CN100418629C - Regeneration process of supported metal phthalocyanine catalyst for mercaptol oxidization - Google Patents
Regeneration process of supported metal phthalocyanine catalyst for mercaptol oxidization Download PDFInfo
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- CN100418629C CN100418629C CNB2005101321956A CN200510132195A CN100418629C CN 100418629 C CN100418629 C CN 100418629C CN B2005101321956 A CNB2005101321956 A CN B2005101321956A CN 200510132195 A CN200510132195 A CN 200510132195A CN 100418629 C CN100418629 C CN 100418629C
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Abstract
The regeneration process of supported metal phthalocyanine catalyst for mercaptol oxidization includes drying the deactivated catalyst in inert gas flow of volume space velocity 1-1000 /hr at 20-180 deg.c for 1-24 hr and the subsequent soaking in alkali solution to obtain catalyst with restored activity. The regeneration process is simple, practical and low in cost, and the regenerated catalyst has well restored activity and high activity stability.
Description
Technical field
The invention relates to a kind of renovation process of catalyst for mercaptol oxidization, specifically a kind of renovation process that is applied to the load-type metal phthalocyanine catalyst of mercaptan oxidation process.
Background technology
Mercaptan extensively is present in the hydrocarbon fluids such as natural gas, liquefied petroleum gas, gasoline, kerosene, jet fuel and diesel oil.The existence of mercaptan can bring serious problems such as stench, corrosion, therefore is necessary it is removed.Usually, the industrial process that mercaptan catalytic oxidation in the hydrocarbon stream is converted into disulphide is called deodorization.
The at present industrial removal of mercaptans method that generally adopts is Mei Luokesi (Merox) catalytic oxidation fixed-bed process.This method is to utilize catalyst to make the mercaptan in the oil product be oxidized to two sulphur products under the condition of aqueous alkali (sodium hydroxide solution) and air existence, and its chemical equation is:
The most frequently used catalyst is metal phthalocyanine compounds such as sulfonated phthalocyanine cobalt or poly-sulfonated phthalocyanine cobalt, and (sulfonation degree of phthalocyanine cobalt is 1～4 to the molecular formula that right figure is two sulfonated phthalocyanine cobalts; The chemical valence of center cobalt atom is+2).Described fixed-bed process be with metal phthalocyanine loaded on solid carrier, by intermittently or continuous mode inject alkali lye and bubbling air and hydrocarbon stream is carried out deodorization handle.The effect of alkali is that mercaptan is converted into the mercaptan anion, and the mercaptan anion can generate the hydrogen-oxygen anion in being oxidized to the process of disulphide, alkali lye does not consume in course of reaction theoretically, but alkali lye can run off, and the generation of water all can have influence on the distribution of alkali lye in the solid carrier duct in the reaction of oily middle acid substance and alkali lye and the deodorising process.
Metal phthalocyanine loaded type catalyst is usually because inactivation needs periodic regeneration.The countermeasure that causes the reason of catalysqt deactivation and take mainly contains: the one, and the loss of metal phthalocyanine makes the load of metal phthalocyanine more firm by optimizing method for preparing catalyst and renovation process, can effectively reduce the loss of metal phthalocyanine; The 2nd, big molecule colloid class material gathers and covers catalyst surface, hides active sites, can remove by washing; The 3rd, mercaptan oxidation is that the water of the process generation of disulphide has diluted the alkali in the catalyst duct, cause the base strength in the duct to reduce, alkali number descends, and adopts alkali liquid washing this moment, can only but be difficult to improve the alkaline environment in the catalyst duct for beds replenishes the alkali lye that runs off.
U.S. Pat 3148156 discloses a kind of renovation process of using the catalyst for mercaptol oxidization of hot wash.U.S. Pat 4009120 disclosed renovation process are with using steam treatment after the hot wash again.U.S. Pat 3326816 disclosed renovation process are water, spirit of vinegar, alcohol washing catalyst successively.U.S. Pat 4213877 discloses a kind of renovation process, and it is active that this method is that the liquid solution washing catalyst in 55～175 ℃ temperature range with quaternary ammonium compound makes it to recover.
Because the salt of metal phthalocyanine may be dissolved in the water, and under higher temperature, can or contain the oxygen air oxidation by oxygen, above-mentioned renovation process has destruction to metal phthalocyanine, as make it to run off or the chemical valence of center cobalt atom is raise and lose activity etc., therefore needing to mend fresh metal phthalocyanine floods to recover catalyst activity again, if catalyst activity just is difficult to recover all catalyst changeouts more of needs, because the metal phthalocyanine price is high, therefore above-mentioned catalyst recovery process cost is higher.
Summary of the invention
The objective of the invention is on the basis of existing technology, a kind of renovation process of metal phthalocyanine type catalyst for mercaptol oxidization is provided, the catalyst of regenerating through this method has higher catalytic activity with better stable.
Renovation process provided by the invention is: is 20～180 ℃ with the catalyst of inactivation in temperature, and under preferred 60～160 ℃ environment, volume space velocity is 1～1000h
-1, preferred 100～800h
-1Nitrogen stream in dry 1～24 hour, preferred 4～12 hours, then with the catalyst that obtains activation recovering behind the dipping by lye.
In the method provided by the invention, meet the oxygen oxidation, adopt the catalyst of nitrogen stream purging, dry inactivation for avoiding metal phthalocyanine.
In the method provided by the invention, described alkali lye is one or more the mixture in hydroxide solution, ammoniacal liquor and the organo-alkali compound solution that is selected from alkali hydroxide soln, alkaline-earth metal, the hydroxide solution of preferred as alkali or ammoniacal liquor.The concentration of described alkali lye is 5～50wt%, preferred 10～25wt%.
Catalyst recovery process provided by the present invention is simple, practical, adopt nitrogen stream under the condition of control temperature, to handle decaying catalyst, guaranteed that the metal phthalocyanine on the catalyst is not damaged in regenerative process, made beds not need to mend metal phthalocyanine into fresh, cost is lower; And the dried carrier of catalyst duct can evenly absorb alkali lye in the regenerative process, and the alkali lye of duct absorption acts synergistically with the metal phthalocyanine of institute's load, makes the catalyst after the regeneration have good active and activity stability.
Description of drawings
Accompanying drawing is to adopt product mercaptan sulfur content that the catalyst of distinct methods regeneration is used for jet fuel removal of mercaptans curve over time; Wherein 1-is the regenerated catalyst of embodiment 1; 2-is the regenerated catalyst of embodiment 2; 3-is the catalyst that adopts conventional method regeneration in the Comparative Examples 1.
The specific embodiment
The following examples will be described further the present invention, but not limit the present invention therefrom.
In each embodiment and in the Comparative Examples, the catalyst of inactivation is provided by Sinopec joint-stock company Luoyang Company, and the trade mark is RDM-02, is carrier with the activated carbon, and the content of sulfonated phthalocyanine cobalt on catalyst is 1wt%.
Embodiment 1
Decaying catalyst is ground into 20～40 orders, gets the 10ml microreactor of packing into, feed nitrogen then and from up to down purge bed, be warming up to 150 ℃ of continuation gradually and purged 4 hours with nitrogen, the volume space velocity of nitrogen stream is 200h
-1, reduce to room temperature afterwards, with the sodium hydroxide solution immersion beds of 15wt%, emit unnecessary alkali lye after spending the night, the catalyst after obtaining regenerating.
Embodiment 2
Decaying catalyst is ground into 20～40 orders, gets the 10ml microreactor of packing into, feed nitrogen then and from up to down purge bed, be warming up to 100 ℃ of continuation gradually and purged 12 hours with nitrogen, the volume space velocity of nitrogen stream is 500h
-1, reduce to room temperature afterwards, with the sodium hydroxide solution immersion beds of 15wt%, emit unnecessary alkali lye after spending the night, the catalyst after obtaining regenerating.
Comparative Examples 1
This Comparative Examples explanation conventional regeneration method is handled the process of decaying catalyst.
The catalyst powder of inactivation is broken into 20～40 orders, gets the 10ml microreactor of packing into, inject the 15wt% sodium hydroxide lye that contains sulfonated phthalocyanine cobalt (200ppm) to bed then, emit unnecessary alkali lye after spending the night, catalyst regeneration process finishes.
Present embodiment illustrates the catalytic activity and the catalytic stability of the regenerated catalyst that obtains with method provided by the invention.
Respectively the catalyzer temperature-elevating to 40 of embodiment 1 and embodiment 2 regeneration ℃ is carried out hydrocarbon stream deodorization reaction, used hydrocarbon stream is that mercaptan sulfur content is a kind of jet fuel cut (density (20 ℃) 0.7828g/cm of 102ppm
3, 162～231 ℃ of boiling ranges), liquid hourly space velocity (LHSV) is 2h
-1, after mercaptan sulfur content in the product is greater than 20ppm, stopping reaction, the deodorization reaction result is seen accompanying drawing.
Comparative Examples 2
This Comparative Examples illustrates the catalytic activity and the catalytic stability of the regenerated catalyst that obtains with conventional method.
Process is with embodiment 3, and difference is to carry out hydrocarbon stream deodorization reaction with the catalyst of Comparative Examples 1 regeneration, and reaction result is seen accompanying drawing.
By accompanying drawing as seen, the decaying catalyst after renovation process provided by the invention is handled has better catalytic activity and activity stability than the catalyst that adopts conventional method regeneration.
Claims (6)
1. the renovation process of a supported metal phthalocyanine catalyst for mercaptol oxidization is characterized in that under temperature is 20～180 ℃ environment, is 1～1000h with the catalyst of inactivation at volume space velocity
-1Nitrogen stream in dry 1～24 hour, then with the catalyst that obtains activation recovering behind the dipping by lye.
2. according to the method for claim 1, it is characterized in that the catalyst of described inactivation is 100～800h at volume space velocity under temperature is 60～160 ℃ environment
-1Nitrogen stream in dry 4～12 hours.
3. according to the method for claim 1, it is characterized in that described alkali lye is one or more the mixture in hydroxide solution, ammoniacal liquor and the organo-alkali compound solution that is selected from alkali hydroxide soln, alkaline-earth metal.
4. according to the method for claim 3, it is characterized in that described alkali lye is alkali-metal hydroxide solution or ammoniacal liquor.
5. according to the method for claim 1, the concentration that it is characterized in that described alkali lye is 5～50wt%.
6. according to the method for claim 5, the concentration that it is characterized in that described alkali lye is 10～25wt%.
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| CNB2005101321956A CN100418629C (en) | 2005-12-23 | 2005-12-23 | Regeneration process of supported metal phthalocyanine catalyst for mercaptol oxidization |
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| CNB2005101321956A CN100418629C (en) | 2005-12-23 | 2005-12-23 | Regeneration process of supported metal phthalocyanine catalyst for mercaptol oxidization |
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| CN100418629C true CN100418629C (en) | 2008-09-17 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101804361A (en) * | 2010-04-07 | 2010-08-18 | 浙江大学 | Preparation method and application of load-type metal phthalocyanine catalyst |
| CN103374382B (en) * | 2012-04-26 | 2015-05-20 | 中国石油化工股份有限公司 | Method for deodorizing light oil |
| CN104588130B (en) * | 2013-10-30 | 2018-08-28 | 中国石油化工股份有限公司 | A kind of regeneration method of deodorization catalyst |
| CN104588131B (en) * | 2013-10-30 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of renovation process of deodorization catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4009120A (en) * | 1975-08-18 | 1977-02-22 | Uop Inc. | Process for the regeneration of a solid bed metal phthalocyanine catalyst system |
| US4213877A (en) * | 1978-12-26 | 1980-07-22 | Uop Inc. | Method of reactivating a catalytic composite of an adsorptive carrier material and a mercaptan oxidation catalyst |
| CN1097795A (en) * | 1994-03-10 | 1995-01-25 | 太原煤炭气化总公司焦化厂 | Purifying coke oven gas by ammonia-soda binuclear phthalocyanine cobalt sulfonate method technology |
| CN1277245A (en) * | 2000-04-20 | 2000-12-20 | 江苏苏钢集团有限公司 | Coke-oven gas desulfurizing and decyanating process |
| US6755964B1 (en) * | 2000-12-15 | 2004-06-29 | Council Of Scientific & Industrial Research | Process for the fixed bed sweetening of petroleum distillates using halogenated metal phthalocyanine as a catalyst |
-
2005
- 2005-12-23 CN CNB2005101321956A patent/CN100418629C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4009120A (en) * | 1975-08-18 | 1977-02-22 | Uop Inc. | Process for the regeneration of a solid bed metal phthalocyanine catalyst system |
| US4213877A (en) * | 1978-12-26 | 1980-07-22 | Uop Inc. | Method of reactivating a catalytic composite of an adsorptive carrier material and a mercaptan oxidation catalyst |
| CN1097795A (en) * | 1994-03-10 | 1995-01-25 | 太原煤炭气化总公司焦化厂 | Purifying coke oven gas by ammonia-soda binuclear phthalocyanine cobalt sulfonate method technology |
| CN1277245A (en) * | 2000-04-20 | 2000-12-20 | 江苏苏钢集团有限公司 | Coke-oven gas desulfurizing and decyanating process |
| US6755964B1 (en) * | 2000-12-15 | 2004-06-29 | Council Of Scientific & Industrial Research | Process for the fixed bed sweetening of petroleum distillates using halogenated metal phthalocyanine as a catalyst |
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