CN104162455A - A water-soluble catalytic cracking multifunctional deactivator and a preparing method thereof - Google Patents
A water-soluble catalytic cracking multifunctional deactivator and a preparing method thereof Download PDFInfo
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- CN104162455A CN104162455A CN201410312992.1A CN201410312992A CN104162455A CN 104162455 A CN104162455 A CN 104162455A CN 201410312992 A CN201410312992 A CN 201410312992A CN 104162455 A CN104162455 A CN 104162455A
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Abstract
A water-soluble catalytic cracking multifunctional deactivator is disclosed. The deactivator comprises following components by weight: 6-30% of an antimony compound and 2-10% of a ligand, with the balance being water. In addition, a preparing method of the deactivator is disclosed. The deactivator has characteristics of capability of deactivating a plurality of metals simultaneously, good dispersity, high activity, low toxicity, miscibility with water, high deposition efficiency of effective components, and significant deactivating effects.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of water-soluble catalytic cracking multi-function metal passivator and preparation method thereof.
Background technology
Needs along with development and the oil deep processing of catalytic cracking technology, catalytic cracking process generally will be mixed refining residual oil, owing to containing more metal (as nickel, iron, vanadium, sodium etc.) in residual oil, these metals are constantly deposited on FCC catalyst, cause catalyst poisoning inactivation and make selective variation, hydrogen and coke yield are increased, and gasoline and yield of light oil reduce.Pollution for metals such as nickel, iron, vanadium, sodium on poising agent, it is industrial except raw material is carried out pretreatment demetalization, generally take the replacement rate of the catalyst that preferred preventing from heavy metal ability is strong, the poising agent that draws off pollution, increasing catalyst and add the character that the means such as passivator are carried out catalyst in improvement system, to adapt to the variation of feedstock property.Wherein using passivator is cheap and the most simple method.
Summary of the invention
Goal of the invention: the object of the invention is to for the deficiencies in the prior art, a kind of simultaneously effectively passivation nickel, vanadium, the passivator to cracking catalyst poisoning are provided.
Another object of the present invention is to disclose the preparation method of above-mentioned passivator.
Technical scheme: in order to reach foregoing invention object, the present invention is specifically achieved like this: a kind of water-soluble catalytic cracking multi-function metal passivator, comprises the component of following percetage by weight: 6～30% antimonial, 2～10% part, surplus water are supplied.
Wherein, passivator also comprises the rare-earth compound of following percetage by weight 0～12%.
Wherein, described antimonial or rare-earth compound are nanoscale compound.
Wherein, described antimonial preparation method mixes with hydroxyl hydroxy acid, acid amides antimony oxide at normal pressure, 80～180 ℃ in the ratio of antimony ion, hydroxyl, amido mol ratio 3～4:0.5～1:2～3.
Wherein, described acid amides is selected from one or more in aliphatic amide or urea.
Wherein, described hydroxycarboxylic acid is selected from Alpha-hydroxy acetic acid, α-hydracrylate, alpha-hydroxybutyric acid, Alpha-hydroxy-α-methylvaleric acid, tartronic acid, hydroxysuccinic acid, 2,4-dihydroxy glutaric acid, 2,3-dihydroxypropionic acid, 2,5-dihydroxy-acid, 2,3,4-trihydroxy-butyric acid, one or more in 2,3-dyhydrobutanedioic acid.
Wherein, described rare-earth compound preparation method reacts lanthanum carbonate or cerous carbonate at normal pressure, 70～105 ℃ with glacial acetic acid, generate water-soluble lanthanum acetate or cerous acetate, acetum concentration m% is 10～30%, mol ratio 1:1～3 of carbonate and acetum.
Wherein, described part is one or more in monoethanolamine, Propanolamine, butanolamine, diethanol amine, triethanolamine.
The method of preparing above-mentioned arbitrary water-soluble catalytic cracking multi-function metal passivator, measures antimonial, part, water or rare-earth compound by formula, adds at normal temperatures and pressures water and is uniformly mixed composite forming.
Beneficial effect: compare with conventional art, tool of the present invention has the following advantages:
1, the passivator that prepared by method provided by the invention has well passivated effect, simultaneously passive metal nickel and vanadium; Method provided by the invention, for plant-scale catalytic cracking reaction, under the high contamination levels that is 7200-8400ppm, is still had to good passivation effect at Nickel Content In Catalyst.Hydrogen content in dry gas is lower than 35%, and the volume ratio of hydrogen and methane is below 1.4, and has higher gasoline and diesel yield.
2, the passivator good dispersion that prepared by method provided by the invention, active high.After organo-metallic compound is adsorbed on catalyst and decomposes, form the metallic compound of high-ratio surface, passivator reaches the object of noxious metals in high efficiency trapping, so passivator has good dispersion, active high feature.
3, the passivator that prepared by method provided by the invention has the advantages that toxicity is low, and owing to having synthesized the main body of water-soluble organo-metallic compound as passivator, not sulfur-bearing, phosphorus in passivator, have and have no irritating odor, and do not corrode the advantages such as skin, hypotoxicity.
4, the passivator that prepared by method provided by the invention can dissolve each other with water, and the heating section before mixing with feedstock oil there will not be precipitation, therefore in filling process, there will not be the phenomenon of blocking pipeline; For example, passivator prepared by method provided by the invention can be infinitely miscible with water, and long-term storage does not produce precipitation, passivator pour point low (its pour point is generally lower than-25 ℃), and flash-point high (all higher than 100 ℃), is convenient to store and transportation.
5, active principle deposition is high, and passivation effect is remarkable.
The specific embodiment
Embodiment 1:
Get mass percent and be 6% antimonial, 10% part, 12% rare-earth compound, surplus water and supply, add at normal temperatures and pressures water and be uniformly mixed composite forming.The compound of described antimony is prepared as: at normal pressure, 80 ℃, antimony oxide is mixed in the ratio of antimony ion, hydroxyl, amido mol ratio 3:0.5:2 with Alpha-hydroxy acetic acid, urea; Described part is monoethanolamine; Being prepared as of described rare-earth compound: lanthanum carbonate is reacted with glacial acetic acid at normal pressure, 70 ℃, generate water-soluble lanthanum acetate, acetum concentration m% is 10%, the mol ratio 1:3 of lanthanum carbonate and acetum.
Embodiment 2:
Get mass percent and be 12% antimonial, 9% part, 10% rare-earth compound, surplus water and supply, add at normal temperatures and pressures water and be uniformly mixed composite forming.The compound of described antimony is prepared as: at normal pressure, 100 ℃, antimony oxide is mixed in the ratio of antimony ion, hydroxyl, amido mol ratio 4:0.5:3 with hydroxysuccinic acid, DMF; Described part is Propanolamine; Being prepared as of described rare-earth compound: cerous carbonate is reacted with glacial acetic acid at normal pressure, 85 ℃, generate water-soluble cerous acetate, acetum concentration m% is 20%, the mol ratio 1:2 of cerous carbonate and acetum.
Embodiment 3:
Getting mass percent is that 18% antimonial, 8% part, surplus water are supplied, and adds at normal temperatures and pressures water and is uniformly mixed composite forming.The compound of described antimony is prepared as: at normal pressure, 120 ℃, antimony oxide and 2,5-dihydroxy-acid, acrylamide are mixed in the ratio of antimony ion, hydroxyl, amido mol ratio 3:0.5:2; Described part is butanolamine.
Embodiment 4:
Get mass percent and be 20% antimonial, 6% part, 6% rare-earth compound, surplus water and supply, add at normal temperatures and pressures water and be uniformly mixed composite forming.The compound of described antimony is prepared as: at normal pressure, 140 ℃, antimony oxide is mixed in the ratio of antimony ion, hydroxyl, amido mol ratio 4:1:2 with hydroxysuccinic acid, α-hydracrylate mixture, DMA; Described part is butanolamine and diethanol amine mixture; Being prepared as of described rare-earth compound: lanthanum carbonate is reacted with glacial acetic acid at normal pressure, 100 ℃, generate water-soluble lanthanum acetate, acetum concentration m% is 10%, the mol ratio 1:1 of lanthanum carbonate and acetum.
Embodiment 5:
Get mass percent and be 25% antimonial, 4% part, 2% rare-earth compound, surplus water and supply, add at normal temperatures and pressures water and be uniformly mixed composite forming.The compound of described antimony is prepared as: at normal pressure, 160 ℃, antimony oxide and 2,3-dyhydrobutanedioic acid, erucyl amide are mixed in the ratio of antimony ion, hydroxyl, amido mol ratio 3:1:3; Described part is diethanol amine; Being prepared as of described rare-earth compound: cerous carbonate is reacted with glacial acetic acid at normal pressure, 105 ℃, generate water-soluble cerous acetate, acetum concentration m% is 15%, the mol ratio 1:3 of cerous carbonate and acetum.
Embodiment 6:
Getting mass percent is that 28% antimonial, 3% part, surplus water are supplied, and adds at normal temperatures and pressures water and is uniformly mixed composite forming.The compound of described antimony is prepared as: at normal pressure, 180 ℃, antimony oxide is mixed in the ratio of antimony ion, hydroxyl, amido mol ratio 4:1:3 with Alpha-hydroxy-α-methylvaleric acid, tartronic acid mixture, polyacrylamide; Described part is Propanolamine and triethanolamine mixture.
Embodiment 7:
Getting mass percent is 30% antimonial, 2% part, 4% rare-earth compound, and surplus water is supplied, and adds at normal temperatures and pressures water and is uniformly mixed composite forming.The compound of described antimony is prepared as: at normal pressure, 100 ℃, antimony oxide and 2,3-dihydroxypropionic acid, acrylamide are mixed in the ratio of antimony ion, hydroxyl, amido mol ratio 4:0.5:2; Described part is triethanolamine; Being prepared as of described rare-earth compound: lanthanum carbonate is reacted with glacial acetic acid at normal pressure, 90 ℃, generate water-soluble lanthanum acetate, acetum concentration m% is 25%, the mol ratio 1:2 of lanthanum carbonate and acetum.
Claims (9)
1. a water-soluble catalytic cracking multi-function metal passivator, is characterized in that, comprises the component of following percetage by weight: 6～30% antimonial, 2～10% part, surplus water are supplied.
2. water-soluble catalytic cracking multi-function metal passivator according to claim 1, is characterized in that, also comprises the rare-earth compound of following percetage by weight 0～12%.
3. water-soluble catalytic cracking multi-function metal passivator according to claim 1 and 2, it is characterized in that, described antimonial preparation method mixes with hydroxyl hydroxy acid, acid amides antimony oxide at normal pressure, 80～180 ℃ in the ratio of antimony ion, hydroxyl, amido mol ratio 4～3:0.5～1:3～2.
4. acid amides according to claim 3 is selected from one or more in aliphatic amide or urea.
5. water-soluble catalytic cracking multi-function metal passivator according to claim 3, it is characterized in that, described hydroxycarboxylic acid is selected from Alpha-hydroxy acetic acid, α-hydracrylate, alpha-hydroxybutyric acid, Alpha-hydroxy-α-methylvaleric acid, tartronic acid, hydroxysuccinic acid, 2,4-dihydroxy glutaric acid, 2,3-dihydroxypropionic acid, 2,5-dihydroxy-acid, 2,3,4-trihydroxy-butyric acid, one or more in 2,3-dyhydrobutanedioic acid.
6. water-soluble catalytic cracking multi-function metal passivator according to claim 2, it is characterized in that, described rare-earth compound preparation method reacts lanthanum carbonate or cerous carbonate at normal pressure, 70～105 ℃ with glacial acetic acid, generate water-soluble lanthanum acetate or cerous acetate, acetum concentration m% is 10～30%, mol ratio 1:1～3 of carbonate and acetum.
7. water-soluble catalytic cracking multi-function metal passivator according to claim 1 and 2, is characterized in that, described part is one or more in monoethanolamine, Propanolamine, butanolamine, diethanol amine, triethanolamine.
8. water-soluble catalytic cracking multi-function metal passivator according to claim 1 and 2, is characterized in that, described antimonial or rare-earth compound are nanoscale compound.
9. the method for the above-mentioned arbitrary water-soluble catalytic cracking multi-function metal passivator of preparation, is characterized in that, by formula, measures antimonial, part, water or rare-earth compound, adds at normal temperatures and pressures water and is uniformly mixed composite forming.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841490A (en) * | 2015-04-08 | 2015-08-19 | 宜兴市中大凯化工有限公司 | Method for preparing double metal deactivator |
| CN105457638A (en) * | 2015-11-12 | 2016-04-06 | 淄博康能达稀土材料有限公司 | Nickel-aluminum oxide, and preparation method and application thereof |
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| US4264434A (en) * | 1978-07-25 | 1981-04-28 | Phillips Petroleum Company | Passivation of metals which contaminate cracking catalysts with antimony tris (hydrocarbyl sulfonate) |
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| CN1294173A (en) * | 1999-10-21 | 2001-05-09 | 王槐平 | Water-soluble fluidized catalytic cracking passivator for metals and its preparing process |
| CA2737386A1 (en) * | 2008-09-18 | 2010-03-25 | Darush Farshid | Systems and methods for producing a crude product |
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| CN102974400A (en) * | 2012-12-11 | 2013-03-20 | 江苏汉光实业股份有限公司 | Catalytic cracking double-metal deactivator |
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2014
- 2014-07-02 CN CN201410312992.1A patent/CN104162455A/en active Pending
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| US4264434A (en) * | 1978-07-25 | 1981-04-28 | Phillips Petroleum Company | Passivation of metals which contaminate cracking catalysts with antimony tris (hydrocarbyl sulfonate) |
| CN1176288A (en) * | 1996-09-09 | 1998-03-18 | 中国石油化工总公司 | Preparation of catalytic cracking and metal passivating agent containing antimonide |
| CN1294173A (en) * | 1999-10-21 | 2001-05-09 | 王槐平 | Water-soluble fluidized catalytic cracking passivator for metals and its preparing process |
| CA2737386A1 (en) * | 2008-09-18 | 2010-03-25 | Darush Farshid | Systems and methods for producing a crude product |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841490A (en) * | 2015-04-08 | 2015-08-19 | 宜兴市中大凯化工有限公司 | Method for preparing double metal deactivator |
| CN105457638A (en) * | 2015-11-12 | 2016-04-06 | 淄博康能达稀土材料有限公司 | Nickel-aluminum oxide, and preparation method and application thereof |
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Application publication date: 20141126 |