CN100494320C - Catalytic cracking fixed bed alkaline-free mercaptan removal method for gasoline - Google Patents
Catalytic cracking fixed bed alkaline-free mercaptan removal method for gasoline Download PDFInfo
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- CN100494320C CN100494320C CNB2006100172959A CN200610017295A CN100494320C CN 100494320 C CN100494320 C CN 100494320C CN B2006100172959 A CNB2006100172959 A CN B2006100172959A CN 200610017295 A CN200610017295 A CN 200610017295A CN 100494320 C CN100494320 C CN 100494320C
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Abstract
The invention disclosed a catalyzing de-thiol method which is free of alkali. The method is meant for the cracking gasoline on fixed bed in the petrochemical industry. The main characteristic of the invention is that activator which is the mixture of alcohol, guanidines and de-thiol catalyst is added before the gasoline entered the thiol oxygenizing tower. The guanidines in the activator make the gasoline easily integrated with macromolecule thiol in the gasoline so it's easier to remove the thiol with the phthalocyanine catalyst. Since thedissolubility of phthalocyanine in quaternary ammonium base, the activating effect is even better. The de-thiol catalyst can make the thiol contact the catalyst more sufficiently; besides, the catalyst in the activator can supplement the catalyst loss on the fixed bed so as to remove the thiol in the gasoline completely. Compared to the present technologies which use alkali during the process, the invention has many advantages such as high effect of de-thiol, low cost, cut down the discharge of alkali waste liquid and environment-friendly.
Description
Technical field
The invention belongs to the petrochemical technology field, especially the fixed bed alkali-free removes the method for catalytic cracking (FCC) sulfur in gasoline alcohol.
Background technology
Mercaptan in catalytic cracking (FCC) gasoline also has unpleasant stink except that having corrodibility and the pollution to air, so the FCC demercaptaning for gasoline claims deodorization again.
Existing deodorization technique is meant that generally making molecular oxygen in the presence of alkaline medium (sodium hydroxide solution) and catalyzer is disulphide, that is: 2RSH+1/2O with mercaptan oxidation
2→ RSSR+H
2O.
US4908122 discloses a kind of deodorizing technology that contains the sour hydrocarbon fraction of mercaptan, this technology make sour hydrocarbon fraction in the presence of oxygen or air with a kind of catalytic composition that can effectively mercaptan oxidation be become disulphide, ammonium hydroxide contacts with quaternary ammonium salt except that oxyhydroxide.Catalytic composition is the phthalocyanine cobalt catalyst that loads on the absorbent charcoal carrier, and the concentration of ammonium hydroxide is the 0.1-200ppm of hydrocarbon-fraction, and quaternary ammonium salt is the chlorate of quaternary ammonium, and concentration is 0.05-500ppm.This invention does not use any highly basic need not make the sour hydrocarbon fraction deodorization by any strong basicity oxyhydroxide yet.The disclosed a kind of sour hydrocarbon fraction deodorizing technology that contains mercaptan of US4923596 is characterised in that: hydrocarbon-fraction is contacted with the alkaline solution of containing metal intercalating agent with the tensio-active agent quaternary ammonium compound in the presence of oxygenant.Preferred quaternary ammonium compound is a quaternary ammonium hydroxide.Between quaternary ammonium compound and metal-chelate mixture, synergy is arranged.Alkaline solution is the aqueous sodium hydroxide solution of 0.1wt%-25wt%.Oxygenant is oxygen or air.The metal-chelate mixture is the phthalocyanine cobalt, and its concentration with 0.1-2000ppm exists.US5413704 discloses a kind of deodorizing technology that contains the sour hydrocarbon fraction of mercaptan, comprise: in the presence of oxygenant and polar compound, the intermediate hydrocarbons cut is contacted with the mixture of being made up of solid alkali and the metal-chelate mixture on being dispersed in non-alkali solid carrier, above-mentioned solid alkali is selected from: (a) alkaline earth metal oxide, (b) metal oxide solid solution, (c) stratified double-hydroxide.Described polar compound is selected from water, unary alcohol, and di-alcohols, the ester class, ketone and their mixture, first-selected polar compound is water and methyl alcohol.CN97101931.2 discloses a kind of technology of aviation kerosene alkali-free sweetening, comprise raw material is navigated coal with after activator solution mixes, carry out mercaptan removal with air by beds, catalyst system therefor is a sulfonated phthalocyanine cobalt, used activator is ZX-1827, and its effect is that sweetening reaction is carried out under homogeneous phase, has avoided the phase transition problem, quicken the RSH oxidation, strengthened the deodorization ability.CN90102633.6 discloses a kind of sulfur method that contains the mercaptan hydrocarbon-fraction, it is in the presence of air and ammonium hydroxide and a kind of quaternary ammonium compound aqueous solution hydrocarbon-fraction to be contacted with the metal phthalocyanine catalyzed combination, the described aqueous solution contains methyl alcohol, and the carrier of metal phthalocyanine catalytic composition is gac, aluminum oxide, silicon oxide, zirconium white etc.The mercaptan removal step of the method for the industrial refining gasoline of CN01135072.5 is that the catalytic gasoline, air and the activator that remove hydrogen sulfide and transform portion mercaptan are sent in the level fixed-bed reactor of back, fixed bed is provided with poly-phthalocyanine cobalt or the cobalt sulfonated phthalocyanine that loads on the pressed active carbon, and mercaptan in the catalytic gasoline and oxygen react under the effect of activator and catalyzer and generates disulphide.Activator is a HA-18 type activator.The disclosed employing solid alkali of CN03137605.3 is to the light-end products process for deep desulphurization, be through alkali cleaning (solid alkali cleaning or liquid alkali cleaning) with gasoline, carry out air sweetening or liquid-liquid extraction desulfurization alcohol through the oxidation deodorizing tower again, oil product carries out the essence filter through separating the shakeout filter tower, gasoline added promoting agent before entering solid soda-wash tower and oxidation deodorizing tower, carry out solid alkali cleaning and oxidation deodorizing after the mixing more respectively, promoting agent is high-efficiency activated dose an of multiple active components.This invents unexposed promoting agent and active ingredient thereof.CN200510066214.X discloses a kind of method for refining catalytic gasoline, to deviate from hydrogen sulfide catalytically cracked gasoline and promotor and air mixed, mixture is that the mercaptan in the catalytically cracked gasoline changes into disulphide so that remove mercaptan sulfur by the mercaptan removal oxidizing tower of desulfurization catalyst is housed.Described promotor is selected from quaternary ammonium hydroxide, trimethyl-glycine, and ephedrine or their mixture, the add-on of promotor is that benchmark is 2-40ppm with catalytically cracked gasoline charging total amount.
Above-mentioned invention has solved the problems of demercaptaning for gasoline by catalyst cracking from different perspectives, all will discharge a large amount of alkali lye, serious environment pollution but liquid-liquid method still is the fixed bed mercaptan removal.
Summary of the invention
Purpose of the present invention just is that the deficiency of contaminate environment provides a kind of catalytic gasoline fixed bed alkaline-free sweetening sulphur method at a large amount of discharging alkali lye in the existing doctor process.
The objective of the invention is to realize in the following manner:
A, the catalytically cracked gasoline that will remove hydrogen sulfide add the 10-80g activator mix by gasoline per ton;
B, mixing back bubbling air, air feeding amount is gasoline 0.03-0.3m per ton
3
C, again with the mixture behind the bubbling air by the mercaptan removal oxidizing tower of solid mercaptan-eliminating catalyst is housed.
Purpose of the present invention can also realize in the following manner:
The described activator of step a is for by weight percentage with 89.5-96.99% alcohols, 3-10% guanidine class and 0.01-0.5% metal phthalocyanine blended mixture.Described alcohols is an ethanol, and the guanidine class is a methylguanidine, dimethylguanidine, trimethylammonium guanidine, tetramethyl guanidine, diethyl guanidine, vulkacit D or their mixture.
Beneficial effect: macromole mercaptan complexing in guanidine class in the activator and quaternary ammonium salt or the quaternary ammonium hydroxide gasoline; make that the mercaptan in the gasoline is easier of the Phthalocyanine-like Catalysts catalytic eliminating; compare with using the quaternary ammonium hydroxide class in the prior art; the solubleness of phthalocyanine-like compound in the guanidine class is greater than its solubleness in quaternary ammonium hydroxide; activation effect is better; mercaptan in the catalytically cracked gasoline is removed thoroughly; effectively replenish the water-soluble loss of the metal phthalocyanine of load in the solid mercaptan-eliminating catalyst; make the solid mercaptan-eliminating catalyst keep good activity and prolongs life; eliminate the discharging of waste lye, protected environment.
Embodiment:
Be described in further detail below in conjunction with embodiment:
A, the catalytically cracked gasoline that will remove hydrogen sulfide add the 10-80g activator mix by gasoline per ton;
B, mixing back bubbling air, air feeding amount is gasoline 0.03-0.3m per ton
3
C, again with the mixture behind the bubbling air by the mercaptan removal oxidizing tower of solid mercaptan-eliminating catalyst is housed.
The described activator of step a is for by weight percentage with 89.5-96.99% alcohols, 3-10% guanidine class and 0.01-0.5% metal phthalocyanine blended mixture.Described alcohols is an ethanol, and the guanidine class is a methylguanidine, dimethylguanidine, trimethylammonium guanidine, tetramethyl guanidine, diethyl guanidine, vulkacit D or their mixture.
The solid mercaptan-eliminating catalyst is by weight percentage the metal phthalocyanine of 0.01-1.0% or the poly-phthalocyanine of metal to be loaded on the gac.
Temperature in the dealcoholysis sulphur oxidizing tower is 20-50 ℃, and pressure is 0.1-1.0MPa, and volume space velocity is 0.5-6.0h
-1
Embodiment 1
1,000,000 tons of catalytic cracking projects of certain large-scale oil refining enterprise adopt 2 120m
3The fixed bed alkaline-free sweetening oxidizing tower switches and to carry out mercaptan removal, and 72 tons of the mercaptan-eliminating catalysts of the gac of 0.22 ton of CuPc sulfonate of load are housed in each mercaptan oxidation tower.The catalytically cracked gasoline elder generation of mercaptan sulfur 32ppm and the activator mix of 30g of containing per ton, and with gasoline feeding 0.05m per ton
3The continuous bubbling air of amount.The activator prescription is: methylguanidine 2.7g, CuPc sulfonate 0.02g, ethanol 27.28g.Mixture feeds in the mercaptan removal oxidizing tower, and temperature is 30 ℃, and pressure is 0.3MPa, and volume space velocity is 1h
-1Behind the mercaptan oxidation tower, the catalytically cracked gasoline mercaptan sulfur content is 2ppm.
Embodiment 2
1,100,000 tons of catalytic cracking projects of certain large-scale oil refining enterprise adopt 2 140m
3The fixed bed alkaline-free sweetening oxidizing tower switches and to carry out mercaptan removal, and 84 tons of the mercaptan-eliminating catalysts of the gac of 0.35 ton of poly-phthalocyanine cobalt of load are housed in each mercaptan oxidation tower.The catalytically cracked gasoline charging elder generation of mercaptan sulfur 41ppm and the activator mix of 45g of containing per ton, and with gasoline feeding 0.2m per ton
3The continuous bubbling air of amount.The activator prescription is: dimethylguanidine 2.7g, phthalocyanine cobalt sulfonate 0.03g, ethanol 42.27g.Mixture feeds in the mercaptan oxidation tower, and temperature is 25 ℃, and pressure is 0.25MPa, and volume space velocity is 1.2h
-1Behind the mercaptan oxidation tower, the catalytically cracked gasoline mercaptan sulfur content is 3.1ppm.
Embodiment 3
800,000 tons of catalytic cracking projects of certain large-scale oil refining enterprise adopt 2 80m
3The fixed bed alkaline-free sweetening oxidizing tower switches and to carry out mercaptan removal, and 48 tons of the mercaptan-eliminating catalysts of the gac of 0.24 ton of phthalocyanine cobalt sulfonate of load are housed in each mercaptan oxidation tower.The catalytically cracked gasoline charging elder generation of mercaptan sulfur 20ppm and the activator mix of 35g of containing per ton, and with gasoline feeding 0.1m per ton
3The continuous bubbling air of amount.The activator prescription is: tetramethyl guanidine 1.8g, phthalocyanine cobalt sulfonate 0.04g, ethanol 33.16g.Mixture feeds in the mercaptan oxidation tower, and temperature is 35 ℃, and pressure is 0.33MPa, and volume space velocity is 1.5h
-1Behind the mercaptan oxidation tower, the catalytically cracked gasoline mercaptan sulfur content is 1ppm.
Embodiment 4
500,000 tons of catalytic cracking projects of certain oil refining enterprise adopt 2 60m
3The fixed bed alkaline-free sweetening oxidizing tower switches and to carry out mercaptan removal, and 36 tons of the mercaptan-eliminating catalysts of the gac of 0.22 ton of CuPc of load are housed in each mercaptan oxidation tower.The catalytically cracked gasoline charging elder generation of mercaptan sulfur 40ppm and the activator mix of 50g of containing per ton, and with gasoline feeding 0.08m per ton
3The continuous bubbling air of amount.The activator prescription is: trimethylammonium guanidine 2g, poly-phthalocyanine cobalt 0.1g, ethanol 47.9g.Mixture feeds in the mercaptan oxidation tower, and temperature is 35 ℃, and pressure is 0.25MPa, and volume space velocity is 0.9h
-1Behind the mercaptan oxidation tower, the catalytically cracked gasoline mercaptan sulfur content is 4.5ppm.
Embodiment 5
800,000 tons of catalytic cracking projects of certain oil refining enterprise adopt 2 80m
3The fixed bed alkaline-free sweetening oxidizing tower switches and to carry out mercaptan removal, and 48 tons of the mercaptan-eliminating catalysts of the gac of 0.34 ton of manganese phthalocyanine sulfonate of load are housed in each mercaptan oxidation tower.The catalytically cracked gasoline charging elder generation of mercaptan sulfur 22ppm and the activator mix of 45g of containing per ton, and with gasoline feeding 0.3m per ton
3The continuous bubbling air of amount.The activator prescription is: diethyl guanidine 3.2g, manganese phthalocyanine 0.14g, Virahol 41.66g.Mixture feeds in the mercaptan oxidation tower, and temperature is 30 ℃, and pressure is 0.25MPa, and volume space velocity is 2h
-1Behind the mercaptan oxidation tower, the catalytically cracked gasoline mercaptan sulfur content is 2.5ppm.
Claims (3)
1, a kind of catalytic cracking (FCC) gasoline fixed bed alkaline-free sweetening method is characterized in that, comprises following method steps:
A, the catalytically cracked gasoline that will remove hydrogen sulfide add the 10-80g activator mix by gasoline per ton;
B, mixing back bubbling air, air feeding amount is gasoline 0.03-0.3m per ton
3
C, again with the mixture behind the bubbling air by the mercaptan removal oxidizing tower of solid mercaptan-eliminating catalyst is housed.
2, catalytic gasoline fixed bed mercaptan removal method according to claim 1 is characterized in that, the described activator of step a is for by weight percentage with 89.5-96.99% alcohols, 3-10% guanidine class and 0.01-0.5% metal phthalocyanine blended mixture.
3, catalytic gasoline fixed bed mercaptan removal method according to claim 2 is characterized in that, described alcohols is an ethanol, and the guanidine class is a methylguanidine, dimethylguanidine, trimethylammonium guanidine, tetramethyl guanidine, diethyl guanidine, vulkacit D or their mixture.
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|---|---|---|---|
| CNB2006100172959A CN100494320C (en) | 2006-11-03 | 2006-11-03 | Catalytic cracking fixed bed alkaline-free mercaptan removal method for gasoline |
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| CNB2006100172959A CN100494320C (en) | 2006-11-03 | 2006-11-03 | Catalytic cracking fixed bed alkaline-free mercaptan removal method for gasoline |
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| CN100494320C true CN100494320C (en) | 2009-06-03 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092574B (en) * | 2007-07-23 | 2010-05-19 | 长春惠工净化工业有限公司 | Method for removing sulfureted hydrogen through fixed bed of catalytic gasoline without liquid alkali |
| CN102614924A (en) * | 2012-03-02 | 2012-08-01 | 长春惠鹏石油化工科技有限公司 | Activating agent of gas oil sweetening catalyst |
| CN103450924B (en) * | 2012-05-29 | 2015-06-24 | 北京安耐吉能源工程技术有限公司 | Method of removing mercaptan in oil product other than hydrogenation |
| CN103768913B (en) * | 2012-10-22 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of method removing hydrogen sulfide and mercaptan in gas |
| CN103911177B (en) * | 2014-03-07 | 2015-11-18 | 湖北华邦化学有限公司 | A kind of saturated liquid hydrocarbon deep desulfurization method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4908122A (en) * | 1989-05-08 | 1990-03-13 | Uop | Process for sweetening a sour hydrocarbon fraction |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4908122A (en) * | 1989-05-08 | 1990-03-13 | Uop | Process for sweetening a sour hydrocarbon fraction |
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Effective date of registration: 20161026 Address after: 116000 A, building -A7-1, colorful city, Dalian economic and Technological Development Zone, Liaoning, China Patentee after: Dalian Engineering Construction Co., Ltd. Address before: Our high tech Industrial Development Zone, Jilin province Changchun street 130021 No. 286 Patentee before: Changchun Huigong Purifying Industry Co., Ltd. |
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Addressee: Huigong Purification Industry Co., Ltd., Changchun Document name: Notification of Passing Examination on Formalities |