CN1115378C - Anti-vanadium assistant for catalytic-cracking catalyst and its application - Google Patents
Anti-vanadium assistant for catalytic-cracking catalyst and its application Download PDFInfo
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- CN1115378C CN1115378C CN 99109680 CN99109680A CN1115378C CN 1115378 C CN1115378 C CN 1115378C CN 99109680 CN99109680 CN 99109680 CN 99109680 A CN99109680 A CN 99109680A CN 1115378 C CN1115378 C CN 1115378C
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Abstract
The present invention provides a vanadium resistant auxiliary agent for catalytic cracking, which is characterized in that the vanadium resistant auxiliary agent as an oil soluble extracted substance formed by combining mixed rare earth ions and an organic extracting agent contains 2 to 20 wt% of mixed rare earth ions (measured by rare earth), 20 to 60 wt% of organic extracting agent and 20 to 80 wt% of organic solvent, wherein the extracting agent is the extracting agent capable of extracting rare earth ions, and naphthenic acid, petroleum sulphoxide or organic phosphate ester is preferable; the organic solvent is the organic solvent capable of dissolving the organic extracting agent; and the auxiliary agent is preferably an organic extracted substance obtained when the rare earth is extracted and separated from mixed rare earth minerals with an extraction method. The vanadium resistant auxiliary agent can be added into catalytically cracked raw oil in use and can also be impregnated in a catalytic cracking catalyst in use.
Description
The invention relates to the anti-vanadiumism auxiliary agent and the application thereof of catalyst for heavy oil catalytic cracking.
The heaviness of crude oil and poor qualityization make heavy metal content increase in the heavy oil (＞350 ℃ of cuts).In the past, Ni content height in the Chinese heavy oil, V content generally is lower than 1ppm, and nickel content generally is higher than 5000ppm on the catalytic cracking poiser, and content of vanadium is generally 1500-2000ppm.Therefore at present China is specifically designed to the catalytic cracking catalyst of anti-vanadium or auxiliary agent kind also seldom.In recent years, Chinese import middle-eastern crude quantity increases year by year; Tarim Basin, Xinjiang Oilfield developing is utilized, and V content generally is higher than 20ppm in its heavy oil, even is higher than 60ppm, V content reaches 7000-11000ppm on the catalytic cracking poiser, the catalytic cracking catalyst structure is damaged, and the agent consumption increases by 80%, quality product and product distribution variation.
The result of existing research V poisoning catalytic cracking catalyst thinks: the V in the heavy oil exists with porphyrin vanadium form, in the catalytic cracking reaction process, V with lower valency (+2 ,+3 ,+4 valencys) be deposited on catalyst surface, in catalyst regeneration process, V is oxidized at a low price, changes V into
2O
5And vanadic acid, these two kinds of compounds further with molecular sieve in reactive aluminum, generate vanadic acid aluminium, molecular sieve structure is damaged.In addition, vanadic acid aluminium can also be decomposed into V
2O
5And Al
2O
3, this makes that vanadium is non-stoichiometric to the destruction of molecular sieve structure.
External each major oil companies are from just the begin one's study catalytic cracking catalyst of anti-vanadiumism of the seventies.A kind of method of the anti-vanadiumism of catalytic cracking catalyst is with alkaline earth metal oxide and V effect in the prior art, suppresses the destruction of V to molecular sieve.The patent USP5 of Engelhard company uses MgO and the kaolin bead anti-vanadium assistant as catalytic cracking catalyst in 300,469.The patent USP4 of Ashland Oil company uses the anti-vanadium assistant of the oxide compound of IIA, IIIB, IVB, VB isofamily element as catalytic cracking catalyst in 485,184.USP4, in 843,052 and USP4,940,531 with tin, titanium mixed oxide as anti-vanadium component, anti-preferably vanadium effect is also arranged.
Another method of the anti-vanadiumism of catalytic cracking catalyst is to introduce rare earth in catalyzer or matrix in the prior art, utilize rare earth oxide can with V
2O
5Generate the character of stable compound, suppress the destruction of V molecular sieve.USP4,900,428 and EP0189267A in the method that proposes be to use soluble ree compound (halogenide, nitrate etc.) solution impregnation catalyst or matrix, rare earth is incorporated in the catalyzer.USP5 proposes in 248,642 and USP5,394,299 with rare earth oxide as active ingredient, and aluminium colloidal sol is as binding agent, and kaolin or modification kaolin are that matrix prepares anti-vanadium assistant, show good anti-vanadium effect.USP4,515,683 and CN88100418A in propose rare earth chloride to be deposited on the Y zeolite with ammoniacal liquor, making with this Y zeolite is that the catalytic cracking catalyst of active component has certain anti-vanadium performance.USP5 proposes in 173,174 directly to join in the catalytic cracking catalyst with the bastnasite of 5-10 weight %, also has certain anti-vanadium effect.
Summing up patent and the document of introducing the rare earth anti-vanadium assistant can find: the content of (1) rare earth anti-vanadium assistant is 2-3m% (accounting for catalyst ratio with rare earth oxide calculates), (2) method that rare earth oxide is incorporated into catalyzer and matrix is: with soluble ree solution impregnation catalyst or matrix, roasting then, (3) with the method that rare earth oxide is incorporated into molecular sieve are: with ammoniacal liquor rare earth ion is deposited on the molecular sieve.Wherein the purpose of (2) and (3) is to reduce rare earth ion and molecular sieve generation ion exchange reaction, promptly reduces the generation of REY.The anti-vanadium ability size order that studies show that different Y zeolites is: USY＞REHY＞REY, in case and rare earth enter the molecular sieve intracrystalline, thereby the chemical combination ability that does not just have with vanadium loses anti-vanadium effect.Therefore, reducing even avoid rare earth ion to enter the Y zeolite intracrystalline is the key that improves the anti-vanadium ability of rare earth.
Because the stock oil of refinery source often changes, make that the content of vanadium also changes thereupon on the catalyzer, also expose the weakness of anti-vanadium catalyst thus, promptly can not change the content of anti-vanadium constituent element on the catalyzer neatly with the variation of stock oil character.At this weakness of catalyzer, we wish to develop a kind of oil-soluble anti-vanadium assistant, this auxiliary agent should have following character: (1) oil soluble, (2) do not decompose under the catalytic cracking feeding preheating temperature (150-250 ℃), (3) catalytic cracking reaction temperature (450-550 ℃) is decomposed down and is deposited on and plays anti-vanadium effect on the catalyzer.
Purpose of the present invention is the anti-vanadium assistant that a kind of like this catalytic cracking catalyst is provided, this auxiliary agent can according to vanadium deposition on the changing conditions of refinery stock oil and the catalyzer what and join neatly in the reaction system, thereby change the content of anti-vanadium constituent element on the catalyzer neatly.Another object of the present invention provides the using method of said anti-vanadium assistant.
Specifically, anti-vanadium assistant provided by the present invention is that mixed rare earth ions combines formed oil soluble extracted species with a kind of organic extractant, this anti-vanadium assistant preferably contains 1-30 weight %, the mixed rare earth ions of preferred 2-20 weight % (by rare earth), the said organic extractant of 20-60 weight %, and the organic solvent of 20-70 weight %; Wherein said extraction agent is can extracting rare-earth ionic organic extractant, wherein preferably naphthenic acid, petrolenum sulfoxide or organophosphate; Said organic solvent be for dissolving the organic solvent of said organic extractant, for example solar oil, kerosene, hexanaphthene, isooctyl alcohol or their mixture, and the present invention has no particular limits it, and wherein preferred organic is kerosene or hexanaphthene.
Said mishmetal is based on La and/or Ce and contains the lucium of other rare earth (as yttrium, neodymium, praseodymium, samarium etc.) on a small quantity in the anti-vanadium assistant provided by the invention, and wherein the content of La is 5-90 weight %, is preferably 10-50 weight %; The content of Ce is 10-95 weight %, is preferably 50-90 weight %; Other content of rare earth is preferably less than 10 weight % less than 20 weight %.
Said naphthenic acid is commercially available common petroleum naphthenic acid in the anti-vanadium assistant provided by the invention, and the present invention has no particular limits it.
Said petrolenum sulfoxide is commercially available common petroleum sulfoxide in the anti-vanadium assistant provided by the invention, and the present invention has no particular limits it.
Said organophosphate tributyl phosphate (the commodity popular name is TBP) preferably in the anti-vanadium assistant provided by the invention, (the commodity popular name is P to the different monooctyl ester of isooctyl phosphoric acid list
507), (the commodity popular name is P to di (isooctyl) phosphate
204), perhaps (the commodity popular name is P to methyl acid phosphate diformazan heptyl ester
305).Wherein preferred organophosphate is a di (isooctyl) phosphate.
Anti-vanadium assistant provided by the present invention preferably extracts from the mishmetal mineral with extraction process and resulting organic extract during rare-earth separating, promptly with the extract intermediate of gained before rare earth not being separated with said extraction agent behind the organic extractant extracting rare-earth mineral that contain organic solvent; Wherein said rare-earth mineral is the various rare-earth minerals with extraction value, and said extraction agent is the organic extractant that generally use in the rare earth extraction field, and the present invention has no particular limits it.
Rare earth extraction objects system of the present invention can be referring to " rare earth " (metallurgical industry press, nineteen ninety-five publishes) of Xu Guangxian chief editor, and wherein described rare-earth extractant may be used to the present invention.
Said catalytic cracking catalyst anti-vanadium assistant provided by the invention is preferably directly taken from the extract of rare earth extraction factory, because can reduce cost like this; But anti-vanadium assistant of the present invention also can prepare according to following method:
(1), with said organic extractant naphthenic acid, petrolenum sulfoxide or organophosphate and said organic solvent according to organic extractant: organic solvent=1: the weight ratio of (1～5) is mixed, and obtains a kind of organic extractant that contains organic solvent;
(2), a kind of aqueous solution of alkali that will be selected from sodium hydroxide, potassium hydroxide or ammonium hydroxide is according to organic extractant: alkali=1: the weight ratio of (0.01～1) joins step (1) gained and contains in the organic extractant of organic solvent, oscillatory reaction 5～60 minutes, make the said organic extractant saponification in the extraction agent, saponification degree is 10-90%; Said saponification degree is meant that exchangeable cation is by the exchange degree that positively charged ion exchanged of said alkali on the said extraction agent.
(3), with mixed rare earth compound (halogenide, the nitrate etc.) aqueous solution of PH=0.1-6.5 according to organic extractant: rare earth=(5～20): 1 weight ratio joins in step (2) the gained mixture, vibrated 5-60 minute, standing demix then, rare earth ion in the rare earth compound solution partly is extracted in the organic phase with the form of extracted species, isolate organic phase, promptly obtain catalytic cracking catalyst anti-vanadium assistant of the present invention.
Among the preparation method of catalytic cracking catalyst anti-vanadium assistant provided by the present invention, said alkaline solution is sodium hydroxide solution preferably.
Among the preparation method of catalytic cracking catalyst anti-vanadium assistant provided by the present invention, said mixed rare earth compound solution is mixed chlorinated rare earth solution or mixeding acid rare-earth solution preferably, said mishmetal is based on La and/or Ce, and can contain the lucium of other rare earth (as yttrium, neodymium, praseodymium, samarium etc.) on a small quantity, wherein the content of La is 5-90 weight %, is preferably 10-50 weight %; The content of Ce is 10-95 weight %, is preferably 50-90 weight %; Other content of rare earth is preferably less than 10 weight % less than 20 weight %.
The using method of catalytic cracking catalyst anti-vanadium assistant provided by the invention is that said auxiliary agent is joined in the stock oil, said auxiliary agent enters into the catalytic cracking reaction system with stock oil, in the catalytic cracking reaction process, rare earth extracted species in the auxiliary agent decomposes, and rare earth is deposited on the component that becomes anti-vanadiumism on the catalytic cracking catalyst; The add-on of said auxiliary agent can be determined flexibly according to the content of vanadium of want on sedimentary rare earth content or the catalyzer, for example makes the rare earth content (weight content) and the content of vanadium (weight content) on the catalyzer that are deposited on the catalyzer suitable.
The another kind of using method of catalytic cracking catalyst anti-vanadium assistant provided by the invention is that catalytic cracking catalyst is flooded with said auxiliary agent, make the rare earth of requirement on the said catalyst soakage, for example dipping is gone up the rare earth of 0.1-2 weight %, dry then and at 400-700 ℃ of roasting 1-5 hour, obtain containing the catalytic cracking catalyst of the anti-vanadiumism of rare-earth additive, can be used for containing in the catalytic cracking reaction of vanadium raw materials oil; Perhaps also can be directly used in catalytic cracking reaction without roasting.
The organic extracted species anti-vanadium assistant of oil soluble rare earth provided by the invention has following advantage: 1) can admix as parallel feeding with catalytically cracked stock, adjust the usage quantity of auxiliary agent according to the V content in the stock oil neatly; 2) also can be deposited on the catalytic cracking catalyst and use; 3) to catch the V performance good for the rare earth element in the auxiliary agent; 4) when containing phosphoric in the auxiliary agent, this phosphoric can excite the active component of molecular sieve in the catalyzer; V content is 5000-11000ppm (accounting for catalyst weight than calculating with V) on catalyzer, contains the cracking activity of catalyzer of anti-vanadium assistant of the present invention and the corresponding anti-vanadium catalytic cracking catalyst that crystallization reservation degree is better than depositing water-solubility rare-earth; 5) when said anti-vanadium assistant provided by the invention be that running cost is lower when directly taking from the extract of rare earth extraction factory.
The following examples will be further described specifically the present invention, but it can not be interpreted as the qualification to protection domain of the present invention.The wherein raw materials used commercial goods that is.
The used evaluation method of each embodiment is as follows:
1: rare earth extraction thing middle-weight rare earths Determination on content
The content of rare earth extraction thing middle-weight rare earths adopts the X-ray fluorescence spectrum method for measuring
2: micro-activity is measured
Adopt RIPP 92-90 standard method (see " petrochemical complex analytical procedure (RIPP test method) ", volumes such as Yang Cuiding, Science Press, nineteen ninety version) measure.
3: the catalyst component content analysis
Form with X-ray fluorescent spectrometry (3013 type) analysis of catalyst.
4: the content of vanadium analysis
Content of vanadium is measured with plasma emission spectrometry.
5: lattice constant and crystallization reservation degree are measured
Adopt RIPP 145-90 and RIPP 146-90 standard method to measure respectively.
6: specific area measuring
Adopt GB/T 5816-1995 standard method to measure
7: pore volume is measured
Adopt RIPP 151-90 standard method to measure.
Embodiment 1-5
Get different organic extractants (as shown in table 1) respectively, add the 10ml isooctyl alcohol, all the other are kerosene, are mixed with the extraction agent solution 100ml of 1M; The concentration that adds different amounts respectively in said extraction agent solution is the sodium hydroxide solution of 10M, and the saponification in 10 minutes of vibrating makes its saponification degree as shown in table 1; (weight percentage of each composition is in its total amount of rare earth: Ce to get 18.62 gram rare earth chlorides again
2O
363%, La
2O
325%, Pr
6O
112.1%, Nd
2O
35.0%, Sm
2O
30.5%, other is 4.4% years old) add water to 100ml, after resulting 0.5M re chloride is regulated PH=2 with dilute hydrochloric acid, be added in the above-mentioned saponified extraction agent solution, oscillation extraction 10 minutes leaves standstill layering in 20 minutes, and isolated organic phase is the organic extracted species anti-vanadium assistant of rare earth of the present invention.Each auxiliary agent middle-weight rare earths content sees Table 1.
Embodiment 6
Get 35.8 gram di (isooctyl) phosphates, add the di (isooctyl) phosphate solution 100ml that kerosene is mixed with 1M.Get 2 milliliters of 10M sodium hydroxide solutions and join in the above-mentioned solution, vibrated 10 minutes, obtain saponified di (isooctyl) phosphate solution.Get 18.62 gram rare earth chlorides again and add water to 100ml, after the 0.5M re chloride that obtains is regulated PH=2.0 with dilute hydrochloric acid, be added in the above-mentioned saponified di (isooctyl) phosphate solution, oscillation extraction 10 minutes, leave standstill layering in 20 minutes, isolated organic phase is the organic extracted species anti-vanadium assistant of rare earth of the present invention.Its content of rare earth sees Table 1.
Embodiment 7
Get 35.8 gram di (isooctyl) phosphates, add the 10ml isooctyl alcohol, all the other are solar oil, are mixed with the di (isooctyl) phosphate solution 100ml of 1M.Get 3 milliliters of 10M sodium hydroxide solutions and join in the above-mentioned solution, vibrated 10 minutes, obtain saponified di (isooctyl) phosphate solution.Get 22.34 gram rare earth chlorides again and add water to 100ml, after the 0.6M re chloride that obtains is regulated PH=3.0 with dilute hydrochloric acid, be added in the above-mentioned saponified di (isooctyl) phosphate solution, oscillation extraction 10 minutes, leave standstill layering in 20 minutes, isolated organic phase is the organic extracted species anti-vanadium assistant of rare earth of the present invention.Its content of rare earth sees Table 1.
Embodiment 8
Get 35.8 gram di (isooctyl) phosphates, add the di (isooctyl) phosphate solution 100ml that hexanaphthene is mixed with 1M.Get 5 milliliters of 10M sodium hydroxide solutions and join in the above-mentioned solution, vibrated 10 minutes, obtain saponified di (isooctyl) phosphate solution.Get 29.79 gram rare earth chlorides again and add water to 100ml, after the 0.8M re chloride that obtains is regulated PH=4.0 with dilute hydrochloric acid, be added in the above-mentioned saponified di (isooctyl) phosphate solution, oscillation extraction 10 minutes, leave standstill layering in 20 minutes, isolated organic phase is the organic extracted species anti-vanadium assistant of rare earth of the present invention.Its content of rare earth sees Table 1.
Embodiment 9
Get 53.7 gram di (isooctyl) phosphates, add the 10ml isooctyl alcohol, all the other are kerosene, are mixed with the di (isooctyl) phosphate solution 100ml of 1.5M.Get 7 milliliters of 10M sodium hydroxide solutions and join in the above-mentioned solution, vibrated 10 minutes, obtain saponified di (isooctyl) phosphate solution.Get 37.24 gram rare earth chlorides again and add water to 100ml, after the 1.0M re chloride that obtains is regulated PH=5.0 with dilute hydrochloric acid, be added in the above-mentioned saponified di (isooctyl) phosphate solution, oscillation extraction 10 minutes, leave standstill layering in 20 minutes, isolated organic phase is the organic extracted species anti-vanadium assistant of rare earth of the present invention.Its content of rare earth sees Table 1.
Embodiment 10
Present embodiment provides a kind of rare earth extraction thing of taking from rare earth extraction factory as anti-vanadiumism auxiliary agent of the present invention, and this rare earth extraction thing is for taking from Sichuan Mianning rare earth factory, and its composition is listed in the table 1.The preparation condition and the content of rare earth of each rare earth extraction thing of table 1
| Embodiment | Extraction agent | Solvent | Extractant concentration in the organic phase (M) | RECl 3Solution ph | Saponification degree (%) | Organic extract middle-weight rare earths content | ||
| Ce (g/L) | La (g/L) | Other rare earth (g/L) | ||||||
| 1 | Naphthenic acid | Isooctyl alcohol+kerosene | 1 | 2 | 80 | 4.7 | 2.7 | 0.4 |
| 2 | Petrolenum sulfoxide | Isooctyl alcohol+kerosene | 1 | 2 | 50 | 2.6 | 1.5 | 0.2 |
| 3 | Tributyl phosphate | Isooctyl alcohol+kerosene | 1 | 2 | 40 | 5.1 | 2.9 | 0.4 |
| 4 | The different monooctyl ester of isooctyl phosphoric acid list | Isooctyl alcohol+kerosene | 1 | 2 | 40 | 7.1 | 4.1 | 0.6 |
| 5 | Di (isooctyl) phosphate | Isooctyl alcohol+kerosene | 1 | 2 | 30 | 5.7 | 3.3 | 0.4 |
| 6 | Di (isooctyl) phosphate | Kerosene | 1 | 2 | 40 | 6.5 | 4.0 | 0.5 |
| 7 | Di (isooctyl) phosphate | Isooctyl alcohol+solar oil | 1 | 3 | 50 | 6.9 | 4.3 | 0.6 |
| 8 | Di (isooctyl) phosphate | Hexanaphthene | 1 | 4 | 55 | 7.0 | 4.3 | 0.6 |
| 9 | Di (isooctyl) phosphate | Isooctyl alcohol+kerosene | 1.5 | 5 | 55 | 7.8 | 5.2 | 0.8 |
| 10 | Di (isooctyl) phosphate | Isooctyl alcohol+kerosene | 1 | 4 | 45 | 6.5 | 4.1 | 0.6 |
Embodiment 11
Get 430 gram (dry basis) kaolins, 907 gram Al
2O
3Content is that aluminium colloidal sol and the 1573 gram water of 20.94 weight % mix making beating 60 minutes, obtains carrier pulp.Getting according to the prepared silica alumina ratio of patent CN1088247A again is 10 SRY molecular sieve, 350 gram (dry basises, Ba Ling petro-chemical corporation catalyst plant commerical prod) joins in the above-mentioned slurries, stir after 20 minutes spraying drying and make microspherical catalyst, then with its (NH with 0.1N
4)
2HPO
4Solution is washed once, and deionization washing twice is filtered, and 120 ℃ of oven dry obtain catalyst sample A.Its lattice constant a
0, crystallization reservation degree, micro-activity, surface-area, pore volume measurement result as shown in table 2.
Embodiment 12
To be added among the 390 gram sample A according to the organic extracted species auxiliary agent of the rare earth that embodiment 6 obtains 200ml, flood 30 minutes, in ventilating kitchen, dry, place 120 ℃ of oven dry of baking oven again, obtain containing 0.6 weight %La with infrared lamp
2O
3, 1.1 weight %CeO
2Sample B.Its lattice constant a
0, crystallization reservation degree, micro-activity, surface-area, pore volume measurement result as shown in table 2.
Embodiment 13
Sample A 550 ℃ of roastings 4 hours in retort furnace through 820 ℃, 100% water vapour burin-in process 4 hours, obtain sample A again
0Its lattice constant a
0, crystallization reservation degree, micro-activity, surface-area, pore volume measurement result as shown in table 2.
Embodiment 14
Get duplicate samples A such as 5 and impregnated in the naphthenic acid vanadium cyclohexane solution of isopyknic different content of vanadium respectively after 60 minutes, dry in ventilating kitchen with infrared lamp, place 120 ℃ of oven dry of baking oven 4 hours again, through 550 ℃ of roastings of retort furnace 4 hours, through 820 ℃, 100% water vapour burin-in process 4 hours, obtain the sample A of different content of vanadium again
1, A
2, A
3, A
4, A
5Its lattice constant a
0, crystallization reservation degree, micro-activity, surface-area, pore volume measurement result as shown in table 2.
Embodiment 15
Sample B is 550 ℃ of roastings of retort furnace 4 hours, through 820 ℃, 100% water vapour burin-in process 4 hours, obtains sample B again
0Its lattice constant a
0, crystallization reservation degree, micro-activity, surface-area, pore volume measurement result as shown in table 2.
Embodiment 16
Get duplicate samples B such as 5 and impregnated in the naphthenic acid vanadium cyclohexane solution of isopyknic different content of vanadium respectively after 60 minutes, dry in ventilating kitchen with infrared lamp, place 120 ℃ of oven dry of baking oven 4 hours again, through 550 ℃ of roastings of retort furnace 4 hours, through 820 ℃, 100% water vapour burin-in process 4 hours, obtain the sample B of different content of vanadium again
1, B
2, B
3, B
4, B
5Its lattice constant a
0, crystallization reservation degree, micro-activity, surface-area, pore volume measurement result as shown in table 2.
Comparative Examples 1
This Comparative Examples provides a kind of anti-vanadiumism catalytic cracking catalyst and effect thereof of routine.
With reference to USP4,515,683 method is deposited on rare earth on the embodiment 11 gained catalyst A.Concrete preparation method is: get the rich cerium type of said 0.5M RECl among the embodiment 1
3Solution 80ml after the dilution of 20ml deionized water, joins it in 1kg (dry basis) catalyst A, stirs 20 minutes, add ammoniacal liquor (3.7N) then and make the slurries pH value reach 11, restir was used deionized water wash three times after 20 minutes, filter, 120 ℃ of oven dry obtain containing 0.7 weight %La
2O
3, 2.2 weight %CeO
2, 0.1 other rare earth of weight % is (with RE
2O
3Meter) comparative catalyst C; After going up vanadium according to the method dipping of embodiment 16 then, obtain the sample C of different content of vanadium
1, C
2, C
3, C
4, C
5Its lattice constant a
0, crystallization reservation degree, micro-activity, surface-area, pore volume measurement result as shown in table 2.
As can be seen from Table 2, when content of vanadium when 0 is increased to 6000ppm, for the sample A of deposition aid not
0, its crystallization reservation degree drops to 9 from 41, has descended 32; And for the sample B of deposition aid
0, its crystallization reservation degree drops to 31 from 37, has descended 6.The above results proves that deposition aid can obviously reduce the destruction of vanadium to catalyzer crystallization reservation degree on the catalyzer.
As can be seen from Table 2, when content of vanadium when 0 is increased to 6000ppm, for the sample A of deposition aid not
0, its micro-activity drops to 19 from 56, has descended 37; And for the sample B of deposition aid
0, its micro-activity drops to 49 from 59, has descended 10.The above results proves that deposition aid can obviously improve the anti-vanadiumism ability of catalyzer on the catalyzer.
As can be seen from Table 2, when content of vanadium when 0 is increased to 6000ppm, for the sample A of deposition aid not
0, its surface-area is from 106m
2/ g drops to 31m
2/ g, 75m has descended
2/ g; And for the sample B of deposition aid
0, its surface-area is from 105m
2/ g drops to 87m
2/ g, 18m has descended
2/ g.The above results proves that deposition aid can obviously improve the surface-area of catalyzer on the catalyzer, reduces the destruction of vanadium to catalyst surface area.
As can be seen from Table 2, when content of vanadium when 0 is increased to 6000ppm, for the sample A of deposition aid not
0, its pore volume drops to 0.079ml/g from 0.120ml/g, and 0.041ml/g has descended; And for the sample B of deposition aid
0, its pore volume drops to 0.100ml/g from 0.119ml/g, and 0.019ml/g has descended.The above results proves that deposition aid can obviously improve the pore volume of catalyzer on the catalyzer, reduces the destruction of vanadium to catalyst pore volume.The physicochemical property of each catalyst sample of table 2
| Sample number into spectrum | Content of vanadium (ppm) | Lattice constant a 0 (nm) | Crystallization reservation degree (%) | Little index alive | Specific surface area (m 2/g) | Pore volume (ml/g) |
| A | 0 | -- | 70 | -- | 181 | 0.077 |
| A 0 | 0 | 2.420 | 41 | 56 | 106 | 0.120 |
| A 1 | 1100 | 2.419 | 27 | 54 | 95 | 0.106 |
| A 2 | 2400 | 2.420 | 27 | 49 | 83 | 0.096 |
| A 3 | 3500 | 2.416 | 18 | 42 | 72 | 0.091 |
| A 4 | 5000 | 2.414 | 18 | 32 | 54 | 0.085 |
| A 5 | 6000 | 2.413 | 9 | 19 | 31 | 0.079 |
| B | 0 | 2.420 | 56 | 64 | 178 | 0.081 |
| B 0 | 0 | 2.418 | 37 | 59 | 105 | 0.119 |
| B 1 | 1100 | 2.422 | 36 | 58 | 100 | 0.110 |
| B 2 | 2400 | 2.420 | 36 | 58 | 97 | 0.105 |
| B 3 | 3500 | 2.422 | 35 | 56 | 95 | 0104 |
| B 4 | 5000 | 2.419 | 32 | 52 | 93 | 0.101 |
| B 5 | 6000 | 2.421 | 31 | 49 | 87 | 0.100 |
| C | 0 | 2.419 | 55 | 67 | 170 | 0.081 |
| C 1 | 1100 | 2.421 | 38 | 60 | 112 | 0.097 |
| C 2 | 2400 | 2.420 | 36 | 60 | 103 | 0.105 |
| C 3 | 3500 | 2.422 | 36 | 59 | 87 | 0.104 |
| C 4 | 5000 | 2.419 | 35 | 53 | 81 | 0.097 |
| C 5 | 6000 | 2.420 | 31 | 47 | 80 | 0.098 |
Embodiment 17
Present embodiment illustrates the result of use of anti-vanadium assistant provided by the invention.
Mixing of rare earth extraction thing anti-vanadium assistant that embodiment 1 is made and Tarim Basin, Xinjiang crude oil greater than 350 ℃ of fraction oil (its character sees Table 3), making the content of rare earth in the gained mixture is 60ppm (promptly roughly suitable with content of vanadium), and with the reaction raw materials of gained mixture as the small fixed flowing bed catalytic cracking, after 20 reaction-regeneration periods, make the above V of deposition 3000ppm in the molecular balance agent, and make the rare earth in the stock oil almost be deposited on the catalyzer quantitatively, feed stock oil shown in the table 3 that does not contain anti-vanadium assistant of the present invention again this moment and carry out evaluation test, the results are shown in Table 4 for gained.Fixed fluidized bed reaction conditions is: 500 ℃ of temperature of reaction, 700 ℃ of regeneration temperatures, agent-oil ratio 4.0, air speed 20 hours
-1, catalyzer loading amount 150 grams.
Comparative Examples 2
The explanation of this Comparative Examples does not add the fixed fluidized bed evaluation result of anti-vanadium assistant of the present invention.
Repeat the operation steps of embodiment 17, different is not add anti-vanadium assistant of the present invention in the stock oil, and the results are shown in Table 4 for gained.
Table 4 is the result show, adds anti-vanadium assistant of the present invention in the stock oil and can make catalyzer obviously play the effect of anti-vanadiumism.
Table 3. stock oil character
The fixed fluidized bed evaluation result of table 4.
| ＞350 ℃ of yield density, the g/cm3 carbon residue, weight % metal content, ppm Fe Cu Ni V | 48.90 0.9365 8.28 15.1 1.01 6.48 58.1 |
| Embodiment 17 adds anti-vanadium assistant of the present invention | Comparative Examples 2 does not add anti-vanadium assistant | |
| V content on the catalyzer, ppm | 3000 | 3000 |
| Ni content on the catalyzer, ppm | 1200 | 1200 |
| Content of rare earth on the catalyzer, ppm | 3500 | -- |
| Material balance, weight % dry gas liquefied gas gasoline, diesel heavy oil coke | 1.59 18.19 45.63 19.12 6.50 8.97 | 1.57 14.23 41.16 21.24 12.95 8.85 |
| Transformation efficiency, weight % | 74.38 | 65.81 |
| Lightweight oil+liquefied gas, weight % | 82.94 | 76.63 |
Claims (14)
1, a kind of vanadium-resistant catalytic cracking assistant, it is characterized in that this anti-vanadium assistant is that mixed rare earth ions combines formed oil soluble extracted species with a kind of organic extractant, this anti-vanadium assistant contains the mixed rare earth ions by rare earth 1-30 weight %, the said organic extractant of 20-60 weight %, and the organic solvent of 20-70 weight %; Wherein said extraction agent is can extracting rare-earth ionic organic extractant; Said organic solvent is for dissolving the organic solvent of said organic extractant.
2, according to the anti-vanadium assistant of claim 1, it is characterized in that this anti-vanadium assistant is to extract and resulting organic extract during rare-earth separating with extraction process from the mishmetal mineral, promptly with the organic extract intermediate of gained before rare earth not being separated with said extraction agent behind the organic extractant extracting rare-earth mineral; Wherein said rare-earth mineral is the various rare-earth minerals with extraction value.
3, according to the anti-vanadium assistant of claim 1 or 2, wherein the content of said mishmetal is 2-20 weight %.
4, according to the anti-vanadium assistant of claim 1 or 2, wherein said mishmetal is based on La and/or Ce and contains the lucium of other rare earth on a small quantity, wherein the content of La is 5-90 weight %, and the content of Ce is 10-95 weight %, and other content of rare earth is less than 20 weight %.
5, according to the anti-vanadium assistant of claim 4, the content of La is 10-50 weight % in the wherein said mixing, and the content of Ce is 50-90 weight %, and other content of rare earth is less than 10 weight %.
6, according to the anti-vanadium assistant of claim 2, wherein said extraction agent is the organic extractant that generally use in the rare earth extraction field.
7, according to the anti-vanadium assistant of claim 1 or 2, wherein said organic extractant is naphthenic acid, petrolenum sulfoxide or organophosphate.
8, according to the anti-vanadium assistant of claim 7, wherein said organophosphate is a tributyl phosphate, the different monooctyl ester of isooctyl phosphoric acid list, di (isooctyl) phosphate, perhaps methyl acid phosphate diformazan heptyl ester.
9, according to the anti-vanadium assistant of claim 8, wherein said organophosphate is a di (isooctyl) phosphate.
10, according to the anti-vanadium assistant of claim 1 or 2, wherein said organic solvent is solar oil, kerosene, hexanaphthene, isooctyl alcohol or their mixture.
11, according to the anti-vanadium assistant of claim 10, wherein said organic solvent is kerosene or hexanaphthene.
12, the method for the anti-vanadiumism of a kind of catalytic cracking catalyst, it is characterized in that this method comprises joins the said anti-vanadium assistant of claim 1 in the stock oil of catalytic cracking reaction, make said auxiliary agent enter reaction system and decompose therein, rare earth in the auxiliary agent is deposited on the catalytic cracking catalyst in the system with stock oil; The add-on of said auxiliary agent is determined according to the content of vanadium of want on sedimentary rare earth content or the catalyzer.
13,, it is characterized in that said anti-vanadium assistant is the said anti-vanadium assistant of claim 2 according to the method for claim 12.
14, the method for the anti-vanadiumism of a kind of catalytic cracking catalyst, it is characterized in that this method comprises catalytic cracking catalyst claim 1 or 2 said auxiliary agents dippings, make on the said catalyst soakage by the rare earth of total rare earth (TRE) 0.1-2 weight %, obtain containing the catalytic cracking catalyst of the anti-vanadiumism of rare-earth additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99109680 CN1115378C (en) | 1999-07-06 | 1999-07-06 | Anti-vanadium assistant for catalytic-cracking catalyst and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99109680 CN1115378C (en) | 1999-07-06 | 1999-07-06 | Anti-vanadium assistant for catalytic-cracking catalyst and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1283667A CN1283667A (en) | 2001-02-14 |
| CN1115378C true CN1115378C (en) | 2003-07-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99109680 Expired - Lifetime CN1115378C (en) | 1999-07-06 | 1999-07-06 | Anti-vanadium assistant for catalytic-cracking catalyst and its application |
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| CN (1) | CN1115378C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102228838B (en) * | 2011-04-21 | 2012-12-12 | 卓润生 | Silicon-carrier lanthanum carbonate catalytic cracking microspherical vanadium-resistant aid and preparation method thereof |
| CN102228839B (en) * | 2011-05-03 | 2012-12-12 | 卓润生 | Silicon-aluminum dual binding agent vanadium-resisting additive and preparation method thereof |
| CN102806076B (en) * | 2011-06-03 | 2014-11-26 | 崔超 | Catalytic cracking microsphere anti-vanadium cocatalyst and preparation method and application thereof |
| CN103055916B (en) * | 2011-10-21 | 2015-06-17 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking catalyst |
| CN103602812A (en) * | 2013-11-18 | 2014-02-26 | 江西理工大学 | Rare-earth organic extractant and back-extraction process thereof |
| CN104878202B (en) * | 2014-02-28 | 2017-04-26 | 中国石油化工股份有限公司 | Method for extracting rare earth from rare earth-containing sludge |
| CN107583672B (en) * | 2016-07-08 | 2019-12-17 | 中国石化扬子石油化工有限公司 | Method for improving activity of vanadium-polluted catalytic cracking catalyst |
| CN108435132A (en) * | 2018-04-02 | 2018-08-24 | 广东石油化工学院 | A kind of auxiliary agent improving fluid catalytic cracking product yield |
-
1999
- 1999-07-06 CN CN 99109680 patent/CN1115378C/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1283667A (en) | 2001-02-14 |
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