 72 gram (dry basis) RPSA molecular sieve (Chang Ling catalyst plant commerical prods, molecular sieve for a kind of ZSM-5 structure type, see CN1194181A), obtain a kind of mixed molecular sieve slurries; Under agitation add 1100 gram pseudo-boehmite (Shandong Aluminum Plant's commerical prod, Al
2O
3Content 57.6%), be that 20.8% technical hydrochloric acid mixes under agitation after the making beating evenly to wherein adding 333 gram concentration, then under agitation to wherein adding 4375 gram waste residues (with embodiment 1), add 946 gram solid contents after the making beating evenly again and be 31.2% halloysite (No. 1, commodity Hunan by name soil, take from catalyst plant raw material workshop, Chang Ling) slurries, making beating evenly back mixes to wherein adding 1869 gram aluminium colloidal sols, adding 162 gram concentration again is that 20.8% technical hydrochloric acid mixes, obtain a kind of catalyst slurry, then with these slurries spray drying forming according to a conventional method, is that 3.5% ammoniumsulphate soln is at twice 60 ℃ of washings 15 minutes down with the catalyzer after the moulding with 40 liters of concentration, use again 60 ℃ hot wash once, behind the filtration drying, the index little alive that records catalyzer is 75.2, and the tear strength index is 2.5.
Comparative Examples 4
Repeat the step of embodiment 4, different is not add said waste residue, and the add-on of halloysite slurries is 1457 grams, and the add-on of other raw material is identical with operation steps.It is 73 that last gained catalyzer records its little index alive, and the tear strength index is 2.3.
Embodiment 5
Present embodiment explanation catalyzer of the present invention and comparative catalyst's heavy oil micro anti-evaluation result.
The catalyzer of embodiment 2 and Comparative Examples 2 gained after accelerating aging 4 hours, 800 ℃ of following water vapour is carried out evaluation test respectively on heavy oil microreactor in fixed bed.Estimate raw materials used oil and be the defeated wax oil of pipe, temperature of reaction is 482 ℃, and air speed is 16.0 hours-1, and agent-oil ratio is 3.0.The gained result is as shown in table 1.
The result of table 1 shows in the carrier with catalyst plant waste residue instead of part kaolin can not bring clearly disadvantageous effect to the cracking products distribution.
Table 1
| Catalyzer | Embodiment 2 | Comparative Examples 2 |
| Transformation efficiency | ????77.75 | ????73.28 |
| Product distribution dry gas C 3～C 4Gasoline solar oil heavy oil coke | ???? ????1.50 ????12.47 ????60.35 ????16.22 ????6.04 ????3.43 | ???? ????1.52 ????11.89 ????56.31 ????15.84 ????10.87 ????3.57 |
Embodiment 6
Present embodiment explanation catalyzer of the present invention and comparative catalyst's fixed fluidized bed evaluation result.
The catalyzer of embodiment 4 and Comparative Examples 4 gained after accelerating aging 17 hours, 800 ℃ of following water vapour is carried out evaluation test respectively on small fixed flowing bed catalytic cracking reaction device in fixed bed.Estimating raw materials used oil is vacuum residuum: the mixing oil of decompressed wax oil=20: 80, and its character is listed in the table 2; Temperature of reaction is 500 ℃, and air speed is 19.6 hours-1, and agent-oil ratio is 4.0.The gained result is as shown in table 3.
The result of table 3 also shows in the carrier with catalyst plant waste residue instead of part natural clay can not bring clearly disadvantageous effect to the cracking products distribution.
Table 2. stock oil character initial boiling point: 224 ℃ of 50 volume % distillates a little: 460 ℃ of density (20 ℃): 0.8995g/cm
3Viscosity (80 ℃): 20.4 centipoise condensation points: 41 ℃ of carbon residues: 2.17 weight % heavy metals (ppm): Na Fe Ni V Ca
1.7???2.0???1.7???0.1?＜0.1
Table 3
| Catalyzer | Embodiment 4 | Comparative Examples 4 |
| Transformation efficiency | ????76.37 | ????73.19 |
| Product distribution H 2????C 1～C 2????C 3～C 4Gasoline solar oil heavy oil coke | ????0.03 ????1.73 ????16.43 ????52.26 ????16.07 ????8.15 ????5.33 | ????0.04 ????1.50 ????15.13 ????51.94 ????17.79 ????9.01 ????4.58 |
Claims (20)
1, a kind of catalyst for cracking petroleum hydrocarbons, it is characterized in that this catalyzer by butt weight by 10-50 weight %, Y zeolite, the shape-selective molecular sieve of 0-15 weight %, the catalyst plant waste residue of the siliceous and/or aluminium of 5～25 weight %, and the carrier of its surplus is formed.
2, according to the catalyzer of claim 1, it is characterized in that this catalyzer is by the Y zeolite of butt weight by 15-40 weight %, the shape-selective molecular sieve that comprises ZSM-5 zeolite or β zeolite of 0-10 weight %, the catalyst plant waste residue of the siliceous and/or aluminium of 10-20 weight %, and the carrier of its surplus is formed.
3, according to the catalyzer of claim 1, wherein said Y zeolite is super steady Y, hyperastable Y-type RE, Rare Earth Y or rare earth HY type molecular sieve.
4, according to the catalyzer of claim 2, the silica alumina ratio of wherein said ZSM-5 zeolite is 20-1000; The silica alumina ratio of said β zeolite is 20-500.
5, according to the catalyzer of claim 1, wherein said catalyst plant waste residue siliceous and/or aluminium be have the catalyst of cracking petroleum kind catalyst plant efflux waste residue, SiO during its butt is formed
2And Al
2O
3Total content more than or equal to 50 heavy %.
6, according to the catalyzer of claim 5, SiO during wherein the butt of said waste residue is formed
2And Al
2O
3Total content more than or equal to 70 heavy %.
7, according to the catalyzer of claim 6, SiO during wherein the butt of said waste residue is formed
2And Al
2O
3Total content more than or equal to 80 heavy %.
8, according to the catalyzer of claim 1, wherein the physical aspect of said waste residue comprise the catalyst of cracking petroleum particle, with Na
+, H
+, NH
4 +Or rare earth ion is molecular sieve, silica gel or the alumino silica gel, the aluminum oxide that comprise y-type zeolite and ZSM-5 zeolite of ionic forms and the clay-type substance that comprises kaolin, metakaolin.
9, according to the catalyzer of claim 1, wherein said carrier is full synthesis carrier or semi-synthetic carrier.
10, according to the catalyzer of claim 9, wherein said carrier is the semi-synthetic carrier that contains natural clay and aluminum oxide and/or silicon oxide.
11, the preparation method of the described catalyst for cracking petroleum hydrocarbons of claim 1 is characterized in that this method comprises: with solid content be the catalyst plant waste residue of the siliceous and/or aluminium of 10～70 weight % join according in the Preparation of Catalyst slurries that contain molecular sieve and carrier of the method preparation of prior art to replace a part of carrier wherein; Thorough mixing evenly after, with gained slurry mixture spraying drying according to a conventional method; In the end in the gained slurry mixture, the add-on of said waste residue is counted 5～25 weight % of whole catalyzer butt gross weight by butt weight.
12, according to the method for claim 11, wherein the solid content of said waste residue is 15～50 weight %.
13, according to the method for claim 11, wherein the add-on of said waste residue is counted the 10-20 weight % of whole catalyzer butt gross weight by butt weight.
14, according to the method for claim 11, wherein the add-on of said molecular sieve is counted 10～50 weight % of whole catalyzer butt gross weight by butt weight.
15, according to the method for claim 11, wherein said carrier is the full synthesis carrier that contains silicon and aluminium.
16, according to the method for claim 11, wherein said carrier is the semi-synthetic carrier that contains natural clay and binding agent.
17, according to the method for claim 16, wherein said natural clay is kaolin, polynite, dust trachelospermum jasminoide or sepiolite, or the mixture more than two kinds in them.
18, according to the method for claim 16, the pseudo-boehmite that wherein said binding agent is sour peptization, aluminium colloidal sol or silicon sol, or the mixture more than two kinds in them.
19, according to the method for claim 16, wherein the add-on of said binding agent is counted the 10-35 weight % of whole catalyzer butt gross weight by butt weight.
20, according to the method for claim 11, wherein the solid content of last gained slurries is 15-50 weight %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991259424A CN1150301C (en) | 1999-12-13 | 1999-12-13 | Petroleum hydrocarbon cracking catalyst and its preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991259424A CN1150301C (en) | 1999-12-13 | 1999-12-13 | Petroleum hydrocarbon cracking catalyst and its preparation |
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| Publication Number | Publication Date |
|---|---|
| CN1299857A true CN1299857A (en) | 2001-06-20 |
| CN1150301C CN1150301C (en) | 2004-05-19 |
Family
ID=5284242
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|---|---|---|---|
| CNB991259424A Expired - Lifetime CN1150301C (en) | 1999-12-13 | 1999-12-13 | Petroleum hydrocarbon cracking catalyst and its preparation |
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| CN101543783B (en) * | 2008-03-27 | 2011-03-30 | 中国石油化工股份有限公司石油化工科学研究院 | Suspension bed hydrocracking catalyst and preparation method and application thereof |
| CN102247881A (en) * | 2010-05-20 | 2011-11-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing rare earth-containing aluminum oxide and application thereof |
| CN102247882A (en) * | 2010-05-20 | 2011-11-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing phosphorus-containing alumina and application of catalyst |
| CN102896000A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Method for utilizing residues of catalyst production |
| CN105728015A (en) * | 2016-02-05 | 2016-07-06 | 青岛惠城环保科技股份有限公司 | Comprehensive utilization method for waste residues and waste liquor generated in catalytic cracking catalyst production |
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| CN114425413A (en) * | 2020-09-21 | 2022-05-03 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent for improving concentration of butylene in liquefied gas and preparation method and application thereof |
| CN115957807A (en) * | 2021-10-09 | 2023-04-14 | 中国石油化工股份有限公司 | Catalytic cracking catalyst containing phosphate waste residues and preparation method thereof |
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-
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- 1999-12-13 CN CNB991259424A patent/CN1150301C/en not_active Expired - Lifetime
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| CN101543783B (en) * | 2008-03-27 | 2011-03-30 | 中国石油化工股份有限公司石油化工科学研究院 | Suspension bed hydrocracking catalyst and preparation method and application thereof |
| CN102247881B (en) * | 2010-05-20 | 2014-05-28 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing rare earth-containing aluminum oxide and application thereof |
| CN102247881A (en) * | 2010-05-20 | 2011-11-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing rare earth-containing aluminum oxide and application thereof |
| CN102247882A (en) * | 2010-05-20 | 2011-11-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing phosphorus-containing alumina and application of catalyst |
| CN102247882B (en) * | 2010-05-20 | 2014-05-28 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing phosphorus-containing alumina and application of catalyst |
| CN102896000B (en) * | 2011-07-29 | 2014-08-20 | 中国石油化工股份有限公司 | Method for utilizing residues of catalyst production |
| CN102896000A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Method for utilizing residues of catalyst production |
| CN105728015A (en) * | 2016-02-05 | 2016-07-06 | 青岛惠城环保科技股份有限公司 | Comprehensive utilization method for waste residues and waste liquor generated in catalytic cracking catalyst production |
| CN109305767A (en) * | 2017-11-16 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of method that harmlessness disposing FCC dead catalyst prepares geo-polymer |
| CN111167510A (en) * | 2020-01-13 | 2020-05-19 | 杨涛 | Petroleum hydrocarbon cracking catalyst and its prepn |
| CN114425413A (en) * | 2020-09-21 | 2022-05-03 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent for improving concentration of butylene in liquefied gas and preparation method and application thereof |
| 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 |
| CN115957807A (en) * | 2021-10-09 | 2023-04-14 | 中国石油化工股份有限公司 | Catalytic cracking catalyst containing phosphate waste residues and preparation method thereof |
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