CN1727052A - Method for preparing high effective sulfur transfer agent for catalytic cracking fume - Google Patents
Method for preparing high effective sulfur transfer agent for catalytic cracking fume Download PDFInfo
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- CN1727052A CN1727052A CN 200510028233 CN200510028233A CN1727052A CN 1727052 A CN1727052 A CN 1727052A CN 200510028233 CN200510028233 CN 200510028233 CN 200510028233 A CN200510028233 A CN 200510028233A CN 1727052 A CN1727052 A CN 1727052A
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- aluminium
- zinc
- mangnesium
- sulfur transfer
- cerium
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Abstract
A process for preparing the efficient sulfur transferring agent used for the catalytic cracking of fume includes such steps as preparing ZnMgAlCe hydrotalcite from the active components (Zn, Mg and Al) and assistant (Ce and V) by codeposition method, preparing V-dipped ZnMgAlCo hydrotalcite by anionic exchange method, proportionally mixing it with kaolin and Al sol, grinding, vacuum drying and calcining. Its advantages are high SOx adsorptivity and desorptivity and high mechanical strength.
Description
Technical field
The present invention relates to the preparation method of high-performance sulfur transfer agent for catalytic cracking flue gas, exactly, be a kind of be the method that key component prepares sulfur transfer additive by zinc mangnesium-aluminium-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
XThe 6-7% 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 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).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 desulfurizing agent.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.).In recent years, more domestic research institutions are the development that key component has been carried out sulfur transfer additive with the magnesium aluminate spinel, but have shortcomings (CN1101247C, CN1122702C, CN1142015C etc.) such as desulfuration efficiency is low, anti-wear performance difference.
Summary of the invention
Houghite (LDHs) is a class new catalytic material that is subjected to extensive concern in recent years.The mixed metal hydroxides with hydrotalcite (HT) 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 objective of the invention is to provide at the deficiencies in the prior art a kind of be the method that key component prepares sulfur transfer additive by zinc mangnesium-aluminium-cerium houghite, the sulfur transfer additive that makes with this method has SO efficiently
XAbsorption and desorption performance and excellent mechanical intensity.
The object of the present invention is achieved like this:
A kind of preparation method of high-performance sulfur transfer agent for catalytic cracking flue gas is to be active component with zinc, magnesium and aluminium, is auxiliary agent with cerium and vanadium, and prepare by following steps: (1) coprecipitation prepares zinc mangnesium-aluminium-cerium houghite (ZnMgAlCe-LDH); (2) anion exchange method prepares vanadium dipping-zinc mangnesium-aluminium-cerium houghite (V/ZnMgAlCe-LDH) product; (3) with gained vanadium dipping-zinc mangnesium-aluminium-cerium houghite (V/ZnMgAlCe-LDH) product and the kaolin of 10～30 parts of weight and the aluminium colloidal sol mixed grinding of 50～100 parts of weight of 60～70 parts of weight, vacuum drying, roasting is prepared into sulfur transfer additive.
It is under 60-80 ℃ that described coprecipitation prepares zinc mangnesium-aluminium-cerium houghite (ZnMgAlCe-LDH), with zinc salt, magnesium salts, the mixed solution of aluminium salt and cerium salt is added drop-wise in the mixed solution of NaOH and sodium carbonate, the dropping time is 0.3-0.7h, the pH value of solution is controlled between 8～10, drip the back and continue to stir 4～18h nucleation crystallization, cooling then, suction filtration, washing are to neutral, at 70-120 ℃ of following vacuum drying 6-8h, at 400～600 ℃ of following roasting 6～8h, obtain zinc mangnesium-aluminium-cerium houghite (ZnMgAlCe-LDH).The mol ratio of zinc (Zn), magnesium (Mg), three kinds of metals of aluminium (Al) is at following range changing 1.0: 1.0～4.5: 1.0～2.0.
It is the zinc mangnesium-aluminium-cerium houghite (ZnMgAlCe-LDH) and ammonium metavanadate solution dipping that above-mentioned steps is obtained that described anion exchange method prepares vanadium dipping-zinc mangnesium-aluminium-cerium houghite (V/ZnMgAlCe-LDH) product, filter then, washing, at 110-130 ℃ of following vacuum drying 6～8h, at 400～600 ℃ of roasting 6～8h, obtain vanadium dipping-zinc mangnesium-aluminium-cerium houghite (V/ZnMgAlCe-LDH) product; The amount of ammonium metavanadate is controlled at and makes V in the product
2O
5Mass content at 2-4%.
Coprecipitation prepares the used active component zinc of zinc mangnesium-aluminium-cerium houghite (ZnMgAlCe-LDH), magnesium and aluminium and selects zinc nitrate, magnesium nitrate, aluminum nitrate for use, and adjuvant used is cerous nitrate and ammonium metavanadate.
The sulfur transfer additive baking temperature is 80～120 ℃, and sintering temperature is 600～700 ℃, and the time is 3～5h.
Compared with prior art, sulfur transfer additive provided by the invention has higher SO
XAbsorption and desorption efficient and mechanical strength advantages of higher.
The specific embodiment
Below will the present invention is further elaborated by specific embodiment:
Embodiment 1
The preparation of the 1st step zinc mangnesium-aluminium-cerium houghite (ZnMgAlCe-LDH)
In the three-neck flask of 1L, add 500g H
2O, 24.8g NaOH and 10.9g Na
2CO
3, 70 ℃ stir after, contain 350g H to wherein dripping
2O, 11.9g Zn (NO
3)
2, 30.7g Mg (NO
3)
2, 14.7g Al
2(NO
3)
3, 4.6g Ce (NO
3)
3Solution, the dropping time is 0.5h, continues to stir into nuclear crystallization 15h after dripping.Cooling then, suction filtration, washing are to neutral, and 70 ℃ of vacuum drying 7h obtain houghite, and 450 ℃ of following roastings get product A 1.
The preparation of the 2nd step vanadium dipping-zinc mangnesium-aluminium-cerium houghite (V/ZnMgAlCe-LDH) product
0.25g NH
4VO
3Be dissolved in 6.8g H
2O, the concentration of solution should make the pH value of solution 6～8, to guarantee VO
3 -Stable existence in solution.This solution contains cerium hydrotalcite A1 with 9.7g and fully mixes, and filters 70 ℃ of following vacuum drying, spends the night, and 450 ℃ of following roastings get product B 1.
The moulding of the 3rd step sulfur transfer additive
Get 5.3gB1 and 10.0 the gram deionized waters join in the reactor, add 1.8g kaolin (Suzhou kaolin company commercial product, igloss 26.7 weight %), to wherein adding 8.8g aluminium colloidal sol (alumina content 21% weight, Chang Ling oil-refining chemical factory catalyst plant), stir after 30 minutes again, making beating, grind, drying, dried product obtains sulfur transfer additive S501 through 600 ℃ of roasting 3h.
Embodiment 2
The preparation of the 1st step zinc mangnesium-aluminium-cerium houghite (ZnMgAlCe-LDH)
In the three-neck flask of 1L, add 500g H
2O, 24.8g NaOH and 11.0g Na
2CO
3, 75 ℃ stir after, contain 350g H to wherein dripping
2O, 14.9g Zn (NO
3)
2, 25.6g Mg (NO
3)
2, 18.5g Al
2(NO
3)
3, 4.6g Ce (NO
3)
3Solution, the dropping time is 0.5h, continues to stir into nuclear crystallization 15h after dripping.Cooling then, suction filtration, washing are to neutral, and 80 ℃ of vacuum drying 6h obtain houghite A2.
The preparation of the 2nd step vanadium dipping-zinc mangnesium-aluminium-cerium houghite (V/ZnMgAlCe-LDH) product
Method gets product B 2 with the 2nd step of embodiment 1.
The moulding of the 3rd step sulfur transfer additive
Method obtains sulfur transfer additive S502 with the 3rd step of embodiment 1.
Embodiment 3
The preparation of the 1st step zinc mangnesium-aluminium-cerium houghite (ZnMgAlCe-LDH)
In the three-neck flask of 1L, add 500g H
2O, 24.8g NaOH and 11.0g Na
2CO
3, 70 ℃ stir after, contain 350g H to wherein dripping
2O, 8.5g Zn (NO
3)
2, 29.2g Mg (NO
3)
2, 21.1g Al
2(NO
3)
3, 3.1g Ce (NO
3)
3Solution, the dropping time is 0.5h, continues to stir into nuclear crystallization 13h after dripping.Cooling then, suction filtration, washing are to neutral, and 90 ℃ of vacuum drying 6h obtain houghite A3.
The preparation of the 2nd step vanadium dipping-zinc mangnesium-aluminium-cerium houghite (V/ZnMgAlCe-LDH) product
Method gets product B 3 with the 2nd step of embodiment 1.
The moulding of the 3rd step sulfur transfer additive
Method obtains sulfur transfer additive S503 with the 3rd step of embodiment 1.
Embodiment 4
The preparation of the 1st step zinc mangnesium-aluminium-cerium houghite (ZnMgAlCe-LDH)
In the three-neck flask of 1L, add 500g H
2O, 24.8g NaOH and 11.0g Na
2CO
3, 70 ℃ stir after, contain 350g H to wherein dripping
2O, 19.6g Zn (NO
3)
2, 17.1g Mg (NO
3)
2, 24.6g Al
2(NO
3)
3, 3.2g Ce (NO
3)
3Solution, the dropping time is 0.5h, continues to stir into nuclear crystallization 15h after dripping.Cooling then, suction filtration, washing are to neutral, and 70 ℃ of vacuum drying 7h obtain houghite A4.
The preparation of the 2nd step V/ZnMgAlCe-LDH
Method gets product B 4 with the 2nd step of embodiment 1.
The moulding of the 3rd step sulfur transfer additive
Method obtains sulfur transfer additive S504 with the 3rd step of embodiment 1.
Embodiment 5-8
The appreciation condition and the evaluation result of sulfur transfer additive performance are as follows:
In fixed-bed quartz reactor, investigate the performance of sulfur transfer additive S501, S502, S503, S504 respectively.Be respectively charged into 2 gram sulfur transfer additives in the quartz fixed bed reactor of 1 centimetre of internal diameter, the nitrogen that charges into flow and be 300 ml/min purged 10 minutes, was warming up to 700 ℃ then, treat catalyst mixture bed constant temperature after, switch and contain 0.5%SO
2, 5.0% oxygen, all the other are the gaseous mixture of nitrogen, adsorb after 60 minutes, switch to nitrogen again, purge 10 minutes, when adsorption process was carried out, tail gas was 1.2% hydrogen peroxide solution by concentration, to absorb the SO that is not adsorbed
2, absorption and purge after, be that 0.2% sodium hydrate aqueous solution titration is absorbed with SO with concentration
2The aqueous solution, be calculated as follows SO in 60 minutes inner catalyst mixtures
2Absorption percentage (SO
2% (V/V)).
SO
2Adsorption rate=(the SO that the 1-absorption liquid absorbs
2Total SO of mM number/by the catalyst mixture bed
2The mM number) * 100%
=(1-V
Absorption/ V
Blank) * 100%
Wherein, V
BlankBehind logical 60 minutes gaseous mixtures of empty reactor, 25 milliliters of NaOH titrating solution volumes that adsorption liquid consumed, V
AbsorptionFor the reactor of loading catalyst mixture by behind 60 minutes gaseous mixtures, 25 milliliters of NaOH titrating solution volumes that absorption liquid consumed, indicator is methyl red and methylene blue mixed indicator during titration.
Weighing absorption SO
2The time catalyst weightening finish and SO
2Desorption H on thermobalance
2The weightlessness of temperature programming record catalyst under the atmosphere.
SO
2The oxidation absorption weightening finish * 100% of the reduction weightlessness/sulfur transfer additive of desorption rate %=sulfur transfer additive
The results are shown in Table 1.
Table 1
| The embodiment numbering | Sulfur transfer additive | SO 2Adsorption rate/% | SO 2Desorption rate/% | Abrasion resistance index |
| 5 | S501 | 80.5 | 97.2 | 2.3 |
| 6 | S502 | 79.2 | 96.5 | 2.4 |
| 7 | S503 | 76.3 | 98.4 | 2.0 |
| 8 | S504 | 74.2 | 95.0 | 2.5 |
Claims (6)
1, a kind of preparation method of high-performance sulfur transfer agent for catalytic cracking flue gas is characterized in that with zinc, magnesium and aluminium be active component, is auxiliary agent with cerium and vanadium, and prepare by following steps: (1) coprecipitation prepares zinc mangnesium-aluminium-cerium houghite; (2) anion exchange method prepares vanadium dipping-zinc mangnesium-aluminium-cerium houghite product; (3) with gained vanadium dipping-zinc mangnesium-aluminium-cerium houghite product and the kaolin of 10～30 parts of weight and the aluminium colloidal sol mixed grinding of 50～100 parts of weight of 60～70 parts of weight, vacuum drying, roasting is prepared into sulfur transfer additive.
2, the preparation method of high-performance sulfur transfer agent for catalytic cracking flue gas according to claim 1, it is characterized in that it is under 60-80 ℃ that described coprecipitation prepares zinc mangnesium-aluminium-cerium houghite, with zinc salt, magnesium salts, the mixed solution of aluminium salt and cerium salt is added drop-wise in the mixed solution of NaOH and sodium carbonate, the dropping time is 0.3-0.7h, the pH value of solution is controlled between 8～10, drip the back and continue to stir 4～18h nucleation crystallization, cooling then, suction filtration, washing is to neutral, at 70-120 ℃ of following vacuum drying 6-8h, at 400～600 ℃ of following roasting 6～8h, obtain zinc mangnesium-aluminium-cerium houghite.
3, the preparation method of high-performance sulfur transfer agent for catalytic cracking flue gas according to claim 1, it is characterized in that it is zinc mangnesium-aluminium-cerium houghite and the ammonium metavanadate solution dipping that above-mentioned steps is obtained that described anion exchange method prepares vanadium dipping-zinc mangnesium-aluminium-cerium houghite product, filter then, washing, at 110-130 ℃ of following vacuum drying 6～8h, at 400～600 ℃ of roasting 6～8h, obtain vanadium dipping-zinc mangnesium-aluminium-cerium houghite product.
4, the preparation method of high-performance sulfur transfer agent for catalytic cracking flue gas according to claim 1 is characterized in that coprecipitation prepares zinc mangnesium-aluminium-cerium houghite used active component zinc, magnesium and aluminium and selects zinc nitrate, magnesium nitrate, aluminum nitrate for use.
5, the preparation method of high-performance sulfur transfer agent for catalytic cracking flue gas according to claim 1 is characterized in that it is cerous nitrate and ammonium metavanadate that coprecipitation prepares the used auxiliary agent of zinc mangnesium-aluminium-cerium houghite.
6, the preparation method of high-performance sulfur transfer agent for catalytic cracking flue gas according to claim 1, the sulfur transfer additive baking temperature is 80～120 ℃, and sintering temperature is 600～700 ℃, and the time is 3～5h.
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| CN100402147C (en) * | 2006-05-19 | 2008-07-16 | 华东师范大学 | High-performance sulfur transfer agent for catalytic cracking flue gas and its preparing process |
| 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 |
| CN104399478A (en) * | 2014-11-07 | 2015-03-11 | 陕西禾合化工科技有限公司 | Method for catalytic preparation of sulfur transfer agent with IIIB group element modified hydrotalcite-like compound structure |
| CN104722311A (en) * | 2015-03-12 | 2015-06-24 | 张伟 | Sulfur-transferring additive for regenerative flue gas in catalytic cracking and preparation method thereof |
| CN109092241A (en) * | 2018-09-04 | 2018-12-28 | 东营科尔特新材料有限公司 | It magnalium zinc-base houghite adsorbent and preparation method and is applied in liquefied gas fine de-sulfur |
| CN111545162A (en) * | 2019-02-12 | 2020-08-18 | 中国石油天然气股份有限公司 | Sulfur dioxide adsorbent and preparation method thereof |
| CN113713800A (en) * | 2021-09-15 | 2021-11-30 | 中国石油化工股份有限公司 | High-temperature flue gas desulfurizer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100402147C (en) * | 2006-05-19 | 2008-07-16 | 华东师范大学 | High-performance sulfur transfer agent for catalytic cracking flue gas and its preparing process |
| 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 |
| CN101905118B (en) * | 2010-06-29 | 2012-07-11 | 北京化工大学 | Preparation method for high-efficiency sulfur transfer agent active component in catalytic cracking flume |
| CN104399478B (en) * | 2014-11-07 | 2017-07-11 | 陕西禾合化工科技有限公司 | One kind prepares sulfur transfer additive method with the family element modified hydrotalcite-like compound catalysis of III B |
| CN104399478A (en) * | 2014-11-07 | 2015-03-11 | 陕西禾合化工科技有限公司 | Method for catalytic preparation of sulfur transfer agent with IIIB group element modified hydrotalcite-like compound structure |
| CN104722311A (en) * | 2015-03-12 | 2015-06-24 | 张伟 | Sulfur-transferring additive for regenerative flue gas in catalytic cracking and preparation method thereof |
| CN104722311B (en) * | 2015-03-12 | 2017-01-18 | 张伟 | Sulfur-transferring additive for regenerative flue gas in catalytic cracking and preparation method thereof |
| CN109092241A (en) * | 2018-09-04 | 2018-12-28 | 东营科尔特新材料有限公司 | It magnalium zinc-base houghite adsorbent and preparation method and is applied in liquefied gas fine de-sulfur |
| CN109092241B (en) * | 2018-09-04 | 2021-08-10 | 东营科尔特新材料有限公司 | Magnesium-aluminum-zinc hydrotalcite adsorbent, preparation method and application thereof in refined desulfurization of liquefied gas |
| CN111545162A (en) * | 2019-02-12 | 2020-08-18 | 中国石油天然气股份有限公司 | Sulfur dioxide adsorbent and preparation method thereof |
| CN111545162B (en) * | 2019-02-12 | 2023-08-22 | 中国石油天然气股份有限公司 | Sulfur dioxide adsorbent and preparation method thereof |
| CN113713800A (en) * | 2021-09-15 | 2021-11-30 | 中国石油化工股份有限公司 | High-temperature flue gas desulfurizer and preparation method thereof |
| CN113713800B (en) * | 2021-09-15 | 2024-06-04 | 中国石油化工股份有限公司 | High-temperature flue gas desulfurizing agent and preparation method thereof |
| RU2818952C1 (en) * | 2023-07-11 | 2024-05-07 | Акционерное общество "Газпромнефть - Омский НПЗ" (АО "Газпромнефть-ОНПЗ") | Cracking catalyst additive to reduce sulfur oxide emissions and method of its preparation |
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