CN1243815C - Process for catalyzing oxygenizing desulfurizing diesel oil - Google Patents

Process for catalyzing oxygenizing desulfurizing diesel oil Download PDF

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Publication number
CN1243815C
CN1243815C CN 200410040923 CN200410040923A CN1243815C CN 1243815 C CN1243815 C CN 1243815C CN 200410040923 CN200410040923 CN 200410040923 CN 200410040923 A CN200410040923 A CN 200410040923A CN 1243815 C CN1243815 C CN 1243815C
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diesel oil
extraction agent
catalyzer
zinc
oil
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CN1624081A (en
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唐晓东
刘亮
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Southwest Petroleum University
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Southwest Petroleum University
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Abstract

The present invention relates to a method for catalyzing, oxygenizing and desulfurizing diesel oil, which comprises the following steps: (1) Oxalate and acetate of cobalt, copper and zinc, benzoate of the cobalt, the copper, the zinc, manganese, iron and aluminum or phthalate of the manganese, the zinc and the copper serve as catalysts, and the catalysts are mixed with the diesel oil according to the dosage of 1000 to 2500 mu g/g; (2) Air serves as an oxidizing agent, and oxidation reaction is catalyzed for 20 to150 min under the condition of 120 to 200 DEG C; (3) The catalysts and the diesel oil are separated after being cooled; (4) An extraction agent of which the N and N-dimethyl formamide density is 60 to 80 wt % and the ethanol density is 20 to 40 wt % is used, and the diesel oil and the extraction agent are mixed and still placed to split phases at the temperature of 20 to 80 DEG C according to the condition that the volume ratio of the diesel oil and the extraction agent is five to obtain a top-phase oil phase and a bottom-phase extraction agent. The air is used as the oxidizing agent by the present invention, and raw materials of the catalysts are easy to obtain. The present invention which is favorable for environmental protection has the advantages of little dosage, obvious effects and periodic duty. The desulfurization percent of the diesel oil reaches more than 70%.

Description

A kind of method of diesel catalytic oxidation desulfurization
Technical field
The present invention relates to the method for diesel oxidation desulfurizing in the petroleum refining process.
Background technology
Organic sulfide mainly contains thioether and thiophene in the diesel oil, and the principal pollutant after the burning are SO x, and to NO x, PM (particulate matter) be formed with promoter action; The SO that sulphides burn generates xNot only corrode the combustion chamber and the exhaust system of engine, crankcase and lubricating oil generate sulfonic acid and various gelatinoid quickens the rotten of lubricating oil but also can enter by the gap of piston ring.The sulphur content of fuel is high more, and the carbon deposit that the combustion chamber generates is many more, and engine scuffing is increased, and causes engine power to descend, and fuel consumption increases; Sulfide also makes catalytic hydro-dearomatization catalyst poison.Global on the other hand environmental consciousness strengthens, and producing clean fuel will be the general trend of development.Therefore, desulfurization has great importance from diesel oil.
Desulfurization is one of important treating process of diesel oil, in the face of the restriction of the diesel oil sulphur content of increasingly stringent and market great demand to the low-sulfur clean diesel, sulfur method always constantly improve and development in.
In industrial production, hydrofining is to adopt both at home and abroad extensively, and hydrogenating desulfurization is meant in the presence of hydrogen, the organic sulfide in the diesel oil is converted into hydrogen sulfide and removes through catalyst action.The catalyzer that uses is generally Co-Mo-Al 2O 3Though this method oil quality is good, there is following problem in the product yield height: reaction conditions is very harsh, and the general requirement working pressure is at 4.0MPa, and temperature is at 320-370 ℃, high-pressure process even require pressure to reach 10MPa; The hydrogenation unit investment is big, and the process cost height causes the diesel oil cost significantly to rise.
Because there is problem economically in diesel hydrogenation for removal sulphur,, is difficult to bear high investment and process cost and consequent diesel oil cost and rises for most of middle-size and small-size refineries.Therefore, the diesel oil non-hydrogenation desulfurization technology is subjected to more attention gradually, and has obtained very big development.From present research situation, the diesel oil non-hydrogenation desulfurization technology mainly comprises adsorption desulfurize, abstraction desulfurization, complexing desulfurization, oxidation sweetening etc.Wherein the diesel oxidation desulfurizing technology is the focus of studying both at home and abroad.Compare with traditional hydrogenating desulfurization technology, have the following advantages:
(1) deep desulfuration; The reaction conditions gentleness, temperature＜100 ℃, atmospheric operation, process cost is low;
(2) need not hydrogen source, pressure-resistant equipment and Claus desulfurizer, technical process is simple, and facility investment is extremely low;
(3) oxidative desulfurization techniques also can be used for denitrogenation;
(4) energy-conservation, low CO 2The environment-protective process of discharging;
(5) the desulfurized diesel oil cetane value also has raising, the matter effect of coming unstuck in addition, and oil stability can also improve.
For example, document (phase Tian Zhefu. cross the plain To I of acidified water oil acidifying desulfurization .PETROTECH, 23 (6) 2000) use 30% H 2O 2The aqueous solution (contain a small amount of carboxylic acid, as acetic acid, trifluoracetic acid is as oxidation promotor) is oxygenant, can make the diesel oil sulphur content reduce to 1 μ g/g from 500～600 μ g/g.This processing condition relax (50 ℃, 0.1MPa is reaction 1h down), and oxygenant is oxidized to the sulfone class with after diesel oil mixes with the sulphur in the oil, uses the NaOH solution washing again, adsorbs to remove sulfocompound through silica gel or aluminium glue.Document (Dolbear G.E, Skov E.R.Selective Oxidation as a Routeto Petroleum Desulfurization.Preprints, 45 (2), 2000) a kind of energy of research selective oxidation-extract the method for sulfide in the diesel oil, this method is called as conversion-abstraction desulfurization technology (Conversion-Extracation Desulfurization is called for short CED).The key of CED technology is to use peroxyacetic acid (by 50%H 2O 2Make with the reactant aqueous solution of acetic acid) as the selective oxidation agent.Organic acid strengthens H as acid catalyst in the oxygenant 2O 2Oxidisability, this oxygenant is at 93.3 ℃, normal pressure down with oil reaction 20min, 99% oxygenant is complete reaction all.Reacted solution is normally colourless, with gas-chromatography to the oxygenatedchemicals analysis revealed, nearly all oxygen all with sulphur in conjunction with generating the sulfone class.Re-use DMSO as extraction agent, after repeatedly extracting, most of sulfone class is removed.In these various oxidation style of having reported, mainly adopt H both at home and abroad 2O 2As oxygenant, use organic acid or illumination etc. to strengthen the oxidation sweetening process, deviate from oxidation state sulfide with extraction agent at last.Although its oxidation effectiveness is better, desulfurization degree is higher, oxygenant H 2O 2Price is high, large usage quantity, regeneration difficulty; And produce a large amount of sulfur-containing waste waters after the oxidation, and dealing with comparatively difficulty, processing costs is also high.Therefore, must properly settle production cost, the catalyst regeneration of diesel oxidation desulfurizing, the problem of wastewater treatment, this technology just has technological competitiveness.
Summary of the invention
The object of the present invention is to provide a kind of method of diesel catalytic oxidation desulfurization, this method catalyzer raw material is easy to get, and cost is low, and consumption is little, pollutes for a short time, can guarantee the diesel product quality of diesel oxidation desulfurizing process for refining.
A kind of method of diesel catalytic oxidation desulfurization may further comprise the steps:
1. with the oxalate and the acetate of cobalt, copper, zinc, the benzoate of cobalt, copper, zinc, manganese, iron, aluminium, or the phthalate of manganese, zinc, copper makes catalyzer, is that the consumption of 1000～2500 μ g/g mixes catalyzer with diesel oil by catalyzer/diesel oil;
2. with air oxidant, catalytic oxidation 20～150min under 120～200 ℃ of conditions;
3. cool off back separating catalyst and diesel oil, catalyzer can be recycled;
4. use N, dinethylformamide concentration is 60～80 weight %, alcohol concn is the extraction agent of 20～40 weight %, volume ratio by diesel oil/extraction agent under 20～80 ℃ of conditions is 5, diesel oil after the oxidation is mixed, leaves standstill phase-splitting with extraction agent, obtain phase oil phase and following extraction agent mutually, so repeatedly for several times.
Be that the consumption of 1000～2500 μ g/g mixes catalyzer preferred 1200～2500 μ g/g with diesel oil by catalyzer/diesel oil among the present invention.With air oxidant,, react 20～150min, preferred 50～80min under preferred 150～180 ℃ of temperature at 120～200 ℃.Cooling back separating catalyst and diesel oil.Use N again, dinethylformamide (DMF) concentration is 60～80 weight %, preferred 60～70 weight %, and alcohol concn is the extraction agent of 20～40 weight %, preferred 30～40 weight %.Under 20～80 ℃, preferred 50～70 ℃ is 5 the diesel oil after the oxidation to be mixed, leave standstill phase-splitting with extraction agent by the finish volume ratio, obtains oil phase (going up phase) and extraction agent (mutually following) two-phase, so repeatedly for several times, and the acquisition refined diesel oil.Extraction agent is for recycling.
Compared with prior art, the novel method of desulfurization from diesel oil provided by the invention is an oxygenant with the air, and the catalyzer raw material of use is easy to get, cost is low, and consumption is little, and the catalyzed oxidation effect is obvious, and no sulfur-bearing is put discharge of wastewater, catalyst recirculation is used, and operate continuously has overcome H 2O 2The shortcoming of oxidation style.The desulfurization degree of diesel oil is reached more than 70%, and the diesel oil sulphur content after the desulfurization reaches European II class diesel quality standard (＜300 μ g/g).
Embodiment
The present invention is further illustrated below by embodiment.The analytical procedure that experiment is adopted:
Adopt GB/T380-88 petroleum products sulphur content determination method, desulfurization degree=(1-purified diesel oil sulphur content/stock oil sulphur content)
Example 1
Press catalyst levels 2400 μ g/g, in the sulphur content that Lanzhou Petrochemical Company is produced is in the 16.612g mixing straight-run diesel oil (commingled crude of being made up of North SinKiang crude oil 40%, South Sinkiang crude oil 47% and soil Kazakhstan crude oil 13% processes) of 1658 μ g/g, add the 0.033g zinc oxalate, with air oxidant, react 60min down at 150 ℃ ± 3 ℃, the reaction postcooling separates diesel oil and catalyzer, and catalyst recirculation is used.Press finish volume ratio=5, get the extraction agent (60 weight %DMF+40% weight ethanol) of 4ml and mix the back thermal agitation specified time with diesel oil after the oxidation, the insulation phase-splitting is reclaimed lower floor's extraction agent and is gone regeneration.Get fresh extraction agent again formation testing is extracted, 4 times so repeatedly, obtain purified straight-run diesel oil, sulphur content is 423 μ g/g, desulfurization degree reaches 74.48%.
Example 2
Press catalyst levels 2000 μ g/g, in the sulphur content that Lanzhou Petrochemical Company is produced is in the 16.612g mixing straight-run diesel oil (forming with example 1) of 1658 μ g/g, add the 0.033g cobaltous acetate, with air oxidant, react 60min down at 150 ℃ ± 3 ℃, the reaction postcooling separates diesel oil and catalyzer, and catalyst recirculation is used.Press the extraction process diesel oil of example 1, obtain purified straight-run diesel oil, sulphur content is 345 μ g/g, and desulfurization degree reaches 79.19%.
Example 3
Press catalyst levels 1500 μ g/g, in the sulphur content that Lanzhou Petrochemical Company is produced is in the 16.612g mixing straight-run diesel oil (forming with example 1) of 1658 μ g/g, add the 0.033g venus crystals, method by example 1 is carried out oxidation, extracting operation to diesel oil, obtain refined straight-run diesel, sulphur content is 545 μ g/g, and desulfurization degree reaches 67.13%.
Example 4
Press catalyst levels 1500 μ g/g, in the sulphur content that Lanzhou Petrochemical Company is produced is in the 16.612g mixing straight-run diesel oil (forming with example 1) of 1658 μ g/g, add the 0.0249g Zinc dibenzoate, with air oxidant, react 60min down at 160 ℃ ± 3 ℃, the reaction postcooling separates diesel oil and catalyzer, and catalyst recirculation is used.Press finish volume ratio=5, get the extraction agent (ethanol of the DMF+30 weight % of 70 weight %) of 4ml and mix the back thermal agitation specified time with diesel oil after the oxidation, the insulation phase-splitting is reclaimed lower floor's extraction agent and is gone regeneration.Get fresh extraction agent again formation testing is extracted, 4 times so repeatedly, obtain purified straight-run diesel oil, sulphur content is 218 μ g/g, desulfurization degree reaches 86.85%.
Example 5
Press catalyst levels 2000 μ g/g, in the sulphur content that Lanzhou Petrochemical Company is produced is in the 16.612g mixing straight-run diesel oil (forming with example 1) of 1658 μ g/g, add the 0.033g manganese benzoate, method by example 4 is carried out oxidation, extracting operation to diesel oil, obtain purified straight-run diesel oil, sulphur content is 199 μ g/g, and desulfurization degree reaches 88.00%.
Example 6
Press catalyst levels 2000 μ g/g, in the sulphur content that Lanzhou Petrochemical Company is produced is in the 16.612g mixing straight-run diesel oil (forming with example 1) of 1658 μ g/g, add 0.0249g phenylformic acid iron, method by example 4 is carried out oxidation, extracting operation to diesel oil, obtain purified straight-run diesel oil, sulphur content is 450 μ g/g, and desulfurization degree reaches 72.86%.
Example 7
Press catalyst levels 2500 μ g/g, in the sulphur content that Lanzhou Petrochemical Company is produced is in the 16.612g mixing straight-run diesel oil (forming with example 1) of 1658 μ g/g, add 0.033g phthalic acid manganese, method by example 4 is carried out oxidation, extracting operation to diesel oil, obtain purified straight-run diesel oil, sulphur content is 709 μ g/g, and desulfurization degree reaches 57.23%.
Example 8
Press catalyst levels 2000 μ g/g, in the sulphur content that Lanzhou Petrochemical Company is produced is in the 16.612g mixing straight-run diesel oil (forming with example 1) of 1658 μ g/g, add the 0.033g zinc phthalate, method by example 4 is carried out oxidation, extracting operation to diesel oil, obtain purified straight-run diesel oil, sulphur content is 749 μ g/g, and desulfurization degree reaches 54.83%.
Example 9
Press catalyst levels 2000 μ g/g, in the sulphur content that Lanzhou Petrochemical Company is produced is in the 16.612g mixing straight-run diesel oil (forming with example 1) of 1658 μ g/g, add 0.033g phthalic acid copper, method by example 4 is carried out oxidation, extracting operation to diesel oil, obtain purified straight-run diesel oil, sulphur content is 570 μ g/g, and desulfurization degree reaches 65.62%.
Example 10
Press catalyst levels 1200 μ g/g, in the sulphur content that Lanzhou Petrochemical Company is produced is in the 16.612g mixing straight-run diesel oil (forming with example 1) of 1658 μ g/g, add the 0.033g cobaltous benzoate, method by example 4 is carried out oxidation, extracting operation to diesel oil, obtain purified straight-run diesel oil, sulphur content is 370 μ g/g, and desulfurization degree reaches 77.68%.

Claims (4)

  1. The method of 1 one kinds of diesel catalytic oxidation desulfurizations may further comprise the steps:
    (1) oxalate or the acetate to be selected from cobalt, copper and zinc, the benzoate of cobalt, copper, zinc, manganese, iron and aluminium, or a kind of catalyzer of doing in the phthalate of manganese, zinc and copper, be that the consumption of 1000～2500 μ g/g mixes catalyzer with diesel oil by catalyzer/diesel oil;
    (2) with air oxidant, catalytic oxidation 20～150min under 120～200 ℃ of conditions;
    (3) cooling back separating catalyst and diesel oil, catalyzer can be recycled;
    (4) use N, the dinethylformamide consumption is 60～80 weight %, the ethanol consumption is the extraction agent of 20～40 weight %, volume ratio by diesel oil/extraction agent under 20～80 ℃ of conditions is 5, diesel oil after the oxidation is mixed, leaves standstill phase-splitting with extraction agent, obtain phase oil phase and following extraction agent mutually, so repeatedly for several times.
  2. 2 the method for claim 1 is characterized in that, are that the consumption of 1200～2500 μ g/g mixes catalyzer with diesel oil by catalyzer/diesel oil in the step (1).
  3. 3 the method for claim 1 is characterized in that, step (2) is reacted 50～80min under 150～180 ℃ of temperature.
  4. 4 the method for claim 1 is characterized in that, N in step (4) extraction agent, dinethylformamide consumption are 60～70 weight %, and the ethanol consumption is 30～40 weight %, and temperature is at 50～70 ℃.
CN 200410040923 2004-10-24 2004-10-24 Process for catalyzing oxygenizing desulfurizing diesel oil Expired - Fee Related CN1243815C (en)

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Publication number Priority date Publication date Assignee Title
CN1315993C (en) * 2005-08-01 2007-05-16 中国石油化工集团公司 Method for reducing sulfur content of fuel oil
US20090242460A1 (en) * 2008-03-26 2009-10-01 General Electric Company Oxidative desulfurization of fuel oil
CN103436287B (en) * 2013-09-23 2015-08-19 南通宝聚颜料有限公司 A kind of metal oxide modified nano iron oxide catalyst carries out the method for diesel oxidation desulfurizing

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