CN105728030A - Novel anti-heavy metal cracking catalyst and preparation method thereof - Google Patents
Novel anti-heavy metal cracking catalyst and preparation method thereof Download PDFInfo
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Abstract
A novel anti-heavy metal cracking catalyst mainly includes, on the basis of dry base of added materials, by weight, 0.5-15% of a large-grain aluminum oxide material, 5-70% of an inorganic oxide adhesive, 15-60% of molecular sieves, 5-50% of clay and 0.5-3% of rare earth oxides (on the basis of Re2O3). The large-grain aluminum oxide material has a pseudo-boehmite structure, a boehmite monohydrate structure or a boehmite trihydrate structure and is 100-1160 nm in granular size. The inorganic oxide adhesive is a mixture of aluminum sol and pseudo-boehmite, wherein the aluminum oxide from the pseudo-boehmite accounts for 3-40 wt% of the catalyst and the aluminum oxide from the aluminum sol accounts for 4-30 wt%. The catalyst is prepared from the large-grain aluminum oxide material and has the effect of enriching nickel, and the rare earth oxides deposited on the surface of the molecular sieve can effectively inhibit damage on the molecular sieve due to vanadium.
Description
Technical field
The present invention relates to catalytic cracking catalyst and preparation method thereof, the Cracking catalyst of specifically a kind of preventing from heavy metal.
Background technology
Catalytic cracking process is the heavy oil lighting technique of heavy oil, one of main source of Shi Ge refinery economic benefit.Due to raw oil limited source, catalytically cracked material has been turned to by traditional vacuum distillate mixes residual oil or pure resid feed.Residual oil does not contain only the macromolecular compound of the easy green cokes such as resin and asphalt, more contains relatively multi-metal (such as nickel, vanadium etc.).In cracking reaction, the metal deposit such as nickel, vanadium on a catalyst, causes catalyst activity to reduce, particularly vanadium, the vanadium of high oxidation state animal migration under high-temperature water thermal environment is strong, and in heavy damage catalyst, the structure of molecules of active components sieve, causes the irreversible inactivation of catalyst.Nickel acts primarily as dehydrogenation, and it can make part charging and crackate dehydrogenation generate oily polycyclic aromatic hydrocarbon polymer or coke, thus causing that selectivity of catalyst is deteriorated (hydrogen and coke yield increase, and liquid yield declines).Therefore, catalytic cracking catalyst is with greater need for the preventing from heavy metal pollution ability with excellence, to improve catalytic cracking unit product slates further, improves refinery's economic benefit.
US4988653 adopts aluminium oxide and rare earth oxide as vanadium trapping agent.EP89306806.4 discloses the catalytic cracking catalyst containing bastnaesite and aluminium oxide, wherein bastnaesite is a kind of Rare-earth Fluoro-carbonate Minerals depositing together typically by zinc and, crude mineral generally containing the rare earth element (in oxide) of 65～80%, has the performance improving catalyst preventing from heavy metal.US5324416 adopts the carbonate of bastnaesite or barium to trap component as metal, adopts the magnesium containing spinel structure as the trapping agent of oxysulfide simultaneously.US4900428 is by rare-earth precipitation or is impregnated on catalyst and plays anti-vanadium effect.CN86107531 and CN8107598A is open with RE (OH)3Rare earth introducing method for precursor.CN1417297A discloses a kind of containing rare earth salts (RE2O3Meter) for the semi-synthetic Hydrocarban coversion catalysts of silica sol binder of 0.1-20%, this catalyst utilizes rare earth-activated silicon oxide, thus improving its heavy oil cracking activity and preventing from heavy metal pollution ability, reduces olefins in FCC gasoline and sulfur content.
Phosphorus and RE composite are deposited on zeolite molecular sieve by CN1436600A, and the Cracking catalyst active amplification made is obvious.Phosphorus and the RE composite of crystallization are deposited on the silicate zeolite of crystallization by JP06170233, and the Cracking catalyst activity stability made is good, and preventing from heavy metal pollution ability is strong, and reduces the content of sulfur dioxide in cracking gasoline.CN00122003.9 adopts the oxalates of rare earth to prepare Cracking catalyst, and prepared catalyst activity is high, and preventing from heavy metal pollution ability is strong and cracking reaction selectivity is good.USP4515683 and ZL88100418 is with ammonia, rare earth chloride is deposited on Y type molecular sieve so that with the catalyst that this Y type molecular sieve is active component, there is certain anti-vanadium performance.
US2003130107, US2003136707, US2003089640, US2010298118 are the effects being realized preventing from heavy metal pollution by the improvement of in-situ crystallization technique, this technology anti-vanadium function is better, but anti-nickel ability is general, in-situ crystallization Catalyst Production technics comparing is complicated simultaneously.EP0228270 and EP0238760 adds the aluminium oxide of a kind of Si modification to improve the structural stability of catalyst, but this technology needs first aluminium oxide to be carried out Si modification, and carries out the process such as roasting, and complex procedures is bigger to catalyst abrasion exponential effect.
CN1068588 discloses a kind of matal deactivator for FCC catalyst, by antimony and or the mixed solution of good fluidity that forms of the hydroxy compounds (I) of bismuth, reaction medium (II) and solubilizing agent (III) three part；CN1294173 is also a kind of water-soluble metal passivator, with antimony, aluminum and Rare Earth Lanthanum (or cerium) for key component, can significantly decrease catalyst poisoning inactivation, improve gasoline and light oil yield, hence it is evident that reduce hydrogen yield；JP1284580 discloses a kind of solution made with the salt of antimony, after adding this solution, can reduce the generation of hydrogen, coke.CN88102585, EP303372, US4585545, EP141988, US4504381 adds the solid nickel component of the solids such as bismuth, antimony, stannum, phosphorus in catalyst preparation process, improves the heavy oil pyrolysis performance of catalyst, reduces the productivity of hydrogen, coke simultaneously, but these metal pair environment are unfriendly, are unfavorable for popularization and application.
The approach of above patent preventing from heavy metal is broadly divided into: (1) molecular sieve is modifiied by rare earth modified, rare-earth precipitation；(2) auxiliary agent is added.All having pros and cons, preventing from heavy metal effect is single, and the purpose of the present invention is aiming at vanadium and the nickel mechanism to catalyst contamination, on the basis of above-mentioned prior art, it is provided that a kind of possess not only anti-vanadium but also the catalytic cracking catalyst of anti-nickel double effects and preparation method thereof.
Summary of the invention
The present invention provides a kind of new preventing from heavy metal Cracking catalyst and preparation method thereof.By the improvement of the formula of catalyst and preparation method, reach not only anti-nickel but also anti-vanadium, coke and hydrogen yield are greatly reduced simultaneously, improve yield of light oil, increase the purpose of heavy oil conversion rate.
Preventing from heavy metal Cracking catalyst of the present invention, by the butt that feeds intake, comprises: (1) 0.5～15 big grain oxidation aluminum of weight %；The inorganic oxide binder of (2) 5～70 weight %；The molecular sieve of (3) 15～60 weight %；The clay of (4) 5～50 weight %；The rare earth oxide of (5) 0.5～3 weight % is (with RE2O3Meter), to be deposited in the addition of molecular sieve upper type.
Described big grain oxidation aluminum has structure of similar to thin diaspore, a diaspore structure or gibbsite structure, it is preferable that have boehmite or the alumina material of a diaspore structure.Sodium oxide content≤0.2 weight the % of this big grain oxidation aluminum, dioxide-containing silica≤0.3 weight %, crystallite dimension is at 100～1160nm, it is preferable that at 200～800nm.
The described inorganic oxide binder a kind of or wherein several mixture in Alumina gel, Ludox, boehmite, sial molten (coagulating) glue, modified sial molten (coagulating) glue, the mixture of preferred Alumina gel and boehmite, wherein account for the 3～40% of catalyst weight from the aluminium oxide of boehmite, it is preferable that 3～30%；Aluminium oxide from Alumina gel accounts for the 4～30% of catalyst weight, it is preferable that 8～22%.Described molecular screening as the mixture of one or more in the zeolite of active component of cracking catalyst and non-zeolite molecular sieve, such as faujasite, has the zeolite of MFI structure, modenite, β zeolite etc. certainly.Described faujasite is selected from y-type zeolite or/and X-type zeolite, and described Y type molecular sieve is selected from one or more the mixture in HY, REY, REHY, USY, REUSY, REDASY, it is preferred to REUSY zeolite；The described zeolite with MFI structure is selected from ZSM-5, phosphorous or/and the zeolite with MFI structure of rare earth, it is preferable that ZSM-5.
The described clay mixture of one or more in Kaolin, halloysite, montmorillonite, kieselguhr, galapectite, brucite, attapulgite, bentonite, meerschaum, it is preferable that Kaolin.
The rare earth oxide precipitated over a molecular sieve in catalyst provided by the present invention is different from the rare earth existence form being occupied molecular sieve cation-bit by ion exchange in solution form contained in Y type molecular sieve, and its precursor is that rare earth ion is deposited on the surface of molecular sieve with precipitant.It is with RE2O3Meter, accounts for 0.5～3 weight % of catalyst.
Described rare earth refers to lanthana, cerium oxide or mixing (multiple) rare earth oxide or its precursor, it is preferable that rare earth chloride and/or nitric acid rare earth, more preferably solution of cerium chloride by oxidation.
Described precipitant refers to ammonia or oxalic acid, ammonium oxalate or phosphorous compound or the water soluble compound such as waterglass, Ludox, it is preferable that ammonia or diammonium phosphate.
Preventing from heavy metal Cracking catalyst of the present invention is prepared by following method:
1) in the reactor, add the water measured, add molecular sieve making beating, then precipitant is added in molecular sieve pulp, be subsequently adding the earth solution measured, stir 0.5h～1h.
2) in the reactor of heating in water bath, the water measured is added；
3) adding the solid constituent in clay, binding agent, big grain oxidation aluminum, stir, the addition of several host materials does not have strict precedence；
4) with acid aluminum weight ratio be 0.05～0.30 mineral acid acidified, mineral acid can by whole for the solid constituent in binding agent peptizations, and to big grain oxidation aluminum can only small part peptization, mineral acid can only add after binding agent solid constituent adding；
5) 45 DEG C～90 DEG C aging 0.5～4h it are warming up to；
6) liquid-containing binder is added after being cooled to room temperature；
7) molecular sieve pulp is added；
8) spray drying forming, roasting, washing, drying after mix homogeneously, obtains finished catalyst.
In the method simulation industry poising agent of heavy metal pollution of the present invention, the content of nickel and vanadium pollutes: by appropriate analytical pure dissolving oxalic acid in distilled water, stirring, is slowly added to analytical pure ammonium metavanadate, and heated and stirred is transparent to solution, cooling, moves into volumetric flask and is configured to certain density solution.By the aqueous solution of nickel nitrate (3000ppmNi, by catalyst butt restatement) and vanadium (5000ppmV, by catalyst butt restatement) solution impregnation in catalyst, 120 DEG C dry after 500～550 DEG C of roasting 1～4h.
Catalyst provided by the invention is owing to have employed a kind of big grain oxidation aluminum; after preparing into catalyst; in the process of heavy oil catalytically cracking equipment cracking masout; under high temperature and steam existent condition, it is possible to be enriched with by the nickel in raw oil, it is substantially reduced its saboteur and sieves the effect of activity; simultaneously; the rare earth oxide of molecular sieve surface precipitation can form stable compound with vanadium, the effective suppression vanadium destruction to molecular sieve, dual function protection molecular sieve activity.In catalyst preparation process, owing to this alumina material only has small part and acid reaction peptization, the pore structure of alumina material self is not corrupted such that catalyst prepared by the method has bigger pore volume.Use catalyst prepared by the method to have the anti-nickel of excellence, pollution of vanadium ability and coke selectivity, coke and hydrogen yield are greatly lowered, improve yield of light oil and heavy oil conversion ratio.
Detailed description of the invention
Catalysts and its preparation method provided by the invention will be described further by example below.
The raw material used in experiment and character:
1, Kaolin, igloss 15 weight %, China Kaolin Co., Ltd's industrial products；
2, galapectite, igloss 20 weight %, commercially available prod；
3, boehmite, sodium oxide 0.101 weight %, silicon dioxide 0.23 weight %, crystallite dimension 7.6nm, igloss 35 weight %, Shanxi Aluminium Plant product；
4, hydrochloric acid, silver chemical reagent work, analytical pure；
5, ammonia, industrial goods, take from Lanzhou Petrochemical catalyst plant；
6, re chloride, industrial goods, 297.3g/L.
7, RDSY, igloss 10 weight %, Lanzhou Petrochemical catalyst plant product；
8, HRSY-4, igloss 20 weight %, Lanzhou Petrochemical catalyst plant product；
9, ZSM-5, igloss 3 weight %, Lanzhou Petrochemical catalyst plant product；
10, nickel nitrate, Xi'an chemical reagent work, analytical pure；
11, ammonium metavanadate, Xi'an chemical reagent work, analytical pure；
12, Alumina gel: aluminium sesquioxide content 21%, takes from Lanzhou Petrochemical catalyst plant；
13, Ludox: dioxide-containing silica 25%, commercially available prod；
14, alumina material a, sodium oxide 0.0865 weight %, silicon dioxide 0.283 weight %, crystallite dimension 80nm, igloss 15.1 weight %, commercially available prod；
15, alumina material b, sodium oxide 0.0849 weight %, silicon dioxide 0.294 weight %, crystallite dimension 100nm, igloss 14.8 weight %, commercially available prod；
16, alumina material c, sodium oxide 0.0901 weight %, silicon dioxide 0.279 weight %, crystallite dimension 420nm, igloss 15.3 weight %, commercially available prod；
17, alumina material d, sodium oxide 0.0886 weight %, silicon dioxide 0.297 weight %, crystallite dimension 1160nm, igloss 15.9 weight %, commercially available prod.
ACE appreciation condition: first by catalyst at 800 DEG C, aging 4h under 100% water vapor condition, be then evaluated on ACE device.Reaction raw materials is the compound of 70% Xinjiang decompression wide fraction oil and 30% Xinjiang decompression residuum, catalyst loading amount 9g, reaction temperature 530 DEG C, oil ratio 5.
For the catalyst of light oil micro-reactor in advance through 800 DEG C, the 100% aging 4h of steam, the appreciation condition of light oil micro-reactor is: the huge port light diesel fuel of 235～335 degrees Celsius is raw material, and oil ratio is 3.2, and weight space velocity is 16h-1, temperature is 460 DEG C.
In example, the pore volume of catalyst adopts water droplet method to test, and abrasion index adopts gas lift method to measure.
Embodiment 1
In making beating tank, add 4L water, add 2114 grams of RDSY, 60 grams of ZSM-5, add 120ml strong aqua ammonia after making beating 0.5h, be subsequently added 96ml re chloride, stir 1h；
In the reactor with heating in water bath, add 4L water, 2313g Kaolin, 1720g boehmite and 33.8g alumina material c, be then slowly added into 170g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, it is subsequently adding 3003 grams of Alumina gel, forms catalyst substrates serosity；
Then molecular sieve pulp is added in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst S-1.
Catalyst S-1 consists of: Kaolin 34.3 weight %, and the aluminium oxide from boehmite is 19.5 weight %, and the aluminium oxide carrying out self-alumina c is 0.5 weight %, aluminium oxide 11 weight % from Alumina gel, Y type molecular sieve 33.2 weight %, ZSM-5 are 1 weight %, and deposition of rare-earth is 0.5 weight %.
Embodiment 2
In making beating tank, add 4L water, add 2114 grams of RDSY, 60 grams of ZSM-5, add 240ml strong aqua ammonia after making beating 0.5h, be subsequently added 192ml re chloride, stir 1h；
In the reactor with heating in water bath, add 4L water, 1888g Kaolin, 415g galapectite, 1235g boehmite and 406g alumina material c, it is then slowly added into 170g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, it is subsequently adding 3003 grams of Alumina gel and forms catalyst substrates serosity；
Then molecular sieve pulp is added in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst S-2.
Catalyst S-2 consists of: Kaolin 28 weight %, galapectite 5.8 weight %, and the aluminium oxide from boehmite is 14 weight %, the aluminium oxide carrying out self-alumina c is 6 weight %, from the aluminium oxide 11 weight % of Alumina gel, Y type molecular sieve 33.2 weight %, ZSM-5 is 1 weight %, and deposition of rare-earth is 1 weight %.
Embodiment 3
In making beating tank, add 4L water, add 2378 grams of HRSY-4,60 grams of ZSM-5, add 480ml strong aqua ammonia after making beating 0.5h, be subsequently added 576ml re chloride, stir 1h；
In the reactor with heating in water bath, add 4L water, 1939g Kaolin, 441g boehmite and 1015g alumina material c, be then slowly added into 170g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, it is subsequently adding 2523 grams of Ludox and forms catalyst substrates serosity；
Then molecular sieve pulp is added in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst S-3.
Catalyst S-3 consists of: Kaolin 31.8 weight %, and the aluminium oxide from boehmite is 5 weight %, and the aluminium oxide carrying out self-alumina c is 15 weight %, silicon oxide 11 weight % from Ludox, Y type molecular sieve 33.2 weight %, ZSM-5 are 1 weight %, and deposition of rare-earth is 3 weight %.
Embodiment 4
In making beating tank, add 4L water, add 1057 grams of RDSY, 1189 grams of HRSY-4,60 grams of ZSM-5, add 120ml strong aqua ammonia after making beating 0.5h, be subsequently added 96ml re chloride, stir 1h；
In the reactor with heating in water bath, add 4L water, 2313g Kaolin, 1720g boehmite and 33.6g alumina material b, be then slowly added into 170g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, it is subsequently adding 3003 grams of Alumina gel and forms catalyst substrates serosity；
Then molecular sieve pulp is added in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst S-4.
Catalyst S-4 consists of: Kaolin 34.3 weight %, and the aluminium oxide from boehmite is 19.5 weight %, and the aluminium oxide carrying out self-alumina b is 0.5 weight %, aluminium oxide 11 weight % from Alumina gel, Y type molecular sieve 33.2 weight %, ZSM-5 are 1 weight %, and deposition of rare-earth is 0.5 weight %.
Embodiment 5
In making beating tank, add 4L water, add 2378 grams of HRSY-4,60 grams of ZSM-5, add 240ml strong aqua ammonia after making beating 0.5h, be subsequently added 192ml re chloride, stir 1h；
In the reactor with heating in water bath, add 4L water, 2279g Kaolin, 1235g boehmite and 409g alumina material d, be then slowly added into 170g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, it is subsequently adding 2523 grams of Ludox and forms catalyst substrates serosity；
Then molecular sieve pulp is added in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst S-5.
Catalyst S-5 consists of: Kaolin 33.8 weight %, and the aluminium oxide from boehmite is 14 weight %, and the aluminium oxide carrying out self-alumina d is 6 weight %, silicon oxide 11 weight % from Ludox, Y type molecular sieve 33.2 weight %, ZSM-5 are 1 weight %, and deposition of rare-earth is 1 weight %.
Comparative example 1
In making beating tank, add 4L water, add 2114 grams of RDSY, 60 grams of ZSM-5, add 240ml strong aqua ammonia after making beating 0.5h, be subsequently added 192ml re chloride, stir 1h；
In the reactor with heating in water bath, add 4L water, 2279g Kaolin, 1235g boehmite and 405g alumina material a, be then slowly added into 170g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, it is subsequently adding 3003 grams of Alumina gel and forms catalyst substrates serosity；
Then molecular sieve pulp is added in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst D-1.
Catalyst D-1 consists of: Kaolin 33.8 weight %, and the aluminium oxide from boehmite is 14 weight %, and the aluminium oxide carrying out self-alumina a is 6 weight %, aluminium oxide 11 weight % from Alumina gel, Y type molecular sieve 33.2 weight %, ZSM-5 are 1 weight %, and deposition of rare-earth is 1 weight %.
Comparative example 2
In making beating tank, add 4L water, add 2114 grams of RDSY, 60 grams of ZSM-5, add 240ml strong aqua ammonia after making beating 0.5h, be subsequently added 192ml re chloride, stir 1h；
In the reactor with heating in water bath, add 4L water, 2279g Kaolin, 1764g boehmite, be then slowly added into 170g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, be subsequently adding 3003 grams of Alumina gel and form catalyst substrates serosity；
Then molecular sieve pulp is added in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst D-2.
Catalyst D-2 consists of: Kaolin 33.8 weight %, and the aluminium oxide from boehmite is 20 weight %, and from the aluminium oxide 11 weight % of Alumina gel, Y type molecular sieve 33.2 weight %, ZSM-5 are 1 weight %, and deposition of rare-earth is 1 weight %.
Comparative example 3
In making beating tank, add 4L water, add 2114 grams of RDSY, 60 grams of ZSM-5, add 240ml strong aqua ammonia after making beating 0.5h, be subsequently added 192ml re chloride, stir 1h；
In the reactor with heating in water bath, add 4L water, 2279g Kaolin, 265g boehmite and 1150g alumina material c, be then slowly added into 170g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, it is subsequently adding 3003 grams of Alumina gel and forms catalyst substrates serosity；
Then molecular sieve pulp is added in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst D-3.
Catalyst D-3 consists of: Kaolin 33.8 weight %, and the aluminium oxide from boehmite is 3 weight %, and the aluminium oxide carrying out self-alumina c is 17 weight %, aluminium oxide 11 weight % from Alumina gel, Y type molecular sieve 33.2 weight %, ZSM-5 are 1 weight %, and deposition of rare-earth is 1 weight %.
Comparative example 4
Adding 4L water in making beating tank, add 2114 grams of RDSY, 60 grams of ZSM-5, pull an oar 0.5h；
In the reactor with heating in water bath, add 4L water, 2347g Kaolin, 1235g boehmite and 406g alumina material c, be then slowly added into 170g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, it is subsequently adding 3003 grams of Alumina gel and forms catalyst substrates serosity；
Then molecular sieve pulp is added in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst S-2.
Catalyst S-2 consists of: Kaolin 34.8 weight %, and the aluminium oxide from boehmite is 14 weight %, and the aluminium oxide carrying out self-alumina c is 6 weight %, and from the aluminium oxide 11 weight % of Alumina gel, Y type molecular sieve 33.2 weight %, ZSM-5 are 1 weight %.
Comparative example 5
Adding 4L water in making beating tank, add 2114 grams of RDSY, 60 grams of ZSM-5, pull an oar 0.5h；
In the reactor with heating in water bath, add 4L water, 2347g Kaolin, 1764g boehmite, be then slowly added into 170g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, be subsequently adding 3003 grams of Alumina gel and form catalyst substrates serosity；
Then molecular sieve pulp is added in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst D-2.
Catalyst D-2 consists of: Kaolin 34.8 weight %, and the aluminium oxide from boehmite is 20 weight %, and from the aluminium oxide 11 weight % of Alumina gel, Y type molecular sieve 33.2 weight %, ZSM-5 are 1 weight %.
Embodiment and comparative example catalyst physicochemical property and micro-activity are in Table 1.
Table 1 catalyst physicochemical property and micro-activity
Embodiment 6
The present embodiment is to prepare catalyst performance evaluation after heavy metal pollution to further illustrate method provided by the invention, and the evaluation result on ACE is in Table 2.
Table 2 catalyst evaluation result on ACE device
Claims (3)
1. a preventing from heavy metal Cracking catalyst, by the butt that feeds intake, mainly comprises: (1) 0.5～15 big grain oxidation aluminum of weight %；The inorganic oxide binder of (2) 5～70 weight %；The molecular sieve of (3) 15～60 weight %；The clay of (4) 5～50 weight %；The rare earth oxide of (5) 0.5～3 weight % is (with RE2O3Meter), to be deposited in the addition of molecular sieve upper type；Wherein said big grain oxidation aluminum has structure of similar to thin diaspore, a diaspore structure or gibbsite structure, sodium oxide content≤0.2 weight %, and dioxide-containing silica≤0.3 weight %, crystallite dimension is at 100～1160nm；Described inorganic oxide binder is the mixture of Alumina gel and boehmite, wherein accounts for the 3～40% of catalyst weight from the aluminium oxide of boehmite, and the aluminium oxide from Alumina gel accounts for the 4～30% of catalyst weight；Described molecular screening is certainly as the mixture of one or more in the zeolite of active component of cracking catalyst and non-zeolite molecular sieve；The described clay mixture of one or more in Kaolin, halloysite, montmorillonite, kieselguhr, galapectite, brucite, attapulgite, bentonite, meerschaum；Described rare earth refers to lanthana, cerium oxide or mixed rare-earth oxide or its precursor；Prepared by following method:
1) in the reactor, add the water measured, add molecular sieve making beating, then precipitant is added in molecular sieve pulp, be subsequently adding the earth solution measured, stir 0.5h～1h；
2) in the reactor of heating in water bath, the water measured is added；
3) adding the solid constituent in clay, binding agent, big grain oxidation aluminum, stir, the addition of several host materials does not have strict precedence；
4) with acid aluminum weight ratio be 0.05～0.30 mineral acid acidified, mineral acid can by whole for the solid constituent in binding agent peptizations, and to big grain oxidation aluminum can only small part peptization, mineral acid can only add after binding agent solid constituent adding；
5) 45 DEG C～90 DEG C aging 0.5～4h it are warming up to；
6) liquid-containing binder is added after being cooled to room temperature；
7) molecular sieve pulp is added；
8) spray drying forming, roasting, washing, drying after mix homogeneously, obtains finished catalyst.
2. a kind of preventing from heavy metal Cracking catalyst according to claim 1, it is characterised in that described big grain oxidation aluminum is the alumina material with boehmite or a diaspore structure, and crystallite dimension is 200～800nm.
3. a kind of preventing from heavy metal Cracking catalyst according to claim 1, it is characterised in that described inorganic oxide binder is the mixture of Alumina gel and boehmite, wherein accounts for the 3～30% of catalyst weight from the aluminium oxide of boehmite；Aluminium oxide from Alumina gel accounts for the 8～22% of catalyst weight.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097287A (en) * | 2016-11-25 | 2018-06-01 | 中国石油天然气股份有限公司 | A kind of catalytic cracking catalyst and preparation method thereof |
| CN109453803A (en) * | 2018-11-28 | 2019-03-12 | 茂名高岭科技有限公司 | A kind of kaolinite soil matrix FCC catalyst and preparation method thereof |
| CN113492014A (en) * | 2020-03-20 | 2021-10-12 | 中国石油化工股份有限公司 | Heavy metal pollution resistant catalytic cracking catalyst, and preparation method and application thereof |
| WO2023051588A1 (en) * | 2021-09-30 | 2023-04-06 | 中国石油化工股份有限公司 | Metal pollution-resistant catalyst and preparation method therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134905A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method for improving solid content of catalytic cracking catalyst slurry |
| CN101134906A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method for improving solid content of catalytic cracking catalyst slurry |
| CN101138740A (en) * | 2006-09-05 | 2008-03-12 | 北京盛大京泰化学研究所 | Cracking catalyst containing nanometer rare-earth oxide and method of preparing the same |
-
2014
- 2014-12-12 CN CN201410773929.8A patent/CN105728030A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134905A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method for improving solid content of catalytic cracking catalyst slurry |
| CN101134906A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method for improving solid content of catalytic cracking catalyst slurry |
| CN101138740A (en) * | 2006-09-05 | 2008-03-12 | 北京盛大京泰化学研究所 | Cracking catalyst containing nanometer rare-earth oxide and method of preparing the same |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097287A (en) * | 2016-11-25 | 2018-06-01 | 中国石油天然气股份有限公司 | A kind of catalytic cracking catalyst and preparation method thereof |
| CN108097287B (en) * | 2016-11-25 | 2021-04-30 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN109453803A (en) * | 2018-11-28 | 2019-03-12 | 茂名高岭科技有限公司 | A kind of kaolinite soil matrix FCC catalyst and preparation method thereof |
| CN113492014A (en) * | 2020-03-20 | 2021-10-12 | 中国石油化工股份有限公司 | Heavy metal pollution resistant catalytic cracking catalyst, and preparation method and application thereof |
| CN113492014B (en) * | 2020-03-20 | 2023-11-10 | 中国石油化工股份有限公司 | Heavy metal pollution resistant catalytic cracking catalyst and preparation method and application thereof |
| WO2023051588A1 (en) * | 2021-09-30 | 2023-04-06 | 中国石油化工股份有限公司 | Metal pollution-resistant catalyst and preparation method therefor |
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Application publication date: 20160706 |