CN1197692A - Catalytic cracking catalyst and its preparation - Google Patents
Catalytic cracking catalyst and its preparation Download PDFInfo
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Abstract
The catalyst has active component, which is selected from octahedral zeolite and ZSM-5 zeolite with cell constant of 2.432-2.474 nm and their mixture, in 5-40% and amorphous Si-Al carrier in 60-95%. It is prepared by adding molecular sieve into Si-Al colloid prepared through three-step cocolloidizing process, and through the processes of pulping, alkalication of size, filtration, acidification of size, spraying, washing and drying. The catalyst prepared by said technological process has moderate accumulation, high activity and selectivity and is very suitable for use in FCC equipment to refine residual oil and secondary processed oil.
Description
The present invention relates to the Cracking catalyst technical field, exactly, is to mix catalytic cracking catalyst of refining part residual oil or secondary operations oil (as burnt wax, depitching wet goods) and preparation method thereof about a kind of wax oil FCC apparatus that is used for.
In recent years, because catalytically cracked material deficiency, China's FCC apparatus is mixed the quantity cumulative year after year of refining residual oil and secondary operations oil, because raw material heaviness and poor qualityization, at first require used catalyst to develop to the super-stable Y molecular sieves catalyst direction of macromolecule sieve content, because molecular sieve content increases, ability to catalyst carrier tolerance molecular sieve amount proposes requirements at the higher level, wish that at first the carrier cohesive force is strong, wear resistence good, because the heaviness of feedstock oil, the macromolecular components of difficult cracking is increased, wish that again carrier has suitable macroporous structure; In addition, in conjunction with the actual conditions of the present FCC apparatus of China, wish again that simultaneously catalyst has suitable medium bulk density (generally 0.5-0.7/ml scope for well).Therefore, at the problems referred to above, people are constantly towards this direction effort, to improve the performance of Cracking catalyst, in this respect, have many reported in literature both at home and abroad, once introduce the full synthesis technique of employing step-by-step precipitation method or coprecipitation respectively as United States Patent (USP) 3650988,3433748,3912619 etc. and prepared Rey type molecular sieve catalyst, it has advantages such as active height, good stability, but catalyst buildup density less (＜0.5g/ml), the carrier cohesive force is poor, the low (molecular sieve content ≯ 15m%) of molecular sieve dosis tolerata; The employing aluminium colloidal sol of United States Patent (USP) 4010116,4086187,3652148 and reports such as 3912619, Ludox or silicon bore the catalyst that sol/gel is the semi-synthesizing technology preparation of binding agent, though the carrier cohesive force is strong, molecular sieve dosis tolerata height (can up to 50m%) abrasion resistance is good, but bulk density is big (general＞as 0.7g/ml), to be not suitable for China's most of FCC apparatus of present stage and to use; And for example: United States Patent (USP) 4247420 provides the medium bulk density of a kind of preparation (0.55-0.65g/ml), the preparation method of anti abrasive Cracking catalyst, its preparation process is to add the dilute sulfuric acid aluminum solutions to make its PH be controlled at 9.0-9.6 in waterglass and clay slurry, add sodium metaaluminate and concentrated sulfuric acid aluminium then, obtain silica-alumina gel, add again and grind good molecule screening the pulp night, and regulate pH value to 3.8-4.0 with the mother liquor of synthetic Nay, filter then, pulp, spray shaping, washing, dry, obtain the catalyst finished product, but this technology is difficult to realize suitability for industrialized production, reason is owing to filter preceding slurries PH low (PH3.8-4.0), particle is thin, slurries are rare, cause strainability poor, effective ingredient is run and is decreased seriously, influence the production capacity of catalyst greatly, hardship is not filtered, then can be owing to contained salinity in the slurries too many (accounting for more than the 20m% of catalyst butt), increase the load of spray-drying and washing procedure, even can cause sticking tower, material collapses, the impurity content height, bitter through repeatedly washing the same phenomenon such as serious that runs off of active principle, in addition, regulate the pH value of catalyst slurry with synthesizing the Nay mother liquor, other has made full use of the sio in the mother liquor
2, but produced thus because the extremely instability that the Nay mother liquor is formed causes the instability of catalyst composition, and then have influence on the performance of catalyst.
The purpose of this invention is to provide three steps of a kind of usefulness altogether the full synthesis technique preparation of glue have a medium bulk density, wear-resistant, strong to big molecule hydrocarbon pyrolysis ability, and have excellent active and good synthetic zeolite catalysts cracking catalyst optionally, and provide this Preparation of catalysts method, this preparation method's technology is simple, is easy to realize industrialization.
Catalyst provided by the invention is with 5-40m%, the faujasite that to be selected from brilliant crisp constant be 2.432-2.474nm of 10-30m% preferably, 2SM-5 zeolite and composition thereof is an active component, be aided with 60-95m%, preferably unformed silica-aluminium oxide of 70-90m% is a kind of mixture that carrier is formed.The crisp constant of the said crystalline substance of the present invention is that the faujasite of 2.432-2.474nm is meant Reusy, Rey and usy molecular sieve and other high silica alumina ratio y type molecular sieve, preferably Reusy molecular sieve.The said unformed silica-alumina support of the present invention is by containing sodium silicate and containing a kind of full silicon-aluminium glue carrier altogether that synthesizes that aluminium salt and aluminate are made through multistep reaction, the percentage by weight of aluminium oxide is 25-40m%, preferably 30-35m% in this silicon-alumina supporter.The said sodium silicate that contains refers generally to waterglass, contains aluminium salt and is meant aluminum sulfate, and said aluminate is meant sodium metaaluminate.
Preparation of catalysts method of the present invention is that the molecular sieve pulp that homogeneous is good joins in complete synthetic silicon-alumina gel that the glue reaction makes altogether through three steps, making beating, in slurries, add aqueous slkali again, regulate PH to 6.0-8.0, preferably 7.0-7.5 filters, pulls an oar, adds inorganic acid solution in slurries, regulate slurries PH to 4.0-5.5,4.2-4.8 preferably, spray shaping, washing, drying then, the catalyst finished product.Catalyst preparation process flow process of the present invention is seen Fig. 1, and its preparation process is:
(1), toward sio
2Content is the 30-80 grams per liter, preferably in the waterglass of 30-50 grams per liter, in stirring the down slow AL of adding
2O
3Content is 10-70 grams per liter, the aluminum sulfate solution of 20-50 grams per liter preferably, and the control pH value is 8.5-10.0, and preferably 9.0-9.6. is aging 0.5-10 hour, si-Al is cogelled, add AL then
2O
3Weight concentration is 10-35m%, preferably (its causticity is than being 0.9-1.3 for the sodium metaaluminate of 20-30m%, 1.0-1.2 preferably) solution, pH value up to the colloid slurries is 11.0-13.0,11.8-12.6 preferably, and then to add concentration in the colloid slurries be the 60-100 grams per liter, the preferably aluminum sulfate solution of 70-90 grams per liter, make the acid gel slurries, above-mentioned common glue of three steps just makes and contains AL
2O
3Be 25-40m%, the silica of 30-35m% (accounting for butt)-alumina support slurries preferably, slurry solid content is 5-8%, its pH value is 3.5-3.9;
(2) molecular sieve pulp that homogeneous is good joins in silica-alumina support slurries that above-mentioned (1) step prepares, and after stirring, regulates the slurries pH value to 6.0-8.0 with aqueous slkali, 7.0-7.5 preferably, filter, press 8-15m% again, preferably the solid content of 9-12m% adds the water making beating;
(3) slowly add inorganic acid solution in above-mentioned (2) step pulp uniform catalyst slurries, regulate the slurries pH value to 4.0-5.5, preferably 4.2-4.8 makes acid catalyst slurry; Then, spray shaping, washing, drying obtain the catalyst finished product.
The said aqueous slkali of the present invention is meant ammoniacal liquor.
The said inorganic acid of the present invention is meant sulfuric acid, hydrochloric acid or nitric acid.
Main points of the present invention are as follows:
(1) is total in the synthetic full preparation of the glue catalyst process of the present invention in three steps, goes on foot in silicon-aluminic acid colloid that glue makes altogether, after stirring when molecular sieve pulp joins three, slowly add aqueous slkali (ammoniacal liquor) (see flow chart the 4. step), regulate pH value to 6.0-8.0, preferably 7.0-7.5 filters.In this operation, key problem in technology is by adding alkali, slurries are alkalized, improve pH value, can obviously improve the rate of filtration, thereby improve the production capacity of catalyst greatly, it is rare to have overcome prior art (as US P4247420) colloid, particle is thin, and filtration difficulty and the serious defective of catalyst active principle loss have just overcome prior art and be difficult to realize industrialized defective.
(2) the filter cake after the above-mentioned filtration, again by 8-15m% preferably the solid content of 9-12m% add water making beating, slowly add inorganic acid solution (sulfuric acid, hydrochloric acid or pin acid) then, regulate the slurries pH value to 4.0-5.5,4.2-4.8 (see flow chart the 6. step) preferably, make acid catalyst slurry, spray shaping, washing, drying obtain the catalyst finished product again.In the above-mentioned acidizing process that adds inorganic acid, key is to reduce the slurries pH value to OK range by adding acid, can obviously improve the bulk density and the intensity of catalyst, thereby improved the abrasion resistance of catalyst, and obtain to have medium bulk density (0.5-0.7g (ml) molecular sieve cracking catalyst, and, compared with the prior art, the pore size distribution scope of catalyst broadens, and has increased the ratio in macropore (hole of 75-10.0A ° of scope), and the big molecule hydrocarbon of cracking is had certain benefit.
Compared with the prior art the present invention has following advantage:
(1) utilizes the prepared catalyst carrier of preparation technology's method of the present invention, different types of molecular sieve and composition thereof had stronger holding capacity and adaptability, this carrier and different molecular sieve compatibility can be prepared suitable different material, the catalyst series that the product under the different device distributes and requires.
(2) catalyst of the present invention has moderate bulk density and good abrasion resistance, and intensity is good.
(3) activity of such catalysts of the present invention and selectivity are better than prior art, especially be example with the Reusy molecular sieve catalyst, in the cracking reaction, under the identical situation of oil ratio, gasoline yield the former than the high 0.5-2.0 of the latter percentage point, heavy oil conversion performance improves 1.0-1.5 percentage point, and coke slightly reduces, to have a good physical and chemical performance relevant with catalyst of the present invention for this, especially it has suitable macroporous structure, more help the cracking of big molecule hydrocarbon than prior art, thereby promote that heavy hydrocarbon is converted into light component more.
(4) fabricating technology provided by the present invention, overcome the defective that prior art is difficult to filter, also overcome simultaneously prior art through repeatedly washing active principle serious, and the defective such as catalyst impurities content height that runs off, because the present invention has overcome the defective that is difficult to filter, dope filtration speed is fast, thereby can improve the production capacity of catalyst significantly, have tangible economic benefit.
(5) preparation method's technology of the present invention is simple, is suitable for large-scale industrial production.
1, the following examples will the invention will be further described.
The analysis test method that the present invention is used
(1) AL
2O
3The EDTA volumetric method
(2) Na
2The O flame spectrometry
(3) Re
2O
3The EDTA volumetric method
(4) SO
4The thermal decomposition iodimetric titration
(5) specific surface low-temperature nitrogen adsorption method
(6) pore volume low-temperature nitrogen adsorption method
(7) mensuration of abrasion index (J, I method):
Certain catalyst samples is put into the abrasion index determinator, under constant gas speed, blew mill 5 hours, except that first hour, the fine powder that produced in four hours of back less than 15 microns account for total receipts amount mass percent 1/4th, promptly calculate average mass percent hourly, be called the abrasion index (m%h of catalyst
-1).
(8) apparent bulk density (being called for short ABD)
With catalyst samples (through 540 ℃, 3 hours roasting rich) funnel by a fixed position in about 30 seconds, pour in 25 milliliters of special-purpose graduated cylinders, can calculate by the weight of catalyst that the density of sample is apparent bulk density (grams per milliliter) under the experiment condition
2, the raw materials used place of production and specification in the invention process:
(1) water glass solution: Chang Ling oil-refining chemical head factory (hereinafter to be referred as long refining) catalyst plant, SiO
2Content is 275.1 grams per liters, Na
2O content is 87.3 grams per liters.
(2) aluminum sulfate solution: long refining catalyst plant, AL
2O
3Content is 91.7 grams per liters, free acid content 9.81 grams per liters.
(3) sodium hydroxide solution: long refining catalyst plant, Na
2O content 318 grams per liters.
(4) aluminium hydroxide: Zhengzhou Aluminium Plant, solid content 64.5%.
(5) ammoniacal liquor: Xiangfan City, Hubei Province reagent ammoniacal liquor factory, chemical pure, NH
3Content＞25m%.
(6) industrial sulphuric acid: long refining catalyst plant, weight concentration 20m%.
(7) REY molecular sieve: long refining catalyst plant, lattice constant is 2.474nm, Re
2O
3Be 19.2m%, Na
2O is 1.56m%.
(8) REUSY molecular sieve: long refining catalyst plant, lattice constant is 2.458nm, solid content 28.0m%.
(9) USy molecular sieve: long refining catalyst plant, brilliant crisp constant is 2.455nm.
(10) ZSM-5 Chemical Plant of Nankai Univ., silica alumina ratio 50, Na
2O＜0.1m%.
(11) synthetic Nay mother liquor: long refining catalyst plant, SiO
2Content 40-60 grams per liter.
2, the preparation of other raw material in the example of the present invention:
Sodium aluminate solution: get 225 liters of sodium hydroxide solutions, heating, when temperature rises to 80 ℃, stir and add 1.30 kilograms of aluminium hydrate powders down slowly, also reacted 0.5-1.5 hour under the stirring at 95-105 ℃, when treating that solution becomes gets limpid no sediment, promptly getting the causticity ratio is 1.1, the sodium aluminate solution of concentration 20-30m%.
Example 1:
3.75 liters of water intaking glass solutions add 16.88 liters of deionized waters, stir evenly, and slowly drip AL
2O
34.36 liters of the dense aluminum sulfate solutions that becomes 28.0 grams per liters, surveying pH value is 9.26, stirs and adds 0.58 kilogram of the sodium aluminate solution that weight concentration is 22m% down aging half an hour under the room temperature, PH is 12.14, adds AL again
2O
3Concentration is 2 88 liters of the aluminum sulfate solutions of 90.1 grams per liters, preferably add 1.64 kilograms of the good REUSY molecular sieve pulps of ball milling, stirred 15 minutes, regulate its pH value to 7.38 with weak aqua ammonia (1: 1), filtering, pull an oar, add sulfuric acid solution, to be acidified to pH value be 4.47, spray shaping, washing, drying obtain catalyst sample, are numbered S-1 then, and it forms proportioning and physical and chemical performance sees Table 1.
Example 2-6:
The preparation method of sample S-2-S-6 is with example 1, and it is different with molecular sieve type just to form proportioning, sees table 1 for details, and physical and chemical performance also sees Table 1.
Comparative Examples 1:
3.75 liters of water intaking glass solutions add 16.88 liters of deionized waters, stir evenly, and slowly drip AL
2O
3Concentration is 3.79 liters of the aluminum sulfate solutions of 28.0 grams per liters, and surveying pH value is 9.30, stirs and adds 0.5 kilogram of the sodium aluminate solution that weight concentration is 22m% down aging half an hour under the room temperature, and PH is 12.20, adds AL again
2O
3Concentration is 3.36 liters of the aluminum sulfate solutions of 77.2 grams per liters, adds 1.64 kilograms of the good REUSY molecular sieve pulps of mill at last, stirs 15 minutes, regulate its pH value to 4.14 with synthetic Nay mother liquor, filter spray shaping, washing, drying, obtain catalyst sample A-1, it is formed proportioning and sees Table 1.
Comparative Examples 2:
3.26 liters of water intaking glass solutions add 14.68 liters of deionized waters, stir evenly, and add levigate kaolin powder 269 grams, pull an oar 15-20 minute, slowly drip AL
2O
3Concentration is 3.79 liters of the aluminum sulfate solutions of 28.0 grams per liters, and the side pH value is 9.50, stirs and adds 0.5 kilogram of the sodium aluminate solution that weight concentration is 22m% down aging half an hour under the room temperature, and PH is 12.47, adds AL again
2O
3Concentration is 2.92 liters of the aluminum sulfate solutions of 77.2 grams per liters, add 1.64 kilograms of the good REUSY molecular sieve pulps of mill at last, stirred 15 minutes, regulate pH value to 4.2 with the mother liquor of synthetic Nay then, filtration, spray shaping, washing, drying, obtain catalyst sample A-2, it is formed proportioning and also sees Table 1.
Comparative Examples 3:
The preparation method of comparative sample A-3 is identical with Comparative Examples 1, and just molecular sieve changes the usy molecular sieve of 30m% into, and its composition, proportioning see Table 1.
| Sample number into spectrum | Be total to glue m% | Kaolin m% | ???JI ???m％h -1 | ??ABD ??g/ml | Zeolite molecular sieve | |
| Content m% | Type | |||||
| ??S-1 | ??77 | ????0 | ????1.5 | ??0.62 | ????23 | ???REUSY |
| ??S-2 | ??72 | ????0 | ????2.0 | ??0.60 | ????28 | ???REUSY |
| ??S-3 | ??85 | ????0 | ????0.9 | ??0.66 | ????15 | ???REY |
| ??S-4 | ??80 | ????0 | ????1.3 | ??0.63 | ????20 | ???REY+ZSM-5 |
| ??S-5 | ??75 | ????0 | ????1.9 | ??0.60 | ????25 | ???REY+USY |
| ??S-6 | ??70 | ????0 | ????2.5 | ??0.58 | ????30 | ???USY |
| Contrast A-1 | ??77 | ????0 | ????1.8 | ??0.58 | ????23 | ???REUSY |
| Contrast A-2 | ??67 | ????10 | ????2.0 | ??0.58 | ????23 | ???REUSY |
| Contrast A-3 | ??70 | ????0 | ????3.2 | ??0.54 | ????30 | ???USY |
Data as can be seen from table 1, utilize the prepared catalyst carrier of process of the present invention that dissimilar molecular sieve and composition thereof is had stronger holding capacity and adaptability, prepared catalyst has good abrasion resistance, intensity is good, and heap is fit to China's most conventional FCC apparatus and uses than moderate.
Example 7:
Catalyst sample S-1 of the present invention and contrast sample A-1 after giving processing on the AS-2400 low temperature n2 absorption apparatus under 300 ℃, are measured the pore structure of catalyst, the surface area of mensuration, pore volume, the average pore size structure is listed in the table 2, and pore size distribution the results are shown in Figure 2.From table 2 and Fig. 2 result as can be seen, compare with the contrast sample, catalyst of the present invention mainly is the ratio (hole of 75-100A ° of scope) that increases macropore, and has unique double-pore structure, and this is undoubtedly favourable to the big molecule hydrocarbon of cracking.
Table 2
| The project sample number into spectrum | Surface area m 2/g | Pore volume ml/g | Average pore size A ° |
| ??S-1 | ??354 | ??0.30 | ???51.3 |
| Contrast A-1 | ??300 | ??0.28 | ???39.5 |
Example 8:
With catalyst sample S-1 of the present invention, S-3 and comparative sample A-1, A-2 through 780 ℃/h, after 100% steam treatment, on the small fixed flowing bed device, estimate, the pipe that feedstock oil is mixed 6.3m% for the defeated decompressed wax oil of pipe is failed decompression residuum, 500 ℃ of reaction temperatures, oil ratio 4.0, air speed 16-18h
-1, its reactivity worth evaluation result is listed in table 3.
As can be seen from Table 3, catalyst sample S-1 of the present invention compares with contrast sample A-1, A-2, and conversion ratio improves nearly 1.3-1.5%, and gasoline increases 0.8-1.8%, and heavy oil reduces 1.1-1.2%, and coke slightly reduces.The also high 1-2% of micro-activity MAT.And be though that the S-3 of active component has good intensity with REY, mix in cracking aspect the product selectivity of slag raw material not as being the S-1 of active component with REUSY.
Table 3
| The sample number into spectrum project | ???S-1 | ????S-3 | ???A-1 | ???A-2 |
| Product distribution m% | ||||
| ???H 2 | ???0.03 | ????0.06 | ???0.04 | ???0.04 |
| ???C 1-C 2 | ???1.22 | ????1.49 | ???1.24 | ???1.20 |
| ???C 3-C 4 | ???14.46 | ????14.64 | ???14.64 | ???14.21 |
| Gasoline | ???54.68 | ????49.63 | ???52.90 | ???53.93 |
| Diesel oil | ???17.04 | ????19.57 | ???17.28 | ???17.02 |
| Heavy oil | ???7.43 | ????9.08 | ???8.60 | ???8.62 |
| Coke | ???5.21 | ????5.53 | ???5.55 | ???5.63 |
| Conversion ratio | ???75.59 | ????71.35 | ???74.12 | ???74.37 |
| Selectivity: % | ||||
| Gasoline | ???72.34 | ????69.56 | ???71.37 | ???72.51 |
| Heavy oil | ???9.83 | ????12.73 | ???11.60 | ???11.59 |
| Coke | ???6.89 | ????7.75 | ???7.49 | ???7.57 |
| MAT (800 ℃/4h) steam ageing, % | ???71.2 | ????71.4 | ???69.0 | ???70.8 |
Example 9:
3.75 liters of water intaking glass solutions add deionized water and stir evenly for 16.88 liters, slowly drip AL
2O
3Concentration is 4.36 liters of the aluminum sulfate solutions of 28.0 grams per liters, and surveying pH value is 9.28, aging half an hour under the room temperature, stirs that to add weight concentration down be that 22m% is (with AL
2O
3Meter) 0.58 kilogram of sodium metaaluminate (the causticity ratio is 1.0) solution, PH is 12.20, adds AL again
2O
3Concentration is 3.36 liters of the aluminum sulfate solutions of 77.2 grams per liters, add 1.64 kilograms of the good REUSY molecular sieve pulps of mill at last, stirred 15 minutes, evenly slurries are divided into two parts, a with weak aqua ammonia (1: 1) adjusting slurries pH value to 7.40, and another part regulated its pH value to 4.18 according to the prior art method with synthetic Nay mother liquor, get equivalent slurries vacuum filtration under the same conditions, filter cake surface moisture content is drained the time in the mensuration Buchner funnel, the results are shown in Table 4, all the other slurries make catalyst by preparation procedure separately, and the chemical analysis results of catalyst sees Table 5.
Table 4
| The slurries sample | The present invention | Correlation technique |
| The dried time of filter (minute) | 15 | ?75 |
Data as can be seen in the table 4, compared with the prior art, use preparation method of the present invention, by adding alkali, slurries are carried out alkaliization, improve slurries pH value to 7.40, can obviously improve the rate of filtration of slurries, compare the rate of filtration of the present invention with correlation technique and improved 5 times, thereby can improve the production capacity of catalyst widely, have tangible economic benefit.
From table 5 data as can be seen, compared with the prior art, use preparation method of the present invention, not only dope filtration speed is fast, and active principle (AL in the catalyst finished product of preparation
2O
3, RE
2O
3) run off and lack, and foreign ion (Na
2O, SO
4) content is low, thereby solved the deficiency of prior art method, be fit to suitability for industrialized production.
Table 5
| The catalyst sample | The present invention | Correlation technique |
| AL 2O 3、m％ | ????31.3 | ???26.6 |
| RE 2O 3、m％ | ????1.5 | ???1.0 |
| Na 2O、m％ | ????0.18 | ???0.35 |
| SO 4 ＝、m％ | ????1.2 | ???1.8 |
Claims (9)
1, catalyst is split in a kind of catalysis. it is characterized in that this catalyst is by 5-40m%, preferably the faujasite that to be selected from brilliant crisp constant be 2.432-2.474nm, ZSM-5 zeolite and composition thereof of 10-30m% be for active component, again with 60-95m%, preferably unformed silica-aluminium oxide of 70-90m% is a kind of mixture that carrier is formed.
2,, it is characterized in that the crisp constant of said crystalline substance is that the faujasite of 2.432-2.474nm is meant REUSY, REY, USY and other high silica alumina ratio Y zeolite according to the said catalyst of claim 1.
3,, it is characterized in that the crisp constant of said crystalline substance is that the faujasite of 2.432-2.474nm is meant REUSY, REY, USY molecular sieve, preferably REUSY molecular sieve according to the said catalyst of claim 1.
4,, it is characterized in that said unformed silica-alumina support is by containing sodium silicate and containing a kind of full silicon-aluminium glue carrier altogether that synthesizes that aluminium salt and aluminate are made through multistep reaction according to the said catalyst of claim 1.
5, according to the said catalyst of claim 4, the percentage by weight that it is characterized in that the aluminium oxide in said unformed silica-alumina support is 25-40m%, preferably 30-35m% (accounting for butt).
6, according to claim 4 and 5 said catalyst, it is characterized in that the said sodium silicate that contains is meant waterglass, contain aluminium salt and be meant aluminum sulfate, aluminate is meant sodium metaaluminate.
7, the said Preparation of catalysts method of claim 1, it is characterized in that proportion of composing according to catalyst, the molecular sieve pulp that homogeneous is good joins the complete synthetic silicon-aluminium that makes through three-step reaction and is total in the rubber cement liquid, making beating, in slurries, add aqueous slkali then, regulate the slurries pH value to 6.0-8.0, preferably 7.0-7.5 filters, add the water making beating, in slurries, add inorganic acid solution again, make the slurries acidifying, regulate pH value to 4.0-5.5,4.2-4.8 preferably, spray shaping, washing, drying obtain the catalyst finished product, and its preparation process is:
(1) preparation silicon-aluminium is total to the glue carrier, and step is:
A) waterglass, aluminum sulfate are added water one and react, the control ph value of reaction is 8.5-10.0, and preferably 9.0-9.6 wore out 0.5-1.0 hour, and it is cogelled to make silicon-aluminium;
What b) the above-mentioned a) step is made is cogelled with the sodium metaaluminate reaction, and (the control causticity is than being 0.9-1.3, preferably 1.0-1.2), making PH is 11.0-13.0, preferably the colloid slurries of 11.8-12.6;
C) with above-mentioned b) go on foot the same again reacting aluminum sulfate of colloid slurries that makes, making PH is the common micelle colloid slurries of 3.5-3.9; Silica-aluminium oxide that above-mentioned three steps make rubber cement liquid altogether contains AL
2O
3Be generally 25-40m%, preferably 30-35m% (accounting for butt).
(2) according to the composition requirement of catalyst, a certain amount of molecular sieve pulp being joined above-mentioned (1) go on foot in the common rubber cement liquid of the acid silicon-aluminium that makes, after stirring, add aqueous slkali in slurries, regulate the slurries pH value to 6.0-8.0, preferably is 7.0-7.5;
(3) dope filtration that above-mentioned (2) step is made is pressed 8-15m% again, and preferably the solid content of 9-12m% adds the water making beating;
(4) lentamente inorganic acid solution is joined above-mentioned (3) and go on foot in the slurries that make, regulate slurries PH to 4.0-5.5, preferably 4.2-4.8 makes acid catalyst slurry.
(5) catalyst slurry spray shaping, washing, the drying that above-mentioned (4) step is made obtains catalyst finished product of the present invention.
8,, it is characterized in that the aqueous slkali in said (2) is an ammoniacal liquor according to the said Preparation of catalysts method of claim 7.
9,, it is characterized in that inorganic acid solution is meant sulfuric acid, hydrochloric acid or nitric acid in said (4) according to the said Preparation of catalysts method of claim 7.
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|---|---|---|---|
| CN97108044A CN1063680C (en) | 1997-04-28 | 1997-04-28 | Catalytic cracking catalyst and its preparation |
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|---|---|---|---|
| CN97108044A CN1063680C (en) | 1997-04-28 | 1997-04-28 | Catalytic cracking catalyst and its preparation |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101636227B (en) * | 2006-12-07 | 2013-06-05 | 格雷斯公司 | Catalytic cracking catalyst compositions having improved bottoms conversion |
| CN104973610A (en) * | 2014-04-10 | 2015-10-14 | 中国科学院大连化学物理研究所 | Preparation method of one-dimensional pore nano molecular sieve |
| CN108940251A (en) * | 2017-05-26 | 2018-12-07 | 中国石油化工股份有限公司 | A kind of preparation method of active catalytic material |
| CN108940351A (en) * | 2017-05-26 | 2018-12-07 | 中国石油化工股份有限公司 | A kind of preparation method of catalysis material |
| CN109718832A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | Prepare the method and Cracking catalyst of Cracking catalyst |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4247420A (en) * | 1979-03-23 | 1981-01-27 | W. R. Grace & Co. | Hydrocarbon conversion catalyst preparation |
| US4542118A (en) * | 1984-02-02 | 1985-09-17 | W. R. Grace & Co. | Catalyst manufacture |
| US4711868A (en) * | 1985-05-20 | 1987-12-08 | Phillips Petroleum Company | Process for preparing silica-alumina |
| US4944864A (en) * | 1985-06-11 | 1990-07-31 | Exxon Research And Engineering Company | Process using cracking calalyst containing strontium carbonate |
| TW252053B (en) * | 1991-11-01 | 1995-07-21 | Shell Internat Res Schappej Bv | |
| CN1034718C (en) * | 1993-07-29 | 1997-04-30 | 中国石油化工总公司 | Cracking catalyst and preparing process thereof |
-
1997
- 1997-04-28 CN CN97108044A patent/CN1063680C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101636227B (en) * | 2006-12-07 | 2013-06-05 | 格雷斯公司 | Catalytic cracking catalyst compositions having improved bottoms conversion |
| CN104973610A (en) * | 2014-04-10 | 2015-10-14 | 中国科学院大连化学物理研究所 | Preparation method of one-dimensional pore nano molecular sieve |
| CN104973610B (en) * | 2014-04-10 | 2017-02-15 | 中国科学院大连化学物理研究所 | Preparation method of one-dimensional pore nano molecular sieve |
| CN108940251A (en) * | 2017-05-26 | 2018-12-07 | 中国石油化工股份有限公司 | A kind of preparation method of active catalytic material |
| CN108940351A (en) * | 2017-05-26 | 2018-12-07 | 中国石油化工股份有限公司 | A kind of preparation method of catalysis material |
| CN108940351B (en) * | 2017-05-26 | 2021-04-06 | 中国石油化工股份有限公司 | Preparation method of catalytic material |
| CN108940251B (en) * | 2017-05-26 | 2021-04-06 | 中国石油化工股份有限公司 | Preparation method of active catalytic material |
| CN109718832A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | Prepare the method and Cracking catalyst of Cracking catalyst |
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|---|---|
| CN1063680C (en) | 2001-03-28 |
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