CN1994534A - Preparation method of sulfur transfer agent for FCC regenerated flue gas - Google Patents
Preparation method of sulfur transfer agent for FCC regenerated flue gas Download PDFInfo
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- CN1994534A CN1994534A CN 200610119524 CN200610119524A CN1994534A CN 1994534 A CN1994534 A CN 1994534A CN 200610119524 CN200610119524 CN 200610119524 CN 200610119524 A CN200610119524 A CN 200610119524A CN 1994534 A CN1994534 A CN 1994534A
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- zinc
- salt
- htl
- mgalznfece
- sulfur transfer
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Abstract
The invention relates to a method for preparing fluid catalyst crack regenerate smoke sulfur transfer agent, wherein it uses co-precipitation method to prepare MgAlZnFeCe-HTL hydrotalcite; mixes 60 deals MgAlZnFeCe-HTL product, 20 deals caoline, 10 deals rare-earth Y, 100 deals aluminum gel (10% solid), and 210 deals chemical water, beating, atomizing and drying. The inventive transfer agent has high-effect SOX adsorption and high mechanical strength, while it can reduce the NOx content of smoke.
Description
Technical field
The present invention relates to the preparation method of fume-clarifying agent, specifically a kind of is the method that key component prepares sulfur transfer agent for FCC regenerated flue gas by magnalium zinc-iron cerium houghite.
Background technology
Fluid catalytic cracking (FCC) is one of main method of oil plant production petrol and diesel oil, SO in the FCC regenerated flue gas
xDischarge capacity account for SO in the air
x6～7% of total emission volumn.SOx is serious environment pollution not only, harm humans health, and SO
xWith water effect in the regenerated flue gas, increased the corrosion of equipment that FCC regenerator and three is revolved etc.Reduce the SO in the FCCC regenerator
xThe main method of discharging is: 1. the washing of flue gas; 2. feedstock oil hydrodesulfurization; 3. catalysis method takes off SO
x(sulfur transfer additive).Because catalysis method takes off SO
xNeed equipment investment hardly, and operating cost is low, so catalysis method takes off SO
xBecome the optimal selection of oil plant.
Initial people are based on metal oxide for the preparation of sulfur transfer additive, as adopting MgO, Al
2O
3Or their mixture is as sulfur transfer additive, but their desulfurization performance unsatisfactory (USP3,835,031,4,071,436, USP4,166,787, USP4,243,556 etc.).People attempt to adopt CeO subsequently
2/ MgO catalyst, but the shortcoming of this material maximum is a reproducibility bad (USP5,627,123).Also there is the people that transition metal oxide has been carried out a lot of work (USP5,366,710, CN1460555A) as sulfur transfer additive.Since the mid-80, some external oil companies concentrate on the research of multicomponent sulfur transfer additive, and wherein studying maximum is magnesium aluminate spinel series, discover the spinelle MgAl that mixes solid solution
2O
4The desulfurization performance of-MgO is very good, but also effective regeneration (USP4,469,589, USP4,963,520, USP5,057,205 etc.).At present, more domestic research units and oil plant are the development that key component has been carried out sulfur transfer additive with the magnesium aluminate spinel, but have shortcomings such as desulfuration efficiency is low, anti-wear performance difference.
Summary of the invention
Houghite (HTLcs) is a class new catalytic material that is subjected to extensive concern in recent years.The mixed metal hydroxides with hydrotalcite (HTL) layered crystal structure that this material is made up of divalence and trivalent metal ion, its composition formula is [M
II 1-xM
III x(OH)
2]
x(A
N-)
X/nMH
2O, wherein M
II=Mg
2+, Zn
2+, Cu
2+, Co
2+, Ca
2+, Ni
2+, Pd
2+, V
2+, Fe
2+, Mn
2+Deng divalent metal; M
III=Al
3+, Fe
3+, Co
3+, Cr
3+, V
3+, Mn
3+, Ni
3+, Rh
3+, Ru
3+, Ga
3+, La
3++Deng trivalent metal cation, A
N-=CO
3 -2, NO
3 -, Cl
-, OH
-, SO
4 2-, PO
4 3-, C
6H (COO
-)
2Etc. inorganic or organic anion.Its key property has: the interchangeability of cationic collocation property, interlayer anion in alkalescence, the laminate.
The object of the present invention is to provide a kind of is the method that key component prepares sulfur transfer additive by magnalium zinc-iron cerium houghite, to solve the existing problem of background technology.
The object of the present invention is achieved like this:
A kind of preparation method of FCC regeneration flue gas sulphur transfer agent, it may further comprise the steps:
The preparation of the 1st step MgAlZnFeCe-HTL houghite
Under 60～90 ℃, with magnesium salts, the mixed solution of aluminium salt, zinc salt, cerium salt and molysite is added drop-wise in the mixed solution of alkali and carbonate, the dropping time is 0.5～2h, and the pH value of solution is controlled between 8～11, drips the back and continues to stir 4～24h, 60～100 ℃ of nucleation crystallization, cooling then, suction filtration, washing are to neutral, and dry 7h under 70-120 ℃ obtains the MgAlZnFeCe-HTL houghite.
The sulfur transfer additive moulding of the 2nd step
Again the aluminium colloidal sol (10% solid content) of the hyperastable Y-type RE (LaUSY) of the kaolin of the MgAlZnFe-HTL product of 60 parts of weight, 20 parts of weight, 10 parts of weight, 100 parts of weight and chemical water mixing making beating, the spray-drying of 210 parts of weight are prepared into sulfur transfer additive.
Described magnesium salts, the mol ratio of Mg, two kinds of metals of Al is 1.0～10 in the mixed solution of aluminium salt, zinc salt, cerium salt and molysite, the mol ratio of Mg, two kinds of metals of Zn is 7.6～38, and the mol ratio of Mg, two kinds of metals of Fe is 11.3～37.5, and the mol ratio of Mg, two kinds of metals of Ce is 24～120.
N in the mixed solution of described alkali and carbonate
OH -=2n
M 2+, n
CO3 2-=0.5 (n
M 2++ n
M 3+).
Described magnesium salts is magnesium nitrate, magnesium sulfate, magnesium chloride, magnesium acetate.
Described aluminium salt is aluminum nitrate, aluminum sulfate, aluminium chloride, aluminum acetate.
Described zinc salt is zinc nitrate, zinc sulfate, zinc chloride, zinc acetate.
Described molysite is ferric nitrate, ferric sulfate, iron chloride.
Described cerium salt is cerous nitrate, cerous sulfate.
Described carbonate is sodium carbonate, ammonium carbonate; Alkali is NaOH, ammoniacal liquor.
Compared with prior art, the sulfur transfer additive of the present invention's preparation not only has SO efficiently
xAbsorption and desorption performance and excellent mechanical intensity, and can reduce NOx content in the flue gas.
The specific embodiment
Below will the present invention is further elaborated by specific embodiment.All embodiment carry out according to operating procedure of the present invention fully.
Embodiment 1
The preparation of the 1st step MgAlZnFeCe-HTL houghite
In the three-neck flask of 10L, add 5L H
2O, 153.0g NaOH and 36.0g Na
2CO
3, 60 ℃ stir after, contain 3.5L water, 307.0g Mg (NO to wherein dripping
3)
26H
2O, 147.0gAl (NO
3)
39H
2O, 21.4g Fe (NO
3)
39H
2O, 15.6g Zn (NO
3)
26H
2O and 4.2gCe (NO
3)
36H
2The solution of O, the dropping time is 0.5h, drips the back and continues to stir 15h, 85 ℃ of nucleation crystallization.Cooling then, suction filtration, washing are to neutral, and 100 ℃ of dry 7h obtain houghite product A l.
The sulfur transfer additive moulding of the 2nd step
Get 60.0g Al and the 203mL deionized water joins in the reactor, add 27.3g kaolin (Suzhou kaolin company commercial product, solid content 73.3%) and 10.0g LaUSY, again to wherein adding 100.0g aluminium colloidal sol (10% solid content, self-control) making beating, stir after 30 minutes, spray-drying obtains sulfur transfer additive S1.
Embodiment 2
The preparation of the 1st step MgAlZnFeCe-HTL houghite
In the three-neck flask of 10L, add 5L H
2O, 542.0g ammoniacal liquor (25%) and 33.7g (NH
4)
2CO
3, 70 ℃ stir after, contain 3.5L water, 307.0g Mg (NO to wherein dripping
3)
26H
2O, 147.0g Al
2(NO
3)
39H
2O,, 21.4g Fe (NO
3)
39H
2O, 15.6g Zn (NO
3)
26H
2O and 16.9gCe (NO
3)
36H
2O, the dropping time is 0.5h, drips the back and continues to stir 15h, 90 ℃ of nucleation crystallization.Cooling then, suction filtration, washing are to neutral, and 80 ℃ of dry 7h obtain houghite product A 2.
The sulfur transfer additive moulding of the 2nd step
In the 2nd step with embodiment 1, obtain sulfur transfer additive S2.
Embodiment 3
The preparation of the 1st step MgAlZnFeCe-HTL houghite
In the three-neck flask of 10L, add 5L H
2O, 156.6g NaOH and 39.0g Na
2CO
3, 90 ℃ stir after, contain 3.5L water, 243.4g MgCl to wherein dripping
26H
2O, 96.2g AlCl
36H
2O, 14.3g FeCl
36H
2O, 7.1g ZnCl
2With 25.3g Ce (NO
3)
36H
2O, the dropping time is 0.5h, drips the back and continues to stir 15h, 90 ℃ of nucleation crystallization.Cooling then, suction filtration, washing are to neutral, and 120 ℃ of dry 7h obtain houghite product A 3.
The sulfur transfer additive moulding of the 2nd step
In the 2nd step with embodiment 1, obtain sulfur transfer additive S3.
Embodiment 4
The preparation of the 1st step MgAlZnFeCe-HTL houghite
In the three-neck flask of 10L, add 5L H
2O, 117.0g NaOH and 11.2g Na
2CO
3, 70 ℃ stir after, contain 3.5L water, 273.4g Mg (SO to wherein dripping
4)
26H
2O, 38.4gAl
2(SO
4)
316H
2O, 14.9g Fe
2(SO
4)
39H
2O, 15.1g ZnSO
47H
2O and 15.7gCe (SO
4)
24H
2O, the dropping time is 0.5h, drips the back and continues to stir 15h, 95 ℃ of nucleation crystallization.Cooling then, suction filtration, washing are to neutral, and 100 ℃ of dry 7h obtain houghite product A 4.
The moulding of the 2nd step sulfur transfer additive
In the 2nd step with embodiment 1, obtain sulfur transfer additive S4.
Embodiment 5
The preparation of the 1st step MgAlZnFeCe-HTL houghite
In the three-neck flask of 10L, add 5L H
2O, 156.0g NaOH and 39.0g Na
2CO
3, 70 ℃ stir after, contain 3.5L water, 257.2g Mg (CH to wherein dripping
3COO)
24H
2O, 147.0gAl (NO
3)
39H
2O, 12.8g Fe (NO
3)
39H
2O, 11.5g Zn (CH
3COO)
22H
2O and 16.9gCe (NO
3)
36H
2O drips the back and continues to stir 15h, 75 ℃ of nucleation crystallization.Cooling then, suction filtration, washing are to neutral, and 100 ℃ of dry 7h obtain houghite product A 5.
The moulding of the 2nd step sulfur transfer additive
In the 2nd step with embodiment 1, obtain sulfur transfer additive S5.
Embodiment 6
The preparation of the 1st step MgAlZnFeCe-HTL houghite
In the three-neck flask of 10L, add 5L H
2O, 156.0g NaOH and 39.0g Na
2CO
3, 70 ℃ stir after, contain 3.5L water, 307.0g Mg (NO to wherein dripping
3)
26H
2O, 147.0gAl (NO
3)
39H
2O, 21.4g Fe (NO
3)
39H
2O, 9.4g Zn (NO
3)
26H
2O and 25.3gCe (NO
3)
36H
2O, the dropping time is 0.5h, the dropping time is 0.5h, drips the back and continues to stir 15h, 100 ℃ of nucleation crystallization.Cooling then, suction filtration, washing are to neutral, and 100 ℃ of dry 7h obtain houghite product A 6.
The moulding of the 2nd step sulfur transfer additive
In the 2nd step with embodiment 1, obtain sulfur transfer additive S6.
Embodiment 7-12
The appreciation condition and the evaluation result of sulfur transfer additive performance are as follows:
With sulfur content is that 1.15% miscella is a raw material, oil ratio is 7, sulfur transfer additive S1, S2, S3, S4, S5, S6 addition are under 2.0% the situation, investigates the performance (flue gas analyzer mensuration) that it removes SOx and NOx in the FCC regenerated flue gas on catalyst inventory is the small-sized riser of 10.0kg respectively.
The results are shown in Table 1.
Table 1
| The embodiment numbering | Transfer agent | SO 2Removal efficiency/% | NOx removal efficiency/% |
| 7 | S1 | 69 | 20 |
| 8 | S2 | 82 | 28 |
| 9 | S3 | 81 | 33 |
| 10 | S4 | 85 | 27 |
| 11 | S5 | 78 | 25 |
| 12 | S6 | 75 | 25 |
Claims (10)
1, a kind of preparation method of sulfur transfer agent for FCC regenerated flue gas is characterized in that it may further comprise the steps: (1) coprecipitation prepares the MgAlZnFeCe-HTL houghite; (2) the MgAlZnFeCe-HTL product of 60 parts (weight portions), 20 parts kaolin, 10 parts hyperastable Y-type RE, 100 parts aluminium colloidal sol (10% solid content) and 210 parts chemical water mixing making beating, spray-drying are prepared into sulfur transfer additive.
2, method according to claim 1, it is characterized in that it is under 60～90 ℃ that coprecipitation prepares the MgAlZnFeCe-HTL houghite, with magnesium salts, the mixed solution of aluminium salt, zinc salt, cerium salt and molysite is added drop-wise in the mixed solution of alkali and carbonate, the dropping time is 0.5～2h, the pH value of solution is controlled between 8～11, drip the back and continue to stir 4～24h, 60～100 ℃ of nucleation crystallization, cooling then, suction filtration, washing are to neutral, dry 7h under 70-120 ℃ obtains the MgAlZnFeCe-HTL houghite.
3, method according to claim 2, it is characterized in that described magnesium salts, the mol ratio of Mg, two kinds of metals of Al is 1.0～10 in the mixed solution of aluminium salt, zinc salt, cerium salt and molysite, the mol ratio of Mg, two kinds of metals of Zn is 7.6～38, the mol ratio of Mg, two kinds of metals of Fe is 1 1.3～37.5, and the mol ratio of Mg, two kinds of metals of Ce is 24～120.
4, method according to claim 2 is characterized in that n in the mixed solution of described alkali and carbonate
OH -=2n
M 2+, n
CO3 2-=0.5 (n
M 2++ n
M 3+).
5, method according to claim 1 is characterized in that described magnesium salts is magnesium nitrate, magnesium sulfate, magnesium chloride, magnesium acetate.
6, method according to claim 2 is characterized in that described aluminium salt is aluminum nitrate, aluminum sulfate, aluminium chloride, aluminum acetate.
7, method according to claim 2 is characterized in that described zinc salt is zinc nitrate, zinc sulfate, zinc chloride, zinc acetate.
8, method according to claim 2 is characterized in that described molysite is ferric nitrate, ferric sulfate, iron chloride.
9. method according to claim 2 is characterized in that described cerium salt is cerous nitrate, cerous sulfate.
10, method according to claim 2 is characterized in that described carbonate is sodium carbonate, ammonium carbonate; Alkali is NaOH, ammoniacal liquor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101195248A CN100478055C (en) | 2006-12-13 | 2006-12-13 | Preparation method of sulfur transfer agent for FCC regenerated flue gas |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101195248A CN100478055C (en) | 2006-12-13 | 2006-12-13 | Preparation method of sulfur transfer agent for FCC regenerated flue gas |
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| Publication Number | Publication Date |
|---|---|
| CN1994534A true CN1994534A (en) | 2007-07-11 |
| CN100478055C CN100478055C (en) | 2009-04-15 |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101185829B (en) * | 2007-09-25 | 2010-09-01 | 华东师范大学 | Catalytic cracking regeneration flue gas sulphur transfer agent and preparation method thereof |
| CN112934172A (en) * | 2021-02-18 | 2021-06-11 | 山东京博石油化工有限公司 | Sulfur transfer agent prepared by coprecipitation and hydrothermal synthesis and preparation method thereof |
-
2006
- 2006-12-13 CN CNB2006101195248A patent/CN100478055C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101185829B (en) * | 2007-09-25 | 2010-09-01 | 华东师范大学 | Catalytic cracking regeneration flue gas sulphur transfer agent and preparation method thereof |
| CN112934172A (en) * | 2021-02-18 | 2021-06-11 | 山东京博石油化工有限公司 | Sulfur transfer agent prepared by coprecipitation and hydrothermal synthesis and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN100478055C (en) | 2009-04-15 |
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Granted publication date: 20090415 Termination date: 20121213 |