CN102921289B - Method for preparation of catalytic cracking flue gas sulfur transfer agent active constituent element - Google Patents
Method for preparation of catalytic cracking flue gas sulfur transfer agent active constituent element Download PDFInfo
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- CN102921289B CN102921289B CN201210442531.7A CN201210442531A CN102921289B CN 102921289 B CN102921289 B CN 102921289B CN 201210442531 A CN201210442531 A CN 201210442531A CN 102921289 B CN102921289 B CN 102921289B
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Abstract
The invention discloses a method for preparation of a catalytic cracking flue gas sulfur transfer agent active constituent element in a citric acid complexation method, and belongs to the technical field of flue gas desulfurization in the petroleum refining industry. According to the method for the preparation of the catalytic cracking flue gas sulfur transfer agent active constituent element, the citric acid complexation method is adopted, and then the catalytic cracking flue gas sulfur transfer agent active constituent element obtained after high-temperature roasting has the characteristics of being high in dispersion, loose and multi-hole, is used for reducing the emission of SOX pollutants in flue gas regenerated in the catalytic cracking process, and has high SOX adsorption capacity and a high oxidation sulfur absorption rate. Compared with the prior art, the method for the preparation of the catalytic cracking flue gas sulfur transfer agent active constituent element is simple, and excellent in effect.
Description
Technical field
The invention belongs to petroleum refining industry's flue gas desulfurization technique field, particularly a kind of citric acid complex method is prepared the method for catalytic cracking fuel gas sulfur transfer additive active component.
Background technology
Fluid catalytic cracking (FCC) is to produce gasoline in current petroleum industry, the important processing technology of diesel oil and liquefied petroleum gas.Conventionally, in FCC feedstock oil, approximately 45% ~ 55% sulphur changes into H in reactor
2s, enters dry gas; 35% ~ 45% enters into fluid product; 5% ~ 10% is deposited on catalyst surface, is brought in regenerator with coke, generates SO in regenerative process
x(be generally 90% SO
2with 10% SO
3mixture), enter atmosphere with flue gas.SO
xnot only etching apparatus, and directly caused the formation of acid rain, serious environment pollution, harm humans health.Along with the increase of imported high sulfur crude oil processing capacity, and the continuous increase of residual oil and mink cell focus ratio in catalytically cracked material, catalytic cracking fuel gas sulfur emissions of oxides is day by day serious, and environmental regulation increasingly stringent, therefore effectively controls regeneration fume from catalytic cracking SO
xdischarge very urgent.
At present, reduce SO in FCC regenerated flue gas
xthe technology of discharge mainly contains following three kinds: the one, select low-sulfur raw material oil, and the 2nd, flue gas washing, the 3rd, use sulfur transfer additive.First two method is not only invested greatly, and operating cost is high, and raw material sources also can more and more be restricted, and flue gas washing technology also can produce large amount of sewage in addition, brings new environmental protection pressure.For the actual conditions of oil plant, by current national environmental protection rules to SO
xdischarge standard requirement, considers environmental protection, economy, technology each side factor, and Oil Refining Industry generally believes and under existence conditions, adopts sulfur transferring assistant method to reduce SO
xdischarge is the most reasonable approach that meets oil plant actual conditions.
Since the mid-80, some external oil companies concentrate on the research of multicomponent sulfur transfer additive, and wherein most study is magnesium aluminate spinel series, find that research mixes the spinelle MgAl of solid solution
2o
4the desulfurization performance of-MgO is very good, also can effective regeneration (USP4469589, USP4963520, USP5057205 etc.).
USP4476245 has announced the preparation method of the spinel composition of a kind of alkaline including earth metal and aluminium: (1) exists a kind of acid solution and a kind of aluminium wherein aqueous slkali containing at least one al composition with anionic form mixes, (2) by the product obtaining and the aqueous solution that contains at least one alkaline earth metal component, the precipitation that (3) roasting obtains.The method also further contacts described precipitation or spinel composition with at least one additional metal component, can under oxidizing condition, promote SO the load of said composition kind is a certain amount of
2be oxidized to SO
3additional metal component, described additional metal is selected from I B, II B, IV B, VI A, VI B, VII A and VIII family metal component, rare earth metal, vanadium, iron, tin, antimony and their mixture.
USP028023 disclose a kind of by first by MgO and Al
2o
3prepare houghite compound presoma and prepare the method for sulfur transfer additive.The method is prepared as follows: preparation comprises the reactant mixture that contains Mg compound and contain Al compound, thereby forms the chemicals of houghite or the compound of non-hydrotalcite, then calcines with rehydrated.
USP5288675 discloses a kind of MgO, La
2o
3, Al
2o
3base sulfur transfer additive preparation method.First prepare lanthanum aluminium hydrous oxide by coprecipitation, after aging and magnesia slurries mix, calcining, then dipping is containing the solution of cerium or vanadium, after 450-750 ℃ of roasting, obtain the sulfur transfer additive that absorption property is good.
And domestic in the last few years sulfur transfer additive research has also been obtained to good progress.CN101905118 discloses a kind of preparation method of catalytic cracking fuel gas sulfur transfer additive active component: the mixing salt solution that (1) is mixed with sub-to solubility magnesium salts, aluminum soluble salt and solubility cerium salt; (2) mixing salt solution of aqueous slkali and step 1 is joined to hybrid reaction in full back-mixing liquid film reactor simultaneously arrive slurries, wherein alkali lye adjusting pH value is 8.5-13; (3) slurries heating crystallization under strong agitation is made to houghite presoma, filtration washing is to neutral.(4) product of roasting, makes the good active component of sulphur transfer performance.
CN101905117 discloses a kind of preparation method of catalytic cracking fuel gas sulfur transfer additive active component: (1) is by hydrotalcite or at high temperature roasting of houghite; (2) product after roasting is made after slurries, added some active metal soluble-salts, at 50-150 ℃ of constant temperature 1-24h, filtration washing; (3) high-temperature roasting product, makes the good active component of sulphur transfer performance.
Can find out from above-mentioned patent, preparation method's complexity of sulfur transfer additive at present, and because adopting infusion process more, active component adds in method, decentralization is not high, and may cause duct to stop up, unavoidable meeting impacts the suction sulphur performance of sulfur transfer additive, causes inhaling sulphur speed and inhales sulfur content and reduce.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of catalytic cracking fuel gas sulfur transfer additive active component.
The present invention adopts citric acid complex method, and the catalytic cracking fuel gas sulfur transfer additive active component then obtaining through high-temperature roasting has high dispersive, and loose porous characteristic, so there is high SO
xsulphur speed is inhaled in adsorption capacity and oxidation.
The preparation method's of catalytic cracking fuel gas sulfur transfer additive active component of the present invention concrete preparation process is as follows:
1) mixed solution of preparation solubility magnesium salts and aluminum soluble salt, magnesium ion and aluminum ions mol ratio are 2-5, then add the sub-cerium salt of solubility or other soluble-salts, are stirred to completely and dissolve; Take catalytic cracking fuel gas sulfur transfer additive active component butt as benchmark, cerium oxide quality percentage composition is 0-20%, and is not 0, and other soluble-salts are 0-20% by the quality percentage composition of oxide, and is not 0;
2) citric acid is added in the mixed solution of step 1) preparation, in the molal quantity of citric acid and mixed solution, the ratio of metal ion molal quantity sum is 1.0-4.0, stirs aging 0.1-2h at 0-100 ℃;
3) continue heating at 80-500 ℃ until solution becomes gel, gel, through 300-1000 ℃ of high-temperature roasting 1-6h, is obtained to catalytic cracking fuel gas sulfur transfer additive active component.
Other soluble-salts described in step 1) are one or more in the soluble-salt of V, Cr, Mn, Fe, Co, Cu, Zn, rare earth metal and noble metal.
Solubility magnesium salts described in step 1) is magnesium chloride, magnesium nitrate or magnesium acetate; Aluminum soluble salt is aluminium chloride, aluminum nitrate or aluminum acetate; The sub-cerium salt of solubility is the sub-cerium of cerous nitrate, cerous chlorate or acetic acid.
Catalytic cracking fuel gas sulfur transfer additive active component prepared by the present invention has high dispersive, and loose porous characteristic, for reducing catalytic cracking process regenerated flue gas SO
xdisposal of pollutants, has high SO
xsulphur speed is inhaled in adsorption capacity and oxidation, and compared with prior art, method of the present invention is simple, effect excellence.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the catalytic cracking fuel gas sulfur transfer additive active component prepared of embodiment 1.
Fig. 2 is that the sulfur transfer additive active component of the catalytic cracking fuel gas sulfur transfer additive active component prepared of embodiment 1 and comparative example is inhaled sulphur curve comparison figure.
The specific embodiment
Below by specific embodiment, the present invention will be described in detail, and all examples operate according to operating procedure of the present invention.
Reagent in following examples is all purchased from Beijing Chemical Plant.
Embodiment 1
Take respectively 61.54g Mg (NO
3)
26H
2o, 30.01g Al (NO
3)
39H
2o, 3.00gCe (NO
3)
36H
2o is dissolved in 250ml water and is made into mixing salt solution, takes 90.44g C
6h
8o
7h
2o(monohydrate potassium) join in mixing salt solution, at 50 ℃, stir lower aging 0.5h, at 150 ℃, be heated into gel, by gel at 700 ℃ in Muffle furnace roasting 2h obtain sulfur transfer additive active component S1.
Embodiment 2
Take respectively 61.54g Mg (NO
3)
26H
2o, 22.51g Al (NO
3)
39H
2o, 1.28gCe (NO
3)
36H
2o, 3.00g Fe (NO
3)
39H
2o is dissolved in 250ml water and is made into mixing salt solution, takes 128.77g C
6h
8o
7h
2o(monohydrate potassium) join in mixing salt solution, at 80 ℃, stir lower aging 0.5h, at 300 ℃, be heated into gel, by gel at 700 ℃ in Muffle furnace roasting 4h obtain sulfur transfer additive active component S2.
Embodiment 3
Take respectively 48.79g MgCl
26H
2o, 22.51g Al (NO
3)
39H
2o, 1.67gCu (NO
3)
23H
2o, is dissolved in 250ml water and is made into mixing salt solution, takes 97.74g C
6h
8o
7h
2o(monohydrate potassium) join in mixing salt solution, at room temperature, stir lower aging 0.5h, at 200 ℃, be heated into gel, by gel at 750 ℃ in Muffle furnace roasting 2h obtain sulfur transfer additive active component S3.
Embodiment 4
Take respectively 36.59g MgCl
26H
2o, 14.48g AlCl
36H
2o, 2.21g FeCl
36H
2o, is dissolved in 250ml water and is made into mixing salt solution, takes 68.78g C
6h
8o
7h
2o(monohydrate potassium) join in mixing salt solution, at room temperature, stir lower aging 50min, at 300 ℃, be heated into gel, by gel at 750 ℃ in Muffle furnace roasting 4h obtain sulfur transfer additive active component S4.
Embodiment 5
Take respectively 46.15g Mg (NO
3)
26H
2o, 22.51g Al (NO
3)
39H
2o, 1.17g CeCl
37H
2o is dissolved in 250ml water and is made into mixing salt solution, takes 76.63g C
6h
8o
7h
2o(monohydrate potassium) join in mixing salt solution, at room temperature, stir lower aging 2h, at 400 ℃, be heated into gel, by gel at 750 ℃ in Muffle furnace roasting 3h obtain sulfur transfer additive active component S5.
Comparative example:
According to the method in WO2005102514, first prepare magnalium hydrotalcite presoma, take respectively 61.54gMg (NO
3)
26H
2o, 30.01g Al (NO
3)
39H
2o is dissolved in 250mL water and is mixed with mixing salt solution; Take respectively 12.80g NaOH and 16.96g Na
2cO
3be dissolved in 250mL water and be mixed with mixed ammonium/alkali solutions.Adopt two methods of dripping, control rate of addition, reacted mixed serum is strong agitation at 100 ℃, backflow crystallization 8h, by the material after crystallization after filtration, wash to pH value for neutral and dry after obtain hydrotalcite precursor, by product and 3.00g Ce (NO
3)
36H
2o makes slurries in water, with ammoniacal liquor, PH is transferred to 9, mixes, slurries are placed at 110 ℃ subsequently at once dry in convection oven, after by dried powder 700 ℃ of roastings 2 hours, obtain sulfur transfer additive active component R1.
Sulfur transfer additive suction sulphur appreciation condition and evaluation result are as follows:
The reaction condition of simulation FCC apparatus regenerator, utilizes TG-DTA analyzer to evaluate the suction sulphur performance of sulfur transfer additive.First stage, taking 15mg(butt) sample of left and right puts into the alumina crucible of hot assay balance, and passing into nitrogen flow is 70ml/min, is warming up to 732 ℃ with the speed of 20 ℃/min; Second stage (the sulphur stage is inhaled in oxidation), passes into gaseous mixture 2% (V) SO
2, 6% (V) O
2, 92% (V) N
2gaseous mixture, total gas flow rate is 70ml/min, 732 ℃ of constant temperature certain hours are so that sulfur content is inhaled in oxidation reaches capacity.
Sulfur content=(saturated oxidation-adsorption SO is inhaled in saturated oxidation
2the quality of the quality-sulfur transfer additive of rear sulfur transfer additive) quality of/sulfur transfer additive
In formula, sulfur transfer additive quality is butt quality.
The oxidation of each sample is inhaled sulphur Evaluation results in table 1.
Sulphur contrast table is inhaled in the each sample oxidation of table 1
Claims (2)
1. a preparation method for catalytic cracking fuel gas sulfur transfer additive active component, is characterized in that, its concrete preparation process is as follows:
1) mixed solution of preparation solubility magnesium salts and aluminum soluble salt, magnesium ion and aluminum ions mol ratio are 2-5, then add the sub-cerium salt of solubility or other soluble-salts, are stirred to completely and dissolve; Take catalytic cracking fuel gas sulfur transfer additive active component butt as benchmark, cerium oxide quality percentage composition is 0-20%, and is not 0, and other soluble-salts are 0-20% by the quality percentage composition of oxide, and is not 0;
2) citric acid is added in the mixed solution of step 1) preparation, in the molal quantity of citric acid and mixed solution, the ratio of metal ion molal quantity sum is 1.0-4.0, stirs aging 0.1-2h at 0-100 ℃;
3) continue heating at 80-500 ℃ until solution becomes gel, gel, through 700-750 ℃ of high-temperature roasting 1-6h, is obtained to catalytic cracking fuel gas sulfur transfer additive active component;
Other soluble-salts described in step 1) are copper nitrate or iron chloride.
2. preparation method according to claim 1, is characterized in that, the solubility magnesium salts described in step 1) is magnesium chloride, magnesium nitrate or magnesium acetate; Aluminum soluble salt is aluminium chloride, aluminum nitrate or aluminum acetate; The sub-cerium salt of solubility is the sub-cerium of cerous nitrate, cerous chlorate or acetic acid.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101185829A (en) * | 2007-09-25 | 2008-05-28 | 华东师范大学 | Catalytic cracking regeneration flue gas sulphur transfer agent and preparation method thereof |
| CN101905117A (en) * | 2010-06-29 | 2010-12-08 | 北京化工大学 | Preparation method of catalytic cracking fuel gas sulfur transfer additive active component |
| CN101905118A (en) * | 2010-06-29 | 2010-12-08 | 北京化工大学 | Preparation method for high-efficiency sulfur transfer agent active component in catalytic cracking flume |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101185829A (en) * | 2007-09-25 | 2008-05-28 | 华东师范大学 | Catalytic cracking regeneration flue gas sulphur transfer agent and preparation method thereof |
| CN101905117A (en) * | 2010-06-29 | 2010-12-08 | 北京化工大学 | Preparation method of catalytic cracking fuel gas sulfur transfer additive active component |
| CN101905118A (en) * | 2010-06-29 | 2010-12-08 | 北京化工大学 | Preparation method for high-efficiency sulfur transfer agent active component in catalytic cracking flume |
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