CN1286291A - Catalytic cracking and desulfurizing catalyst for refining light oil products - Google Patents
Catalytic cracking and desulfurizing catalyst for refining light oil products Download PDFInfo
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- CN1286291A CN1286291A CN 00120711 CN00120711A CN1286291A CN 1286291 A CN1286291 A CN 1286291A CN 00120711 CN00120711 CN 00120711 CN 00120711 A CN00120711 A CN 00120711A CN 1286291 A CN1286291 A CN 1286291A
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Abstract
A catalytic cracking and desulfurizing catalyst for refining light oil, e.g. gasoline or diesel oil, features that it contains higher-acidity component and rare-earth element and has high hydrogen transfer activity, resulting in selective adsorption of sulfide and high desulfurizing selectivity.
Description
The present invention relates to a kind of novel catalytic cracking and desulfurizing catalyst that is used for refining light oil products (gasoline, diesel oil), it is the improvement that belongs in the petroleum refining process the process for refining and the catalyzer of oil product.It mainly is to consider at first must contain acid stronger component (as SAPO series zeolite, MCM series zeolite, ZSM-5, β zeolite, HY and USY etc.) in the catalyzer when the design catalyzer, secondly the hydrogen transfer activity of catalyzer must be strong, to promote removing of sulphur, consider in catalyzer, to add proper amount of rare-earth (as La, Ce, Pr, Nd and Sm etc.).Make catalyzer have certain acid and stronger hydrogen transfer activity simultaneously, the function that also must have selective absorption sulphide, thereby select close sulfide Cu, Zn, Fe, Al, As, Hg, Ni, Zr, Sn, Ga and Ti etc. oxide compound or be carrier by the compound or complex oxide that these metal oxides are formed, thereby make this catalyzer help the absorption and the conversion of sulfide, and improve the desulfuration selectivity of catalyzer.
At present, in refining of petroleum industry, the sulphur 90% in the gasoline (quality percentage composition, down together) is above from the catalytically cracked gasoline component, thereby the sulphur content of reduction catalytically cracked gasoline is to reduce the key of content of sulfur in gasoline.Though it is a kind of very effective sulfur method that catalytically cracked gasoline is carried out hydrogenation, the cost height of hydrogenation, the octane value of gasoline also can decrease because of alkene is saturated.Wormsbecher and Kim (U.S.Pat.No.5,525,210 and U.S.Pat.No.5,376,608) Fa Ming catalytically cracked gasoline sweetening additive can add in the catalytic cracking reaction process at any time, also can be prepared in the catalytic cracking catalyst, can play the effect of desulfurization, but the desulfurization degree is limited, adds sweetening additive and can only make the sulphur content in the catalytically cracked gasoline reduce less than 30%.The hydrogenation ability of China refinery is lower, and most catalytically cracked materials are without hydrotreatment, and sulphur content is higher, the sulphur content height in the catalytically cracked gasoline of production, and the sulphur content of the catalytically cracked gasoline that has can be up to more than the 1500 μ g/g.The sulphur content that wants the gasoline that sulfur-bearing is high drops to below China's new gasoline standard 800 μ g/g, and don't wants the hydrogenation means that adopt cost high, just must the brand-new sulfur method of exploitation.
The catalytic cracking and desulfurizing catalyst that purpose of the present invention is provided for refining light oil products with regard to being to avoid above-mentioned the deficiencies in the prior art part, it mainly makes by rare earth element being added on the acid stronger molecular sieve, and be carrier with the metal oxide of close sulfide, when making it have stronger cracking activity, hydrogen transfer activity, can adsorb sulfide by selection type, thus the sulfide in the selection type cracking lightweight oil.Its major technology characteristics are by pickling process and roasting method the form of rare earth with oxide compound to be dispersed on the acid zeolite, again the zeolite of dipping and special metal hydroxides are carried out uniform mixing in proportion, and then pass through washing, drying and pulverize on request to get final product.
In order better to realize above-mentioned purpose of the present invention, planner of the present invention is that the process with pickling process and roasting method is designed to: the rare earth that floods 0.1～30% (quality) on acid zeolite, 60～200 ℃ of dryings after 5～10 hours, 200～700 ℃ of roastings 0.5～10 hour, rare earth is dispersed on the zeolite with the form of oxide compound again; The preparation process of special metal hydroxides is designed to: will have than the soluble salt of the metal of adsorptive power and the soluble salt of rare earth are dissolved in the distilled water by force sulfide, be mixed with concentration at 0.5～30% solution, the KOH with 0.1～15%, NaOH or NH
3H
2The aqueous solution of O is made precipitation agent, in whipping process, be added drop-wise in the metal salt solution, to pH value be 7～9, metal-salt is changed into fully the precipitation of hydroxide thing of metal; Carried out mixed uniformly process in proportion and be designed to flooding the zeolite of rare earth and special metal hydroxides: the zeolite that will flood rare earth is by 2～50% joining in the throw out of metal hydroxides of being prepared into finished catalyst, fully stir, zeolite and throw out are mixed, left standstill then 5～10 hours.Then, the zeolite that mixes, left standstill and sedimentary mixture stirred 10～60 minutes once more after, carry out suction filtration, and with an amount of distilled water wash 3～5 times.The gained filter cake is 50～200 ℃ of dryings 10～24 hours, and roasting 1～24 hour in 300～900 ℃ retort furnace is then pulverized and sieved.
Come enumeration design philosophy of the present invention and design advantage below in conjunction with embodiment.
When actual design desulfurization catalyst of the present invention, planner of the present invention thinks that the sulfide in the catalytically cracked gasoline has mercaptan, thioether and thiophene-based material etc., and in the majority with the thiophene-based material.Mercaptan, thioether can be on an acidic catalyst remove wherein sulphur through hydrogen transference, cracking reaction; The thiophene-based material is first cracking open loop on the B acid site of an acidic catalyst earlier then, generates the middle species of thio-alcohol, and species pass through hydrogen transference, cracking reaction again in the middle of the thio-alcohol, and sulphur wherein changes into H2S and removes.According to this principle, when the design catalyzer, at first must contain acid stronger component in the catalyzer, as SAPO series zeolite, MCM series zeolite, ZSM-5, β zeolite, HY and USY etc.; Secondly the hydrogen transfer activity of catalyzer must be strong, to promote removing of sulphur, considers to add proper amount of rare-earth in catalyzer, as La, Ce, Pr, Nd and Sm etc.Catalyzer also must have the function of selective absorption sulphide having certain acid and stronger hydrogen transfer activity simultaneously, so just can help the absorption and the conversion of sulfide, improves the desulfuration selectivity of catalyzer.The stronger material of sulfide adsorptive power is comprised the oxide compound of Cu, Zn, Fe, Al, As, Hg, Ni, Zr, Sn, Ga and Ti etc. or the compound or complex oxide of being made up of these metal oxides.
In the process of actual fabrication desulfurization catalyst of the present invention, the concrete principle steps of its desulfurization catalyst preparation is:
1. (quality) rare earth after 5～10 hours, again 200～700 ℃ of roastings 0.5～10 hour, makes rare earth be dispersed on the zeolite with the form of oxide compound 60～200 ℃ of dryings down together at first to flood 0.1～30% on acid zeolite.
2. one or more are had the soluble salt of metal of strong adsorptive power and the soluble salt of rare earth to sulfide and be dissolved in the distilled water, be mixed with concentration at 0.5～30% solution, the KOH with 0.1～15%, NaOH or NH
3H
2The aqueous solution of O is made precipitation agent, in whipping process, be added drop-wise in the metal salt solution, to pH value be 7～9, metal-salt is changed into fully the precipitation of hydroxide of metal.
The zeolite that 3. will flood rare earth fully stirs by 2～50% joining in the precipitation of being prepared into finished catalyst, and zeolite and throw out are mixed, and leaves standstill then 5～10 hours.
After the throw out that 4. will be mixed with zeolite stirs 10～60 minutes once more, carry out suction filtration, and with an amount of distilled water wash 3～5 times.The gained filter cake is 50～200 ℃ of dryings 10～24 hours, and roasting 1～24 hour in 300～900 ℃ retort furnace is then pulverized and sieved.
So promptly prepared specific surface at 50～400m
2The catalytic cracking and desulfurizing catalyst that is used for refining light oil products of/g with selective adsorption, cracking sulfide.
According to above-mentioned ultimate principle step, the embodiment of concrete preparation is as follows: 1. the preparation that is used for the desulfurization catalyst of treated gasoline sees example 1 and example 2 for details.The catalytic cracking and desulfurizing catalyst that is used for refined diesel oil sees example 3 and example 4 for details.Example 1: 1. take by weighing HY zeolite 9.9g, adopt to be dipped into just wet method and to divide 3 dippings to contain the solution 10mL that lanthanum trioxide is 0.01g/mL, flood all in 100 ℃ baking oven drying 1 hour, at every turn then 500 ℃ of roastings 2 hours.The 10g that obtains contains the HY zeolite of 1% rare earth, fully grinds to form behind the fine powder standby.2. getting salic, nickel oxide and zinc oxide respectively is each 300mL of nitrate solution of 0.1g/mL, admixed together after, under continuous stirring condition, drip 10% ammonia soln, the nitrate of each metal in the solution is changed into precipitation of hydroxide.3. drop to after pH value equals 7.5, the HY zeolite powder that 10g is contained rare earth joins in the precipitation, after stirring, leaves standstill 6 hours.4. before filtering, fully stir once more.Use 50mL distilled water wash 5 times in the filtration procedure, to remove the NH in the precipitation as far as possible
4 +And NO
3 -Filter cake in 150 ℃ baking oven dry 20 hours, roasting 4 hours in 600 ℃ retort furnace again.The break-up of catalyst that obtains, sieve out the particle of 0.078～0.18mm, carry out evaluation experimental.Micro anti-evaluation is the result show, the catalyzer of preparation has tangible sweetening effectiveness under experiment condition, and the yield height of gasoline, and loss is few.Example 2: 1. take by weighing USY zeolite 19.6g, adopt to be dipped into just wet method and to divide 6 dippings to contain the solution 40mL that lanthanum trioxide is 0.01g/mL, flood all in 100 ℃ baking oven drying 1 hour, at every turn then 500 ℃ of roastings 2 hours.The 20g that obtains contains the USY zeolite of 2% rare earth, fully grinds to form behind the fine powder standby.2. get each 300mL of nitrate solution that salic, zirconium white and zinc oxide are respectively 0.1g/mL, 0.05g/mL and 0.1g/mL respectively, after admixed together, the hydrochloric acid soln 1OmL that adds 0.1mol/L, then under continuous stirring condition, the ammonia soln of dropping 15% changes into precipitation of hydroxide with each metal in the solution.3. drop to after pH value equals 7.5, the USY zeolite powder that 20g is contained rare earth joins in the precipitation, after stirring, leaves standstill 6 hours.4. before filtering, fully stir once more.Use 100mL distilled water wash 5 times in the filtration procedure, to remove the NH in the precipitation as far as possible
4 +And NO
3 -Filter cake in 150 ℃ baking oven dry 20 hours, roasting 10 hours in 750 ℃ retort furnace again.The break-up of catalyst that obtains, sieve out the particle of 0.078～0.18mm, carry out evaluation experimental.Micro anti-evaluation is the result show, the catalyzer of preparation has excellent sweetening effectiveness under experiment condition.Desulfurization degree all is close to or higher than 50% under different temperature of reaction, and the 1778 μ g/gs of the sulphur content of gasoline before by reaction are reduced to below the 800 μ g/g under being higher than 470 ℃ reaction conditions, have reached the restriction of China's new gasoline standard to sulphur content; And the yield of gasoline all is equal to or higher than 95%, yield of gasoline even can be under cold condition up to more than 98%, and the amount of dry gas is considerably less in the cracked gaseous product, mainly is C3 and C4, remains valuable fuel and industrial chemicals, loses considerably less.Example 3: 1. take by weighing HY zeolite 9.9g, employing is dipped into just wet method and divides 3 dippings to contain the solution 10mL that lanthanum trioxide is 0.01g/mL, has flooded all dry 1h in 100 ℃ baking oven, then at 500 ℃ of roasting 2h at every turn.The 10g that obtains contains the HY zeolite of 1% rare earth, fully grinds to form behind the fine powder standby.2. getting salic, nickel oxide and zinc oxide respectively is each 300mL of nitrate solution of 0.1g/mL, admixed together after, under continuous stirring condition, drip 10% ammonia soln, the nitrate of each metal in the solution is changed into precipitation of hydroxide.3. drop to after pH value equals 7.5, the HY zeolite powder that 10g is contained rare earth joins in the precipitation, after stirring, leaves standstill 6h.4. before filtering, fully stir once more.Use 50mL distilled water wash 5 times in the filtration procedure, to remove the NH in the precipitation as far as possible
4 +And NO
3 -Filter cake is dry 20h in 150 ℃ baking oven, again roasting 4h in 600 ℃ retort furnace.The break-up of catalyst that obtains, sieve out the particle of 0.078～0.18mm, carry out evaluation experimental.
Fixed fluidized bed evaluation result shows that the catalyzer of preparation has tangible sweetening effectiveness under experiment condition, and the yield height of diesel oil, and loss is few.Example 4: 1. take by weighing USY zeolite 19.6g, employing is dipped into just wet method and divides 6 dippings to contain the solution 40mL that lanthanum trioxide is 0.01g/mL, has flooded all dry 1h in 100 ℃ baking oven, then at 500 ℃ of roasting 2h at every turn.The 20g that obtains contains the USY zeolite of 2% rare earth, fully grinds to form behind the fine powder standby.2. get aluminium hydroxide, cupric nitrate and zinc nitrate 500g, 300g and 1000g respectively, place the beaker of a 2000mL.The hydrochloric acid soln 1000mL that adds 0.05mol/L in beaker stirs 2h in 60 ℃ constant temperature is water-soluble, take out then, makes it be cooled to room temperature.Under continuous stirring condition, drip 10% ammonia soln, each metal in the solution is changed into precipitation of hydroxide.3. drop to after pH value equals 7.5, the USY zeolite powder that 100g is contained rare earth joins in the precipitation, after stirring, leaves standstill 6h.4. before filtering, fully stir once more.Use 300mL distilled water wash 5 times in the filtration procedure, to remove the NH in the precipitation as far as possible
4 +, Cl
-And NO
3 -Filter cake is dry 20h in 150 ℃ baking oven, again roasting 10h in 750 ℃ retort furnace.The break-up of catalyst that obtains, sieve out the particle of 0.078～0.18mm, carry out evaluation experimental.
The result of fixed fluidized bed evaluation: the catalyzer of preparation has excellent sweetening effectiveness under experiment condition.Under different temperature of reaction desulfurization near or surpass 50%, the 2800 μ g/gs of the sulphur content of diesel oil before by reaction are reduced to below the 1200 μ g/g under being higher than 470 ℃ reaction conditions, far below the restriction of China's diesel oil standard to sulphur content; And the yield of diesel oil all is equal to or higher than 92%.The amount of dry gas is considerably less in the cracked gaseous product, mainly is C3 and C4, remains valuable fuel and industrial chemicals, loses considerably less.
Compared with prior art, the light-end products catalytic cracking and desulfurizing catalyst of preparing by said process proves guaranteeing to have tangible sweetening effectiveness under the situation that liquid is received through little anti-and fixed fluidized bed evaluation.1. for gasoline refining:
Micro anti-evaluation is the result show, is that 480 ℃, catalyzer loading amount are that 5g, agent-oil ratio are under 2.5 the situation in temperature of reaction, sulphur content be the catalytically cracked gasoline of 1778 μ g/g (Ignition Lamp Method is measured, down with) after reaction, yield of gasoline
Be 96.4%, sulphur content is reduced to 771.8 μ g/g, and the range of decrease is 56.61%; Other condition is constant, temperature is reduced to 420 ℃ reacts, and yield of gasoline is 98.2%, and sulphur content is reduced to 938.4 μ g/g, and the range of decrease is 47.22%; This catalytically cracked gasoline is cut out cut more than 100 ℃, its sulphur content is up to 2800 μ g/g, at catalyzer loading amount and agent-oil ratio still for 5g and 2.5, temperature of reaction is to react under 466 ℃ the condition, and yield of gasoline is 93.8%, sulphur content is reduced to 925.9 μ g/g, decreases by 66.93%.With sulphur content is that another catalytically cracked gasoline of 891.6 μ g/g is that raw material reacts, be respectively at temperature, catalyzer loading amount and agent-oil ratio under the condition of 465 ℃, 5g and 2.5 and react, yield of gasoline is 98.7%, and sulphur content is reduced to 274.6 μ g/g, and the range of decrease is up to 69.20%.The sweetening effectiveness of catalyzer has obtained checking on fixed fluidized bed catalytic cracking reaction evaluating apparatus.With sulphur content is that 100 ℃ the catalytically cracked gasoline cut of being higher than of 2800 μ g/g is a raw material, in the catalyzer loading amount is that 250g, oil inlet quantity are that 55g, temperature are to react under 440 ℃ the condition, the content of sulfur in gasoline that obtains is 1290 μ g/g, and the sulphur content range of decrease is 53.93%.In the reaction product, the yield of C1～C2 is 0.305%, and C3～C4 yield is 3.76%, and coke is 0.95%, and other is a gasoline.Wherein dry gas and coke are the cracking loss, and the two amounts to 1.26%.2. for diesel refining:
The catalytic cracking and desulfurizing catalyst of preparing that is used for diesel refining proves guaranteeing to have tangible sweetening effectiveness under the situation that liquid is received through fixed fluidized bed evaluation:
Fixed fluidized bed evaluation result shows, is that 460 ℃, catalyzer loading amount are that 250g, agent-oil ratio are under 5 the situation in temperature of reaction, sulphur content be the straight-run diesel oil of 2800 μ g/g (Ignition Lamp Method is measured, down with) after reaction, diesel yield
Be 94%, sulphur content is reduced to 1200 μ g/g, and the range of decrease is 57%.Improve temperature of reaction, though diesel yield can descend, sulphur content can further reduce.The gas that cracking is generated and catalyzer decide the charcoal result shows, the insufficient total amount 2% of dry gas and coke illustrates that cracking loses less.
As seen, the diesel oil catalytic cracking and desulfurizing catalyst significant desulfurization effect of development, under suitable reaction conditions, desulfurization degree is more than 50%, and cracking selectivity height, and the cracking loss is little.
The above results proves absolutely, the significant desulfurization effect of the catalytic cracking and desulfurizing catalyst that is used for refining light oil products of the present invention's preparation, and under suitable reaction conditions, desulfurization degree is more than 50%, even near 70%; And to the cracking selectivity height of sulfide, the oil product loss is little.
Claims (5)
1. the catalytic cracking and desulfurizing catalyst that is used for refining light oil products.It mainly be with the dipping rare earth element the stronger molecular sieve of acidity be active ingredient, be carrier with metal oxide, composite oxide of metal or the complex oxide that sulfide is had stronger selection adsorptivity effect.Sulfide is had stronger adsorbing carrier work in coordination with the sulfide in the selective cracking light-end products mutually with active ingredient with stronger cracking and hydrogen transfer activity.It is characterized in that by adopting dipping, roasting method that the form of rare earth with oxide compound is dispersed on the acid zeolite, the metal hydroxides that zeolite and co-precipitation are made carries out uniform mixing in proportion again, and then by washing, drying and roasting, pulverizing gets final product on request.
2. the catalytic cracking and desulfurizing catalyst that is used for refining light oil products according to claim 1, the process that it is characterized in that described pickling process and roasting method is to flood 0.1～30% (quality on acid zeolite, rare earth down together), 60～200 ℃ of dryings after 5～10 hours, 200～700 ℃ of roastings 0.5～10 hour, rare earth is dispersed on the zeolite with the form of oxide compound again.
3. the catalytic cracking and desulfurizing catalyst that is used for refining light oil products according to claim 1, the preparation process that it is characterized in that described special metal hydroxides is will have the soluble salt of metal of strong adsorptive power to sulfide and the soluble salt of rare earth is dissolved in the distilled water, be mixed with concentration at 0.5～30% solution, the KOH with 0.1～15%, NaOH or NH
3H
2The aqueous solution of O is made precipitation agent, in whipping process, be added drop-wise in the metal salt solution, to pH value be 7～9, metal-salt is changed into fully the precipitation of hydroxide thing of metal.
4. according to claim 1 or the 3 described catalytic cracking and desulfurizing catalysts that are used for refining light oil products, it is characterized in that it is by 2～50% joining in the throw out of metal hydroxides of being prepared into finished catalyst with the zeolite of dipping rare earth that described zeolite that will flood rare earth and special metal hydroxides carry out mixed uniformly process in proportion, fully stir, zeolite and throw out are mixed, left standstill then 5～10 hours.
5. the catalytic cracking and desulfurizing catalyst that is used for refining light oil products according to claim 1, it is characterized in that described washing, drying and the process of pulverizing on request are after the zeolite that will mix, leave standstill and sedimentary mixture stir 10～60 minutes once more, carry out suction filtration, and with an amount of distilled water wash 3～5 times.The gained filter cake is 50～200 ℃ of dryings 10～24 hours, and roasting 1～24 hour in 300～900 ℃ retort furnace is then pulverized and sieved.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7485595B2 (en) | 2003-05-30 | 2009-02-03 | China Petroleum & Chemical Corporation | Molecular sieve-containing catalyst for cracking hydrocarbons and a method for preparing the same |
| CN101966470A (en) * | 2010-09-25 | 2011-02-09 | 东华大学 | Rare-earth desulfurization catalyst and preparation method thereof |
| CN101190416B (en) * | 2006-12-01 | 2011-06-15 | 石大卓越科技股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN102430412A (en) * | 2011-09-16 | 2012-05-02 | 中国海洋石油总公司 | Method for preparing desulfurizer capable of absorbing catalytic cracking gas at high selection |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5376608A (en) * | 1993-01-27 | 1994-12-27 | W. R. Grace & Co.-Conn. | Sulfur reduction in FCC gasoline |
| CN1054151C (en) * | 1996-12-10 | 2000-07-05 | 中国石油化工总公司 | Catalyst for hydrodesulfurization fraction oil |
-
2000
- 2000-07-11 CN CN00120711A patent/CN1102640C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7485595B2 (en) | 2003-05-30 | 2009-02-03 | China Petroleum & Chemical Corporation | Molecular sieve-containing catalyst for cracking hydrocarbons and a method for preparing the same |
| CN101190416B (en) * | 2006-12-01 | 2011-06-15 | 石大卓越科技股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN101966470A (en) * | 2010-09-25 | 2011-02-09 | 东华大学 | Rare-earth desulfurization catalyst and preparation method thereof |
| CN102430412A (en) * | 2011-09-16 | 2012-05-02 | 中国海洋石油总公司 | Method for preparing desulfurizer capable of absorbing catalytic cracking gas at high selection |
| CN102430412B (en) * | 2011-09-16 | 2013-07-31 | 中国海洋石油总公司 | Method for preparing desulfurizer capable of absorbing catalytic cracking gas at high selection |
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