CN103028391A - Catalytic cracking material for reducing sulfur content of gasoline and preparation method thereof - Google Patents
Catalytic cracking material for reducing sulfur content of gasoline and preparation method thereof Download PDFInfo
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- CN103028391A CN103028391A CN201210578595XA CN201210578595A CN103028391A CN 103028391 A CN103028391 A CN 103028391A CN 201210578595X A CN201210578595X A CN 201210578595XA CN 201210578595 A CN201210578595 A CN 201210578595A CN 103028391 A CN103028391 A CN 103028391A
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- vanadium
- catalytic cracking
- gasoline
- mullite
- kaolin
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Abstract
The invention discloses a catalytic cracking material for reducing sulfur content of gasoline. The material comprises a vanadium-bearing mullite material, and can further comprise one or more rare earth metal oxides. The vanadium-bearing mullite material is prepared by introducing a vanadium-bearing compound into kaolin, roasting at a relatively lower temperature and conducting phase change reaction. A rare earth compound is added by an impregnation or coprecipitation method. The catalytic cracking material can serve as a catalytic cracking assistant to be used with the existing catalytic cracking catalyst after spray granulation forming, or serve as a carrier component for preparing a catalytic cracking catalyst having a sulfur reduction function for the gasoline. Vanadium in the catalytic cracking material is fixed in a mullite crystalline phase, so that the catalytic cracking material has a good effect on sulfur reduction, and a structure of a catalyst molecular sieve cannot be damaged.
Description
Technical field
The present invention relates in a kind of catalytic cracking process material that reduces content of sulfur in gasoline and preparation method thereof, further say a kind of have reduce the sulfur content of catalytic cracking gasoline function contain vanadium mullite material and preparation method thereof.
Background technology
China unleaded gasoline for vehicle national standard (GB17930-1999) requires content of sulfur in gasoline ≯ 800 μ g/g, further requires sulfur content ≯ 500 μ g/g in 2005, and Beijing, Shanghai and Guangzhou further require sulfur content ≯ 150 μ g/g.And China's catalytic cracking (FCC) gasoline accounts for more than 80% of gasoline product total amount, and approximately 90% sulphur is from FCC gasoline in the gasoline product, and therefore, the sulfur content that reduces FCC gasoline becomes the key of producing low-sulfur gasoline up to standard.
Reduce the sulfur content of FCC gasoline, can adopt the preliminary treatment of FCC raw material, in the FCC process, use the sulfur content that suitable catalyst or auxiliary agent directly reduce FCC gasoline, the methods such as post processing of FCC gasoline products.These methods may be used alone, can also be used in combination.The FCC raw material is added hydrogen pretreatment, can reduce simultaneously the sulfur content of FCC gasoline and fraction oil, but the operating condition of hydrogenation is harsh, processing cost is higher, and octane number can reduce because of olefin saturated.Using sulfur-reducing material in FCC apparatus, directly reduce content of sulfur in gasoline such as catalyst or auxiliary agent, do not need the additional investment apparatus for establishing, do not affect distribution and the quality of cracked product, is a kind of method of cost-effective reduction FCC content of sulfur in gasoline.
Disclose a kind of composition in the US Patent No. 6482315, comprise a large amount of vanadium of the upper load of the inorganic oxide (preferential oxidation aluminium) that is selected from aluminium oxide, silica, clay and its mixture (5～10 heavy %).During load 2%, realize gasoline sulfur-reducing 33%.Yet, directly adopt inorganic oxide as the carrier of load vanadium, can't be effectively fixing vanadium, these vanadium can generate flowable low-melting compound and transfer to molecular sieve inside under the high temperature regeneration condition of catalytic cracking process, in thermal and hydric environment, form vanadic acid, thereby saboteur's sieve reduces the FCC catalyst activity.
CN1974726 discloses a kind of desulphurization catalyst, contains with V in the microballoon that is comprised of zeolite and porous inorganic oxide matrix
2O
5Meter also preferably contains antimony at the average grain diameter of the 0.3～3wt% particle shape vanadium oxide at 0.1～10 μ m in the microballoon, think that antimony may generate SbVO with the part vanadium
4, Sb
2VO
5, Sb
0.9V
0.1O
4Deng compound, suppress the dehydrogenation reaction that vanadium causes.Yet, although this particle shape vanadium oxide is high with the affinity of sulfide, the vanadium oxide surface is exposed to high temperature hydro-thermal regenerative environ-ment lower time, still has flowable, be easy to the molecular sieve diffusion in the FCC catalyst, generate vanadic acid and saboteur's sieve structure in the thermal and hydric environment.Antimony may have certain capture ability to vanadium, but toxicity is larger.
CN1261618A and CN1281887A disclose a kind of desulphurization catalyst composition that reduces liquid crackate sulfur content in the catalytic cracking process, comprise a kind of porous molecular screen, preferential oxidation attitude vanadium metal is present in molecular sieve pore passage inside, and the amount of vanadium metal is 0.2～5% of molecular sieve weight.But ins and outs mesolite molecular sieve content is up to 50%, and this has larger adverse effect to catalyst strength and cost.And, in catalyst reaction and high temperature hydro-thermal regenerative process, inevitable some molecular sieve structure can cave in, destroy, thereby with the vanadium in its duct " release " out, further form again the destruction of vanadic acid aggravation molecular sieve, therefore, this method of introducing vanadium metal in molecular sieve can make the equilibrium activity of catalyst reduce.
CN1754941 disclose contain v element and the second metallic element in a kind of skeleton structure molecular sieve as the desulfurization constituent element, such as the CeVAPO-5 molecular sieve, desulfurization degree can reach more than 42%, but this preparation cost that contains the vanadium molecular sieve is higher.
CN1232803A discloses a kind of method of low temperature mullite synthesizing, and kaolin and phase transformation auxiliary agent are mixed, and 600～900 ℃ of roasting rear sections generate mullite, obtain the higher mullite of purity with the bronsted lowry acids and bases bronsted lowry extracting at last.Although the phase transformation auxiliary agent comprises vanadic anhydride, aphthenic acids vanadium, ammonium metavanadate etc. and contains the vanadium material, but addition (in metallic element) is lower, be no more than 7% of kaolin weight, and the mullite that generates is through the degree of depth extracting of follow-up bronsted lowry acids and bases bronsted lowry, mullite purity improves greatly, but the basic extracting of vanadium wherein totally, therefore do not have the function that reduces the catalytic cracking process content of sulfur in gasoline.
Summary of the invention
The objective of the invention is to overcome the existing shortcoming that contains vanadium catalytically cracked gasoline sulfur prodegradant or catalyst, prevent that namely contained vanadium from generating flowable low-melting compound in catalytic cracking reaction and high temperature hydro-thermal regenerative process, " release " out and generate vanadic acid from the structure position, saboteur's sieve structure reduces catalyst activity.
In order to solve the problems of the technologies described above, the invention provides a kind of catalytic cracking material that reduces content of sulfur in gasoline, this material comprises a kind of mullite material that contains vanadium, take the gross weight of material as calculating benchmark, contains with V
2O
5The vanadium of 1～35 % by weight of meter and the mullite of 10～99 % by weight.Preferably contain with V
2O
5The vanadium of meter 5～25 % by weight.
Optionally, also comprise the rare-earth oxide of 1～10 % by weight in described a kind of catalytic cracking material that reduces content of sulfur in gasoline, rare earth metal is selected from one or more in lanthanum, cerium, praseodymium, neodymium, samarium, europium, the gadolinium.
The preparation method who the invention provides the catalytic cracking material of described reduction content of sulfur in gasoline comprises:
(1) mixes, filters with kaolin with the solution impregnation kaolin of vanadium-containing compound or with the solution of vanadium-containing compound;
(2) the resulting filter cake of step (1) is carried out drying, roasting makes the mullite material that contains vanadium, 800～1300 ℃ of sintering temperatures, roasting time 0.5～10 hour.Preferred 900～1100 ℃ of sintering temperature.
Vanadium-containing compound among the described preparation method is selected from one or more in ammonium metavanadate, vanadic sulfate, the oxalic acid vanadyl.Among the described preparation method, kaolin can be the microballoon of kaolin fine powder or the spray-dried moulding of kaolin.
Kaolin has hot phase transition property, usually need to just begin to have a small amount of mullite crystalline phase to generate greater than 1100 ℃ of roastings the time, and therefore power consumption is higher.Some phase transformation auxiliary agent can promote crystal transition, reduces phase transition temperature.Vanadium-containing compound among the preparation method of the present invention can be used as the phase transformation auxiliary agent that kaolinite forms mullite, thereby reduces sintering temperature.
That adopts that this preparation method obtains contains the vanadium mullite material, and vanadium wherein is fixed in the mullite crystalline phase.For fear of there being the vanadium species of effectively not fixed, such as V
2O
5, can adopt rare oxalic acid solution that prepared material is washed and removes.
Contain when comprising rare-earth oxide in the vanadium mullite material when of the present invention, the introducing of rare-earth oxide can be adopted several different methods commonly used at present, such as infusion process, and coprecipitation etc.Infusion process: the solution impregnation of rare earth compound is contained the vanadium mullite material, then dry, roasting.Coprecipitation: with rare earth metal salt, mix such as the solution of rare earth chloride, solution and the kaolin of vanadium-containing compound, regulate the pH value of mixture with ammoniacal liquor, make rare earth, vanadium and kaolin form coprecipitate, filter, with isolated drying precipitate, roasting, generation contains the vanadium mullite material, and wherein contains rare-earth oxide.Rare-earth oxide has the effect of catching vanadium, such as the vanadium in the catalytically cracked stock, can reduce vanadium to the pollution of catalyst, improves and falls the sulphur effect.
The catalytic cracking material of the reduction content of sulfur in gasoline described in the present invention can be used in combination as assistant for calalytic cracking and existing catalytic cracking catalyst after the moulding, perhaps for the preparation of the catalytic cracking catalyst with gasoline sulfur-reducing function.
Compared with prior art, the present invention has the following advantages:
Vanadium in the material of the present invention and mullite crystalline phase form special structure, mullite can be fixed on vanadium in the crystalline phase effectively, therefore, under the high temperature hydro-thermal regeneration condition of catalytic cracking, vanadium does not wherein have flowability, thereby can not pollute molecular sieve, thereby can effectively keep the higher activity of catalyst, simultaneously, contain and comprise a large amount of vanadium in the vanadium mullite material, can give full play to it and fall the sulphur ability.
The preparation method who contains the vanadium mullite material provided by the invention is simple, sintering temperature is lower.Usually, kaolin turns the brilliant temperature that forms a large amount of mullites and is approximately more than 1200 ℃, and vfanadium compound can be used as the phase transformation auxiliary agent, effectively reduces kaolin and turns the brilliant temperature that forms mullite.
The catalytic cracking material of reduction content of sulfur in gasoline provided by the invention both can directly adopt forming technique to be prepared into assistant for calalytic cracking, also can be used as the carrier material of preparation catalytic cracking catalyst, and it is convenient to use.
Description of drawings
Accompanying drawing is the XRD figure that contains the vanadium mullite material in the embodiment of the invention 1.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment, but therefore content constraints protection scope of the present invention of specific embodiment not.
Among the embodiment, the content of vanadium is with the X-ray fluorescence spectra quantitative analysis; Crystalline phase is with XRD determining; Content of sulfur in gasoline adopts the GC-FPD chromatographic determination.
Embodiment 1
The present embodiment prepares the described vanadium mullite material that contains.Get the 8g ammonium metavanadate, add the 2000mL deionized water, add oxalic acid to solid and dissolve fully, add the 600g Kaolin of Suzhou again, 85 ℃ flooded 6 hours, and 120 ℃ of dryings were ground 100 mesh sieves, and 1250 ℃ of roasting 1h prepare and contain the vanadium mullite material.This is contained the vanadium mullite material with rare oxalic acid solution washing 3 times, be washed till neutrality with deionized water, in 120 ℃ of dryings.The sample number into spectrum that obtains is V1.Content of vanadium in the X-ray fluorescence spectra analytic sample, and be scaled with V
2O
5Metering, the sample content of vanadium is 1.5%; XRD analysis sample crystalline phase, the XRD collection of illustrative plates of V1 is seen accompanying drawing, uses the characteristic peak of black round dot mark mullite among the figure; Measure and calculation mullite content wherein is 85%.
Embodiment 2
The present embodiment prepares the described vanadium mullite material that contains.Get the 35g ammonium metavanadate, add the 2000mL deionized water, adding oxalic acid to solid dissolves fully, add again 600g Kaolin of Suzhou atomized microball (take from Shanghai receive auxiliary agent Co., Ltd of section), 85 ℃ flooded 6 hours, 120 ℃ of dryings were ground 100 mesh sieves, and 950 ℃ of roasting 3h prepare and contain the vanadium mullite material.This is contained the vanadium mullite material with rare oxalic acid solution washing 3 times, be washed till neutrality with deionized water, in 120 ℃ of dryings.The sample number into spectrum that obtains is V2.Content of vanadium in the X-ray fluorescence spectra analytic sample, and be scaled with V
2O
5Metering, the sample content of vanadium is 7.2%; XRD analysis sample crystalline phase, the mullite content of measuring wherein is 68%.
Embodiment 3
The present embodiment prepares the described vanadium mullite material that contains.Get the 110g vanadic sulfate, add 300mL deionized water to solid and dissolve fully, add again the 600g Kaolin of Suzhou, 85 ℃, fully mix 6 hours, filter, filter cake ground 100 mesh sieves 120 ℃ of dryings, and 900 ℃ of roasting 5h prepare and contain the vanadium mullite material.This is contained the vanadium mullite material with rare oxalic acid solution washing 3 times, be washed till neutrality with deionized water, in 120 ℃ of dryings.The sample number into spectrum that obtains is V3.Content of vanadium in the X-ray fluorescence spectra analytic sample, and be scaled with V
2O
5Metering, the sample content of vanadium is 17%; XRD analysis sample crystalline phase, the mullite content of measuring wherein is 66%.
Embodiment 4
The present embodiment prepares the described vanadium mullite material that contains.Get 377g oxalic acid vanadyl, add the 350mL deionized water, adding oxalic acid to solid dissolves fully, add again 600g Kaolin of Suzhou atomized microball (take from Shanghai receive auxiliary agent Co., Ltd of section), 85 ℃, fully mix 6 hours, filter, filter cake ground 100 mesh sieves 120 ℃ of dryings, and 850 ℃ of roasting 9h prepare and contain the vanadium mullite material.This is contained the vanadium mullite material with rare oxalic acid solution washing 3 times, be washed till neutrality with deionized water, in 120 ℃ of dryings.The sample number into spectrum that obtains is V4.Content of vanadium in the X-ray fluorescence spectra analytic sample, and be scaled with V
2O
5Metering, the sample content of vanadium is 32%; XRD analysis sample crystalline phase, the mullite content of measuring wherein is 40%.
Embodiment 5
What the present embodiment preparation comprised rare-earth oxide contains the vanadium mullite material.Get respectively 3g, 10g, 16g rare earth chloride (rare earth Science and Technology Co., Ltd. of Inner Mongol Baogang), adding 400mL, pH are 3.5 acid water dissolving, add respectively again vanadium mullite material (V3) 80g among the embodiment 3, fully mix, then add respectively a certain amount of 1% weak aqua ammonia, stop to add during control pH to 9.Filter after mixing 1 hour, filter cake is 100 ℃ of dryings, and then at 680 ℃ of lower roasting 3h, the weight percentage of resulting sample middle rare earth metal oxide is respectively 1.6%, 5.5%, 8.8%, is numbered respectively V3-R1, V3-R2, V3-R3.
Embodiment 6
According to boehmite 20w%, aluminium colloidal sol 10w%, the vanadium mullite material that contains of embodiment 1,3,5 preparations is respectively 70w%, the spray-dried sulfur prodegradant of making.(Shanghai is received auxiliary agent Co., Ltd of section and is produced micro-activity 85 with the sulfur prodegradant that obtains and catalytic cracking catalyst FCA; Content of rare earth is with rare earth oxide RE
2O
3Meter is 6.8w%; Sodium content is with Na
2O meter is 0.25w%) in 12: 88 ratio physical mixed, under 800 ℃, 100w% water vapour, wore out 4 hours respectively.Take the huge port light diesel fuel as raw material, minisize reaction test (MAT) device evaluation micro-activity.Adopt small fixed flowing bed that the desulfurization performance of sample is estimated, cracking stock oil is provided by oil of SPC, 500 ℃ of reaction temperatures, and catalyst loading amount 143g, oil inlet quantity 22g the results are shown in Table 1.
Comparative Examples 1
Separately adopt small fixed flowing bed that the desulfurization performance of sample is estimated with catalytic cracking catalyst FCA aging sample that obtained in 4 hours under 800 ℃, 100w% water vapour as blank Comparative Examples, the results are shown in the table 1.
Table 1 micro-activity and desulfurization performance evaluation
Data can be found out from table 1, compare with the comparative catalyst, add the auxiliary agent that catalytic cracking material of the present invention makes after, can effectively reduce the sulfur content in the gasoline; When containing rare-earth oxide in the catalysis material, can further reduce the sulfur content in the gasoline, and along with the increase of rare earth metal oxidation content, desulfurization degree improves.The vanadium mullite material has good reduction content of sulfur in gasoline as assistant for calalytic cracking the function that contains of the present invention is described.
When the content of vanadium in the catalytic cracking material of the present invention changed, little on the micro-activity impact of catalyst, activity still maintained higher level, shows that vanadium effectively is fixed in the mullite crystalline phase, can not produce destruction to molecular sieve structure.
Embodiment 7
V3-R3 in the embodiment 5 is as carrier component, the catalyst that preparation has the gasoline sulfur-reducing function.With boehmite 200g, aluminium colloidal sol 100g, V3-R3 contain vanadium mullite material 84g, REHY molecular sieve (the Shanghai good chemical industry of celestial being Co., Ltd produces) 350g, and Kaolin of Suzhou 350g mixes, making beating, the spray-dried catalyst A of making.Fixed fluidized bed evaluation result sees Table 2.
Comparative Examples 2
The preparation method does not just contain V3-R3 in the carrier component with embodiment 7, and substitutes with kaolin.With boehmite 200g, aluminium colloidal sol 100g, REHY molecular sieve (Shanghai receive auxiliary agent Co., Ltd of section produce) 350g, Kaolin of Suzhou 462g mix, making beating, the spray-dried catalyst B of making.Fixed fluidized bed evaluation result sees Table 2.Light oil yield is the weight percentage sum of the rear gasoline of reaction and diesel oil in the table 2; It is the weight percentage sum of gasoline, diesel oil and liquefied gas that total liquid is received; Conversion ratio refers to the weight percentage sum of dry gas, liquefied gas, gasoline, diesel oil and coke in the product distribution.
The evaluation result of table 2 catalyst
Can be found out by table 2 data, compare with comparative catalyst B, when containing the vanadium mullite material as the carrier component of catalyst, catalyst A demonstrates the function of good reduction content of sulfur in gasoline with of the present invention, and product distributes without significant change.
Claims (7)
1. catalytic cracking material that reduces content of sulfur in gasoline, this material comprises a kind of mullite material that contains vanadium, take the gross weight of material as calculating benchmark, contains with V
2O
5The vanadium of 1～35 % by weight of meter, the mullite of 10～99 % by weight.
2. catalytic cracking material according to claim 1, it is characterized in that, also comprise the rare-earth oxide of 1～10 % by weight in described a kind of catalytic cracking material that reduces content of sulfur in gasoline, rare earth metal is selected from one or more in lanthanum, cerium, praseodymium, neodymium, samarium, europium, the gadolinium.
3. catalytic cracking material according to claim 1 is characterized in that, contains with V in the described catalytic cracking material
2O
5The vanadium of 5～25 % by weight of meter.
4. the preparation method of the catalytic cracking material of the described reduction content of sulfur in gasoline of claim 1 comprises:
(1) mixes, filters with kaolin with the solution impregnation kaolin of vanadium-containing compound or with the solution of vanadium-containing compound;
(2) the resulting filter cake of step (1) is carried out drying, roasting makes the mullite material that contains vanadium, 800～1300 ℃ of sintering temperatures, roasting time 0.5～10 hour.
5. according to preparation method claimed in claim 4, it is characterized in that, described vanadium-containing compound is selected from one or more in ammonium metavanadate, vanadic sulfate, the oxalic acid vanadyl.
6. according to preparation method claimed in claim 4, it is characterized in that, the sintering temperature that described generation contains the vanadium mullite material is 900～1100 ℃.
7. according to preparation method claimed in claim 4, it is characterized in that, described kaolin is the microballoon of kaolin fine powder or the spray-dried moulding of kaolin.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111908485A (en) * | 2020-07-01 | 2020-11-10 | 湖南聚力催化剂股份有限公司 | Preparation method of Y-type molecular sieve |
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