CN1072617A - The renovation process of waste molecular sieve cracking catalyzer - Google Patents
The renovation process of waste molecular sieve cracking catalyzer Download PDFInfo
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- CN1072617A CN1072617A CN 91111093 CN91111093A CN1072617A CN 1072617 A CN1072617 A CN 1072617A CN 91111093 CN91111093 CN 91111093 CN 91111093 A CN91111093 A CN 91111093A CN 1072617 A CN1072617 A CN 1072617A
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Abstract
The present invention proposes the catalyst of deposed molecular sieve in ammonium sulfate roasting-water leaching method regeneration cracking process, main feature is to utilize ammonium sulfate and dead catalyst baking mixed, make heavy metal contaminants nickel and other metals form solable matter, directly make regenerated catalyst through water logging, filtration, drying then, or product of roasting is through water logging, after filtering, washing, again through step regenerated catalysts such as ion-exchanges.Through the catalyst activity that this method is handled, selectivity improves greatly, can return in the cracking process to recycle.This method is simple, and is applied widely.
Description
The invention belongs to the PETROLEUM PROCESSING field, promptly develop a kind of simple and easy to do heavy metal contaminants on the waste molecular sieve cracking catalyzer that removes, catalyst activity is recovered, selectively changing and the new technology that can recycle.
In catalytic cracking process, heavy metal contaminants nickel, vanadium, copper, iron etc. will constantly be deposited on catalyst surface in the raw material, when they after depositing to a certain degree on the catalyst, product distribution, the product quality of cracking process are changed, hydrogen and coke output increase greatly, and the productive rate of light-end products such as conversion ratio and gasoline significantly descends, and shows that activity of such catalysts reduces, and selectivity degenerates.At present, in actual industrial production, generally all be to keep certain catalytic activity and selectivity by adding fresh catalyst and extracting the old catalyst of part out, prevent that simultaneously foreign metal reaches higher level on the catalyst.For slag oil cracking, because content of beary metal is higher in the raw material, the catalyst make up rate that needs is big, causes cracking technology cost height especially.As the industrial employed catalyst of China, when content of beary metal reach several thousand ppm(1,000,000/) after just can not recycle use.In addition, the stacking of dead catalyst also will cause environmental pollution.Therefore, the regeneration of dead catalyst has become problem that urgency is to be solved in the PETROLEUM PROCESSING field.
In recent years, each state all attaches great importance to the research of catalyst of deposed molecular sieve regeneration, has mainly proposed the method for two class regeneration of spent catalyst at present.
1. magnetic method: the magnetic of utilizing pollution metal to have makes dead catalyst be divided into magnetic and non magnetic two parts, and the nonmagnetic portion circulation is used for cracking process.This technology is difficult to industrialization, and still need get rid of dead catalyst, and the loss of catalyst is more serious.
2. chemical method: the ammonium citrate method of having reported also is only limited to laboratory research (U.S.P.4280897) at present.U.S. ChemCat company is devoted to the reproduction operation of dead catalyst in recent years always, developed a series of DEMETER regeneration technologies (" Reactivation and Passivation of Equilibrium FCC Catalyst "-NPRA Annual Meeting 1987 such as Frank J.Elvin, 03,29), and the Meraux in U.S. Louisiana state has built up in the world, and first hand removes metal pollutant, recycle the factory of catalyst, this technology divided for three steps carried out:
The first step: remove heavy metal contaminants.At first logical hydrogen sulfide gas is converted into nickel sulfide with nickel oxide, and logical then chlorine makes vanadium, iron form the VOCl of high volatility
3And FeCl
3And remove NiCl
2Then the water dissolving is removed.
Second step: adopt hydrogen peroxide and be dissolved with SO
2The distilled water of gas carries out oxidation, reduction washing to catalyst, further increases the removal efficiency of metal, and passivation metal remained pollutant.
The 3rd step: with ammonium sulfate solution catalyst is carried out ion-exchange, increase activity of such catalysts.
Above-mentioned technological process is long, especially uses hydrogen sulfide gas and the band intense stimulus and the poisonous chlorine of severe toxicity, makes antipollution investment very big.Under general condition, promote this technology, will run into a lot of difficulties.In addition, heavy metal contaminants mainly is a vanadium on the external waste residue cracking catalyst for oil, the situation low with China high vanadium of nickel is just in time opposite, in order to solve the problem of above-mentioned existence, and at the characteristics of China's dead catalyst, the present invention proposes the method that a kind of ammonium sulfate roasting-aqueous solution leaches regenerated catalyst, make that heavy metal contaminants removes on the catalyst of deposed molecular sieve, catalyst activity recovers, and selectivity improves, and can recycle.
The present invention adopts the waste molecular sieve cracking catalyzer in ammonium sulfate roasting-aqueous solution lixiviation process regeneration cracking process.The molecular sieve catalyst and the ammonium sulfate that are about to after contaminated by heavy metals mix, the roasting of heating, and product of roasting makes regenerated catalyst through water logging, filtration, washing, drying.Perhaps product of roasting is after water logging-filtration-washing, again through ion-exchange, refilter, wash, drying makes regenerated catalyst.
The regenerate method of waste molecular sieve cracking catalyzer of the present invention, be to mix with ammonium sulfate by catalyst of deposed molecular sieve, the roasting of in Muffle furnace and other stove, heating, heavy metal contaminants on the catalyst partly is converted into the water-soluble Sulfates material of energy, as nickelous sulfate, ferric sulfate etc., through processing steps such as water logging, filtration, washings heavy metal contaminants is deviate from again, the catalyst of deposed molecular sieve activation recovering, selectivity improves.Ammonium sulfate consumption and sintering temperature are two key factors among the present invention.In general, the ammonium sulfate consumption increases, and metal removal rate increases, and reduces but also be accompanied by leachate pH simultaneously, and promptly leachate acidity increases, and this structure to catalyst is totally unfavorable, and therefore, the ammonium sulfate consumption should be controlled in the proper range.In addition, each catalyst all has a limiting temperature, after roasting is higher than limiting temperature, often makes the structural deterioration of catalyst, and catalytic activity reduces, and sintering temperature is too low, and extrusion rate of heavy metals is also low.For above-mentioned reasons, the present invention adopts the weight ratio of ammonium sulfate and catalyst mix to be: ammonium sulfate: catalyst=0.25-1.5: 1, and sintering temperature 250-600 ℃, roasting time was not less than 10 minutes, generally adopt more than 15 minutes to well, this moment, both reached abundant reaction.The optimum weight ratio of its mixture is: ammonium sulfate: catalyst=0.5-1.0: 1, and optimum calcination temperature is 300-500 ℃.
Ammonium sulfate and catalyst mix roasting afterproduct need cool off, and through water logging the heavy metal sulfate that roasting forms are dissolved in the water, and water soaking temperature is a room temperature-90 ℃, and liquid-solid ratio is little to the influence of metal extrusion rate, generally adopts 2: 1(ml/g) above getting final product.Product of roasting is filtered into wet cake through water logging, is washed with water to till the sulfate radical-free ion, and is dry under 50-100 ℃ again, makes regenerated catalyst.Wet cake is available water or weak aqua ammonia slurrying also, promptly adopts pulping and washing, to improve activity of such catalysts.Because in alkalescence or acid solution, catalyst structure is easily destroyed, thereby during washing, the pH value generally is controlled in the 6-10 scope.In addition, the present invention points out that product of roasting also can adopt ion-exchange to improve the performance of catalyst after water logging, filtration, washing.In order to improve the exchange degree of rare earth ion, catalyst can be earlier and ammonium sulfate exchange (concentration of ammonium sulfate generally adopts 1-30%), mixed rare earth solution with solubility exchanges again, also can be directly with after the mixed rare earth solution exchange, adopt heat treatment, promptly by calcination process, to increase rare earth ion exchanged.Wherein rare-earth salts comprises rare earth chloride, water soluble salt solution such as rare earth nitrades, and the concentration of rare earth ion is in 3-45 grams per liter scope.
The active size of Cracking catalyst generally represents with activity index, usually with gasoline yield as activity index, to molecular sieve catalyst, also with conversion ratio as activity index.Selectivity is meant that catalyst needs the choice reaction ability of product and minimizing byproduct (coke, dry gas etc.) to increase.Weigh that optionally index is a lot, generally can select H for use
2The size of productive rate such as/conversion ratio, coke/conversion ratio ratio is come optionally quality of evaluate catalysts.The renovation process that adopts the present invention to propose can make the activity of molecular sieve catalyst and selectivity improve greatly, and hydrogen and coke output reduce, gasoline yield improves, and as for heavy metal contaminants on the molecular sieve catalyst, the highest extrusion rate can reach nickel 53.0% respectively, iron 42.6%, vanadium 65.6%.The lattice structure of catalyst is intact, the cracking process that is used for capable of circulation, and do not need further to remove pollutant.This method is simple, and is applied widely, all suitable to the Y zeolite catalyst and the super steady type molecular sieve catalyst of rare earth exchanged.
Below in conjunction with example the present invention is done comparatively detailed explanation:
Example one:
Experimental raw equilibrium catalyst first is the Y zeolite catalyst of rare earth exchanged, and carrier is a synthesizing Si-Al.The main component of catalyst and pollution metal content are shown in table 1..Experiment control ammonium sulfate/catalyst=1: the 1(weight ratio), 300 ℃ of sintering temperatures, roasting time 0.5 hour, product of roasting water soaking temperature are 60 ℃, and liquid-solid ratio is 5/1(ml/g), leaching is after 15 minutes in water bath with thermostatic control, get filter cake after filtration, again filter cake is added water slurrying, carry out pulping and washing to the sulfate radical-free ion, dry under 70 ℃ then, make regenerated catalyst.During pulping and washing, control pH is 7, and the nickel extrusion rate 60% after measured, and iron extrusion rate 49%, regeneration rear catalyst carry out activity and optionally estimate on the small fixed flowing bed catalytic cracking unit, and testing result is as shown in table 2:
The chemical analysis of table 1. equilibrium catalyst first
Ni% Fe% Cu% V% SiO
2% Al
2O
3% total amount of rare earth %
0.78 0.23 0.0032?0.032?54.06 39.22 2.2
Activity and selection index after the regeneration of table 2 equilibrium catalyst first
The catalyst of product yield (heavy %) poising agent first after the present invention handles
H
20.71 0.25
C
+ 5Gasoline 48.98 44.65
Light diesel fuel 19.17 21.09
Coke 6.89 4.89
Conversion ratio 63.98 57.02
H
2/ conversion ratio 0.0111 0.0044
Coke/conversion ratio 0.11 0.0858
Gasoline/conversion ratio 0.765 0.783
Nickel content 0.78 0.50 on the catalyst
Example two.
Raw material is with example one, 400 ℃ of sintering temperatures, roasting time 1.0 hours, ammonium sulfate/catalyst=0.75: the 1(weight ratio), 80 ℃ of extraction temperatures, liquid-solid ratio 8/1(ml/g), with weak aqua ammonia filter cake slurrying is washed to the sulfate radical-free ion, the control slurry pH value is 9, and other conditions are with example 1, the result is a nickel extrusion rate 52.3%, iron extrusion rate 40%.
Performance indications after the table 3 equilibrium catalyst first weak aqua ammonia pulping and washing
The catalyst of product yield (heavy %) poising agent first after the present invention handles
H
20.71 0.26
C
+ 5Gasoline 48.98 53.03
Light diesel fuel 19.17 19.82
Coke 6.89 5.00
Conversion ratio 63.98 65.89
H
2/ conversion ratio 0.0111 0.0042
Coke/conversion ratio 0.11 0.0794
Gasoline/conversion ratio 0.765 0.785
Nickel content 0.78 0.49 on the catalyst
Example three.
Experimental raw is with example one, ammonium sulfate/catalyst=0.5: the 1(weight ratio), 500 ℃ of sintering temperatures, roasting 2 hours, 30 ℃ of water soaking temperatures, the product of roasting water logging is filtered, and other conditions of washing are with example 1.The washing rear catalyst at first exchanges with ammonium sulfate in the flask at the bottom of having the garden of condenser pipe, and behind the filtration washing, catalyst is used mixed rare earth chlorides R again
ECl
3Solution exchange refilters afterwards, washs till do not have a chlorion.Used ammonium sulfate concentration is 1.0 mol, 1.0 hours swap times, [R
ECl
3]=72.5g/l exchanges 3 hours, and temperature and liquid-solid ratio are 90 ℃, and 10/1(ml/g), the activity and the selection index of regenerated catalyst are as shown in table 4.
Performance indications after the table 4 equilibrium catalyst first rare earth exchanged
The catalyst of product yield (heavy %) poising agent first after the present invention handles
H
20.71 0.21
C
+ 5Gasoline 48.98 45.85
Light diesel fuel 19.17 20.07
Coke 6.89 5.58
Conversion ratio 63.98 59.29
H
2/ conversion ratio 0.0111 0.0035
Coke/conversion ratio 0.11 0.091
Gasoline/conversion ratio 0.765 0.773
Example four.
Conditions such as raw material and roasting, water logging are with example 3, and wet cake carries out secondary exchange after baking with mixed rare earth solution to be handled.Give-and-take conditions: [R
ECl
3.6H
2O]=30g/l, 90 ℃ of temperature of exchange, time and liquid-solid ratio were respectively 1.0 hours, 2/1(ml/g), and 350 ℃ of sintering temperatures, roasting time 1.0 hours repeats once to exchange after exchange, the roasting, roasting for the first time again, and twice exchange roasting condition is identical.Last washing catalyst is not to there being chlorion, and the performance of catalyst is measured in dry back, the results are shown in following table:
Performance indications behind the table 5 equilibrium catalyst first secondary exchange after baking
The catalyst of product yield (heavy %) poising agent first after the present invention handles
H
20.71 0.237
C
+ 5Gasoline 48.98 51.95
Light diesel fuel 19.17 19.28
Coke 6.89 4.06
Conversion ratio 63.98 63.11
H
2/ conversion ratio 0.0111 0.00375
Coke/conversion ratio 0.11 0.064
Gasoline/conversion ratio 0.765 0.823
Embodiment five.
Experimental raw poising agent second still is the Y zeolite catalyst of rare earth exchanged, contains the semi-synthetic carrier of kaolin, and the main component of catalyst and pollution metal content are as shown in table 6.Experiment condition is with example four, and the activity and the selection index of regeneration rear catalyst are listed in the table 7.Obviously under the situation that this technology can remain unchanged substantially in the activity of catalyst second, its selectivity is had a greater degree of improvement.Thereby explanation this method also can be applicable to the semi-synthetic carrier Cracking catalyst of rare earth containing zeolite.
The chemical analysis of table 6 equilibrium catalyst second
Ni% Fe% SiO
2% Al
2O
3% total amount of rare earth %
0.49 0.78 40.24 45.92 2.5
Activity and selection index after the regeneration of table 7 catalyst second
The catalyst of product yield (heavy %) poising agent second after the present invention handles
H
20.48 0.18
C
+ 5Gasoline 38.01 39.81
Light diesel fuel 18.34 19.50
Coke 5.48 3.60
Conversion ratio 55.80 54.61
H
2/ conversion ratio 0.009 0.003
Coke/conversion ratio 0.098 0.066
Gasoline/conversion ratio 0.618 0.729
Nickel content 0.49 0.33 on the catalyst
Iron content 0.78 0.62 on the catalyst
Claims (9)
1, a kind of renovation process of waste molecular sieve cracking catalyzer, it is characterized in that dead catalyst mixes with ammonium sulfate, the roasting of heating, product of roasting is through water logging, filtration, washing, drying, directly make regenerated catalyst, or product of roasting is after water logging, filtration, washing, again through ion-exchange, refilter, wash, drying makes regenerated catalyst.
2, according to the described method of claim 1., it is characterized in that sintering temperature is 250-600 ℃, ammonium sulfate is 0.25-1.5 with waste cracking catalyst mixed weight ratio: 1, roasting time is more than 10 minutes.
3, according to the described method of claim 1., it is characterized in that sintering temperature is 300-500 ℃, ammonium sulfate is 0.5-1.0 with dead catalyst mixed weight ratio: 1.
4, according to claim 1. or 2 or 3. described methods, the water soaking temperature that it is characterized in that product of roasting is a room temperature-90 ℃, and liquid-solid ratio is 2/1(ml/g) more than.
5, according to the described method of claim 1., it is characterized in that said washing is that water directly washs, also available water or weak aqua ammonia carry out pulping and washing with product slurrying.
6,, it is characterized in that the washing of said product of roasting after water logging is filtered for washing with water, or water or weak aqua ammonia carry out pulping and washing with product slurrying according to the described method of claim 4.
7, according to the described method of claim 5, when it is characterized in that pulping and washing, pH is controlled in the 6-10 scope.
8, according to the described method of claim 6, when it is characterized in that washing, pH is controlled in the 6-10 scope.
9, according to the described method of claim 1, it is characterized in that the ion-exchange of said product of roasting after water logging, filtration, washing is that product exchanges with ammonium sulfate earlier, again with mixed rare earth solution exchange, or product carries out calcination process after with the mixed rare earth solution exchange again.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91111093A CN1035104C (en) | 1991-11-27 | 1991-11-27 | Regenerating method for waste molecular sieve cracking catalyzer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91111093A CN1035104C (en) | 1991-11-27 | 1991-11-27 | Regenerating method for waste molecular sieve cracking catalyzer |
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| Publication Number | Publication Date |
|---|---|
| CN1072617A true CN1072617A (en) | 1993-06-02 |
| CN1035104C CN1035104C (en) | 1997-06-11 |
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ID=4910469
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|---|---|---|---|
| CN91111093A Expired - Fee Related CN1035104C (en) | 1991-11-27 | 1991-11-27 | Regenerating method for waste molecular sieve cracking catalyzer |
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| CN1060101C (en) * | 1997-03-31 | 2001-01-03 | 中国石油化工总公司 | Method for reactivation of catalyst containing ZSM-5 molecular sieve |
| CN1060100C (en) * | 1997-02-26 | 2001-01-03 | 中国石油化工总公司 | Reactivation method of cracking catalyst containing molecular sieve |
| CN1078100C (en) * | 1998-08-14 | 2002-01-23 | 中国石油化工集团公司 | Process for regenerating deactivated catalyst containing Y-type zeolite |
| CN1099318C (en) * | 1997-05-06 | 2003-01-22 | 中国石油化工总公司 | Dry demetallization regeneration technology for residue and/or heavy oil catalytic cracking catalyst |
| CN101239333B (en) * | 2007-02-05 | 2011-04-27 | 石大卓越科技股份有限公司 | Preparation of catalyst for poor-quality oil catalytic cracking |
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| US4444902A (en) * | 1981-12-22 | 1984-04-24 | Mobil Oil Corporation | Activation of high silica zeolites |
| US4871702A (en) * | 1988-01-04 | 1989-10-03 | Mobil Oil Corp. | Ammonium activation of zeolites in the presence of gaseous ammonia |
| US4814066A (en) * | 1988-05-19 | 1989-03-21 | Phillips Petroleum Company | Reactivation of spent catalytic cracking catalyst |
| US4954244A (en) * | 1989-06-22 | 1990-09-04 | Phillips Petroleum Company | Treatment of spent cracking catalysts |
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| CN1099318C (en) * | 1997-05-06 | 2003-01-22 | 中国石油化工总公司 | Dry demetallization regeneration technology for residue and/or heavy oil catalytic cracking catalyst |
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| Publication number | Publication date |
|---|---|
| CN1035104C (en) | 1997-06-11 |
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