CN109304150A - A kind of method that catalytic cracking spent catalyst manufactures innoxious adsorbent material - Google Patents
A kind of method that catalytic cracking spent catalyst manufactures innoxious adsorbent material Download PDFInfo
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- CN109304150A CN109304150A CN201711133849.6A CN201711133849A CN109304150A CN 109304150 A CN109304150 A CN 109304150A CN 201711133849 A CN201711133849 A CN 201711133849A CN 109304150 A CN109304150 A CN 109304150A
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- catalytic cracking
- spent catalyst
- cracking spent
- innoxious
- adsorbent material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
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Abstract
The invention proposes a kind of methods that catalytic cracking spent catalyst manufactures innoxious adsorbent material; by catalytic cracking spent catalyst heat temperature raising in the reactor; the mixed gas that nitrogen and hydrogen are continually fed into the dead catalyst after heating carries out reduction reaction; streams closed after obtained reaction is discharged into solid material cooler; Quench is carried out using nitrogen protection; it is cooled to when temperature of charge is down to room temperature and stops nitrogen protection, obtain innoxious adsorbent material.The present invention realizes the harmlessness disposing of catalytic cracking spent catalyst by using the method that hydrogen heat-treats, and eliminates the deleterious oxidation nickel that may contain in catalytic cracking spent catalyst, while obtaining can be used as the adsorbent material of chemicals or oil leak.
Description
Technical field
The present invention relates to solid waste resource recoveries to utilize field, and in particular to a kind of catalytic cracking spent catalyst manufacture nothing
The method of evilization adsorbent material.
Background technique
In China, catalytic cracking catalyst dosage accounts for about the 85% of the total dosage of oil refining catalyst, catalytic cracking catalyst warp
It crosses in the present apparatus after repeated regeneration use, partial catalyst is destroyed or due to absorption due to molecular sieve structure by thermal and hydric environment
Excessive heavy metal and carbon distribution, can irreversible inactivation and be discharged, the catalytic cracking spent catalyst that this part is discarded
It is put into " National Hazard waste register ", belongs to hazardous waste.In China, the yield of annual catalytic cracking spent catalyst is about
It is 100,000 tons, to prevent pollution environment, it is necessary to carry out harmless treatment disposition or resource utilization to it.Currently used processing
Method of disposal include direct landfill, magnetic separation separation, Extraction of rare earth element, as supplement raw material of cement etc..
Chinese patent CN 104495924A is related to a kind of side by oil plant catalytic cracking spent catalyst production ammonium metavanadate
Method.Oil plant catalytic cracking spent catalyst is recycled, logical peracid treatment, precipitating produce ammonium metavanadate, the inclined vanadium produced
Sour ammonium purity reaches 99% or more, and recovery efficiency is high.Chinese patent CN102586606 describes a kind of useless FCC/ from the nickel containing vanadium
The method of recovering rare earth, vanadium, nickel in ROC catalyst, the patent is equally existing to obtain raw material progress acid processing containing rare earth ion
Liquid obtains rare-earth products finally by oxalic acid, ammonium bicarbonate precipitation then by double salt precipitation.Though having many patents and grinding
Study carefully the method for describing various recovering rare earths, but since low (general content is in 800ppm for nickel taste in catalytic cracking spent catalyst
Left and right), do not have the economic value of extraction, while the new dangerous wastes such as a large amount of spent acid alkali can be generated in sour treatment process, because
The method economic benefit and environmental benefit of this recovering rare earth are general.
The method of landfill cannot fundamentally remove the hazard property of waste, and occupy large amount of land resources, this
Kind method is unsustainable.
Nickel in catalytic cracking spent catalyst can change the condensation performance of cement, and the country has cement kiln collaboration at present
The enterprise for disposing dangerous waste ability is fewer, therefore the method as cement supplement raw material is also difficult to popularize in an all-round way.
Catalytic cracking spent catalyst, which belongs to the reason of hazardous waste, two o'clock, first is that wherein the leaching concentration containing total nickel can
Can exceed that the limit value of national standard 5mg/L, second is that wherein may the content containing nickel oxide be more than national standard 0.1% limit
Value.
Innoxious research is carried out using hydrogen thermal reduction to catalytic cracking spent catalyst to have not been reported, and therefore, utilizes hydrogen
Gas thermal reduction carries out innoxious technology and had both provided a kind of method of innoxiousization, it is innoxious after product can further into
Row resource circulation utilization, is of great significance.
Summary of the invention
For the status of existing catalytic cracking spent catalyst, the invention proposes a kind of catalytic cracking spent catalysts to manufacture nothing
The method of evilization adsorbent material realizes the harmlessness disposing of catalytic cracking spent catalyst by using the method for hydrogen thermal reduction,
The deleterious oxidation nickel that may contain in catalytic cracking spent catalyst is eliminated, while obtaining can be used as chemicals or oil leak
Adsorbent material.
A kind of method that catalytic cracking spent catalyst manufactures innoxious adsorbent material, comprising the following steps:
(1) catalytic cracking spent catalyst is subjected to break process, obtains catalytic cracking spent catalyst powder；
(2) catalytic cracking spent catalyst powder is heated to 310-360 DEG C in the reactor, heating rate 20-30
℃/min；
(3) gaseous mixture of nitrogen and hydrogen is continually fed into the catalytic cracking spent catalyst powder after step (2) heating
Body carries out reduction reaction；
(4) streams closed after reaction that step (3) obtains is discharged into Quench in solid material cooler, kept away during this
Exempt from material ingress of air, and continues to be passed through nitrogen protection cooling, nitrogen gas purity 99.99%, cooling into cooler dead catalyst
30-70 DEG C of rate/min is cooled to when temperature of charge is down to room temperature and stops nitrogen protection, obtains innoxious adsorbent material.
Preferably, the break process of catalytic cracking spent catalyst described in step (1) grinds for ball milling.
Preferably, the specific surface area of catalytic cracking spent catalyst powder described in step (1) is higher than 200m2/kg。
Preferably, heating rate is 25 DEG C/min in step (2), is heated to 350 DEG C.
Preferably, the volume content of hydrogen is 0.5~3% in mixed gas described in step (3).
Preferably, the volume content of hydrogen is 3% in mixed gas described in step (3).
Preferably, the time of reduction reaction is 20-60min in step (3).
Preferably, the time of reduction reaction is 40min in step (3).
Preferably, rate of temperature fall described in step (4) is 50 DEG C/min.
Preferably, the innoxious adsorbent material being prepared add extrusion granulation production glomeration after certain adhesive,
The adsorbent materials of different shapes such as grain dress, strip, sheet.
Technical characterstic for a better understanding of the invention is briefly described as follows technical principle and theoretical foundation of the invention:
Catalytic cracking spent catalyst, which belongs to the reason of hazardous waste, two o'clock, first is that wherein the leaching concentration containing total nickel can
Can exceed that the limit value of national standard 5mg/L, second is that wherein may the content containing nickel oxide be more than national standard 0.1% limit
Value.Nickelous on catalytic cracking spent catalyst is reduced to zero-valent nickel by control reaction condition by the present invention, to eliminate oxygen
Change nickel there are a possibility that, and metallic nickel is more difficult by Ore Leaching with the nickel of compound state compared with, and leaching concentration is lower, thus reality
Now catalytic cracking spent catalyst is innoxious.Simultaneously, the process that heat adds hydrogen innoxious is also to catalytic cracking spent catalyst
Microporous structure and specific surface area are improved, and adsorption capacity relatively plus before hydrogen significantly improves, and can be used as chemicals or oil product
The adsorbent material of leakage.
The beneficial effects of the present invention are:
The harmlessness disposing that catalytic cracking spent catalyst is realized by using the method for hydrogen thermal reduction, eliminates catalysis and splits
Change the nickel oxide that may contain in dead catalyst, and compared before the relatively reduction of the product after reduction, the leaching concentration of nickel is also far below
The requirement of national standard limit value, microporous structure and specific surface area are also improved, to realize the useless catalysis of catalytic cracking
The thorough innoxious and recycling of agent.
Specific embodiment
Combined with specific embodiments below, the present invention will be further described:
Embodiment 1
(1) catalytic cracking spent catalyst progress ball milling is ground, obtains catalytic cracking spent catalyst powder；
(2) 100kg catalytic cracking spent catalyst powder is taken to be heated to 310 DEG C in the reactor, 20 DEG C of heating rate/
min；
(3) gaseous mixture of nitrogen and hydrogen is continually fed into the catalytic cracking spent catalyst powder after step (2) heating
Body carries out reduction reaction, and the volume content of hydrogen is 0.5% in mixed gas, reacts 60min；
(4) streams closed after reaction that step (3) obtains is discharged into Quench in solid material cooler, kept away during this
Exempt from material ingress of air, and continues to be passed through nitrogen protection cooling, nitrogen gas purity 99.99%, cooling into cooler dead catalyst
30 DEG C/min of rate is cooled to when temperature of charge is down to room temperature and stops nitrogen protection, obtains innoxious adsorbent material.
(5) the innoxious adsorbent material for obtaining step (4) squeezes after adding certain adhesive according to practical use needs
Pressure is granulated the adsorbent materials of different shapes such as production glomeration, grain dress, strip, sheet.
Embodiment 2
(1) catalytic cracking spent catalyst progress ball milling is ground, obtains catalytic cracking spent catalyst powder；
(2) 100kg catalytic cracking spent catalyst powder is taken to be heated to 360 DEG C in the reactor, 30 DEG C of heating rate/
min；
(3) gaseous mixture of nitrogen and hydrogen is continually fed into the catalytic cracking spent catalyst powder after step (2) heating
Body carries out reduction reaction, and the volume content of hydrogen is 3% in mixed gas, reacts 20min；
(4) streams closed after reaction that step (3) obtains is discharged into Quench in solid material cooler, kept away during this
Exempt from material ingress of air, and continues to be passed through nitrogen protection cooling, nitrogen gas purity 99.99%, cooling into cooler dead catalyst
70 DEG C/min of rate is cooled to when temperature of charge is down to room temperature and stops nitrogen protection, obtains innoxious adsorbent material.
(5) the innoxious adsorbent material for obtaining step (4) squeezes after adding certain adhesive according to practical use needs
Pressure is granulated the adsorbent materials of different shapes such as production glomeration, grain dress, strip, sheet.
Embodiment 3
(1) catalytic cracking spent catalyst progress ball milling is ground, obtains catalytic cracking spent catalyst powder；
(2) 100kg catalytic cracking spent catalyst powder is taken to be heated to 350 DEG C in the reactor, 25 DEG C of heating rate/
min；
(3) gaseous mixture of nitrogen and hydrogen is continually fed into the catalytic cracking spent catalyst powder after step (2) heating
Body carries out reduction reaction, and the volume content of hydrogen is 3% in mixed gas, reacts 40min；
(4) streams closed after reaction that step (3) obtains is discharged into Quench in solid material cooler, kept away during this
Exempt from material ingress of air, and continues to be passed through nitrogen protection cooling, nitrogen gas purity 99.99%, cooling into cooler dead catalyst
50 DEG C/min of rate is cooled to when temperature of charge is down to room temperature and stops nitrogen protection, obtains innoxious adsorbent material.
(5) the innoxious adsorbent material for obtaining step (4) squeezes after adding certain adhesive according to practical use needs
Pressure is granulated the adsorbent materials of different shapes such as production glomeration, grain dress, strip, sheet.
Embodiment 4
(1) catalytic cracking spent catalyst progress ball milling is ground, obtains catalytic cracking spent catalyst powder；
(2) 100kg catalytic cracking spent catalyst powder is taken to be heated to 330 DEG C in the reactor, 25 DEG C of heating rate/
min；
(3) gaseous mixture of nitrogen and hydrogen is continually fed into the catalytic cracking spent catalyst powder after step (2) heating
Body carries out reduction reaction, and the volume content of hydrogen is 1.5% in mixed gas, reacts 30min；
(4) streams closed after reaction that step (3) obtains is discharged into Quench in solid material cooler, kept away during this
Exempt from material ingress of air, and continues to be passed through nitrogen protection cooling, nitrogen gas purity 99.99%, cooling into cooler dead catalyst
60 DEG C/min of rate is cooled to when temperature of charge is down to room temperature and stops nitrogen protection, obtains innoxious adsorbent material.
(5) the innoxious adsorbent material for obtaining step (4) squeezes after adding certain adhesive according to practical use needs
Pressure is granulated the adsorbent materials of different shapes such as production glomeration, grain dress, strip, sheet.
Certainly, the above description is not a limitation of the present invention, and the present invention is also not limited to the example above, this technology neck
The variations, modifications, additions or substitutions that the technical staff in domain is made within the essential scope of the present invention also should belong to of the invention
Protection scope.
Claims (10)
1. a kind of method that catalytic cracking spent catalyst manufactures innoxious adsorbent material, which comprises the following steps:
(1) catalytic cracking spent catalyst progress ball milling is ground, obtains catalytic cracking spent catalyst powder；
(2) catalytic cracking spent catalyst powder is heated to 310-360 DEG C in the reactor, 20-30 DEG C of heating rate/
min；
(3) be continually fed into the catalytic cracking spent catalyst powder after step (2) heating the mixed gas of nitrogen and hydrogen into
Row reduction reaction；
(4) streams closed after reaction that step (3) obtains is discharged into Quench in solid material cooler, avoids object during this
Expect ingress of air, and continues to be passed through nitrogen protection cooling, nitrogen gas purity 99.99%, rate of temperature fall into cooler dead catalyst
It 30-70 DEG C/min, is cooled to when temperature of charge is down to room temperature and stops nitrogen protection, obtain innoxious adsorbent material.
2. the method that a kind of catalytic cracking spent catalyst according to claim 1 manufactures innoxious adsorbent material, feature
It is, the break process of catalytic cracking spent catalyst described in step (1) grinds for ball milling.
3. the method that a kind of catalytic cracking spent catalyst according to claim 1 manufactures innoxious adsorbent material, feature
It is, the specific surface area of catalytic cracking spent catalyst powder described in step (1) is higher than 200m2/kg。
4. the method that a kind of catalytic cracking spent catalyst according to claim 1 manufactures innoxious adsorbent material, feature
It is, heating rate is 25 DEG C/min in step (2), is heated to 350 DEG C.
5. the method that a kind of catalytic cracking spent catalyst according to claim 1 manufactures innoxious adsorbent material, feature
It is, the volume content of hydrogen is 0.5~3% in mixed gas described in step (3).
6. the method that a kind of catalytic cracking spent catalyst according to claim 5 manufactures innoxious adsorbent material, feature
It is, the volume content of hydrogen is 3% in mixed gas described in step (3).
7. the method that a kind of catalytic cracking spent catalyst according to claim 1 manufactures innoxious adsorbent material, feature
It is, the time of reduction reaction is 20-60min in step (3).
8. the method that a kind of catalytic cracking spent catalyst according to claim 7 manufactures innoxious adsorbent material, feature
It is, the time of reduction reaction is 40min in step (3).
9. the method that a kind of catalytic cracking spent catalyst according to claim 1 manufactures innoxious adsorbent material, feature
It is, rate of temperature fall described in step (4) is 50 DEG C/min.
10. a kind of -9 catalytic cracking spent catalysts described in any one manufacture innoxious adsorbent material according to claim 1
Method, which is characterized in that the innoxious adsorbent material add extrusion granulation production glomeration after certain adhesive, grain dress,
The adsorbent material of strip or sheet.
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| CN201711133849.6A CN109304150A (en) | 2017-11-16 | 2017-11-16 | A kind of method that catalytic cracking spent catalyst manufactures innoxious adsorbent material |
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|---|---|---|---|---|
| US4459371A (en) * | 1983-01-24 | 1984-07-10 | Uop Inc. | FCC Sulfur oxide acceptor |
| CN101592449A (en) * | 2008-05-29 | 2009-12-02 | 中国石油化工股份有限公司 | Heat-exchange method in a kind of reactivation process of flue gas desulfuration and denitrification adsorbent |
| CN103820632A (en) * | 2013-11-25 | 2014-05-28 | 上海派特贵金属有限公司 | Pretreatment method for precious metal in scraped automobile exhaust catalyst |
| CN105728027A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Adsorption desulfurization catalyst and preparation method thereof |
| CN106552680A (en) * | 2016-12-07 | 2017-04-05 | 四川润和催化新材料股份有限公司 | A kind of method of FCC dead catalyst Demetalizing reactivating |
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2017
- 2017-11-16 CN CN201711133849.6A patent/CN109304150A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4459371A (en) * | 1983-01-24 | 1984-07-10 | Uop Inc. | FCC Sulfur oxide acceptor |
| CN101592449A (en) * | 2008-05-29 | 2009-12-02 | 中国石油化工股份有限公司 | Heat-exchange method in a kind of reactivation process of flue gas desulfuration and denitrification adsorbent |
| CN103820632A (en) * | 2013-11-25 | 2014-05-28 | 上海派特贵金属有限公司 | Pretreatment method for precious metal in scraped automobile exhaust catalyst |
| CN105728027A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Adsorption desulfurization catalyst and preparation method thereof |
| CN106552680A (en) * | 2016-12-07 | 2017-04-05 | 四川润和催化新材料股份有限公司 | A kind of method of FCC dead catalyst Demetalizing reactivating |
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Application publication date: 20190205 |