CN101219327A - Sulfur transfer agent for catalytic cracking regeneration flue gas and method for producing the same - Google Patents
Sulfur transfer agent for catalytic cracking regeneration flue gas and method for producing the same Download PDFInfo
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- CN101219327A CN101219327A CNA2007100471122A CN200710047112A CN101219327A CN 101219327 A CN101219327 A CN 101219327A CN A2007100471122 A CNA2007100471122 A CN A2007100471122A CN 200710047112 A CN200710047112 A CN 200710047112A CN 101219327 A CN101219327 A CN 101219327A
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- transfer agent
- nitrate
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Abstract
The invention discloses a sulfur transfer agent of catalytic cracking regeneration flue gas and a preparation method thereof, which is characterized in that sodium metaaluminate is dissolved in a mixture of sodium hydroxide and sodium carbonate, thus forming solution A; an aqueous solution mixture of ferric nitrate, magnesium nitrate and copper nitrate form solution B. Both the solution A and the solution B are dripped into a container for reaction, thus obtaining Mg-Al-Cu-Fe hydrotalcites. The sulfur transfer agent is obtained through drying and baking the Mg-Al-Cu-Fe hydrotalcites. The sulfur transfer agent prepared by the invention not only has high absorption capacity of SOX, but also has good regeneration performance.
Description
Technical field
The present invention relates to fume-clarifying agent and preparation method, specifically a kind of catalytic cracking regeneration flue gas sulphur transfer agent and preparation method thereof.
Background technology
The ratio of residual oil and mink cell focus constantly increases in the raising of China's high-sulfur raw material processing capacity and the FCC apparatus charging, makes SO in the FCC regenerated flue gas
XThe pollution that discharging caused more serious.Along with the increasingly stringent of legislations of environmental protection and the enhancing of environmental consciousness, SO in the control catalytic cracking unit
XDischarging, become the focus of scientific research.Reduce the SO in the FCC 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).Wherein catalysis method takes off SO
XDo not need device for modifying, and easy and simple to handle, be an economical and effective technological approaches.
By using sulfur transfer additive can obviously reduce SO in the FCC regenerated flue gas
XDischarging pollution that atmosphere is caused, and again can be with SO in the FCC regenerated flue gas
XBe converted into H
2S, sulfur transfer additive obtains regeneration simultaneously, by adopting Claus method with H
2S is converted into sulphur and reclaims.In recent years, some external oil companies concentrate on the research of multicomponent sulfur transfer additive, discover the spinelle MgAl that mixes solid solution
2O
4The desulfurization performance of-MgO is better, and can effective regeneration (USP4,469,589, USP4,963,520, USP5,057,205 etc.).In magnesium aluminate spinel, introduce one or more transition metal and rare earth metal component as redox co-accelerator (as iron, vanadium and cerium etc.) (CN1101247C, CN1122702C, CN1142015C etc.), but the rare earth metal price is comparatively expensive; Can cause the FCC catalyst poisoning when content of vanadium is too high simultaneously.
Usually the preparation method of sulfur transfer additive have that the oxide cocondensation is legal, coprecipitation, glue method and the more spray drying process of industrial application altogether.By contrast, mix between prepared each metallic element of sulfur transfer additive of coprecipitation, help improving it and inhale sulphur and reducing power.
Summary of the invention
A kind of catalytic cracking regeneration flue gas sulphur transfer agent that provides at the deficiencies in the prior art and preparation method thereof is provided, and this sulfur transfer additive not only has high SO
XAdsorption capacity, and regenerability is good, and the preparation method is easy.
The object of the present invention is achieved like this:
A kind of catalytic cracking regeneration flue gas sulphur transfer agent, characteristics are: sodium metaaluminate is dissolved in the mixed solution of NaOH and sodium carbonate, form solution A, solution A again with the aqueous solution B of ferric nitrate, magnesium nitrate and copper nitrate react magnalium copper iron houghite, magnalium copper iron houghite drying, roasting get described sulfur transfer additive.
The method for preparing above-mentioned sulfur transfer additive is: with sodium metaaluminate as the aluminium source, it is dissolved in the mixed solution of NaOH and sodium carbonate, form solution A, under 60～80 ℃, with solution A and ferric nitrate, the mixed solution B of magnesium nitrate and copper nitrate drips altogether in reaction vessel, the dropping time is 0.5～1.0h, the pH value of reaction solution is controlled at 8～10, drip the back and continue to stir 4～18h nucleation crystallization, cooling then, suction filtration, wash to neutral,, get magnalium copper iron houghite at 70～120 ℃ of down dry 6～12h, at 500～700 ℃ of following roasting 4～8h, get target product.
The concentration of described solution B is 0.5～2.0mol/L; The mol ratio of sodium metaaluminate, NaOH, sodium carbonate and water was 0.15～1.5: 2.8～4.0 when solution A formed: 0.1～0.8: 55.6; Two kinds of solution equal-volume reactions, wherein the mol ratio of magnesium (Mg), aluminium (Al), copper (Cu), four kinds of metals of iron (Fe) is 0.5～8.0: 1.0: 0.015～0.20: 0.04～0.30.
Compared with prior art, sulfur transfer additive provided by the invention not only has high SO
XAdsorption capacity, and regenerability is good; And has a NO in the potential flue gas removing
XAbility.
The specific embodiment
Below will the present invention is further elaborated by specific embodiment:
Embodiment 1
With 100g H
2O, 2.0g NaAlO
2, 11.9g NaOH and 1.5g Na
2CO
3Put into container, stir, form solution A; 100g H
2O, 30.8g Mg (NO
3)
26 H
2O, 1.8g Fe (NO
3)
39H
2O, 0.2gCu (NO
3)
23 H
2O puts into another container, stirs, and forms solution B; Under 70 ℃ solution A, solution B are dropped in the three-neck flask of 1L simultaneously, the dropping time is 0.5h, and the pH value of solution is controlled at 9, drip the back and continue to stir 15h nucleation crystallization, cooling then, suction filtration, washing are extremely neutral, 80 ℃ of dry 8h, and 700 ℃ of roasting 4h get product A 1.
Embodiment 2
With 100g H
2O, 9.8g NaAlO
2, 15.1g NaOH and 6.76g Na
2CO
3Put into container, stir, form solution A; 100g H
2O, 15.4g Mg (NO
3)
26 H
2O, 3.0g Fe (NO
3)
39H
2O, 0.45gCu (NO
3)
23 H
2O puts into another container, stirs, and forms solution B; Under 60 ℃ solution A, solution B are dropped in the three-neck flask of 1L simultaneously, the dropping time is 0.5h, and the pH value of solution is controlled at 8, drip the back and continue to stir 18h nucleation crystallization, cooling then, suction filtration, washing are extremely neutral, 100 ℃ of dry 7h, and 600 ℃ of roasting 6h get product A 2.
Embodiment 3
With 100g H
2O, 1.2g NaAlO
2, 11.7g NaOH and 1.0g Na
2CO
3Put into container, stir, form solution A; 100g H
2O, 30.8g Mg (NO
3)
26 H
2O, 1.8g Fe (NO
3)
39H
2O, 0.2gCu (NO
3)
23 H
2O puts into another container, stirs, and forms solution B; Under 80 ℃ solution A, solution B are dropped in the three-neck flask of 1L simultaneously, the dropping time is 1.0h, and the pH value of solution is controlled at 10, drip the back and continue to stir 4h nucleation crystallization, cooling then, suction filtration, washing are extremely neutral, 70 ℃ of dry 10h, and 500 ℃ of roasting 8h get product A 3.
Embodiment 4
With 100g H
2O, 2.0g NaAlO
2, 11.9g NaOH and 1.5g Na
2CO
3Put into container, stir, form solution A; 100g H
2O, 30.8g Mg (NO
3)
26 H
2O, 0.5g Fe (NO
3)
39H
2O, 0.2gCu (NO
3)
23 H
2O puts into another container, stirs, and forms solution B; Under 70 ℃ solution A, solution B are dropped in the three-neck flask of 1L simultaneously, the dropping time is 0.5h, and the pH value of solution is controlled at 9, drip the back and continue to stir 10h nucleation crystallization, cooling then, suction filtration, washing are extremely neutral, 120 ℃ of dry 6h, and 700 ℃ of roasting 4h get product A 4.
Embodiment 5
With 100g H
2O, 2.0g NaAlO
2, 11.9g NaOH and 1.5g Na
2CO
3Put into container, stir, form solution A; 100g H
2O, 30.8g Mg (NO
3)
26 H
2O, 2.6g Fe (NO
3)
39H
2O, 0.2gCu (NO
3)
23 H
2O puts into another container, stirs, and forms solution B; Under 70 ℃ solution A, solution B are dropped in the three-neck flask of 1L simultaneously, the dropping time is 0.5h, and the pH value of solution is controlled at 9, drip the back and continue to stir 12h nucleation crystallization, cooling then, suction filtration, washing are extremely neutral, 70 ℃ of dry 12h, and 700 ℃ of roasting 4h get product A 5.
Embodiment 6
With 100g H
2O, 2.0g NaAlO
2, 11.9g NaOH and 1.5g Na
2CO
3Put into container, stir, form solution A; 100g H
2O, 30.8g Mg (NO
3)
26 H
2O, 1.8g Fe (NO
3)
39H
2O, 0.1gCu (NO
3)
23 H
2O puts into another container, stirs, and forms solution B; Under 70 ℃ solution A, solution B are dropped in the three-neck flask of 1L simultaneously, the dropping time is 0.5h, and the pH value of solution is controlled at 9, drip the back and continue to stir 15h nucleation crystallization, cooling then, suction filtration, washing are extremely neutral, 80 ℃ of dry 8h, and 700 ℃ of roasting 4h get product A 6.
Embodiment 7
With 100g H
2O, 2.0g NaAlO
2, 11.9g NaOH and 1.5g Na
2CO
3Put into container, stir, form solution A; 100g H
2O, 30.8g Mg (NO
3)
26 H
2O, 1.8g Fe (NO
3)
39H
2O, 1.0gCu (NO
3)
23 H
2O puts into another container, stirs, and forms solution B; Under 70 ℃ solution A, solution B are dropped in the three-neck flask of 1L simultaneously, the dropping time is 0.5h, and the pH value of solution is controlled at 9, drip the back and continue to stir 15h nucleation crystallization, cooling then, suction filtration, washing are extremely neutral, 80 ℃ of dry 8h, and 700 ℃ of roasting 5h get product A 7.
The appreciation condition and the evaluation result of sulfur transfer additive performance are as follows:
The reaction condition of analog stream fluidized catalytic cracking (FCC) device utilizes the micro-thermal analysis balance to estimate the performance of sulfur transfer additive.Phase I: take by weighing the porcelain crucible that sample about 2.0mg is put into hot assay balance, logical nitrogen 40mL/min is warming up to 700 ℃, constant temperature 10min with the speed of 5 ℃/min; Second stage: sulphur is inhaled in oxidation, feeds gaseous mixture 2% (v) SO
2, 8% (v) O
2(the v) N with 90%
2, total gas flow rate is 50mL/min, 700 ℃ of constant temperature 35min; Phase III: reduction and desulfurization, the temperature of thermobalance are reduced to 600 ℃, feed gaseous mixture 33% (v) H
2(the v) N with 67%
2, total gas flow rate is 50mL/min, constant temperature 40min.Adsorption capacity SO
XAdsorption capacity is represented, hydrogen reducing performance H
2Reduction degree is represented.
The results are shown in Table 1
Table 1
| The embodiment numbering | Sulfur transfer additive | SO XAdsorption capacity/% | Adsorption time/min | H 2Reduction degree/% | Recovery time/min |
| 1 | A1 | 165.84 | 6 | 100 | 10 |
| 2 | A2 | 110.21 | 6 | 100 | 9 |
| 3 | A3 | 168.97 | 6 | 100 | 10 |
| 4 | A4 | 169.55 | 18 | 98.5 | 20 |
| 5 | A5 | 150.00 | 6 | 100 | 8 |
| 6 | A6 | 168.64 | 9 | 100 | 10 |
| 7 | A7 | 153.54 | 6 | 100 | 11 |
Claims (3)
1. catalytic cracking regeneration flue gas sulphur transfer agent, it is characterized in that: sodium metaaluminate is dissolved in the mixed solution of NaOH and sodium carbonate, form solution A, solution A is reacted with ferric nitrate, magnesium nitrate and copper nitrate mixed solution B again, get magnalium copper iron houghite, magnalium copper iron houghite drying, roasting get described sulfur transfer additive.
2. method for preparing the described catalytic cracking regeneration flue gas sulphur transfer agent of claim 1, it is characterized in that with sodium metaaluminate as the aluminium source, it is dissolved in the mixed solution of NaOH and sodium carbonate, form solution A, under 60～80 ℃, with solution A and ferric nitrate, the mixed solution B of magnesium nitrate and copper nitrate drips altogether in reaction vessel, the dropping time is 0.5～1.0h, the pH value of reaction solution is controlled at 8～10, drips the back and continues to stir 4～18h nucleation crystallization, cooling then, suction filtration, washing is to neutral, at 70～120 ℃ of down dry 6～12h, get magnalium copper iron houghite,, get target product at 500～700 ℃ of following roasting 4～8h.
3. preparation method according to claim 2, the concentration that it is characterized in that described solution B is 0.5～2.0mol/L; The mol ratio of sodium metaaluminate, NaOH, sodium carbonate and water was 0.15～1.5: 2.8～4.0 when solution A formed: 0.1～0.8: 55.6; Two kinds of solution equal-volume reactions, wherein the mol ratio of magnesium, aluminium, copper, four kinds of metals of iron is 0.5～8.0: 1.0: 0.015～0.20: 0.04～0.30.
Priority Applications (1)
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|---|---|---|---|
| CNA2007100471122A CN101219327A (en) | 2007-10-17 | 2007-10-17 | Sulfur transfer agent for catalytic cracking regeneration flue gas and method for producing the same |
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|---|---|---|---|
| CNA2007100471122A CN101219327A (en) | 2007-10-17 | 2007-10-17 | Sulfur transfer agent for catalytic cracking regeneration flue gas and method for producing the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102151484A (en) * | 2011-01-27 | 2011-08-17 | 山东大学 | Catalytic cracking regenerated flue gas sulfur transfer agent and preparation method thereof |
| CN102755817A (en) * | 2012-07-17 | 2012-10-31 | 中国石油天然气股份有限公司 | Method for preparing catalytic cracking flue gas sulfur transfer additive with high specific surface area |
| CN105664680A (en) * | 2016-03-29 | 2016-06-15 | 黄河三角洲京博化工研究院有限公司 | Liquid FCC regenerative flue gas sulfur transfer agent |
-
2007
- 2007-10-17 CN CNA2007100471122A patent/CN101219327A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102151484A (en) * | 2011-01-27 | 2011-08-17 | 山东大学 | Catalytic cracking regenerated flue gas sulfur transfer agent and preparation method thereof |
| CN102151484B (en) * | 2011-01-27 | 2013-06-19 | 山东大学 | Catalytic cracking regenerated flue gas sulfur transfer agent and preparation method thereof |
| CN102755817A (en) * | 2012-07-17 | 2012-10-31 | 中国石油天然气股份有限公司 | Method for preparing catalytic cracking flue gas sulfur transfer additive with high specific surface area |
| CN102755817B (en) * | 2012-07-17 | 2015-01-21 | 中国石油天然气股份有限公司 | Method for preparing catalytic cracking flue gas sulfur transfer additive with high specific surface area |
| CN105664680A (en) * | 2016-03-29 | 2016-06-15 | 黄河三角洲京博化工研究院有限公司 | Liquid FCC regenerative flue gas sulfur transfer agent |
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Open date: 20080716 |