CN103801390A - Heavy oil catalytic cracking catalyst and preparation method thereof - Google Patents
Heavy oil catalytic cracking catalyst and preparation method thereof Download PDFInfo
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- CN103801390A CN103801390A CN201410081779.4A CN201410081779A CN103801390A CN 103801390 A CN103801390 A CN 103801390A CN 201410081779 A CN201410081779 A CN 201410081779A CN 103801390 A CN103801390 A CN 103801390A
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Abstract
The invention discloses a preparation method of a catalytic cracking catalyst used in a petroleum refining process and belongs to the technical field of preparation of catalysts. The method comprises the following steps: uniformly pulping and mixing a molecular sieve, pseudo-boehmite, clay and deionized water; adding alumina sol or not to prepare catalyst slurry; then performing spray drying, and roasting the catalyst slurry for 2-4h at the temperature of 300-600 DEG C; performing exchange washing through an ammonium sulfate and ammonium dihydrogen phosphate solution with the temperature of 40-99 DEG C and the mass concentration of 5-20 percent, wherein ammonium sulfate and ammonium dihydrogen phosphate account for 1-10 mass percent of a roasted product; drying the solution into an oven at the temperature of 50-150 DEG C to obtain the catalyst. According to the method, the solid content of the catalyst slurry is controlled by viscosity, the mesopore volume is increased, increase of the pore volume of the catalyst by virtue of addition of inorganic acid, carbon black, a surfactant or other mesoporous materials is not needed, and the heavy oil conversion rate is improved.
Description
Technical field
The invention belongs to catalyst preparation technical field, the preparation method of the catalytic cracking catalyst particularly using in a kind of petroleum refining process.
Background technology
Due to heavy and the in poor quality of feedstock oil, selective in order to improve heavy oil cracking ability and the diesel oil of catalyst, catalyst must provide a certain amount of mesopore volume.The method of increase catalyst mesopore volume that prior art adopts mainly contains and adds inorganic acid to carry out peptization to boehmite, adds carbon black etc. to carry out pore-creating by burning-off material, adds surfactant or other mesoporous materials etc.
Summary of the invention
The object of this invention is to provide a kind of catalyst for heavy oil catalytic cracking and preparation method thereof.The method is controlled the solid content of catalyst slurry by viscosity, increase mesoporous volume, without adding inorganic acid, carbon black, surfactant or other mesoporous materials to increase catalyst pore volume.
The preparation method of catalyst for heavy oil catalytic cracking of the present invention is: molecular sieve, boehmite, clay and deionized water making beating are mixed, add simultaneously or do not add aluminium colloidal sol, make catalyst slurry, spraying is dry afterwards, again through 300-600 ℃ of roasting 2-4h, then the ammonium sulfate that is 5-20% by 40-99 ℃ of mass concentration and ammonium dihydrogen phosphate exchange washing, and the consumption of ammonium sulfate and ammonium dihydrogen phosphate (ADP) is the 1-10% of product quality after roasting; Finally be placed in 50-150 ℃ of baking oven oven dry and obtain catalyst.
Described catalyst slurry composition is counted molecular sieve 15-50% by butt quality, and clay 15-65%, by Al
2o
3the boehmite of meter and aluminium colloidal sol is 10-35% altogether, and wherein aluminium colloidal sol addition is no more than 10% of boehmite amount; The solid content of catalyst slurry is 25-52wt%.
The preparation method's of the catalyst for heavy oil catalytic cracking of high-yield diesel oil of the present invention concrete operation step is: first molecular sieve and boehmite are mixed, add part deionized water, after ultrasonic 3-10min, under stirring, add clay, now add or do not add aluminium colloidal sol, then add while stirring remaining deionized water, making beating 5-30min makes catalyst slurry, spraying is dry afterwards, again through 300-600 ℃ of roasting 2-4h, then the ammonium sulfate that is 5-20% by 40-99 ℃ of mass concentration and ammonium dihydrogen phosphate exchange washing, the consumption of ammonium sulfate and ammonium dihydrogen phosphate (ADP) is the 1-10% of product quality after roasting, finally be placed in 50-150 ℃ of baking oven oven dry and obtain catalyst.
Described molecular sieve is y-type zeolite, or one or more mixture in y-type zeolite and ZSM-5 zeolite, Omega zeolite, β zeolite; The wherein mixture of preferred y-type zeolite or y-type zeolite and ZSM-5 zeolite.
Described clay is one or more in kaolin, galapectite, sepiolite, tired de-soil, imvite; Wherein preferred kaolin, galapectite, sepiolite or their mixture; Most preferably kaolin.
Described boehmite replaces with boehmite, gibbsite, bayerite or η aluminium oxide.
The viscosity of described catalyst slurry is controlled at 1000-200000 centipoise scope.
The present invention controls the solid content of catalyst slurry by viscosity, increase mesopore volume, without adding inorganic acid, carbon black, surfactant or other mesoporous materials to increase catalyst pore volume.Catalyst for heavy oil catalytic cracking prepared by the present invention improves heavy oil transformation rate, and gasoline, diesel is selective.
Accompanying drawing explanation
Fig. 1 is the result comparison diagram of heavy oil transformation rate, diesel oil and the gasoline yield of the catalyst prepared of embodiment 4 and the reaction of industrial catalyst MLC-500 catalytic cracking heavy oil.
The specific embodiment
The present invention is further illustrated for the following examples, but protection scope of the present invention is not subject to the restriction of these embodiment.
In each embodiment and comparative example, adopt ColeParmer98936 rotating cylinder viscosimeter to measure slurry viscosity, the viscosity providing is the result that uses R4 rotating shaft gained under 2.5rpm rotating speed.In each embodiment, the content ratio of molecular sieve, boehmite, clay, aluminium colloidal sol is by the mass percent of butt quality, and boehmite and aluminium colloidal sol are pressed Al
2o
3meter.
Embodiment 1
Get 18% ReY molecular sieve, 10% ZSM-5 molecular sieve, 4%Omega zeolite and 4% the β zeolite (commercial goods of Shanxi Teng Mao Science and Technology Ltd., trade mark TMY, rare earth oxide content is 16.2wt%) and 10% boehmite (alumina content is 67.64wt%) mix after, add part deionized water, after ultrasonic 3min, under stirring, add the aluminium colloidal sol (alumina content is 20.92%) of 51% kaolin (purchased from China Kaolin Co., Ltd) and 3%, then adding deionized water to regulate slurry solid content is 30%, stir 5min, measuring now viscosity is 13320cp, after making beating 5min, spraying is dry, to spray dried product through 300 ℃ of roasting 2h, then exchange washing with 20wt% ammonium sulfate and the ammonium dihydrogen phosphate of 40 ℃, the consumption of ammonium sulfate and ammonium dihydrogen phosphate (ADP) be after roasting product quality 5%, finally be placed in 50 ℃ of baking ovens oven dry and obtain catalyst A.
Embodiment 2
Get 28% ReY molecular sieve and 10% the ZSM-5 molecular sieve (commercial goods of Shanxi Teng Mao Science and Technology Ltd., trade mark TMY) and 20% boehmite (alumina content is 67.64wt%) mix after, add part deionized water, after ultrasonic 5min, under stirring, add the aluminium colloidal sol (alumina content is 20.92%) of 39% galapectite (purchased from China Kaolin Co., Ltd) and 5%, then adding deionized water to regulate slurry solid content is 32%, stir 10min, measuring now viscosity is 24240cp; After making beating 10min, spraying is dry, to spray dried product through 400 ℃ of roasting 2.5h, then exchange washing with 18wt% ammonium sulfate and the ammonium dihydrogen phosphate of 50 ℃, the consumption of ammonium sulfate and ammonium dihydrogen phosphate (ADP) be after roasting product quality 10%, be finally placed in 70 ℃ of baking ovens and dry and obtain catalyst B.
Embodiment 3
Get the β zeolite (commercial goods of Shanxi Teng Mao Science and Technology Ltd. of 18% ReY molecular sieve, 14%Omega zeolite and 4%, trade mark TMY, rare earth oxide content is 16.2wt%) and 25% boehmite (alumina content is 67.64wt%) mix after, add part deionized water, after ultrasonic 7min, under stirring, add the aluminium colloidal sol (alumina content is 20.92%) of 32% imvite (purchased from China Kaolin Co., Ltd) and 7%, then adding deionized water to regulate slurry solid content is 35%, stir 15min, measuring now viscosity is 32880cp; After making beating 15min, spraying is dry, to spray dried product through 450 ℃ of roasting 3h, then exchange washing with 15wt% ammonium sulfate and the ammonium dihydrogen phosphate of 70 ℃, the consumption of ammonium sulfate and ammonium dihydrogen phosphate (ADP) be after roasting product quality 8%, be finally placed in 110 ℃ of baking ovens and dry and obtain catalyst C.Embodiment 4
Get 36% the ReY molecular sieve (commercial goods of Shanxi Teng Mao Science and Technology Ltd., trade mark TMY, rare earth oxide content is 16.2wt%) and 10% boehmite (alumina content is 67.64wt%) mix after, add part deionized water, after ultrasonic 5min, under stirring, add the aluminium colloidal sol (alumina content is 20.92%) of 51% kaolin (purchased from China Kaolin Co., Ltd) and 3%, then adding deionized water to regulate slurry solid content is 38%, stir 15min, measuring now viscosity is 136200cp; After making beating 30min, spraying is dry, to spray dried product through 540 ℃ of roasting 2h, then exchange washing with 10wt% ammonium sulfate and the ammonium dihydrogen phosphate of 90 ℃, the consumption of ammonium sulfate and ammonium dihydrogen phosphate (ADP) be after roasting product quality 8%, be finally placed in 110 ℃ of baking ovens and dry and obtain catalyst D.
46% the ReY molecular sieve (commercial goods of Shanxi Teng Mao Science and Technology Ltd., trade mark TMY, rare earth oxide content is 16.2wt%) and 35% η aluminium oxide stone (alumina content is 67.64wt%) mix after, add part deionized water, after ultrasonic 10min, add 19% sepiolite (purchased from China Kaolin Co., Ltd) under stirring, then adding deionized water to regulate slurry solid content is 40%, stir 30min, measuring now viscosity is 198130cp; After making beating 30min, spraying is dry, to spray dried product through 540 ℃ of roasting 4h, then exchange washing with 5wt% ammonium sulfate and the ammonium dihydrogen phosphate of 99 ℃, the consumption of ammonium sulfate and ammonium dihydrogen phosphate (ADP) be after roasting product quality 3%, be finally placed in 150 ℃ of baking ovens and dry and obtain catalyst E.
Test case 1
Catalyst prepared by above-described embodiment 4 and industrial catalyst MLC-500 be aging 17h under 800 ℃, 100% steam respectively, then respectively they is filled in fixed fluidized bed device (chemical research institute of PetroChina Company Limited.).Amount of fill is 200g separately; Mass space velocity is 15h
-1, oil ratio (weight) is under 6 conditions, heavily urge VGO+45%VR heavy oil to carry out catalytic cracking reaction in described fixed fluidized bed device grand celebration, and change temperature and make embodiment 4 and MLC-500 catalyst reach same conversion, and analyze the composition of catalytic cracking production, result is as shown in accompanying drawing 1 and following table 1.
Table 1
Can be found out by table 1 and accompanying drawing 1 data, under the same conditions, adopt catalytic cracking catalyst provided by the invention, heavy oil transformation rate, diesel oil and gasoline yield are all higher than industrial contrast medium, and coke yield is lower than industrial catalyst, good residual oil cracking performance and gasoline, diesel oil, coke selectivity energy are described.
Claims (7)
1. the preparation method of a catalyst for heavy oil catalytic cracking, it is characterized in that, the method is: molecular sieve, boehmite, clay and deionized water making beating are mixed, add simultaneously or do not add aluminium colloidal sol, make catalyst slurry, spraying is afterwards dry, then through 300-600 ℃ of roasting 2-4h, then the ammonium sulfate that is 5-20% by 40-99 ℃ of mass concentration and ammonium dihydrogen phosphate exchange washing, and the consumption of ammonium sulfate and ammonium dihydrogen phosphate (ADP) is the 1-10% of product quality after roasting; Finally be placed in 50-150 ℃ of baking oven oven dry and obtain catalyst.
2. method according to claim 1, is characterized in that, described catalyst slurry composition is counted molecular sieve 15-50% by butt quality, and clay 15-65%, by Al
2o
3the boehmite of meter and aluminium colloidal sol is 10-35% altogether, and wherein aluminium colloidal sol addition is no more than 10% of boehmite amount; The solid content of catalyst slurry is 25-52wt%.
3. preparation method according to claim 2, it is characterized in that, the preparation method's of the catalyst for heavy oil catalytic cracking of high-yield diesel oil of the present invention concrete operation step is: first molecular sieve and boehmite are mixed, add part deionized water, after ultrasonic 3-10min, under stirring, add clay, now add or do not add aluminium colloidal sol, then add while stirring remaining deionized water, making beating 5-30min makes catalyst slurry, spraying is dry afterwards, again through 300-600 ℃ of roasting 2-4h, then the ammonium sulfate that is 5-20% by 40-99 ℃ of mass concentration and ammonium dihydrogen phosphate exchange washing, the consumption of ammonium sulfate and ammonium dihydrogen phosphate (ADP) is the 1-10% of product quality after roasting, finally be placed in 50-150 ℃ of baking oven oven dry and obtain catalyst.
4. according to the arbitrary described preparation method of claim 1-3, it is characterized in that, described molecular sieve is y-type zeolite, or one or more mixture in y-type zeolite and ZSM-5 zeolite, Omega zeolite, β zeolite; The wherein mixture of preferred y-type zeolite or y-type zeolite and ZSM-5 zeolite.
5. according to the arbitrary described preparation method of claim 1-3, it is characterized in that, described clay is one or more in kaolin, galapectite, sepiolite, tired de-soil, imvite; Wherein preferred kaolin, galapectite, sepiolite or their mixture; Most preferably kaolin.
6. according to the arbitrary described preparation method of claim 1-3, it is characterized in that, described boehmite replaces with boehmite, gibbsite, bayerite or η aluminium oxide.
7. according to the arbitrary described preparation method of claim 1-3, it is characterized in that, the viscosity of described catalyst slurry is controlled at 1000-200000 centipoise scope.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108499600A (en) * | 2018-04-19 | 2018-09-07 | 四川润和催化新材料股份有限公司 | A kind of catalytic cracking catalyst of high-yield diesel oil and preparation method thereof |
| CN109647365A (en) * | 2017-10-12 | 2019-04-19 | 中国石油天然气股份有限公司 | A kind of preparation method of catalyst for heavy oil catalytic cracking |
| CN111744541A (en) * | 2020-06-23 | 2020-10-09 | 中国石油天然气集团有限公司 | Catalytic cracking catalyst containing high-silicon shape-selective molecular sieve and preparation method thereof |
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| CN101386788A (en) * | 2007-09-12 | 2009-03-18 | 中国石油化工股份有限公司 | Catalyst for heavy oil catalytic cracking and preparation method thereof |
| CN101829592A (en) * | 2009-03-10 | 2010-09-15 | 中国石油天然气股份有限公司 | Preparation method of fluidizing, catalyzing and cracking catalyst with high solid content |
| JP2012140287A (en) * | 2010-12-28 | 2012-07-26 | Jgc Catalysts & Chemicals Ltd | New faujasite type zeolite, method for production thereof, and catalyst including the faujasite type zeolite used for catalytic cracking of hydrocarbon |
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Patent Citations (6)
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| CN1083512A (en) * | 1993-08-26 | 1994-03-09 | 中国石化兰州炼油化工总厂 | A kind of preparation method who comprises the catalytic cracking catalyst of molecular sieve |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109647365A (en) * | 2017-10-12 | 2019-04-19 | 中国石油天然气股份有限公司 | A kind of preparation method of catalyst for heavy oil catalytic cracking |
| CN108499600A (en) * | 2018-04-19 | 2018-09-07 | 四川润和催化新材料股份有限公司 | A kind of catalytic cracking catalyst of high-yield diesel oil and preparation method thereof |
| 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 |
| CN111744541A (en) * | 2020-06-23 | 2020-10-09 | 中国石油天然气集团有限公司 | Catalytic cracking catalyst containing high-silicon shape-selective molecular sieve and preparation method thereof |
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Application publication date: 20140521 |