CN102921289A - 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 PDF

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CN102921289A
CN102921289A CN2012104425317A CN201210442531A CN102921289A CN 102921289 A CN102921289 A CN 102921289A CN 2012104425317 A CN2012104425317 A CN 2012104425317A CN 201210442531 A CN201210442531 A CN 201210442531A CN 102921289 A CN102921289 A CN 102921289A
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preparation
catalytic cracking
sulfur transfer
flue gas
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CN102921289B (en
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孔颉琛
宋家庆
徐向宇
霍志萍
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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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

A kind of preparation method of catalytic cracking fuel gas sulfur transfer additive active component
Technical field
The invention belongs to petroleum refining industry flue gas desulfurization technique field, particularly a kind of citric acid complex method prepares the method for catalytic cracking fuel gas sulfur transfer additive active component.
Background technology
Fluid catalytic cracking (FCC) is to produce gasoline in the current petroleum industry, the important processing technology of diesel oil and liquefied petroleum gas.Usually, about 45% ~ 55% sulphur changes into H in the FCC feedstock oil in reactor 2S enters dry gas; 35% ~ 45% enters into fluid product; 5% ~ 10% is deposited on catalyst surface, is brought in the regenerator with coke, generates SO in regenerative process X(be generally 90% SO 2With 10% SO 3Mixture), enter atmosphere with flue gas.SO XEtching apparatus not only, and directly caused the formation of acid rain, serious environment pollution, harm humans is healthy.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 the catalytically cracked material, the catalytic cracking fuel gas sulfur emissions of oxides is day by day serious, and the environmental regulation increasingly stringent, therefore effective control regeneration fume from catalytic cracking SO xDischarging very urgent.
At present, reduce SO in the FCC regenerated flue gas XThe technology of discharging 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.Front two kinds of methods are not only invested greatly, and operating cost is high, and raw material sources also can more and more be restricted, and the 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, press present national environmental protection rules to SO XThe discharge standard requirement considers environmental protection, economy, technology each side factor, and Oil Refining Industry generally believes and adopts the sulfur transferring assistant method to reduce SO under existence conditions XDischarging is the most reasonable approach that meets the 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, but also 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: mix a kind of acid solution and a kind of wherein aluminium (1) with the aqueous slkali that contains at least a al composition that anionic form exists, (2) with the product and the aqueous solution that contains at least a alkaline earth metal component, the precipitation that (3) roasting obtains that obtain.The method also further contacts described precipitation or spinel composition with at least a additional metal component, can promote SO under oxidizing condition in that the load of said composition kind is a certain amount of 2Be oxidized to SO 3The additional 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 discloses a kind of by first by MgO and Al 2O 3Prepare the method that the houghite compound presoma prepares sulfur transfer additive.The method prepares as follows: preparation comprises the reactant mixture that contains the Mg compound and contain the 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.Prepare lanthanum aluminium hydrous oxide with coprecipitation first, after aging, mix with the magnesia slurries, calcining, dipping contains the solution of cerium or vanadium again, afterwards 450-750 ℃ of roasting, obtains the good sulfur transfer additive of absorption property.
And domestic sulfur transfer additive research has also been obtained preferably made progress in the last few years.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 the inferior cerium salt of solubility magnesium salts, aluminum soluble salt and solubility; (2) mixing salt solution of aqueous slkali and step 1 is joined simultaneously in the full back-mixing liquid film reactor hybrid reaction to slurries, wherein to regulate pH value be 8.5-13 to alkali lye; (3) slurries heating crystallization under strong agitation is made the 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 with hydrotalcite or at high temperature roasting of houghite; (2) product after the roasting is made slurries after, add some reactive 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, the preparation method of sulfur transfer additive is complicated at present, and owing to adopting infusion process more, active component adds in the method, decentralization is not high, and may cause the duct to stop up, unavoidable meeting impacts the suction sulphur performance of sulfur transfer additive, causes inhaling sulphur speed and inhales the sulfur content reduction.
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 that then obtains through high-temperature roasting has high dispersive, and loose porous characteristic is 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 inferior cerium salt of solubility or other soluble-salts, are stirred to fully dissolving; Take the 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, the ratio of metal ion molal quantity sum is 1.0-4.0 in the molal quantity of citric acid and the mixed solution, the 0-100 ℃ of lower 0.1-2h that wears out that stirs;
3) 80-500 ℃ of lower the continuation heated until solution becomes gel, and gel through 300-1000 ℃ of high-temperature roasting 1-6h, is namely got catalytic cracking fuel gas sulfur transfer additive active component.
In the soluble-salt that described other soluble-salts of step 1) are V, Cr, Mn, Fe, Co, Cu, Zn, rare earth metal and noble metal one or more.
Solubility magnesium salts described in the step 1) is magnesium chloride, magnesium nitrate or magnesium acetate; Aluminum soluble salt is aluminium chloride, aluminum nitrate or aluminum acetate; The inferior cerium salt of solubility is the inferior cerium of cerous nitrate, cerous chlorate or acetic acid.
The catalytic cracking fuel gas sulfur transfer additive active component of the present invention's preparation has high dispersive, and loose porous characteristic is used 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, and effect is excellent.
Description of drawings
Fig. 1 is the XRD spectra of the catalytic cracking fuel gas sulfur transfer additive active component of embodiment 1 preparation.
Fig. 2 is that the catalytic cracking fuel gas sulfur transfer additive active component of embodiment 1 preparation and the sulfur transfer additive active component of Comparative Examples are inhaled sulphur curve comparison figure.
The specific embodiment
Below the present invention will be described in detail by specific embodiment, and all examples operate according to operating procedure of the present invention.
Reagent in following examples is all available from the Beijing Chemical Plant.
Embodiment 1
Take by weighing 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 by weighing 90.44g C 6H 8O 7H 2The O(monohydrate potassium) join in the mixing salt solution, under 50 ℃, stir lower aging 0.5h, under 150 ℃, be heated into gel, with gel under 700 ℃ in Muffle furnace roasting 2h obtain sulfur transfer additive active component S1.
Embodiment 2
Take by weighing 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 by weighing 128.77g C 6H 8O 7H 2The O(monohydrate potassium) join in the mixing salt solution, under 80 ℃, stir lower aging 0.5h, under 300 ℃, be heated into gel, with gel under 700 ℃ in Muffle furnace roasting 4h obtain sulfur transfer additive active component S2.
Embodiment 3
Take by weighing 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 by weighing 97.74g C 6H 8O 7H 2The O(monohydrate potassium) join in the mixing salt solution, at room temperature, stir lower aging 0.5h, under 200 ℃, be heated into gel, with gel under 750 ℃ in Muffle furnace roasting 2h obtain sulfur transfer additive active component S3.
Embodiment 4
Take by weighing 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 by weighing 68.78g C 6H 8O 7H 2The O(monohydrate potassium) join in the mixing salt solution, at room temperature, stir lower aging 50min, under 300 ℃, be heated into gel, with gel under 750 ℃ in Muffle furnace roasting 4h obtain sulfur transfer additive active component S4.
Embodiment 5
Take by weighing 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 by weighing 76.63g C 6H 8O 7H 2The O(monohydrate potassium) join in the mixing salt solution, at room temperature, stir lower aging 2h, under 400 ℃, be heated into gel, with gel under 750 ℃ in Muffle furnace roasting 3h obtain sulfur transfer additive active component S5.
Comparative Examples:
According to the method among the WO2005102514, prepare first the magnalium hydrotalcite presoma, take by weighing respectively 61.54gMg (NO 3) 26H 2O, 30.01g Al (NO 3) 39H 2O is dissolved in the 250mL water and is mixed with mixing salt solution; Take by weighing respectively 12.80g NaOH and 16.96g Na 2CO 3Be dissolved in the 250mL water and be mixed with mixed ammonium/alkali solutions.Adopt two methods of dripping, control rate of addition, reacted mixed serum be 100 ℃ of lower strong agitation, backflow crystallization 8h, with the material after the crystallization after filtration, wash to pH value and get hydrotalcite precursor after for neutral and drying, with 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 under 110 ℃ subsequently at once dry in convection oven, after with 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 the TG-DTA analyzer to estimate the suction sulphur performance of sulfur transfer additive.Phase I, take by weighing the 15mg(butt) about sample put into the alumina crucible of hot assay balance, 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
The sulfur transfer additive quality is the butt quality in the formula.
The oxidation of each sample is inhaled the sulphur Evaluation results and is seen Table 1.
The sulphur contrast table is inhaled in each sample oxidation of table 1
Figure BDA00002373023700061

Claims (3)

1. the preparation method of a 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 inferior cerium salt of solubility or other soluble-salts, are stirred to fully dissolving; Take the 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, the ratio of metal ion molal quantity sum is 1.0-4.0 in the molal quantity of citric acid and the mixed solution, the 0-100 ℃ of lower 0.1-2h that wears out that stirs;
3) 80-500 ℃ of lower the continuation heated until solution becomes gel, and gel through 300-1000 ℃ of high-temperature roasting 1-6h, is namely got catalytic cracking fuel gas sulfur transfer additive active component.
2. preparation method according to claim 1 is characterized in that, one or more in the soluble-salt that described other soluble-salts of step 1) are V, Cr, Mn, Fe, Co, Cu, Zn, rare earth metal and noble metal.
3. preparation method according to claim 1 and 2 is characterized in that, the solubility magnesium salts described in the step 1) is magnesium chloride, magnesium nitrate or magnesium acetate; Aluminum soluble salt is aluminium chloride, aluminum nitrate or aluminum acetate; The inferior cerium salt of solubility is the inferior cerium of cerous nitrate, cerous chlorate or acetic acid.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103861437A (en) * 2014-03-20 2014-06-18 中国石油大学(华东) Catalytic cracking flue gas sulfur transfer agent adopting mixed crystal phases as well as preparation method and application thereof
CN106178924A (en) * 2016-08-25 2016-12-07 金浦新材料股份有限公司 A kind of preparation method of catalytic cracking fuel gas sulfur transfer additive

Citations (3)

* Cited by examiner, † Cited by third party
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103861437A (en) * 2014-03-20 2014-06-18 中国石油大学(华东) Catalytic cracking flue gas sulfur transfer agent adopting mixed crystal phases as well as preparation method and application thereof
CN103861437B (en) * 2014-03-20 2016-03-30 中国石油大学(华东) Multiphase catalytic cracking fuel gas sulfur transfer additive prepared by secondary growth method and application
CN106178924A (en) * 2016-08-25 2016-12-07 金浦新材料股份有限公司 A kind of preparation method of catalytic cracking fuel gas sulfur transfer additive
CN106178924B (en) * 2016-08-25 2019-02-01 金浦新材料股份有限公司 A kind of preparation method of catalytic cracking fuel gas sulfur transfer additive

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