CN104815703B - Method for resuscitating spent catalytic cracking catalyst through gas-solid reaction with SiCl4 - Google Patents
Method for resuscitating spent catalytic cracking catalyst through gas-solid reaction with SiCl4 Download PDFInfo
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Abstract
The invention discloses a method for resuscitating spent catalytic cracking catalyst through gas-solid reaction with SiCl4 and relates to the solid waste disposal and application field. The resuscitating method includes steps of doing mixing roasted spent catalytic cracking catalyst material with gaseous SiCl4, and reacting to obtain catalyst product; using de-ionized water to wash the catalyst product till the pH value of filtered water is constant, and using organic acid to carry out acid pickling treatment on the washed catalyst; using de-ionized water to wash the catalyst subjected to acid pickling, filtering, mixing the obtained catalyst with rare earth chloride solution, stirring to obtain mixed size, filtering the mixed size, and drying to obtain the resuscitated catalyst. The resuscitating method uses gas-solid hybrid reaction between SiCl4 and spent catalyst and uses acid pickling treatment and rare earth deposition, the resuscitating method is simple, the heavy metal content of the resuscitated catalyst is low, the specific surface area is high, and the activity stability is good.
Description
Technical field：
The present invention relates to a kind of and SiCl4The rejuvenation method of gas-solid reaction catalytic cracking spent catalyst, belongs to solid waste
Thing process and application.
Background technology：
Catalytic cracking catalyst is the maximum a kind of catalyst of application amount in oil refining process.Catalytic cracking catalyst is being used
During the reason such as cracked reaction green coke, high-temperature water hot recycling and heavy metal pollution and inactivate.For active slightly higher, metal
The relatively very low poising agent of content can apply to some catalytic cracking units or use as the agent that goes into operation, and very low for activity
The higher poising agent of (specific surface is relatively low), content of beary metal then becomes useless agent.
For the processing method of waste acetic acid, method the more commonly used at present is to bury, can be right but bury
Soil and groundwater resource is polluted；Therefore, lot of domestic and international researcher does a lot of work to the useless catalytic cracking of reuse
Catalyst, especially carries out replacing fresh catalyst after resurrection process to it.As ChemCat companies of the U.S. use H2S and Cl2Gas
Ni, V, Fe are removed with dead catalyst reaction, then with hydrogen peroxide and containing SO2Water catalyst is aoxidized, washing is reduced, then
Ammonium is exchanged, and makes revivification of catalyst.CCTI companies of the U.S. develop ACT processing systems on the basis of Demet techniques, with Demet
Technique is similar.The processing step is various, not easy to operate.Shah utilizes chelating agent (second phthalein acetone, ethylenediamine tetra-acetic acid, citric acid
Ammonium etc.) process metal poisoning FCC catalyst.As a result show, through the catalyst of chelant reaction treatment, H2With the yield of dry gas
It is decreased obviously, but the activity change of catalyst is little.Flvin is using ammonium salt and rare earth compound solution to through chlorination, sulfuration
And the FCC equilibrium catalysts (the Y zeolites containing USY and rare earth exchanged) after other methods process have carried out ion exchange, compare
Catalyst activity, selectivity and partial catalyst demetalization degree after distinct methods process.From in terms of the result of the test of Flvin,
Sulfuration and chlorination process very effective to removing heavy metal, particularly nickel；The ion exchange of ammonium salt and rare earth is to improving catalyst
Activity is helpful.Domestic Zheng Lian justice etc. is studied using the method that oxidation acid leaching is washed, but demetalization rear catalyst
Activity not be improved significantly, for this purpose, they are also adopted by the method for ammonium salt activation process to improve catalyst activity.Kindheartedness
Tinkling of pieces of jade etc. processes spent FCC catalyst, nickel removal rate highest accessible 50% using oxalic acid and liquor potassic permanganate；It is 1: 7 in solid-to-liquid ratio,
Temperature be under the conditions of 80～100 DEG C it is simple with 1.5% NH4NO3Solution processes catalyst 0.5h, it is possible to remove more than 50%
Nickel；With 33% HClO4Process, catalyst nickel removal rate can just reach 50%, and use 100% HClO4Process catalyst,
Nickel removal efficiency reaches as high as 66.7%.Li Chunyi etc. adopts HCl, HNO3, H2SO4And HClO4Deng inorganic acid pickling and oxidation and
Pickling (hydrogen peroxide and oxalic acid) composite algorithm carries out demetalization to FCC dead catalyst and brings back to life research, as a result shows, inorganic acid all has
Vanadium removal effect, not with nickel removal effect, the nickel removal effect of oxidation and pickling composite algorithm is then more preferably.CN101219396A adopts nothing
Machine acid and organic acid are processed FCC dead catalyst, the heavy metal partial removal of dead catalyst, specific surface area is increased and living
Property improve.
Above the rejuvenation method mostly processing step of existing FCC dead catalyst is more complicated, operates cumbersome, some sides
Method is although relatively easy, but is extremely difficult to preferable effect, and especially the removal efficiency of heavy metal is relatively low.
The content of the invention：
For the problems referred to above, the technical problem to be solved in the present invention is to provide one kind and SiCl4Gas-solid reaction catalytic cracking
The rejuvenation method of dead catalyst.
The present invention and SiCl4The rejuvenation method of gas-solid reaction catalytic cracking spent catalyst, it comprises the following steps：(1) will
Catalytic cracking spent catalyst material after fired process and gas phase SiCl4Mixing is reacted, and the reaction time is at 0.5-40 point
Clock, obtains catalyst product；
(2) deionized water is washed to the pH value of filter water to the catalyst product obtained by step (1) and is kept constant,
Then pickling processes are carried out to the catalyst after washing with organic acid；
(3) deionized water is washed and filtered to the catalyst obtained by step (2), wherein deionized water and catalyst
Mass ratio be 6-12: 1；
(4) catalyst for obtaining step (3) and re chloride are mixed, water and catalyst butt in slurries
Ratio is 6-10: 1, ratio 0.005-0.04 of rare earth (in terms of rare earth oxide) and catalyst butt: 1；
(5) after is filtered the mixed serum obtained by step (4), then at 120-400 DEG C of dried process 0.25-4 hour
Catalyst must be brought back to life.
Preferably, catalytic cracking spent catalyst temperature of charge is 250-450 DEG C in described step (1), SiCl4With urge
Change mass ratio 0.05-0.5: 1 of the butt of cracking dead catalyst material.
Preferably, the organic acid in described step (2) can be in formic acid, oxalic acid, citric acid and tartaric acid
It is a kind of or arbitrarily several.
Preferably, in described step (2) pickling time be 0.25-6 hours, pickling pH value be 1-5, pickling temperature
For 60-120 DEG C.
Preferably, mixing time is 0.3-1.5 hours in described step (4), slurry pH value is controlled in 3.3-4.5.
Beneficial effects of the present invention：The drawbacks of it can overcome prior art, it adopts SiCl4With dead catalyst gas-solid mixing
Reaction, pickling processes and rare earth deposition, its rejuvenation method is simple, and flexible operation, the catalyst content of beary metal after resurrection is low,
Specific surface area is high, and activity stability is good.
Description of the drawings：
For ease of explanation, the present invention is embodied as and accompanying drawing is described in detail by following.
Fig. 1 is the physico-chemical property schematic diagram of catalytic cracking spent catalyst raw material used in each embodiment of the invention；
Fig. 2 is the physico-chemical property schematic diagram of the resurrection catalyst in the present invention obtained by each embodiment；
The resurrection catalyst that Fig. 3 present invention is obtained carries out Catalytic Cracking Performance on small fixed flowing bed-tion reacting device
Evaluate the physico-chemical property figure of feedstock oil used；
Fig. 4 carries out Catalytic Cracking Performance evaluation to bring back to life catalyst in the present invention on small fixed flowing bed-tion reacting device
Interpretation of result figure.
Specific embodiment：
This specific embodiment is employed the following technical solutions：It comprises the following steps：(1) by the catalysis after fired process
Cracking dead catalyst material and gas phase SiCl4Mixing is reacted, and the reaction time, in 0.5-40 minutes, obtains catalyst product；
(2) deionized water is washed to the pH value of filter water to the catalyst product obtained by step (1) and is kept constant,
Then pickling processes are carried out to the catalyst after washing with organic acid；
(3) deionized water is washed and filtered to the catalyst obtained by step (2), wherein deionized water and catalyst
Mass ratio be 6-12: 1；
(4) catalyst for obtaining step (3) and re chloride are mixed, water and catalyst butt in slurries
Ratio is 6-10: 1, ratio 0.005-0.04 of rare earth (in terms of rare earth oxide) and catalyst butt: 1；
(5) after is filtered the mixed serum obtained by step (4), then at 120-400 DEG C of dried process 0.25-4 hour
Catalyst must be brought back to life.
Preferably, catalytic cracking spent catalyst temperature of charge is 250-450 DEG C in described step (1), SiCl4With urge
Change mass ratio 0.05-0.5: 1 of the butt of cracking dead catalyst material.
Preferably, the organic acid in described step (2) can be in formic acid, oxalic acid, citric acid and tartaric acid
It is a kind of or arbitrarily several.
Preferably, in described step (2) pickling time be 0.25-6 hours, pickling pH value be 1-5, pickling temperature
For 60-120 DEG C.
Preferably, mixing time is 0.3-1.5 hours in described step (4), slurry pH value is controlled in 3.3-4.5.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel it should be appreciated that the present invention is not restricted to the described embodiments, the simply explanation described in above-described embodiment and specification this
The principle of invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these changes
Change and improvement is both fallen within scope of the claimed invention.The claimed scope of the invention by appending claims and its
Equivalent thereof.
Embodiment 1：By the catalytic cracking spent catalyst (400 DEG C of temperature of charge) of fired process and gas phase SiCl4Carry out
Hybrid reaction, (catalytic cracking spent catalyst raw material is designated as former agent in this embodiment, and its physical and chemical performance parameter is as shown in Figure 1),
SiCl4It is 0.25 with the mass ratio of catalytic cracking spent catalyst butt, the reaction time is 10 minutes.By reacted catalyst sample
Product carry out washing and filtering with 10 times of deionized waters, then carry out catalyst and oxalic acid solution mixing 1 hour, control solution
PH value is 3.0, and solution temperature is maintained at 90 DEG C.Catalyst sample after to pickling is washed, institute's deionized water water yield
10 times of catalyst butt quality, are then after filtering mixed catalyst and lanthanum chloride solution, and mixing time is
45 minutes, the mass ratio of lanthanum chloride (being counted with lanthana) and catalyst butt as 0.015: 1, water and catalyst butt matter in slurries
Than being 8: 1, slurry pH value is controlled to 3.7 to amount.After above-mentioned slurries are filtered, then the catalyst sample to obtaining is dried
Process, baking temperature is 300 DEG C, and drying time is 45 minutes, must finally bring back to life catalyst sample, is designated as sample 1.Products therefrom
Physico-chemical property see Fig. 2.In Fig. 2, specific surface area and pore volume are determined using BET method.
Embodiment 2：By the catalytic cracking spent catalyst (350 DEG C of temperature of charge) of fired process and gas phase SiCl4Carry out
Hybrid reaction, (catalytic cracking spent catalyst raw material is with embodiment 1 in this embodiment), SiCl4It is dry with catalytic cracking spent catalyst
The mass ratio of base is 0.35, and the reaction time is 20 minutes.Reacted catalyst sample is washed with 10 times of deionized waters
Filter, then carry out catalyst and citric acid solution mixing 1.5 hours, it is 3.5 to control solution ph, and solution temperature is protected
Hold at 95 DEG C.Catalyst sample after to pickling is washed, institute's deionized water 9 times of catalyst butt quality of the water yield,
Then after filtering catalyst and rare earth chloride (lanthanum chloride: cerium chloride mass ratio is 6: 4) solution mixed, is stirred
Time is 60 minutes, the mass ratio of rare earth chloride (being counted with rare earth oxide) and catalyst butt as 0.025: 1, in slurries water with urge
Agent butt mass ratio is 9: 1, and slurry pH value is controlled to 3.6.After above-mentioned slurries are filtered, then the catalyst sample to obtaining
Product are dried process, and baking temperature is 350 DEG C, and drying time is 30 minutes, must finally bring back to life catalyst sample, is designated as sample
2.The physico-chemical property of products therefrom is shown in Fig. 2.
Embodiment 3：By the catalytic cracking spent catalyst (250 DEG C of temperature of charge) of fired process and gas phase SiCl4Carry out
Hybrid reaction, (catalytic cracking spent catalyst raw material is with embodiment 1 in this embodiment), SiCl4With catalytic cracking spent catalyst
The mass ratio of butt is 0.15, and the reaction time is 40 minutes.Reacted catalyst sample is washed with 8 times of deionized waters
Filter, then carry out catalyst and tartaric acid solution mixing 3 hours, it is 5.0 to control solution ph, and solution temperature keeps
At 60 DEG C.Catalyst sample after to pickling is washed, institute's deionized water 7 times of catalyst butt quality of the water yield, so
Afterwards catalyst and rare earth chloride (lanthanum chloride: cerium chloride mass ratio is 7: 3) solution mixed after filtering, during stirring
Between be 50 minutes, the mass ratio of rare earth chloride (being counted with rare earth oxide) and catalyst butt as 0.01: 1, water and catalysis in slurries
Agent butt mass ratio is 7: 1, and slurry pH value is controlled to 3.8.After above-mentioned slurries are filtered, then the catalyst sample to obtaining
Process is dried, baking temperature is 250 DEG C, and drying time is 1 hour, must finally bring back to life catalyst sample, is designated as sample 3.
The physico-chemical property of products therefrom is shown in Fig. 2.
Embodiment 4：By the catalytic cracking spent catalyst (450 DEG C of temperature of charge) of fired process and gas phase SiCl4Carry out
Hybrid reaction, (catalytic cracking spent catalyst raw material is designated as former agent in this embodiment, and its physical and chemical performance parameter is as shown in Figure 1),
SiCl4It is 0.05 with the mass ratio of catalytic cracking spent catalyst butt, the reaction time is 0.5 minute.By reacted catalyst
Sample carries out washing and filtering with 5 times of deionized waters, then by catalyst and oxalic acid and citric acid mixed solution (oxalic acid and citric acid
Mass ratio be 1: 1) carry out mix 15 minutes, control solution ph be 1.0, solution temperature is maintained at 70 DEG C.To acid
Catalyst sample after washing is washed, institute's deionized water 12 times of catalyst butt quality of the water yield, then after filtering will
Catalyst and solution of cerium chloride by oxidation are mixed, and mixing time is 18 minutes, and cerium chloride (in terms of cerium oxide) is done with catalyst
The mass ratio of base is 0.005: 1, and water and catalyst butt mass ratio are 6: 1 in slurries, and slurry pH value is controlled to 4.5.Will be above-mentioned
After slurries are filtered, then the catalyst sample to obtaining is dried process, and baking temperature is 200 DEG C, and drying time is 1.5
Hour, catalyst sample must be finally brought back to life, it is designated as sample 4.The physico-chemical property of products therefrom is shown in Fig. 2.
Embodiment 5：By the catalytic cracking spent catalyst (300 DEG C of temperature of charge) of fired process and gas phase SiCl4Carry out
Hybrid reaction, (catalytic cracking spent catalyst raw material is designated as former agent in this embodiment, and its physical and chemical performance parameter is as shown in Figure 1),
SiCl4It is 0.5 with the mass ratio of catalytic cracking spent catalyst butt, the reaction time is 30 minutes.By reacted catalyst sample
Product carry out washing and filtering with 12 times of deionized waters, then by catalyst and oxalic acid and tartaric mixed solution (oxalic acid and winestone
Sour mass ratio is 1: 1) carries out mixing 2 hours, it is 4.0 to control solution ph, and solution temperature is maintained at 100 DEG C.To acid
Catalyst sample after washing is washed, institute's deionized water 8 times of catalyst butt quality of the water yield, then will be urged after filtering
Agent and lanthanum chloride solution are mixed, and mixing time is 1.5 hours, lanthanum chloride (in terms of lanthana) and catalyst butt
Mass ratio be 0.04: 1, water and catalyst butt mass ratio are 10: 1 in slurries, and slurry pH value is controlled to 4.0.By above-mentioned slurry
After liquid is filtered, then the catalyst sample to obtaining is dried process, and baking temperature is 150 DEG C, and drying time is 2.5 little
When, catalyst sample must be finally brought back to life, it is designated as sample 5.The physico-chemical property of products therefrom is shown in Fig. 2.
Embodiment 6：By the catalytic cracking spent catalyst (280 DEG C of temperature of charge) of fired process and gas phase SiCl4Carry out
Hybrid reaction, (catalytic cracking spent catalyst raw material is designated as former agent in this embodiment, and its physical and chemical performance parameter is as shown in Figure 1),
SiCl4It is 0.2 with the mass ratio of catalytic cracking spent catalyst butt, the reaction time is 35 minutes.By reacted catalyst sample
Product carry out washing and filtering with 9 times of deionized waters, then by catalyst and oxalic acid, citric acid and tartaric mixed solution (oxalic acid,
Citric acid and tartaric mass ratio are 1: 1: 1) carry out mixing 1 hour, it is 2.5 to control solution ph, and solution temperature is protected
Hold at 80 DEG C.Catalyst sample after to pickling is washed, institute's deionized water 11 times of catalyst butt quality of the water yield,
Then catalyst and lanthanum chloride solution mixed after filtering, mixing time is 35 hours, and lanthanum chloride is (with lanthana
Meter) with the mass ratio of catalyst butt it is 0.012: 1, water and catalyst butt mass ratio are 8: 1 in slurries, slurry pH value control
For 3.9.After above-mentioned slurries are filtered, then the catalyst sample to obtaining is dried process, and baking temperature is 120 DEG C,
Drying time is 4 hours, must finally bring back to life catalyst sample, is designated as sample 6.The physico-chemical property of products therefrom is shown in Fig. 2.* in Fig. 2
MAT is expressed as the micro anti-active index of catalytic cracking catalyst, as shown in Figure 2, Fe, Ni, V in the catalyst after resurrection, Ca and
The content of beary metal such as Na are low, and specific surface area and micro anti-active index are significantly improved.
The resurrection catalyst obtained by above-described embodiment is carried out into catalysis on small fixed flowing bed-tion reacting device (FFB) to split
Change performance evaluation.Evaluate catalyst to be former agent and bring back to life the mixing of catalyst (mixed catalyst is labeled as embodiment numbering), its
Central Plains agent accounts for the 30% of mixed catalyst, brings back to life catalyst and accounts for the 70% of mixed catalyst.Reaction condition is as follows：Reaction temperature is
500 DEG C, oil ratio is 4.0, and mass space velocity is 20h-1.Raw materials used oil nature is as shown in figure 3, cracking reaction Evaluation results
As shown in figure 4, can be drawn by Fig. 4：Bring back to life catalyst and be applied in catalytic cracking unit the coke yield that can reduce device, together
When can improve the yield of gasoline and liquefied gas.
Claims (5)
1. a kind of and SiCl4The rejuvenation method of gas-solid reaction catalytic cracking spent catalyst, it is characterised in that：Its rejuvenation method bag
Include the following steps：(1) by the catalytic cracking spent catalyst material after fired process and gas phase SiCl4Mixing is reacted, instead
In 0.5-40 minutes between seasonable, catalyst product is obtained；
(2) deionized water is washed to the pH value of filter water to the catalyst product obtained by step (1) and is kept constant, then
Pickling processes are carried out to the catalyst after washing with organic acid；
(3) deionized water is washed and filtered to the catalyst obtained by step (2), wherein the matter of deionized water and catalyst
Amount is than being 6-12: 1；
(4) catalyst for obtaining step (3) is mixed with re chloride, the quality of water and catalyst butt in slurries
Ratio is 6-10: 1, rare earth, and in terms of rare earth oxide, and the ratio of catalyst butt is 0.005-0.04: 1；
(5) after is filtered the mixed serum obtained by step (4), must answer then at 120-400 DEG C of dried process 0.25-4 hour
Catalyst living.
2. according to claim 1 a kind of and SiCl4The rejuvenation method of gas-solid reaction catalytic cracking spent catalyst, its feature
It is：Catalytic cracking spent catalyst temperature of charge is 250-450 DEG C in described step (1), SiCl4With the useless catalysis of catalytic cracking
Mass ratio 0.05-0.5: 1 of the butt of agent material.
3. according to claim 1 a kind of and SiCl4The rejuvenation method of gas-solid reaction catalytic cracking spent catalyst, its feature
It is：Organic acid in described step (2) is one kind in formic acid, oxalic acid, citric acid and tartaric acid and arbitrarily several.
4. according to claim 1 a kind of and SiCl4The rejuvenation method of gas-solid reaction catalytic cracking spent catalyst, its feature
It is：The time of pickling is 0.25-6 hours in described step (2), and pickling pH value is 1-5, and pickling temperature is 60-120 DEG C.
5. a kind of rejuvenation method with SiCl4 gas-solid reaction catalytic cracking spent catalysts according to claim 1, its feature
It is：Mixing time is 0.3-1.5 hours in described step (4), and slurry pH value is controlled in 3.3-4.5.
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| CN106622395A (en) * | 2015-10-29 | 2017-05-10 | 中国石油化工股份有限公司 | Method for modifying catalytic cracking equilibrium agent |
| CN106552680B (en) * | 2016-12-07 | 2019-06-04 | 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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| US4800185A (en) * | 1986-08-11 | 1989-01-24 | Chemcat Corporation | Regeneraation of metal contaminated hydrocarbon conversion catalytsts |
| CN1239678C (en) * | 2003-05-30 | 2006-02-01 | 中国石油化工股份有限公司 | Catalytic cracking catalyst demetallated reactivating process |
| CN100525917C (en) * | 2006-11-17 | 2009-08-12 | 中国石油天然气股份有限公司 | Method for the revival of catalytic cracking catalyzer metal-removing by adopting a gas-phase reduction method |
| CN101219396B (en) * | 2008-01-28 | 2010-10-20 | 青岛惠城石化科技有限公司 | Method for reliving FCC dead catalyst |
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