CN104607255B - Low-L-acid and high-B-acid catalytic cracking catalyst and preparation method thereof - Google Patents
Low-L-acid and high-B-acid catalytic cracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method for a catalytic cracking catalyst for petrifaction, and particularly relates to a low-L-acid and high-B-acid catalytic cracking catalyst and a preparation method thereof. The preparation method comprises the following steps: adding a catalytic cracking catalyst into deionized water, adding boric acid solution at the temperature of 20-90 DEG C, adding inorganic acid, carrying out suction filtration and washing on the product subjected to reaction, and drying and roasting the obtained filter cake to obtain the low-L-acid and high-B-acid catalytic cracking catalyst. According to the preparation method for the low-L-acid and high-B-acid catalytic cracking catalyst provided by the invention, a boron element is introduced into the catalytic cracking catalyst, so that the surface L-acid content of the catalytic cracking catalyst is reduced, and the B-acid content thereof is increased; the low-L-acid and high-B-acid catalytic cracking catalyst is capable of increasing a raw material conversion rate, effectively increasing the yields of catalytic cracking gasoline and diesel oil, and reducing the yield of light hydrocarbons when being used for catalytic cracking micro-reaction.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalyst preparation method of petrochemical industry, the high B-acid catalytic cracking of specially low L acid
Catalyst and preparation method thereof.
Technical background
Catalytic cracking is mink cell focus secondary operations, one of important means of clear gusoline such as production gasoline, diesel oil, as master
The catalytic cracking catalyst for leading the reaction of petroleum hydrocarbon Journal of Molecular Catalysis is mainly made up of active component i.e. molecular sieve and substrate, also sometimes
By the effect of binding agent.Commercial Application requires that catalytic cracking catalyst has good physics, chemical property, such as：Specific surface
Greatly, high mechanical strength, heat stability be strong, surface has acidity etc..Catalytic cracking catalyst has simultaneouslySour (B-acid)
With Lewis acid (L acid).Wherein, active component Y type molecular sieve has B-acid and L acid simultaneously, used as main binding agent and substrate
Alumina surface generally only has L acid, and this two classes acidic site can play a part of cracking to hydrocarbon molecules.Research table
It is bright, L acid to unsaturated compound have very strong absorbability, be susceptible to polymerization and deep dehydrogenation reaction, produce coke and
Dry gas.And hydro carbons is mainly cracked on B-acid position by carbenium ion mechanism, the coke choosing of catalyst can be effectively reduced
Selecting property.So adjust the acidity on catalytic cracking catalyst surface, catalyst surface is set to have less L acid and the more B-acid can be with
Coke is reduced while improving catalytic cracking product yield.
CN 104084233A disclose the method with boron oxide modified micro porous molecular sieve ZSM-5 and MCM-22, with five boric acid
Ammonium is that boron oxide is carried on micro porous molecular sieve outer surface by boron oxide presoma by impregnation-calcination method, reduces molecular sieve surface
Acidity, catalyst Pyrogentisinic Acid's para-position alkyl that the method is obtained is combined to p-methyl phenol and paraethyl phenol process has well
Shape selective catalysis performance.But the method does not make embodiments and test to the acidity change of molecular sieve.
CN 103191776A are disclosed and are directly prepared boron aluminum molecular screen B-ZSM-5 with boric acid, and infusion process and ion are handed over
Change and ZSM-5 carried out the method that post processing obtains boracic ZSM-5.Effect of the molecular sieve that the method is obtained in MTP reactions
Preferably.But the method does not provide the modified acid characterization and test data of molecular sieve.
CN 102728335A disclose the method with boron modification aluminium oxide, first with low-carbon alcohol solution by aluminum oxide precursor
Body soaks, and adds the boric acid solution formed by polyhydric alcohol and boric acid, the volatilization and its relatively low surface tension due to low-carbon alcohols
Can be the boron surface for being dispersed in aluminium oxide evenly, preventing B solution to be added directly on aluminium oxide causes the poly- of local boron
Collection.The method effectively improves the specific surface and pore volume of carrier.
Disclose in the patents such as CN 1052501A, CN 1082387C, CN 1609178A with different boron-containing compounds come
The method of modified aluminas.These methods are all successfully incorporated into boron element in the body phase of aluminium oxide, but for aluminium oxide
Acid change all do not make and specific characterize and test.
CN 1768945A disclose the preparation method of the alumina support of a kind of siliceous and titanium, plastic of the silicon in aluminium oxide
During add, improve the surface area of aluminium oxide, aperture and pore volume；Titanium is added after plastic, before aging, is further improved
The surface acidity of aluminium oxide, the total acid content and B-acid content for making alumina surface is significantly improved.CN 1110304A disclose one kind
With silicon and the method for P Modification aluminium oxide, silicon, phosphorus are separately added into using substep plastic method, make silicon and phosphorus alumina surface point
Dissipate and be more uniformly distributed.
CN 1853774A disclose a kind of method of use Si modification aluminium oxide, and alkalescence is added in the aqueous solution of aluminium salt
Aqueous silicate solution, adjusts pH and forms gel, then aging, filtration, washing.Measure what Si modification was crossed with pyridine infrared spectrometry
Alumina surface comprises only L acid, without B-acid.
The content of the invention
For above-mentioned technical problem, the invention provides a kind of Surface L ewis acid (L acid) is low, while being rich in surfaceThe catalytic cracking catalyst of sour (B-acid), with and preparation method thereof, concrete technical scheme is：
The preparation method of the high B-acid catalytic cracking catalyst of low L acid, comprises the following steps：
(1) catalytic cracking catalyst is added and is sufficiently stirred in deionized water, under 20-90 DEG C of bath temperature, added
The boric acid solution of 0.05-2.0mol/L, wherein H3BO3It is 2%~20% with the mass ratio of catalytic cracking catalyst；
(2) add mineral acid in the mixed liquor obtained to step (1), mineral acid be hydrochloric acid, nitric acid, one kind of sulphuric acid or
Two or more mixture, adjust the mixed system pH value for 2.0-6.0；Then successive reaction 0.5-24h in 20-90 DEG C of water-bath；
(3) gained mixture is filtered, is washed, the filter cake of gained is dried at 50-200 DEG C, at 500 DEG C -700 DEG C
Roasting 2-24h, obtains the high B-acid catalytic cracking catalyst of low L acid.
Can be used for processing molecular sieve active component, or boehmite.
The preparation method of the high B-acid catalytic cracking catalyst of low L acid that the present invention is provided, by boron element catalytic cracking is incorporated into
In catalyst, reduce catalytic cracking catalyst Surface L acid content, B-acid content is improved, and can be improved as catalytic cracking micro- inverse time
Feed stock conversion, effectively improves the yield of catalytically cracked gasoline, diesel oil, reduces lower carbon number hydrocarbons yield.
Description of the drawings
Fig. 1 is the XRD diffraction patterns of embodiment and comparative example gained sample；
Fig. 2 is the pyridine adsorption FTIR spectrogram of embodiment and comparative example gained sample.
Specific embodiment
It is described in conjunction with the embodiments the specific embodiment of the present invention.
Embodiment 1
20 grams of Industrial Catalysis Cracking catalyst are taken, M is labeled as, stirring to pulp in 50ml water is added to.Then in 80 DEG C of water
Under the conditions of bath, the boric acid solution of the 0.65mol/L of 50ml is added, the catalytic cracking catalyst suspension being acidified is obtained, during reaction
Between keep 0.5h.The dust technology regulation pH value that 1.0mol/L is added in gained mixture is 3.0, is continued in 80 DEG C of stirring in water bath
Under the conditions of successive reaction 24h.Finally, by reacted sample sucking filtration, washing, 8h is dried at 110 DEG C, then at 500 DEG C
Roasting 4h, obtains Product Labeling for sample A.
Embodiment 2
20 grams of Y type molecular sieves are taken, is labeled as being designated as N, add stirring to pulp in 50ml water.Then in 80 DEG C of water bath conditions
Under, the boric acid solution of the 0.65mol/L of 50ml is added, obtain the boehmite suspension being acidified, response time 0.5h.Gained
Mixture in add the dust technology of 1.0mol/L to adjust pH value be 3.0, continue continuous anti-under the conditions of 80 DEG C of stirring in water bath
Answer 24h,.Finally, by reacted sample sucking filtration, washing, 8h is dried under the conditions of 110 DEG C, then the roasting 4h at 500 DEG C,
Obtain modified molecular screen sample B.
Embodiment 3
20 grams of Y type molecular sieves are taken, is labeled as being designated as N, in impregnated in the aqueous acid of boron containing 0.4g, under room temperature 12h is stood.
Then gained sample is dried into 8h at 80 DEG C, roasting 4h obtains sample C at 500 DEG C.
Embodiment 4
Take 20 grams of boehmites and add stirring to pulp in 50ml water.Then under 80 DEG C of water bath conditions, in mixed liquor
The boric acid solution of the 0.65mol/L of 50ml is added, the boehmite suspension being acidified is obtained, 0.5h is reacted.Add
It is 3.0 that the dust technology of 1.0mol/L adjusts pH value, continues successive reaction 24h under the conditions of 80 DEG C of stirring in water bath,.Finally, will be anti-
Sample sucking filtration, washing after answering, is dried 8h under the conditions of 110 DEG C, and then the roasting 4h at 500 DEG C, obtains modified aluminas sample
Product D.
Comparative example
20 grams of boehmites are dried into 8h under the conditions of 110 DEG C, then roasting 4h obtains common aluminium oxide at 500 DEG C
Comparative sample E.
The performance of product obtained as above is detected that gained testing result is shown in Table 1 specific surface area, aperture and pore volume number
According to, XRD diffraction patterns of Fig. 1 and the pyridine adsorption FTIR spectrogram of Fig. 2.
Specific surface area, aperture and pore volume data determine (Micromeretics using low temperature nitrogen physisorphtion
Tristar3000).The surface acid property of aluminium oxide is determined with infrared spectrometry, using pyridine as absorption probe.
The specific surface area of table 1, aperture and pore volume testing result
| Sample | Specific surface area SBET/(m2/g) | Pore volume V/ (cm3/g) |
| A | 155 | 0.192 |
| B | 607 | 0.385 |
| C | 578 | 0.376 |
| D | 346 | 0.667 |
| E | 304 | 0.680 |
| M | 144 | 0.193 |
| N | 583 | 0.382 |
Above example and comparative example products therefrom is micro- anti-for catalytic cracking heavy oil, and gained reaction result data is shown in Table
2, it can be seen that the modified catalytic cracking catalyst sample A for obtaining, before unmodified compared with, light oil yield is significantly improved, liquid
Activating QI and dry gas yied are substantially reduced.
The micro- converse result of the catalytic cracking heavy oil of table 2
| Product/% | Sample M | Sample A |
| Dry gas | 2.08 | 1.28 |
| Liquefied gas | 16.40 | 10.21 |
| Hydrogen | 0.15 | 0.07 |
| Gasoline | 41.47 | 47.72 |
| Diesel oil | 24.01 | 25.11 |
| Heavy oil | 7.41 | 7.15 |
| Light oil yield | 65.48 | 72.83 |
| Coke | 5.79 | 5.67 |
| Conversion ratio | 89.86 | 89.99 |
| Total liquid recovery | 81.88 | 83.04 |
Claims (1)
1. the preparation method of the high B-acid catalytic cracking catalyst of a kind of low L acid, it is characterised in that the method is comprised the following steps：
(1) catalytic cracking catalyst is added and is sufficiently stirred in deionized water, under 20-90 DEG C of bath temperature, add 0.05-
The boric acid solution of 2.0mol/L, wherein H3BO3It is 2%~20% with the mass ratio of catalytic cracking catalyst；
(2) mineral acid is added in the mixed liquor obtained to step (1), adjusts the mixed system pH value for 2.0-6.0；Then
Successive reaction 0.5-24h in 20-90 DEG C of water-bath；Described mineral acid is that one or more in hydrochloric acid, nitric acid, sulphuric acid are mixed
Compound；
(3) by gained mixture sucking filtration, washing, the filter cake of gained is dried at 50-200 DEG C, the roasting 2- at 500 DEG C -700 DEG C
24h, obtains the high B-acid catalytic cracking catalyst of low L acid.
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| CN106669646B (en) * | 2016-11-28 | 2019-06-11 | 中国石油天然气股份有限公司 | A kind of meso-porous alumina and its preparation method and application rich in B acid |
| CN107365887A (en) * | 2017-06-07 | 2017-11-21 | 常州豫春化工有限公司 | A kind of preparation method of fluxing type slagging agent |
| CN109225353B (en) * | 2017-07-11 | 2021-09-21 | 连云港师范高等专科学校 | Method for reactivating waste FCC catalyst by controlled leaching, metal passivation and effective component compensation |
| CN109694720B (en) * | 2017-10-20 | 2021-01-08 | 中国石油化工股份有限公司 | Catalytic cracking method of high-nitrogen raw material |
| CN108499600B (en) * | 2018-04-19 | 2021-03-30 | 润和催化剂股份有限公司 | Catalytic cracking catalyst for increasing diesel oil yield and preparation method thereof |
| CN111822033B (en) * | 2019-04-23 | 2023-04-07 | 中国石油化工股份有限公司 | Hydrocarbon oil catalytic cracking catalyst rich in naphthenic cyclic hydrocarbon, and preparation method and application method thereof |
| CN111822043B (en) * | 2019-04-23 | 2023-06-09 | 中国石油化工股份有限公司 | Boron-containing catalytic cracking catalyst for producing more ethylene, preparation method and application method thereof |
| CN112108173B (en) * | 2019-06-21 | 2023-06-30 | 中国石油天然气股份有限公司 | Catalyst preparation method for reducing diesel oil yield |
| CN112138642A (en) * | 2020-09-27 | 2020-12-29 | 福州大学 | Preparation method and application of cracking catalyst |
| CN113617343A (en) * | 2021-08-31 | 2021-11-09 | 福州大学 | Biomass oil deoxidation catalyst and preparation method and application thereof |
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| CN103896318A (en) * | 2014-04-02 | 2014-07-02 | 中国石油大学(华东) | Preparation method of bronsted acid-rich mesoporous alumina |
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| CN103896318A (en) * | 2014-04-02 | 2014-07-02 | 中国石油大学(华东) | Preparation method of bronsted acid-rich mesoporous alumina |
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| Surface structure and acidity of alumina-boria catalysts;Satoshi Sato et al.;《Journal of Molecular Catalysis A: Chemical》;19951231;第104卷;第171-177页 * |
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