CN103861437A - Catalytic cracking flue gas sulfur transfer agent adopting mixed crystal phases as well as preparation method and application thereof - Google Patents
Catalytic cracking flue gas sulfur transfer agent adopting mixed crystal phases as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a catalytic cracking flue gas sulfur transfer agent adopting mixed crystal phases as well as a preparation method and application thereof. The sulfur transfer agent is prepared by using three mixed crystal phases including magnesium oxide, magnesium titanate and magnesium aluminate spinel as desulfurization carriers and desulfurization active centers, and loading metal oxides as redox accelerants by adopting a secondary growth method, wherein based on the total weight of the sulfur transfer agent, the mass percents of magnesium oxide, magnesium titanate, spinel and the metal oxides are respectively 1-50%, 1-90%, 1-90% and 5-50%. The sulfur transfer agent has the beneficial effects that a composite structure is formed by utilizing titanium-magnesium structure materials and a magnesium aluminate spinel material, thus greatly enhancing the desulfurization effect of the sulfur transfer agent and prolonging the service life of the sulfur transfer agent and expanding the composition range of the sulfur transfer agent.
Description
Technical field
The invention relates to catalytic cracking fuel gas sulfur transfer additive of a kind of multiphase and preparation method thereof and application.
Background technology
Catalytic cracking (FCC) device is one of more serious device of oil plant disposal of pollutants.In recent years, along with the increase of oil plant Sulfur-Containing Crude, the sulfur content of catalytically cracked material also improves constantly.It is reported, the sulphur in raw material approximately has 45-55% in reactor, to change into H
2s enters dry gas, approximately has 35-45% to enter into fluid product, approximately has 5-10% to be brought in regenerator with coke, generates SO in the time burning
x(wherein SO
2account for 90%, SO
3account for 10%), become FCC apparatus SO
xsource.SO
xenter atmosphere with flue gas, this has not only caused serious equipment corrosion, and has aggravated environmental pollution.
Using sulfur transfer additive is effective sulfur method.Sulfur transfer additive is divided into two kinds of liquid sulfur transfer agent and solid sulfur transfer agents.Solid sulfur transfer agent with its convenient transportation, catalytic cracking major catalyst poisoned to little feature substituted gradually liquid sulfur transfer agent.The development of solid sulfur transfer agent, the eighties in 20th century, this type of sulfur transfer additive reducing power was poor in the past mainly take metal oxide as main; 20th century the mid-80, owing to finding the redox property of spinelle uniqueness, developed the sulfur transfer additive of spinel serial, developed again subsequently hydrotalcite type sulfur transfer additive.Composition and preparation method about the sulfur transfer additive of other type study less.
Preparation method about sulfur transfer additive is more, has sol-gal process, coprecipitation and infusion process.Sol-gal process is relatively simple.Coprecipitation is commonplace method.For example: USP4472532 discloses the preparation method of the spinel composition of a kind of alkaline-earth metal and aluminium, it is that the alkaline solution that at least acidic aqueous solution containing a kind of alkaline earth metal component exists with anionic form with aluminium is mixed, form the mixture of an alkaline including earth metal and aluminum precipitation, in mixed process, the pH value of liquid phase remains on the scope of 7.0-8.5, and then roasting obtains the spinel composition of alkaline including earth metal and aluminium.The method also comprises the process that at least one additional metal component is added to above-mentioned precipitation or dipping above-mentioned composition, and described additional metal component is selected from I B, II B in the periodic table of elements, IV B, VI A, VI B, VII A and VIII family metal, rare earth metal, vanadium, tin, antimony and their mixture.CN1883794A discloses the preparation method of the spinel composition of a kind of alkaline-earth metal and aluminium, iron, the method is that a kind of aqueous solution of alkaline-earth metal is mixed with the solution that aluminium, iron exist with ionic species, mix with alkaline solution again, in mixed process, the pH value of liquid phase remains on the scope of 8-10, and last roasting sediment obtains the spinel composition of alkaline including earth metal and aluminium, iron.The disclosed technical scheme of CN1883794A is to utilize the method for co-precipitation and flood the method combining to prepare the iron magnalium hydrotalcite that contains copper, forms the sulfur transfer additive with higher sulphur absorbable ability after roasting.The disclosed technical scheme of CN1331569C is to utilize coprecipitation to prepare the MgAlZn-FeCe-HTL houghite of vanadium impregnated, and then by hydrotalcite and kaolin, Y and aluminium colloidal sol are made slurries spraying and prepared sulfur transfer additive.The disclosed technical scheme of CN101905117B adopts roasting restoring method, utilizes the magnesia-alumina hydrotalcite precursor of high-temperature roasting cerium-carrying to prepare sulfur transfer additive.
Part sulfur transfer additive also can adopt infusion process preparation.As USP4497902 mixes magnesia, a water Alpha-alumina and calcium oxide, add obtain after nitric acid kneading, roasting a kind of containing magnesia, Ca
3al
10o
18and magnesium aluminate spinel (MgAl
2o
4) mixture, the upper cerium of dipping subsequently, roasting forms sulfur transfer additive.CN1994535A adopts the method for original position dipping on boehmite, to flood the salting liquid of magnesium, zinc, iron, cerium, forms solid sulfur transfer agent after drying and roasting.
In the composition of most sulfur transfer additive, all contain the carrier materials such as kaolin, its Main Function is the mechanical strength that improves sulfur transfer additive, can meet the requirement of catalytic cracking recirculating fluidized bed.But the carriers such as kaolin all contain the silica of 40% left and right of having an appointment, silica can react with magnesia and generate magnesium silicate with magnesia in long-term operation process, reduce the desulphurizing activated centric quantity of sulfur transfer additive, also made silica strengthen the function reduction of intensity.
Summary of the invention
One object of the present invention is that composition and the preparation method to existing sulfur transfer additive improves, and a kind of catalytic cracking fuel gas sulfur transfer additive of multiphase is provided, to strengthen desulfurized effect and the service life of sulfur transfer additive.
Another object of the present invention is to provide a kind of method of the catalytic cracking fuel gas sulfur transfer additive of preparing described multiphase.
Another object of the present invention is to provide the application of described sulfur transfer additive, particularly it is in the application as in catalytic cracking fuel gas sulfur transfer additive.
For achieving the above object, the present invention utilizes diauxic growth method synthetic using magnesia, magnesium titanate and three kinds of multiphases of magnesium aluminate spinel as desulfurization carrier and desulphurizing activated center, metal oxide-loaded as redox promoter, prepare catalytic cracking fuel gas sulfur transfer additive.
Particularly, on the one hand, the invention provides a kind of catalytic cracking fuel gas sulfur transfer additive of multiphase, this sulfur transfer additive is using magnesia, magnesium titanate and three kinds of multiphases of magnesium aluminate spinel as desulfurization carrier and desulphurizing activated center, metal oxide-loaded as redox promoter, adopt diauxic growth method to prepare, take the gross weight of this sulfur transfer additive as benchmark, wherein, the quality percentage composition of magnesia, magnesium titanate, magnesium aluminate spinel and metal oxide is respectively 1%-50%, 1%-90%, 1%-90% and 5%-50%.
According to preferred specific embodiments of the present invention, in the catalytic cracking fuel gas sulfur transfer additive of multiphase of the present invention, magnesian preferred mass percentage composition is 30%-40%.
According to preferred specific embodiments of the present invention, in the catalytic cracking fuel gas sulfur transfer additive of multiphase of the present invention, the preferred mass percentage composition of magnesium titanate is 15%-25%.
According to preferred specific embodiments of the present invention, in the catalytic cracking fuel gas sulfur transfer additive of multiphase of the present invention, the preferred mass percentage composition of magnesium aluminate spinel is 20%-30%.
According to preferred specific embodiments of the present invention, in the catalytic cracking fuel gas sulfur transfer additive of multiphase of the present invention, the preferred mass percentage composition of metal oxide is 20%-30%.
According to specific embodiment of the invention scheme, in the catalytic cracking fuel gas sulfur transfer additive of multiphase of the present invention, the metal oxide of load is selected from one or more in the oxide of Cu, Fe, V, Ni, Ce, Sr, Ag, Zn, Nb, La, Ba.When selecting when multiple, the difference content of each metal oxide in sulfur transfer additive can suitably be adjusted as required, should control total content within the scope of 5%-50%, and more preferably the difference content of each metal oxide is more than 5%.According to the preferred embodiments of the invention, the oxide that described metal oxide is following metal: Cu and Fe, Fe and Ce, Sr and Zn, or Fe, Ce and Sr.
On the other hand, the present invention also provides a kind of method of the catalytic cracking fuel gas sulfur transfer additive of preparing described multiphase, the method is mainly first to adopt anti-phase coprecipitation to prepare the titanium magnesium structure sulfur transfer additive of rich magnesia type, and then dipping aluminium source, after-treatment forms the catalytic cracking fuel gas sulfur transfer additive with multiphase.
According to specific embodiment of the invention scheme, the method for the catalytic cracking fuel gas sulfur transfer additive of the multiphase described in preparation provided by the invention comprises step:
1. by magnesium source, titanium source with there is redox and promote the soluble-salt of metal of performance to join in water or alcoholic solvent, stir 2-10h in 20-80 ℃ of constant temperature, obtain mixed solution;
2. under stirring condition, it is in 5-95 ℃, the concentration aqueous slkali that is 0.1-10mol/L that the mixed solution that 1. step is prepared is dropwise added to temperature, then stirs 0.1-10h, makes slurries;
3. by step 2. gained slurries put into the reactor with polytetrafluoro liner, in 20-180 ℃ of crystallization 10-80h, then suction filtration, wash to pH value as 7-10, then at 80-150 ℃, dry 5-15h, roasting 2-8h at 500-900 ℃, obtains having magnesian titanium magnesium structural material more than needed;
4. by the step method dipping aluminium source that 3. gained titanium magnesium structural material adopts equal-volume repeatedly to flood, then dry 1-50h in 20-190 ℃, roasting 2-8h at 500-900 ℃, obtains having the catalytic cracking fuel gas sulfur transfer additive of multiphase.
The quality percentage composition that in preparation method of the present invention, in each raw material consumption reference object product, magnesia, magnesium titanate, magnesium aluminate spinel and metal oxide account for sulfur transfer additive carries out proportioning.
According to specific embodiment of the invention scheme, in the method for the catalytic cracking fuel gas sulfur transfer additive of the multiphase described in preparation of the present invention, magnesium source is one or more in magnesium chloride, magnesium nitrate, magnesium acetate, magnesium carbonate, magnesium sulfate; Titanium source is one or more in the chloride of titanium sesquisulfate, titanium sulfate, butyl titanate and titanium; Aluminium source is one or more in aluminum nitrate, aluminium chloride, aluminum sulfate and sodium metaaluminate.The soluble-salt with the metal of redox promotion performance refers to the source metal that forms metal oxide in product.
In a specific embodiments of the present invention, in the method for the catalytic cracking fuel gas sulfur transfer additive of the multiphase described in preparation of the present invention, magnesium source is magnesium sulfate; Titanium source is titanium sesquisulfate or titanium sulfate; Aluminium source is aluminium chloride.Further, in this embodiment, preferred, there is redox and promote that the soluble-salt of the metal of performance is ferric nitrate and copper nitrate.
In another specific embodiments of the present invention, in the method for the catalytic cracking fuel gas sulfur transfer additive of the multiphase described in preparation of the present invention, magnesium source is magnesium nitrate, magnesium carbonate and magnesium sulfate; Titanium source is titanium sesquisulfate or titanium sulfate; Aluminium source is aluminum sulfate.Further, in this embodiment, preferred, there is redox and promote that the soluble-salt of the metal of performance is ferric nitrate and cerous nitrate.
In another specific embodiments of the present invention, in the method for the catalytic cracking fuel gas sulfur transfer additive of the multiphase described in preparation of the present invention, magnesium source is magnesium chloride, magnesium acetate; Titanium source is butyl titanate; Aluminium source is aluminium chloride.Further, in this embodiment, preferred, there is redox and promote that the soluble-salt of the metal of performance is strontium nitrate and zinc nitrate.
In another specific embodiments of the present invention, in the method for the catalytic cracking fuel gas sulfur transfer additive of the multiphase described in preparation of the present invention, magnesium source is magnesium chloride, magnesium nitrate; Titanium source is titanium sesquisulfate or titanium sulfate; Aluminium source is aluminum nitrate.Further, in this embodiment, preferred, there is redox and promote that the soluble-salt of the metal of performance is strontium nitrate, ferric nitrate and cerous nitrate.
In another specific embodiments of the present invention, in the method for the catalytic cracking fuel gas sulfur transfer additive of the multiphase described in preparation of the present invention, magnesium source is magnesium nitrate; Titanium source is titanium sesquisulfate or titanium sulfate; Aluminium source is aluminum nitrate.Further, in this embodiment, preferred, there is redox and promote that the soluble-salt of the metal of performance is ferric nitrate and cerous nitrate.
According to specific embodiment of the invention scheme, in the method for the catalytic cracking fuel gas sulfur transfer additive of the multiphase described in preparation of the present invention, the alcoholic solvent of step in is 1. one or more in absolute ethyl alcohol, ethylene glycol, n-butanol, isobutanol and isopropyl alcohol.
According to specific embodiment of the invention scheme, in the method for the catalytic cracking fuel gas sulfur transfer additive of the multiphase described in preparation of the present invention, the aqueous slkali of step in is 2. formulated by one or more in NaOH, sodium carbonate, potassium hydroxide, ammoniacal liquor.
According to specific embodiment of the invention scheme, in the method for the catalytic cracking fuel gas sulfur transfer additive of the multiphase described in preparation of the present invention, control step 2. in pH value >=10 of final slurries.
On the other hand, the application of the sulfur transfer additive that the present invention also provides described multiphase in catalytic cracking flue gas desulfurization is processed.
On the other hand, the present invention also provides a kind of catalytic cracking flue gas desulfuration processing method, and the method comprises the process that the sulfur transfer additive of multiphase of the present invention carries out desulfurization of applying.Concrete processing procedure can be with reference to the prior art operation in affiliated field.Utilize sulfur transfer additive of the present invention to carry out desulfurization and can reach good desulfurized effect, and sulfur transfer additive of the present invention its wear-resistant ability in the situation that not adding the anti-wear agents such as kaolin just can meet industrialized production requirement.
Generally speaking, the invention provides catalytic cracking fuel gas sulfur transfer additive of a kind of multiphase and preparation method thereof and application, sulfur transfer additive of the present invention is a kind of desulfurizing assistant agent that utilizes titanium magnesium structural material and dimension stone of magnesia alumina spinel to form composite construction, it is well desulphurizing activated that the present invention has confirmed that this sulfur transfer additive has by experiment, and sulfur transfer additive of the present invention its wear-resistant ability in the situation that not adding the anti-wear agents such as kaolin just can meet industrialized production requirement.The present invention has strengthened desulfurized effect and the service life of sulfur transfer additive greatly, has widened the compositing range of sulfur transfer additive.
Accompanying drawing explanation
Fig. 1: the XRD spectra of the sulfur transfer additive material that the embodiment of the present invention 2 obtains.
Fig. 2: the desulfurized effect test result of the sulfur transfer additive of various embodiments of the present invention and comparative example.
The specific embodiment
Understand for technical characterictic of the present invention, object and beneficial effect being had more clearly, existing technical scheme of the present invention is carried out to following detailed description, but can not be interpreted as restriction that can practical range of the present invention.
Embodiment 1
By 43.77g MgSO
4, 30.16g Ti (SO
4)
29H
2o, 15.15g Fe (NO
3)
39H
2o, 9.06gCu (NO
3)
23H
2o is dissolved in 200g H
2in O, be mixed with solution A, and at room temperature stir (make slurries fast rotational, but be unlikely to the slurries beaker that flies out) 4h; 30g NaOH is dissolved in to 200g H
2in O, be configured to solution B; Solution A is dropwise joined in the solution B of 60 ℃ of heating water baths of vigorous stirring, be added dropwise to complete rear continuation and stir 4h, obtain slurries C, keep pH value>=10 of slurries in whole mixed process, slurries C is put into the reactor with polytetrafluoro liner, in 80 ℃ of crystallization 18h, then cooling, suction filtration, washing are to neutral, 120 ℃ of dry 10h, 700 ℃ of roasting 2h obtain intermediate product Z1; By 16.8g AlCl
3be dissolved in the deionized water of 20ml obtaining solution D, and it is upper to adopt method that equal-volume repeatedly floods that solution D be impregnated in to Z1, then dries 10h for 120 ℃, 700 ℃ of roasting 2h, obtain product W1.
Embodiment 2
By 22.8g MgSO
4, 11.4g Mg (NO
3)
26H
2o, 9.58g MgCO
3, 40.24g Ti (SO
4)
29H
2o, 15.15g Fe (NO
3)
39H
2o, 6.78g Ce (NO
3)
36H
2o is dissolved in 200g H
2in O, be mixed with solution A, and at room temperature stir 4h; By 30g NaOH, 10g KOH is dissolved in 200g H
2in O, be configured to solution B; Solution A is dropwise joined in the solution B of 60 ℃ of heating water baths of vigorous stirring, be added dropwise to complete rear continuation and stir 4h, obtain slurries C, keep pH value>=10 of slurries in whole mixed process, slurries C is put into the reactor with polytetrafluoro liner, in 90 ℃ of crystallization 20h, then cooling, suction filtration, washing are to neutral, 120 ℃ of dry 10h, 800 ℃ of roasting 2h obtain intermediate product Z2; By 30.21g Al
2(SO
4)
3be dissolved in 50ml deionized water obtaining solution D, and it is upper to adopt method that equal-volume repeatedly floods that solution D be impregnated in to Z2, then dries 10h for 120 ℃, 800 ℃ of roasting 2h, obtain product W2.
Embodiment 3
By 30.13g MgCl
26H
2o, 38.54g C
4h
6o
4mg6H
2o, 47.12g C
16h
36o
4ti, 6.77gSr (NO
3)
2, 3.67g Zn (NO
3)
26H
2o is dissolved in 200g absolute ethyl alcohol, is mixed with solution A, and at room temperature stirs 4h; By 25g NaOH, 15g KOH, 8g NaCO
3be dissolved in 200g H
2in O, be configured to solution B; Solution A is dropwise joined in the solution B of 60 ℃ of heating water baths of vigorous stirring, be added dropwise to complete rear continuation and stir 4h, obtain slurries C, keep pH value>=10 of slurries in whole mixed process, slurries C is put into the reactor with polytetrafluoro liner, in 70 ℃ of crystallization 17h, then cooling, suction filtration, washing are to neutral, 110 ℃ of dry 10h, 800 ℃ of roasting 2h obtain intermediate product Z3; By 16.8g AlCl
3be dissolved in 20ml deionized water obtaining solution D, and it is upper to adopt method that equal-volume repeatedly floods that solution D be impregnated in to Z3, then dries 10h for 120 ℃, 800 ℃ of roasting 2h, obtain product W3.
Embodiment 4
By 50.13g MgCl
26H
2o, 11.4g Mg (NO
3)
26H
2o, 98.18g Ti
2(SO
4)
3solution (15%-18wt%), 6.77g Sr (NO
3)
2, 15.15g Fe (NO
3)
39H
2o, 6.78g Ce (NO
3)
36H
2o is dissolved in 200g absolute ethyl alcohol, is mixed with solution A, and at room temperature stirs 4h; By 45g NaOH, 15g KOH, 8g NaCO
3be dissolved in 200g H
2in O, be configured to solution B; Solution A is dropwise joined in the solution B of 60 ℃ of heating water baths of vigorous stirring, be added dropwise to complete rear continuation and stir 4h, obtain slurries C, keep pH value>=10 of slurries in whole mixed process, slurries C is put into the reactor with polytetrafluoro liner, in 70 ℃ of crystallization 17h, then cooling, suction filtration, washing are to neutral, 110 ℃ of dry 10h, 700 ℃ of roasting 2h obtain intermediate product Z4; By 32.98gAl (NO
3)
39H
2o is dissolved in 30ml deionized water obtaining solution D, and it is upper to adopt method that equal-volume repeatedly floods that solution D be impregnated in to Z4, then dries 10h for 120 ℃, and 700 ℃ of roasting 2h, obtain product W4.
Embodiment 5
By 75.65g Mg (NO
3)
26H
2o, 98.18g Ti
2(SO
4)
3solution (15%-18wt%), 10.46gFe (NO
3)
39H
2o, 10.78g Ce (NO
3)
36H
2o is dissolved in 200g absolute ethyl alcohol, is mixed with solution A, and at room temperature stirs 4h; By 45g NaOH, 15g KOH, 8g NaCO
3be dissolved in 200g H
2in O, be configured to solution B; Solution A is dropwise joined in the solution B of 60 ℃ of heating water baths of vigorous stirring, be added dropwise to complete rear continuation and stir 4h, obtain slurries C, keep pH value>=10 of slurries in whole mixed process, slurries C is put into the reactor with polytetrafluoro liner, in 70 ℃ of crystallization 17h, then cooling, suction filtration, washing are to neutral, 110 ℃ of dry 10h, 700 ℃ of roasting 2h obtain intermediate product Z5; By 32.98g Al (NO
3)
39H
2o is dissolved in 30ml deionized water obtaining solution D, and it is upper to adopt method that equal-volume repeatedly floods that solution D be impregnated in to Z5, then dries 10h for 120 ℃, and 700 ℃ of roasting 2h, obtain product W5.
Comparative example 1
Take 40g boehmite, join 160g H
2in O, stir, then dropwise add while stirring 5.39g hydrochloric acid, rapid stirring 30min, forms alumina gel A; 21.36g MgO is joined to 53.4g H
2in O, make magnesium slurry B; Magnesium is starched in the alumina gel A that B joins vigorous stirring, stirred 1h, form slurries C; By 10.78gFe (NO
3)
39H
2o, 14.83g Ce (NO
3)
36H
2o joins appropriate H
2o, is mixed with solution D, solution D is joined in the slurries C of vigorous stirring, stirs 8h, and then at 120 ℃ of dry 10h, 700 ℃ of roasting 2h obtain product R1.
Comparative example 2
Take 40g boehmite, join 160g H
2in O, stir, then dropwise add while stirring 5.39g hydrochloric acid, rapid stirring 30min, forms alumina gel A; 5.85g kaolin is joined in the alumina gel A of vigorous stirring, form slurries B; 21.36g MgO is joined to 53.4g H
2in O, make magnesium slurry C; Magnesium is starched in the slurries B that C joins vigorous stirring, stirred 1h, form slurries D; By 10.78g Fe (NO
3)
39H
2o, 14.83gCe (NO
3)
36H
2o joins appropriate H
2in O, be mixed with solution E, solution E joined in the slurries D of vigorous stirring, stir 8h, then at 120 ℃ of dry 10h, 700 ℃ of roasting 2h obtain product R2.
Fig. 1 is the XRD spectra of the synthetic sample of the embodiment of the present invention 2, proves that synthetic sample is the mixture of rich magnesium type magnesium aluminate spinel and magnesium titanate.
The desulfurized effect of the sulfur transfer additive that embodiment W1-W5 and comparative example R1, R2 are provided carries out experiment test, and concrete test comprises the following steps:
Sulfur transfer additive is ground to form to the particle that diameter is 80-120 μ m, take 0.5g, pack in the fixed-bed micro-reactor that internal diameter is 6mm, be heated to 700 ℃, pass into SO
2with the mist of air, volume flow is 220ml/min, wherein SO
2volumetric concentration be 2000ppm; After passing into gas, get gas, SO in measurement gas one time every 10min
2concentration.Measuring instrument is German import moral Figure 35 0 type flue gas analyzer.
Concrete desulfurized effect test result as shown in Figure 2.As seen from the figure: the desulfurized effect of W1-W5 and R1, R2 has larger difference.And by comparative example W5 and comparative example R1, R2, can find out that the sulfur transfer additive of multiphase structure has well desulphurizing activated.And contrast R1 and R2 can find out, have added its desulphurizing activated sulfur transfer additive that does not add wear resistant components of the kaolinic sulfur transfer additive R2 of wear resistant components and have declined to some extent.
The abrasion index of each embodiment and comparative example is in table 1.
Table 1
| Sequence number | Sample number into spectrum | Abrasion index, %/h |
| 1 | W1 | 3.1 |
| 2 | W2 | 2.8 |
| 3 | W3 | 3.1 |
| 4 | W4 | 2.1 |
| 5 | W5 | 2.4 |
| 6 | R1 | 7.5 |
| 7 | R2 | 2.6 |
As can be seen from Table 1, rich magnesium type magnesium aluminate spinel type sulfur transfer additive is not in the time adding kaolin as wear resistant components, it is wear-resistant, and ability can not meet demand of industrial production, when add 10.34% kaolin as wear resistant components after its mechanical strength can reach industrial requirement.And the sulfur transfer additive W1-W5 of the multiphase the present invention relates to just can meet industrialized production requirement not adding its wear-resistant ability in kaolinic situation.
Claims (10)
1. the catalytic cracking fuel gas sulfur transfer additive of a multiphase, this sulfur transfer additive is using magnesia, magnesium titanate and three kinds of multiphases of magnesium aluminate spinel as desulfurization carrier and desulphurizing activated center, metal oxide-loaded as redox promoter, adopt diauxic growth method to prepare, take the gross weight of this sulfur transfer additive as benchmark, wherein, the quality percentage composition of magnesia, magnesium titanate, magnesium aluminate spinel and metal oxide is respectively 1%-50%, 1%-90%, 1%-90% and 5%-50%.
2. sulfur transfer additive according to claim 1, wherein, the metal oxide of load is selected from one or more in the oxide of Cu, Fe, V, Ni, Ce, Sr, Ag, Zn, Nb, La, Ba.
3. sulfur transfer additive according to claim 1, the gross weight shifting take this sulphur is as benchmark, and wherein, the quality percentage composition of magnesia, magnesium titanate, magnesium aluminate spinel and metal oxide is respectively 30%-40%, 15%-25%, 20%-30% and 20%-30%.
4. a method of preparing the catalytic cracking fuel gas sulfur transfer additive of the multiphase described in claim 1～3 any one, the method comprising the steps of:
1. by magnesium source, titanium source with there is redox and promote the soluble-salt of metal of performance to join in water or alcoholic solvent, stir 2-10h in 20-80 ℃ of constant temperature, obtain mixed solution;
2. under stirring condition, it is in 5-95 ℃, the concentration aqueous slkali that is 0.1-10mol/L that the mixed solution that 1. step is prepared is dropwise added to temperature, then stirs 0.1-10h, makes slurries;
3. by step 2. gained slurries put into the reactor with polytetrafluoro liner, in 20-180 ℃ of crystallization 10-80h, then suction filtration, wash to pH value as 7-10, then at 80-150 ℃, dry 5-15h, roasting 2-8h at 500-900 ℃, obtains having magnesian titanium magnesium structural material more than needed;
4. by the step method dipping aluminium source that 3. gained titanium magnesium structural material adopts equal-volume repeatedly to flood, then dry 1-50h in 20-190 ℃, roasting 2-8h at 500-900 ℃, obtains having the catalytic cracking fuel gas sulfur transfer additive of multiphase.
5. method according to claim 4, wherein, described magnesium source is one or more in magnesium chloride, magnesium nitrate, magnesium acetate, magnesium carbonate, magnesium sulfate; Titanium source is one or more in the chloride of titanium sesquisulfate, titanium sulfate, butyl titanate and titanium; Aluminium source is one or more in aluminum nitrate, aluminium chloride, aluminum sulfate and sodium metaaluminate.
6. method according to claim 4, wherein, the alcoholic solvent of step in is 1. one or more in absolute ethyl alcohol, ethylene glycol, n-butanol, isobutanol and isopropyl alcohol.
7. method according to claim 4, wherein, the aqueous slkali of step in is 2. formulated by one or more in NaOH, sodium carbonate, potassium hydroxide, ammoniacal liquor.
8. according to the method described in claim 4 or 7, wherein, control step 2. in pH value >=10 of final slurries.
9. the application of the sulfur transfer additive described in claim 1～3 any one in catalytic cracking flue gas desulfurization is processed.
10. a catalytic cracking flue gas desulfuration processing method, the method comprises the process that the sulfur transfer additive described in application rights requirement 1～3 any one carries out desulfurization.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475077A (en) * | 2014-11-20 | 2015-04-01 | 沈阳三聚凯特催化剂有限公司 | Preparation method of catalytic cracking flue gas desulfurization agent |
| 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 |
| CN106268278A (en) * | 2016-08-30 | 2017-01-04 | 中国石油大学(华东) | A kind of catalytic cracking fuel gas sulfur transfer additive of new structure and preparation method thereof |
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| CN102921289A (en) * | 2012-11-08 | 2013-02-13 | 北京化工大学 | Method for preparation of catalytic cracking flue gas sulfur transfer agent active constituent element |
| CN102935322A (en) * | 2012-10-30 | 2013-02-20 | 陕西高新能源发展有限公司 | Method for preparing catalytic cracking sulfur transfer agents |
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| CN102921289A (en) * | 2012-11-08 | 2013-02-13 | 北京化工大学 | Method for preparation of catalytic cracking flue gas sulfur transfer agent active constituent element |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104475077A (en) * | 2014-11-20 | 2015-04-01 | 沈阳三聚凯特催化剂有限公司 | Preparation method of catalytic cracking flue gas desulfurization agent |
| 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 |
| CN106268278A (en) * | 2016-08-30 | 2017-01-04 | 中国石油大学(华东) | A kind of catalytic cracking fuel gas sulfur transfer additive of new structure and preparation method thereof |
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| CN103861437B (en) | 2016-03-30 |
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