CN100355861C - Assisted catalyst for catalyzing cracking and preparation process thereof - Google Patents
Assisted catalyst for catalyzing cracking and preparation process thereof Download PDFInfo
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- CN100355861C CN100355861C CNB2005100691443A CN200510069144A CN100355861C CN 100355861 C CN100355861 C CN 100355861C CN B2005100691443 A CNB2005100691443 A CN B2005100691443A CN 200510069144 A CN200510069144 A CN 200510069144A CN 100355861 C CN100355861 C CN 100355861C
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Abstract
The present invention relates to a catalytic cracking cocatalyst for increasing the yield of diesel oil and a preparation method thereof. The cocatalyst is prepared by calcining spray microspheres at the high temperature of higher than 900DEG C, extracting the spray microspheres into pore canals through strong alkalis, such as sodium hydroxide, etc., and finally loading phosphorus and rare earth; the spray microspheres are prepared from kaoline as a main composition raw materials. The cocatalyst which does not contain any zeolite component has a sodium oxide content lower than 0.6%, and simultaneously, the cocatalyst contains 1 to 3.5 mass% of phosphorus and 1 to 5 mass% of rare earth oxide. A certain quantity of cocatalyst, which is added under the condition of no change of a catalyst originally adopted for an oil refining device, has the advantages of diesel oil yield improvement of an FCC catalytic device, product distribution improvement and utilization rate improvement of the existing catalyst variety, and additionally, the auxiliary agent also has the characteristics of simple preparation process, low cost, etc.
Description
Technical field
The present invention relates to a kind of assisted catalyst for catalyzing cracking and preparation method thereof, more particularly, is a kind of promotor with increasing output of diesel oil function and preparation method thereof.
Background technology
On the oil product market, the world today, the conspicuous contradiction of diesel oil supply and demand causes oil refining industry to improving the attention of diesel yield.Refinery presses for every technology that can improve diesel yield.And adopt FCC catalyzer with high-yield diesel oil function or auxiliary agent because less investment, instant effect, characteristics such as simple and easy to do become a kind of means that generally adopt, the research and development of such catalyzer also become a big focus of catalyzer industry thereupon.
The catalyst series of high-yield diesel oils such as MLC-500, the DMC-2 that present domestic many diesel catalytic converters mainly are the developments of Shi Ke institute, CC-20D, and the prepared Convert agent of in-situ crystallization technology of the application uniqueness of external Engelhard company exploitation, this agent both can be used as catalyzer and had used separately, also can be used as auxiliary agent and use, have certain effect at tool aspect the volume increase lightweight oil.But above several catalyzer mostly contains zeolite component, and preparation flow is longer, thereby cost is higher.
No matter it seems that in view of the above exploitation does not contain the catalyzer of zeolite component, with low cost, high-yield diesel oil, with form and the flexible composite use of other Primary Catalystss of auxiliary agent, be from cost or from operating, and should have more competitive edge.
U.S. Pat 4847225, US4894143 have narrated a kind of preparation that does not contain the CLS type assistant for calalytic cracking of zeolite.Its technology is with kaolin and the making beating of aluminium colloidal sol, and spraying drying after 927～1204 ℃ of roastings, with the sodium hydroxide solution reaction, is extracted the part activated silica out, falls sodium through washing and ion-exchange again, and load or not load alkaline-earth metal make CLS-Al
2O
3Type or MgO/CLS-Al
2O
3The type auxiliary agent.This auxiliary agent improves the diesel yield aspect and has certain effect at pressure fuel, but awaits further to improve.
Summary of the invention
The objective of the invention is to overcome above deficiency, with kaolin be main raw material prepare a kind of do not contain any zeolite component, with low cost, effect obviously, the catalytic cracking diesel oil auxiliary agent of flexible operation.
The assisted catalyst for catalyzing cracking of high-yield diesel oil of the present invention does not contain zeolite component, it is characterized in that on kaolin roasting microballoon, by mass percentage, load has 1～3.5% phosphorus, 1～5% rare earth oxide, and pore volume is between 0.2～0.5ml/g, and sodium oxide is lower than 0.6%; Wherein kaolin roasting microballoon is meant and contains the microballoon that kaolinic atomized microball obtains through 900 ℃～1100 ℃ high-temperature roasting.Wherein the content of phosphorus and rare earth can not be too low, and the effect of too low then these two kinds of material roles is not outstanding.But can not be too high, content of rare earth is too high, and then carbon deposit increases, the selectivity variation of the too high then expected product of phosphorus content.
The preparation method of assisted catalyst for catalyzing cracking provided by the present invention is: the mixture that will contain kaolin, water glass and sodium hydroxide adds water, and to make the slurries spray shaping be microballoon, and atomized microball forms the roasting microballoon 900 ℃～1100 ℃ following roastings.Sodium hydroxide, water, roasting microballoon are dropped in the stainless steel cauldron, and mixed system is under agitation in 80～95 ℃ of reactions, and extracting goes out wherein to have the active material of alkali reaction, forms the duct; The extract product microballoon is carried out pickling, sodium oxide is reduced to below 0.6%; Introduce phosphorus and rare earth to form the rare-earth phosphorate precipitation mode at last, make on the kaolin microsphere, (m%, as follows) counts by mass percentage, and load has 1～3.5% phosphorus, 1～5% rare earth oxide.
Concrete preparation method is as follows:
One, the preparation of extract product microballoon
Preparation process is followed successively by:
1. the mixture that will contain kaolin, water glass and sodium hydroxide adds water and makes slurries, and spray-dried one-tenth microballoon, kaolin comprise soft kaolin, hard kaolinite, coal gangue; The add-on of water glass (in silicon oxide) is 0～5% of a kaolin butt, and the add-on of sodium hydroxide is counted 0～5% of kaolin butt with sodium oxide.
2. atomized microball makes kaolin wherein change into based on spinel and with the roasting microballoon of a small amount of mullite through the heat release phase transformation 900～1100 ℃ of roastings, and mullite content had better not be above 15% in the roasting microballoon.
3. sodium hydroxide, water, roasting microballoon are dropped in the reactor, under whipped state,, remove filtrate in 80～95 ℃ of extractings 0.5～4 hour, the filter cake deionized water wash, filter, be drying to obtain the extract product microballoon, microballoon of the present invention is the microballoon of 40～100 μ m preferably.
Two, the post-modification of extracting microballoon is handled
1. pickling: acid solution and extracting microballoon are dropped into stainless steel cauldron successively, under whipped state, handled 0.2～2 hour in 60～95 ℃, fall sodium, wherein sodium oxide is reduced to purpose below 0.6% to reach washing.
The pickling condition: acid solution/extracting microballoon (mass ratio)=1～5, the used acid of pickling can be hydrochloric acid, phosphoric acid, sulfuric acid and oxalic acid, citric acid, tartrate.The pickling number of times is not done requirement, is no more than 0.6% as long as guarantee the sodium oxide content of final product.
2. precipitate phosphorus and rare earth: deionized water, above-mentioned extracting microballoon, earth solution and phosphorated ammonium salt are dropped into stainless steel cauldron successively, under whipped state,, precipitate to form rare-earth phosphorate in 60～95 ℃ of processing 0.5～2 hour.Used rare earth can be one or more in mixed chlorinated rare earth, the mixeding acid rare-earth, and phosphorus can ammonium phosphate, one or more forms in primary ammonium phosphate and the Secondary ammonium phosphate are introduced.
Actual conditions is: rare earth is with RE
2O
3Meter: RE
2O
3/ extracting microballoon (mass ratio)=0.01～0.05, phosphorus compound are in P: P/ extracting microballoon (mass ratio)=0.010～0.035.
At last, more after filtration, drying, get final product finished catalyst.
Major advantage of the present invention and effect:
Because this promotor carries out pore-creating with the alkali extraction process on hard burned microballoon, make the finished product on sterie configuration, has the flourishing pore structure of 0.2～0.5ml/g.Carrying out modification in conjunction with elements such as pickling and precipitation phosphorus, rare earths in addition handles, make the finished product on chemistry constitutes, have the acid sites of suitable heavy oil cracking and reasonably strength of acid distribution, thereby on reactivity worth, have the characteristics that the preventing from heavy metal ability is strong, activity stability is good.Therefore, constitute the condition that two aspects all possess middle runningss such as pressure fuel, high-yield diesel oil from sterie configuration and chemistry.Because this auxiliary agent does not contain zeolite component, thereby cost is comparatively cheap.This auxiliary agent and existing commercial catalysts are composite, under the situation that does not change the catalytic cracking unit operational condition, can play the diesel yield that improves device, the effect that improves the product distribution, can improve the utilization ratio of existing catalizer variety simultaneously, in practical application, have obvious superiority.
Embodiment
Further the present invention is described below, but the present invention is not limited in these examples with embodiment.
(1) used analysis test method among the embodiment.
1. the main analytical procedure that the present invention relates to sees Table 1
The main analytical procedure that table 1 the present invention relates to
| Project | Method | Standard code |
| Na 2O，m％ | Flame photometry | Q/SYLS 0568-2002 |
| RE 2O 3，m％ | Colorimetry | Q/SYLS 0580-2002 |
| P，m％ | Phosphorus molybdenum colorimetry | Q/SYLS 0586-2002 |
| SiO 2，m％ | Volumetry | Q/SYLS 0529-2002 |
| Pore volume, ml/g | The tetracol phenixin absorption method | Q/SYLS 0601-2002 |
2. catalyst selectivity evaluation: fixed fluidized bed method, wear out live catalyst 10 hours with 100% water vapour at 800 ℃ earlier before measuring.Estimate used stock oil character and see Table 2, the intermingled dregs ratio example is 30%.500 ℃ of temperature of reaction, catalystoil ratio are 3.75, catalyzer Intake Quantity 150g, oil inlet quantity 40g, air speed 16h
-1(what need to specify is, the appreciation condition in the table 7 changes to some extent, and agent/oil is 4, and air speed is 15h
-1).
Table 2 catalyst selectivity is evaluated raw materials used oil nature
| Project | Xinjiang decompression wide fraction wax oil | Xinjiang vacuum residuum |
| Carbon residue, the m% flash-point, ℃ pour point, ℃ | 0.012 136 38 | 9.6 316 / |
| Ultimate analysis: N, m% C, m% H, m% | 0.014 85.87 13.32 | 0.55 86.00 12.25 |
| Heavy metal is analyzed Cu, ppm Pb, ppm Fe, ppm Ni, ppm V, ppm As, ppm | 0.03 ＜0.1 1.55 0.14 0.04 ＜0.2 | 0.073 0.20 3.22 20.8 1.90 0.87 |
| The PONA analysis stable hydrocarbon, m% aromatic hydrocarbons, the m% colloid, m% | 91.2 7.7 1.1 | 55.7 41.5 2.7 |
| Molecular weight, M | 293 | / |
(2) raw materials used specification among the embodiment
Raw materials used specification sees Table 3 among the embodiment.
The specification of the raw material that adopts among table 3 embodiment
| Material name | Specification |
| Sodium hydroxide | Chemical pure |
| Water glass | 250g/l (in silicon-dioxide), industrial goods |
| Kaolin | S-2 kaolin (Suzhou product) |
| Mixed chlorinated rare earth solution | Industrial goods, the silver Rare Earth Company |
| Mixeding acid rare-earth solution | Industrial goods, packet header Zheng Chang metallic substance limited liability company |
| Secondary ammonium phosphate | Chemical pure |
| Primary ammonium phosphate | Chemical pure |
| The LV-23 catalyzer | Industrial goods, the production of blue refining catalyst plant |
| The LBO-12 catalyzer | Industrial goods, the production of blue refining catalyst plant |
| The LANET-35 catalyzer | Industrial goods, the production of blue refining catalyst plant |
Embodiment 1
(1) preparation of extract product microballoon:
1Kg (butt) Suzhou product kaolin, 80ml water glass and 27g sodium hydroxide are added water make slurries, spray shaping obtains the atomized microball of 0.9Kg.Atomized microball 930 ℃ of roastings in muffle furnace are got the roasting microballoon in 3 hours, wherein contain the mullite about 8%.Under whipped state, successively sodium hydroxide 60g, deionized water, roasting microballoon 500g are dropped in the stainless steel reactor, be warmed up to 90 ℃ of reactions 1.5 hours.Reaction removes by filter mother liquor after finishing, and the deionized water wash of heat is to PH=7, and filtration, drying obtain the extract product microballoon.
(2) the extract product aftertreatment prepares promotor:
The hydrochloric acid soln 500ml that adds 1mol/l in the stainless steel still, whipped state drop into down under the extract product 100g of preparation as stated above, 90 ℃ of conditions and handled 1 hour, filter, and wash 10 minutes under whipped state with the 500ml deionized water again, filter.With 150ml deionized water, mixed chlorinated rare earth solution (RE
2O
3Concentration is 350g/l) 14ml, ammonium phosphate 14g and above-mentioned washed product put in the stainless steel cauldron successively, under the state that stirs, handle 1h in 90 ℃, products therefrom after filtration, after the drying promotor A, its sodium oxide content is 0.39%, pore volume 0.24ml/g.
Application experiment: commercial catalysts LV-23 is composite as Primary Catalysts and increasing output of diesel oil promotor A of the present invention, the fluidized-bed evaluation that fixes, the performance of carrying out composite front and back compares.Evaluation result sees Table 4.
Table 4 compares with the composite front and back of commercial catalysts LV-23 performance
| Catalyzer | LV-23 | LV-23+20% promotor A | |
| Product distributes, m% | Dry gas | 1.47 | 1.42 |
| Liquefied gas | 12.74 | 11.97 | |
| Gasoline | 50.48 | 50.01 | |
| Diesel oil | 20.33 | 21.98 | |
| Heavy oil | 7.43 | 8.01 | |
| Coke | 5.99 | 4.98 | |
| Transformation efficiency, m% | 70.68 | 68.38 | |
| Yield of light oil, m% | 70.81 | 71.99 | |
| Total liquid is received m% | 83.55 | 83.96 | |
Embodiment 2
(1) preparation of extract product microballoon:
Kaolin, 160ml water glass, 54g sodium hydroxide and water are produced in 2Kg (butt) Suzhou make slurries, obtain the atomized microball of 1.9Kg at spray shaping.Atomized microball 900 ℃ of roastings in muffle furnace are got the roasting microballoon in 4 hours, wherein contain the mullite about 5%.Under whipped state, successively sodium hydroxide 880g, deionized water 5L, roasting microballoon 1.1kg are dropped in the stainless steel reactor, be warmed up to 80 ℃ of reactions 1 hour.Reaction removes by filter mother liquor after finishing, and with deionized water wash, filtration drying, obtains the extract product microballoon.
(2) the extract product aftertreatment prepares promotor:
The hydrochloric acid soln 1l that in the stainless steel still, adds 0.5mol/l, whipped state drops into down under the extract product 200g of preparation as stated above, 90 ℃ of conditions and handled 1 hour, carries out repeatedly three times, filters, washed 10 minutes under whipped state with the 1l deionized water again, filter.With 200ml deionized water, mixed chlorinated rare earth solution (RE
2O
3Concentration is 350g/l) 5ml, primary ammonium phosphate 7g and above-mentioned washed product put in the stainless steel cauldron successively, under the state that stirs, handle 1h in 95 ℃, products therefrom after filtration, after the drying cocatalyst B, its sodium oxide content is 0.46%, pore volume 0.21ml/g.
Application experiment: commercial catalysts LBO-12 is composite as Primary Catalysts and increasing output of diesel oil cocatalyst B of the present invention, the fluidized-bed evaluation that fixes, the performance of carrying out composite front and back compares.Evaluation result sees Table 5.
Table 5 compares with the composite front and back of commercial catalysts LBO-12 performance
| Catalyzer | LBO-12 | The LBO-12+20% cocatalyst B | |
| Product distributes, m % | Dry gas | 2.20 | 2.10 |
| Liquefied gas | 16.30 | 15.80 | |
| Gasoline | 50.90 | 49.99 | |
| Diesel oil | 1 5.88 | 18.00 | |
| Heavy oil | 6.72 | 7.10 | |
| Coke | 7.00 | 6.01 | |
| Transformation efficiency, m% | 76.40 | 73.90 | |
| Yield of light oil, m% | 66.78 | 67.99 | |
| Total liquid is received m% | 83.08 | 83.79 | |
Embodiment 3
(1) preparation of extract product microballoon:
1.5Kg (butt) Suzhou product kaolin, 120ml water glass and 41g sodium hydroxide are added water make slurries, spray shaping obtains the atomized microball of 1.2Kg.Atomized microball 980 ℃ of roastings in muffle furnace are got the roasting microballoon in 1 hour, wherein contain the mullite about 10%.Under whipped state, successively sodium hydroxide 100g, deionized water 500mL, roasting microballoon 500g are dropped in the stainless steel reactor, be warmed up to 80 ℃ of reactions 3 hours.Reaction removes by filter mother liquor after finishing, and the deionized water wash of heat obtains the extract product microballoon to PH=7, filtration drying.
(2) the extract product aftertreatment prepares promotor:
The hydrochloric acid soln 100ml that in the stainless steel still, adds 1.5mol/l, whipped state drops into down under the extract product 100g of preparation as stated above, 80 ℃ of conditions and handled 0.5 hour, carries out twice repeatedly, filters, washed 10 minutes under whipped state with the 500ml deionized water again, filter.Again with 500ml deionized water, mixed chlorinated rare earth solution (RE
2O
3Concentration is 350g/l) 14ml, Secondary ammonium phosphate 9g and above-mentioned washed product put in the stainless steel cauldron successively, under the state that stirs, handle 2h in 60 ℃, products therefrom after filtration, after the drying promotor C, its sodium oxide content is 0.26%, pore volume 0.29ml/g.
Application experiment: commercial catalysts LANET-35 is composite as Primary Catalysts and increasing output of diesel oil promotor C of the present invention, the fluidized-bed evaluation that fixes, the performance of carrying out composite front and back compares.Evaluation result sees Table 6.
Table 6 compares with the composite front and back of commercial catalysts LANET-35 performance
| Catalyzer | LANET-35 | LANET-35+20% promotor C | |
| Product distributes, m% | Dry gas | 2.31 | 2.00 |
| Liquefied gas | 19.50 | 19.30 | |
| Gasoline | 49.03 | 48.60 | |
| Diesel oil | 14.86 | 16.33 | |
| Heavy oil | 5.90 | 6.24 | |
| Coke | 6.87 | 6.03 | |
| Transformation efficiency, m% | 77.71 | 75.93 | |
| Yield of light oil, m% | 63.89 | 64.93 | |
| Total liquid is received m% | 83.39 | 84.23 | |
From table 4,5,6 results as seen, with composite before compare, composite dose have diesel yield height, yield of light oil height, total liquid is received characteristics such as high, that coke selectivity is good.It is composite to illustrate that diesel oil promotor of the present invention can play with multiple catalyzer, promotes the effect of the catalyst system high-yield diesel oil after composite.
Embodiment 4
(1) preparation of extract product microballoon:
1Kg (butt) Suzhou product kaolin is added water make slurries, spray shaping obtains the atomized microball of 1.1Kg.Atomized microball 1070 ℃ of roastings in muffle furnace are got the roasting microballoon in 2 hours, wherein contain the mullite about 3%.Under whipped state, successively sodium hydroxide 200g, deionized water 1.2L, roasting microballoon 400g are dropped in the stainless steel reactor, be warmed up to 95 ℃ of reactions 1 hour.Reaction removes by filter mother liquor after finishing, and deionized water wash, filtration drying obtain the extract product microballoon.
(2) the extract product aftertreatment prepares promotor:
The hydrochloric acid soln 300ml that adds 3mol/l in the stainless steel still, whipped state drop into down under the extract product 100g of preparation as stated above, 90 ℃ of conditions and handled 1.5 hours, filter, and wash 10 minutes under whipped state with the 500ml deionized water again, filter.Again with 100ml deionized water, mixeding acid rare-earth solution (RE
2O
3Concentration is 256g/l) 14ml, primary ammonium phosphate, Secondary ammonium phosphate respectively adds 6.5g and above-mentioned washed product is put in the stainless steel cauldron successively, under the state that stirs, handle 1h in 95 ℃, products therefrom after filtration, after the drying promotor D, its sodium oxide content is 0.30%, pore volume 0.28ml/g.
Comparative Examples 1
Prepare promotor by embodiment 2 described methods, just do not introduce phosphorus and rare earth, obtain promotor E.
Comparative Examples 2
Prepare MgO/CLS-Al by patent US4847225 embodiment 4 described methods
2O
3Type promotor F.
Comparative Examples 3
Prepare promotor by embodiment 1 described method, just in step (2), do not introduce phosphorus, obtain promotor G.
Comparative Examples 4
Prepare promotor by embodiment 3 described methods, just in step (2), do not introduce rare earth, obtain promotor H.
Promotor D of the present invention, Comparative Examples gained promotor E, F, G, H and LV-23 are carried out composite, and carry out fixed fluidized bed evaluation, the results are shown in Table 7.
Table 7 uses the fixed fluidized bed evaluation result of different catalyzer, promotor relatively
| Catalyzer | Product distributes, m% | Transformation efficiency, m% | Yield of light oil, m% | Total liquid is received m% | |||||
| Dry gas | Liquefied gas | Gasoline | Diesel oil | Heavy oil | Coke | ||||
| LV-23 | 2.00 | 14.95 | 50.81 | 17.38 | 6.56 | 6.88 | 74.64 | 68.19 | 83.14 |
| LV-23+20 % auxiliary agent D | 1.82 | 14.29 | 49.93 | 19.47 | 7.39 | 5.70 | 71.74 | 69.40 | 83.69 |
| LV-23+20 % auxiliary agent E | 2.01 | 15.29 | 50.27 | 18.25 | 7.50 | 5.54 | 73.11 | 68.52 | 83.81 |
| LV-23+20 % auxiliary agent F | 1.99 | 15.03 | 50.14 | 18.59 | 6.78 | 5.93 | 73.09 | 68.73 | 83.76 |
| LV-23+20 % auxiliary agent G | 2.10 | 15.38 | 50.40 | 18.10 | 6.41 | 6.14 | 74.02 | 68.50 | 83.88 |
| LV-23+20 % auxiliary agent H | 2.03 | 14.87 | 50.38 | 18.64 | 7.19 | 5.41 | 72.69 | 69.02 | 83.89 |
By data in the table as seen, carry out composite in same ratio and LV-23 catalyzer, by the composite effect that all has increasing output of diesel oil in various degree of technology of the present invention prepared auxiliary agent D, E, G, H and LV-23, wherein the increasing output of diesel oil effect of auxiliary agent E, G, H and the increasing output of diesel oil effect for preparing auxiliary agent F by U.S. Pat 4847225 embodiment 4 described methods quite or slightly poor, the increasing output of diesel oil effect of auxiliary agent D is better than auxiliary agent F.This shows that introducing phosphorus and rare earth in the preparation technology of diesel oil auxiliary agent of the present invention in step (2) simultaneously is very important to the increasing output of diesel oil function of further this auxiliary agent of reinforcement.
Claims (12)
1. an assisted catalyst for catalyzing cracking is characterized in that on kaolin roasting microballoon, and by mass percentage, load has 1～3.5% phosphorus, 1～5% rare earth oxide, and pore volume is between 0.2～0.5ml/g, and sodium oxide is lower than 0.6%; Wherein kaolin roasting microballoon is meant and contains the microballoon that kaolinic atomized microball obtains through 900 ℃～1100 ℃ high-temperature roasting.
2. promotor according to claim 1 is characterized in that described kaolin comprises one or more in soft kaolin, hard kaolinite, the coal gangue.
3. promotor according to claim 1 is characterized in that mullite content is no more than 15% in the described roasting microballoon.
4. the preparation method of the described assisted catalyst for catalyzing cracking of claim 1, it is characterized in that: the mixture that will contain kaolin, water glass and sodium hydroxide adds water and makes slurries, spray shaping is a microballoon, atomized microball forms the roasting microballoon that contains spinel, Mo Laishi 900 ℃～1100 ℃ following roastings; Sodium hydroxide, water, roasting microballoon are dropped in the stainless steel cauldron, and mixed system is under agitation in 80～95 ℃ of reactions, and extracting goes out wherein to have the active material of alkali reaction, forms the duct; The extract product microballoon is carried out pickling, sodium oxide is reduced to below 0.6%; Introduce phosphorus and rare earth to form the rare-earth phosphorate precipitation mode at last.
5. according to the described method of claim 4, the add-on that it is characterized in that water glass is 0～5% of kaolin butt quality in silicon oxide.
6. according to the described method of claim 4, the add-on that it is characterized in that sodium hydroxide is 0～5% of kaolin butt quality in sodium oxide.
7. according to the described method of claim 4, it is characterized in that the mass ratio of highly basic extracting time institute water, sodium hydroxide, roasting microballoon is: NaOH/ roasting microballoon=0.1～0.9, water/roasting microballoon=1～5.
8. according to the described method of claim 4, it is characterized in that the pickling condition is: the mass ratio of acid solution/extracting microballoon is 1～5,60～95 ℃ to be handled 0.2～2 hour.
9. according to the described method of claim 4, it is characterized in that the used acid of pickling is one or more in hydrochloric acid, phosphoric acid, sulfuric acid and oxalic acid, citric acid, the tartrate.
10. according to the described method of claim 4, it is characterized in that the actual conditions of coprecipitation mode introducing phosphorus, rare earth is: rare earth is with RE
2O
3Meter, RE
2O
3The mass ratio of/extracting microballoon is 0.01～0.05; Phosphorus compound is in P, and the mass ratio of P/ extracting microballoon is 0.010～0.035.
11., it is characterized in that rare earth adopts one or more in mixed chlorinated rare earth, the mixeding acid rare-earth according to the described method of claim 4.
12., it is characterized in that one or more form is introduced in phosphorus employing adding ammonium phosphate, primary ammonium phosphate, the Secondary ammonium phosphate according to the described method of claim 4.
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| CN103240113B (en) * | 2012-02-07 | 2015-08-19 | 中国石油天然气股份有限公司 | The preparation method of in-situ crystallization type catalytic cracking catalyst |
| CN104588071B (en) * | 2013-10-31 | 2017-07-25 | 中国石油化工股份有限公司 | A kind of mesoporous catalysis material of phosphorous, magnesium and rare earth |
| CN104588053B (en) * | 2013-10-31 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of mesopore material of high cracking activity |
| CN104588054B (en) * | 2013-10-31 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of mesoporous catalysis material of phosphorous and rare earth |
| CN104692407B (en) * | 2015-02-28 | 2016-08-31 | 中国石油天然气股份有限公司 | A kind of ITH structure rare-earth silicon-aluminum molecular sieve and synthetic method thereof |
| CN106378204A (en) * | 2016-08-12 | 2017-02-08 | 青岛惠城环保科技股份有限公司 | Preparation method for metal capturing agent |
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|---|---|---|---|---|
| US4894143A (en) * | 1984-10-05 | 1990-01-16 | W. R. Grace & Co.-Conn. | Catalytic cracking process employing an aluminum silicon spinel-mullite-gamma alumia containing catalyst |
| CN1334314A (en) * | 2000-07-19 | 2002-02-06 | 中国石油天然气股份有限公司兰州炼化分公司 | Vanadium-resistant catalytic cracking assistant containing Y-type molecular sieve and its preparing process |
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| CN1861754A (en) | 2006-11-15 |
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