CN100525917C - Method for the revival of catalytic cracking catalyzer metal-removing by adopting a gas-phase reduction method - Google Patents
Method for the revival of catalytic cracking catalyzer metal-removing by adopting a gas-phase reduction method Download PDFInfo
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- CN100525917C CN100525917C CNB2006101146044A CN200610114604A CN100525917C CN 100525917 C CN100525917 C CN 100525917C CN B2006101146044 A CNB2006101146044 A CN B2006101146044A CN 200610114604 A CN200610114604 A CN 200610114604A CN 100525917 C CN100525917 C CN 100525917C
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Abstract
The invention relates to a reliving method of the catalytic cracking catalyst demetalization by adopting a gas phase reduction method. The method is mainly used for removing the contamination metals (Ni, V, Fe, etc.) in the fluid catalytic cracking (FCC) catalyst and for recovering the activity of the catalyst. The method is mainly characterized in that the method adopts the hydrogen or refinery dry gas as the reducer and has obvious advantages compared with the H2S gas phase sulphuration used in traditional catalyst demetalization technology. The process mainly includes three steps of gas phase recovery, acid washing and water washing.
Description
Technical field
A kind of rejuvenation method that adopts gas phase reduction process to catalytic cracking catalyst by removing metals involved in the present invention, this method mainly are the pollution metals (Ni, V and Fe etc.) that is used for removing catalytic cracking catalyst, and recover activity of such catalysts.This method mainly comprises vapour phase reduction, pickling and three steps of washing, its major technology characteristics have adopted hydrogen, plant catalytic cracking dry gas, CO, natural gas or methane, ethane etc. exactly, preferably select hydrogen or oil refinery dry gas as reducing agent, with employed H in the traditional catalyst demetalization technology
2Significant advantage has been compared in the gas phase sulfuration of S.
Background technology
Catalytic cracking (FCC) is the core process of refinery, and undertaking with heavy oil, residual oil is the important task that raw material is produced gasoline, diesel oil and liquefied gas.The merchantable gasoline of China about 80% is from the FCC process, as seen its critical role in petroleum refining industry.The present FCC annual working ability of China has surpassed 100,000,000 tons, because Ni, V to the pollution of FCC catalyst, make its activity and selectivity in use descend along with the accumulation of metal.In order to keep activity of such catalysts to maintain certain level, except using matal deactivator, also have to constantly extract out poising agent, replenish fresh dose.From the situation of China National Petroleum Corporation (CNPC), because of the crude oil difference of each refinery's processing, the metallic pollution degree of catalyst is also different, but on average, fresh dose magnitude of recruitment is about 0.08% (wt) of FCC processing capacity.Calculate if process 100,000,000 tons of oil by annual FCC process, the annual dead catalyst that produces just reaches 80,000 tons.If with fresh dose of 20,000 yuan of calculating per ton, light is bought fresh dose of expense just needs 1,600,000,000 yuan of expenditures.Moreover, how the dead catalyst of generation is handled, and also is a difficult problem.From external situation, the whereabouts of spent FCC catalyst has following several basically: when garbage loading embeading falls, recycling (amount seldom), as adsorbent purify waste water, as the additive of pitch, replace frit that kaolin potting porcelain uses etc. as the additive of insulating materials, the research that also has.Wherein mainly still working as garbage disposal has fallen.Spent FCC catalyst is worked as garbage disposal, can not neglect the pollution of environment, and pollution metal wherein may constitute potential threat to underground water resource, and in addition, what the metal in the catalyst had also may have radioactivity.Therefore, how handling spent FCC catalyst, turn waste into wealth, is the important topic that oil refining and efforts at environmental protection person face.
With spent FCC catalyst demetalization regeneration, be best processing approach.As far back as twentieth century five, the sixties, just have technology to realize industrialization, that representative is Demet series of processes technology (US4824814, US4800185, US4267032, US4293403, US4234452, US4163710, US4163709, US4102811, US4102444).The Demet-III technology generally speaking comprises following three step: H
2S sulfuration, Cl
2(or other chloride) chlorination (Demet-III makes this step into air oxidation) and washing.Sulfuration and chlorination all need be carried out under the hot conditions more than 500 ℃, and the subsequent washing process comprises oxidation rinsing and reduction washing.Although this technology metal removal effect ideal, the processing procedure of its harsh treatment conditions, complexity has seriously restricted applying of this technology.At the with serious pollution situation of V, Atlanatic Richfield company has released Demet～IV technology, and this worker is at 800 ℃ of left and right sides calcined catalysts, and wherein V is changed into V
2O
5, and then respectively water or ethanol, saturated SO
2Solution washing.
Through the catalyst after the Demet PROCESS FOR TREATMENT, most of metal has removed from catalyst, activity of such catalysts also obtains recovery to a certain degree, but the bad stability of catalyst, Pavel etc. (US6046125, WO9951336) has proposed further to handle demetallated catalyst with the solution that contains Al, rare earth etc. for this reason, metal on the catalyst is when further descending, and activity of such catalysts and stability can improve to a certain extent.
At home, the An Jiuyu of No.1 Petroleum Chemical Factory, Tianjin Petrochemical Industry Co etc. has also applied for and the similar patent of Demet-II (CN1098031A), process comprises sulfuration, chlorination, washing, drying etc., claims that the Ni removal efficiency reaches 70～90%, the V removal efficiency is 20%.The Wu Guozhi of Luoyang Petrochemical Engineering Co., China Petrochemical Corp etc. has applied for being similar to the technology (ZL1024326C) of Demet-III at home, and process comprises sulfuration, oxidation, SO
2Solution reduction washing and H
2O
2The solution oxide washing is carried out ion-exchange with ammonium salt aqueous solution after handling again, improves activity of such catalysts, and the removal efficiency of Ni, V and Fe is respectively 60～85%, 30～45% and 30～40%.Carry out ion-exchange with ammonium salt and improve activity of such catalysts, even not demetalization, activity also can obtain big spoke degree and improve (US4954244, US4800185).
The common drawback of above-mentioned technology is to use H earlier
2S vulcanizes Ni, H
2S is severe toxicity, the extremely strong gas of corrosivity, adopts this method to carry out demetalization, has great danger, and problem of environmental pollution is comparatively serious.
Except said method, with chelating agent and Ni reactions such as citric acids, generate chelate, wash with water then, Ni is taken off (CN1018840B, US4280897) from catalyst.This method treatment conditions gentleness, but the removal efficiency of metal is very low.Carbonylation method also can be used for taking off the Ni (US4293403, ZL97109778.X) on the FCC catalyst.Carbonylation can only take place with the Ni that newly restores in CO, generates volatile carbonyl nickel.Thereby this process need reduces to catalyst earlier, carrying out carbonylation under certain pressure then in CO atmosphere.Although this process is simple, operating condition is not harsh yet, the carbonyl nickel product of the high attached value of all right by-product, and regrettably carbonylation carries out very slowly, thereby the actual removal efficiency of Ni is very low.
Summary of the invention
Purpose of the present invention is with regard to being to avoid the deficiencies in the prior art to point out and a kind of rejuvenation method that adopts gas phase reduction process to catalytic cracking catalyst by removing metals is provided, this method mainly is to adopt gas as reducing agent, can remove the pollution metal (Ni, V and Fe etc.) in the catalytic cracking catalyst fast, and recover activity of such catalysts.Its major technology characteristics have adopted hydrogen, plant catalytic cracking dry gas, CO, natural gas or methane, ethane etc. exactly, preferably select hydrogen or dry gas as reducing agent, and its technical process mainly comprises vapour phase reduction, pickling and three steps of washing:
(1) vapour phase reduction of catalyst
Adopt hydrogen or oil refinery dry gas as reducing agent, reduction temperature is between 500-850 ℃, and the pressure of reduction can carry out under normal pressure, also can carry out under pressurized conditions.Reduction finished the back and was cooled to below 100 ℃ in the atmosphere of used reducing gas between 10 minutes to 20 hours recovery time;
(2) pickling of catalyst
Both can select the inorganic acid of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or perchloric acid class, also can select the organic acid of formic acid, oxalic acid, acetate class, the concentration of acid is 0.01～50%, acid solution and catalyst quality are than 0.5～50, and the general pickling of pickling number of times is advisable for 1～4 time, and the temperature of pickling is between the room temperature to 100 ℃, be preferably in 60～90 ℃, the time of pickling is 30 minutes to 3 hours, and the catalyst that pickling finishes spends deionised water 1～3 time again in filter process;
(3) drying of catalyst
Go oven dry after catalyst of having washed and ammonium salt aqueous solution or the ammonium salt solution that contains aluminium ion, rare earth ion exchange, temperature is at 100～200 ℃.
In order to implement above-mentioned purpose of the present invention better, in enforcement of the present invention, employed reducing agent can be hydrogen, plant catalytic cracking dry gas, CO, natural gas or methane, ethane etc., preferably select hydrogen or dry gas as reducing agent, reduction temperature is preferably between 650-750 ℃ and carries out between 500-850 ℃.The pressure of reduction can carry out under normal pressure, also can carry out under pressurized conditions.Recovery time was preferably between 30 minutes to 10 hours between 10 minutes to 20 hours.Reduction finishes the back and lowers the temperature under nonoxidizing atmosphere, is preferably in the atmosphere of used reducing gas to be cooled to below 100 ℃, carries out pickling then.Acid can be selected inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, also can select organic acids such as formic acid, oxalic acid, acetate, preferably selects nitric acid.The concentration of acid is preferably in below 5%, to reduce the destruction to catalyst at 0.01-50%.Acid solution compares at 0.5-50 with catalyst quality, is preferably between the 2-10.The pickling number of times is different and different because of acid solution and catalyst quality ratio, and general pickling is advisable for 1-4 time.The temperature of pickling is between the room temperature to 100 ℃, is preferably in 60-90 ℃.The time of each pickling is 30 minutes to 3 hours, is preferably in about 1 hour.The catalyst that pickling finishes spends deionised water 1-3 time again in filter process.The catalyst of having washed goes oven dry after can exchanging with ammonium salt aqueous solution or the ammonium salt solution that contains aluminium ion, rare earth ion, also can directly go oven dry.
Through the catalyst that above-mentioned steps is handled, the removal efficiency of Ni is at 30-90%, and the removal efficiency of V is at 20-60%, and the removal efficiency of Fe is at 20-50%.5-20 unit of activity of such catalysts rising, and catalyst is very stable.
The specific embodiment
Below in conjunction with embodiment in detail technical characterstic of the present invention is described in detail.
Take by weighing 20g FCC poising agent, wherein the content of pollution metal is respectively Ni 1.3%, V 0.05%, Fe 0.56%, and micro-activity is 56.At 700 ℃, H
2Middle reduction 6h washs 3 times at 90 ℃ of nitric acid with 0.5% then, each 1h, and the mass ratio of each acid solution and catalyst is 4.Catalyst after the pickling is used deionized water rinsing 3 times when filtering, about each 20ml, then 120 ℃ of dryings.
After said process was handled, the micro-activity of catalyst had been elevated to 75, and activity has still reached 67 after the steam burin-in process, has shown good stable.Metal Ni has removed 76%, and V has removed 45%, and Fe has removed 32%.
Claims (3)
1. adopt the rejuvenation method of gas phase reduction process to catalytic cracking catalyst by removing metals, this method is that the employing gas phase reduction process removes the pollution metal on the catalytic cracking catalyst, be metallic nickel, vanadium and iron, it is characterized in that the employed reducing agent of this method is the dry gas of hydrogen or refinery, its operating procedure is:
1. catalyst reduces in gas phase
Adopt hydrogen or oil refinery dry gas as reducing agent, reduction temperature is between 500～850 ℃, and the pressure that reduces is normal pressure, and reduction finished the back and was cooled to below 100 ℃ in the atmosphere of used reducing gas between 10 minutes to 20 hours the recovery time;
2. the pickling of catalyst
Select hydrochloric acid, sulfuric acid, nitric acid or perchloric acid for use, or select formic acid, oxalic acid, acetate to carry out pickling, the concentration of acid is 0.01～50%, acid solution compares 0.5～50 with catalyst quality, pickling 1～4 time, the temperature of pickling are at 60～90 ℃, and the time of pickling is 30 minutes to 3 hours, the catalyst that pickling finishes spends deionised water 1～3 time again in filter process;
3. the drying of catalyst
Go oven dry after catalyst of having washed and ammonium salt aqueous solution or the ammonium salt solution that contains aluminium ion, rare earth ion exchange, temperature is at 100～200 ℃.
2. employing gas phase reduction process according to claim 1 is to the rejuvenation method of catalytic cracking catalyst by removing metals, the concentration of acid that it is characterized in that pickling is below 5%, acid solution and catalyst quality are than between 2～10, the temperature of pickling is 60～90 ℃, and the time of each pickling is 30 minutes to 3 hours.
3. employing gas phase reduction process according to claim 1 is to the rejuvenation method of catalytic cracking catalyst by removing metals, the ammonium salt solution that it is characterized in that catalyst and the ammonium salt solution after the pickling or contain aluminium ion, rare earth ion carries out ion-exchange, and ammonium salt wherein is ammonium chloride or ammonium nitrate.
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| CN102527208B (en) * | 2010-12-30 | 2014-12-31 | 中国石油化工股份有限公司 | Method for removing sulfur oxide and nitrogen oxide in catalytic cracking regenerated smoke |
| CN104815702B (en) * | 2015-04-10 | 2018-08-31 | 于向真 | The rejuvenation method of catalytic cracking spent catalyst |
| CN104815703B (en) * | 2015-04-15 | 2017-05-10 | 中国石油大学(华东) | Method for resuscitating spent catalytic cracking catalyst through gas-solid reaction with SiCl4 |
| CN109382146B (en) * | 2017-08-11 | 2021-08-03 | 中国石油天然气股份有限公司 | FCC (fluid catalytic cracking) balancing agent reviving and modifying method |
| CN114425439A (en) * | 2020-09-18 | 2022-05-03 | 中国石油化工股份有限公司 | Method for reactivating waste catalytic cracking catalyst |
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Non-Patent Citations (2)
| Title |
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| FCC 催化剂氢气还原活化脱镍研究. 李春义等.化学学报，第63卷第14期. 2005 |
| FCC 催化剂氢气还原活化脱镍研究. 李春义等.化学学报，第63卷第14期. 2005 * |
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