CN108192664A - A kind of high sour product sulfur removal technology - Google Patents
A kind of high sour product sulfur removal technology Download PDFInfo
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- CN108192664A CN108192664A CN201810078702.XA CN201810078702A CN108192664A CN 108192664 A CN108192664 A CN 108192664A CN 201810078702 A CN201810078702 A CN 201810078702A CN 108192664 A CN108192664 A CN 108192664A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention discloses a kind of high sour product sulfur removal technologies, are as follows：High sulfur crude and hydrogen peroxide are mixed, stirring is placed in super ultrasound reactor, takes out after reaction and stand at room temperature, obtain product oil A after mixing；Air is passed through progress light provocative reaction in product oil A, diesel oil is promoted to generate active oxygen species in situ, obtains the product oil B containing active oxygen species；The light source power of the smooth provocative reaction is 600 800W, and the reaction time is 6 8h, and the flow velocity of the air is 25 35min‑1.The present invention carries out desulfurization using three-step approach, oxidation selectivity and desulfurization degree are high, and used oxidant/catalyst is easily separated and following cycle uses, air is used as indirect oxidation agent, at low cost, in addition relatively low reaction temperature or shorter reaction time or less oxidizer may be used in the present invention, and product quality and yield can improve, low energy consumption, lays a good foundation for its industrial applications.
Description
Technical field
The present invention relates to oily desulfuration field, specifically a kind of high sour product sulfur removal technology.
Background technology
Organosulfur compound in fuel oil is a kind of harmful substance.SO is generated after burningXAcid rain is resulted in, is caused pair
The pollution of environment and the damage to human health.For vehicle fuel, then SOXTo HC in vehicle exhaust, CO particularly NOXAnd PM
Discharge have apparent facilitation, so as to cause the increase of pollutant effulent.SOXEngine can also be corroded, reduce engine
Service life.In view of in vehicle fuel oil sulphur harm, world many countries and area all promulgated stringenter diesel oil in succession
Standard.The great demand of diesel oil is cleaned to low-sulfur in face of stringent petrol and diesel oil sulfur content limitation and market, countries in the world are numerous and confused
It is dedicated to developing various desulfurization of fuel oil technologies.
At present, mainly have in terms of deep desulfuration and add two kinds of techniques of hydrogen and Fei Jia hydrogen.Although hydrodesulfurization desulfurization is imitated
Fruit is apparent, good product quality, but operating condition is harsh, needs a large amount of hydrogen, and costly.Non- hydrodesulfurization is main
There are catalytic oxidation, H2O2Oxidizing process, complexometry and biological desulfurization etc..Wherein oxidative desulfurization techniques development is more early, and technique
Study more and more, at present, there are many oxidant species of oxidative desulfurization techniques, and leading position is in by oxidant of hydrogen peroxide,
It is good oxidant, therefore get the favour of people that water and oxygen, non-secondary pollution, while oxygen are generated after decomposition.In order to
Increase reaction speed and oxidation efficiency, usually add proper catalyst, the catalyst applied at present mainly includes machine acid catalysis
Agent, heteropolyacid catalyst etc..H2O2Organic acid oxidation system is to be applied to the desulfurization oxidation system of simulation oil product earliest, common
Organic acid includes formic acid, acetic acid and acetic anhydride etc..H2O2Although organic acid oxidation system reaction condition is milder, oxidability
Also it is relatively strong, higher desulfurization degree can be reached, but organic acid portion is dissolved in the quality that fuel is influenced in oil product, and liquid organic acid
There are it is disposable cannot regenerate, cost recovery is higher the shortcomings of.
Invention content
The purpose of the present invention is to provide a kind of at low cost, simply high sour product sulfur removal technology of method, in solution
State the problem of being proposed in background technology.
To achieve the above object, the present invention provides following technical solution：
A kind of high sour product sulfur removal technology, is as follows：
（1）High sulfur crude and hydrogen peroxide are mixed, 15-25min is stirred with the stir speed (S.S.) of 250-350r/min, after mixing
Merging supersonic frequency is 25-30kHz, the ultrasonic wave sound intensity is 0.4-0.5W/cm2Ultrasound reactor in, react 20-40min
After take out and stand at room temperature, obtain product oil A；
（2）Air is passed through progress light provocative reaction in product oil A, diesel oil is promoted to generate active oxygen species in situ, obtains containing and live
The product oil B of property oxygen species；The light source power of the smooth provocative reaction be 600-800W, reaction time 6-8h, the air
Flow velocity be 25-35min-1；
（3）Titanium Sieve Molecular Sieve powder, polymerized monomer polyenoid based compound and pore-foaming agent are sufficiently mixed, existed in initiator
Under, the addition of initiator is Titanium Sieve Molecular Sieve powder and the 1-3% of polymerized monomer polyenoid based compound total weight, in 80-120
DEG C carry out polymerisation 8-12h, obtain blocks of solid catalyst；Then catalyst solid particle is obtained through broken, is urged above-mentioned
Agent solid particle is added in halogenated hydrocarbons after swelling 5-7h, is extracted activation 3-5h at 30-50 DEG C using extraction solvent, is obtained titanium
Si molecular sieves and resin compounded catalyst；
（4）There is MoO by product oil B, in load3SiO2In the presence of Titanium Sieve Molecular Sieve and resin compounded catalyst, oxygen is carried out
Change desulphurization reaction, reaction temperature is 50-70 DEG C, reaction time 2.5-3.5h, removes sulfur-containing compound, obtains product oil C；
（5）By graphite and Cu (NO3)2·3H2O is added in the concentrated sulfuric acid, is then slowly added into potassium permanganate, stirs 0.5-2.5h,
Add the attapulgite slurry of a concentration of 1-2g/L, ultrasonic disperse 0.8-1.2h；It is 10- to add in aqueous slkali to system pH
13, composite suspension liquid is made, adds in reducing agent solution under stirring condition into the composite dispersion liquid of gained, reacts 40-50min,
Filtering is washed, dry, and compound desulfuration adsorbent is made；
（6）The product oil C carries out desulphurization reaction in the presence of compound desulfuration adsorbent in efficient mass transfer reactor, reaction
Temperature is 80-100 DEG C, liquid hourly space velocity (LHSV) 20-30h-1, desulfurization product oil is obtained by filtration after the completion of reaction.
As further embodiment of the present invention：
The polymerized monomer polyenoid based compound is divinylbenzene, divinyl toluene and one kind or more in biethenyl-xylene
Kind.
As further embodiment of the present invention：
The pore-foaming agent is one or more in gasoline, C5-C13 n-alkanes, C4-C12 fatty alcohols.
As further embodiment of the present invention：
The initiator is two isobutanol of benzoyl peroxide and/or azo.
As further embodiment of the present invention：
The extraction solvent is one or more in benzene,toluene,xylene, ethyl acetate, butyl acetate, ethyl alcohol and butanol.
As further embodiment of the present invention：
The Titanium Sieve Molecular Sieve and the specific surface area of resin compounded catalyst of obtaining is 150-200m2/ g, Kong Rongwei 0.2-
0.3cm3/ g, side pressure strength 10-15N.mm-1。
As further embodiment of the present invention：
The aqueous slkali is sodium hydroxide solution, one kind in potassium hydroxide solution, ammonium hydroxide or carbonic acid hydrogen ammonium salt solution.
As further scheme of the invention：
The reducing agent solution is one kind in formalin, acetaldehyde solution, glucose solution or hydrazine hydrate.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention carries out desulfurization using three-step approach, and oxidation selectivity and desulfurization degree are high, and used oxidant/catalyst is easily separated
Used with following cycle, use air as indirect oxidation agent, it is at low cost, in addition it is of the invention may be used relatively low reaction temperature,
Or shorter reaction time or less oxidizer, product quality and yield can improve, low energy consumption, is its industry
Change application to lay a good foundation.
Specific embodiment
The technical solution of this patent is described in more detail With reference to embodiment.
Embodiment 1
A kind of high sour product sulfur removal technology, is as follows：
（1）High sulfur crude and hydrogen peroxide are mixed, 15min is stirred with the stir speed (S.S.) of 250r/min, merging is super after mixing
Acoustic frequency is 25kHz, the ultrasonic wave sound intensity is 0.4W/cm2Ultrasound reactor in, react 20min after take out it is quiet at room temperature
It puts, obtains product oil A；
（2）Air is passed through progress light provocative reaction in product oil A, diesel oil is promoted to generate active oxygen species in situ, obtains containing and live
The product oil B of property oxygen species；The light source power of the smooth provocative reaction be 600W, reaction time 6h, the flow velocity of the air
For 25min-1；
（3）Titanium Sieve Molecular Sieve powder, polymerized monomer polyenoid based compound and pore-foaming agent are sufficiently mixed, existed in initiator
Under, the addition of initiator is the 1% of Titanium Sieve Molecular Sieve powder and polymerized monomer polyenoid based compound total weight, in 80 DEG C of progress
Polymerisation 8h obtains blocks of solid catalyst；Then catalyst solid particle is obtained through broken, by above-mentioned catalyst solid
Grain is added in halogenated hydrocarbons after swelling 5h, is extracted activation 3h at 30 DEG C using extraction solvent, is obtained Titanium Sieve Molecular Sieve and answered with resin
Close catalyst；The Titanium Sieve Molecular Sieve and the specific surface area of resin compounded catalyst of obtaining is 150m2/ g, Kong Rongwei 0.2cm3/ g,
Side pressure strength is 10N.mm-1；
（4）There is MoO by product oil B, in load3SiO2In the presence of Titanium Sieve Molecular Sieve and resin compounded catalyst, oxygen is carried out
Change desulphurization reaction, reaction temperature is 50 DEG C, reaction time 2.5h, removes sulfur-containing compound, obtains product oil C；
（5）By graphite and Cu (NO3)2·3H2O is added in the concentrated sulfuric acid, is then slowly added into potassium permanganate, stirs 0.5h, then add
Enter the attapulgite slurry of a concentration of 1g/L, ultrasonic disperse 0.8h；It is 10 to add in aqueous slkali to system pH, and composite suspension is made
Liquid adds in reducing agent solution under stirring condition into the composite dispersion liquid of gained, reacts 40min, filters, and washs, dry, is made
Compound desulfuration adsorbent；
（6）The product oil C carries out desulphurization reaction in the presence of compound desulfuration adsorbent in efficient mass transfer reactor, reaction
Temperature is 80 DEG C, liquid hourly space velocity (LHSV) 200h-1, desulfurization product oil is obtained by filtration after the completion of reaction.
Embodiment 2
A kind of high sour product sulfur removal technology, is as follows：
（1）High sulfur crude and hydrogen peroxide are mixed, 18min is stirred with the stir speed (S.S.) of 280r/min, merging is super after mixing
Acoustic frequency is 26kHz, the ultrasonic wave sound intensity is 0.42W/cm2Ultrasound reactor in, react 25min after take out it is quiet at room temperature
It puts, obtains product oil A；
（2）Air is passed through progress light provocative reaction in product oil A, diesel oil is promoted to generate active oxygen species in situ, obtains containing and live
The product oil B of property oxygen species；The light source power of the smooth provocative reaction be 650W, reaction time 6.5h, the stream of the air
Speed is 28min-1；
（3）Titanium Sieve Molecular Sieve powder, polymerized monomer polyenoid based compound and pore-foaming agent are sufficiently mixed, existed in initiator
Under, the addition of initiator for Titanium Sieve Molecular Sieve powder and polymerized monomer polyenoid based compound total weight 1.5%, 90 DEG C into
Row polymerisation 9h, obtains blocks of solid catalyst；Then catalyst solid particle is obtained through broken, by above-mentioned catalyst solid
Particle is added to be swollen 5.5h in halogenated hydrocarbons after, activation 3.5h extract at 35 DEG C using extraction solvent, obtain Titanium Sieve Molecular Sieve and
Resin compounded catalyst；The Titanium Sieve Molecular Sieve and the specific surface area of resin compounded catalyst of obtaining is 160m2/ g, Kong Rongwei
0.22cm3/ g, side pressure strength 11N.mm-1；
（4）There is MoO by product oil B, in load3SiO2In the presence of Titanium Sieve Molecular Sieve and resin compounded catalyst, oxygen is carried out
Change desulphurization reaction, reaction temperature is 55 DEG C, reaction time 2.8h, removes sulfur-containing compound, obtains product oil C；
（5）By graphite and Cu (NO3)2·3H2O is added in the concentrated sulfuric acid, is then slowly added into potassium permanganate, is stirred 1h, is added
The attapulgite slurry of a concentration of 1.2g/L, ultrasonic disperse 0.9h；It is 11 to add in aqueous slkali to system pH, and composite suspension is made
Liquid adds in reducing agent solution under stirring condition into the composite dispersion liquid of gained, reacts 42min, filters, and washs, dry, is made
Compound desulfuration adsorbent；
（6）The product oil C carries out desulphurization reaction in the presence of compound desulfuration adsorbent in efficient mass transfer reactor, reaction
Temperature is 85 DEG C, liquid hourly space velocity (LHSV) 22h-1, desulfurization product oil is obtained by filtration after the completion of reaction.
Embodiment 3
A kind of high sour product sulfur removal technology, is as follows：
（1）High sulfur crude and hydrogen peroxide are mixed, 20min is stirred with the stir speed (S.S.) of 300r/min, merging is super after mixing
Acoustic frequency is 28kHz, the ultrasonic wave sound intensity is 0.45W/cm2Ultrasound reactor in, react 30min after take out it is quiet at room temperature
It puts, obtains product oil A；
（2）Air is passed through progress light provocative reaction in product oil A, diesel oil is promoted to generate active oxygen species in situ, obtains containing and live
The product oil B of property oxygen species；The light source power of the smooth provocative reaction be 700W, reaction time 7h, the flow velocity of the air
For 30min-1；
（3）Titanium Sieve Molecular Sieve powder, polymerized monomer polyenoid based compound and pore-foaming agent are sufficiently mixed, existed in initiator
Under, the addition of initiator is the 2% of Titanium Sieve Molecular Sieve powder and polymerized monomer polyenoid based compound total weight, in 100 DEG C of progress
Polymerisation 10h obtains blocks of solid catalyst；Then catalyst solid particle is obtained through broken, by above-mentioned catalyst solid
Particle is added in halogenated hydrocarbons after swelling 6h, is extracted activation 4h at 40 DEG C using extraction solvent, is obtained Titanium Sieve Molecular Sieve and resin
Composite catalyst；The Titanium Sieve Molecular Sieve and the specific surface area of resin compounded catalyst of obtaining is 180m2/ g, Kong Rongwei
0.25cm3/ g, side pressure strength 12N.mm-1；
（4）There is MoO by product oil B, in load3SiO2In the presence of Titanium Sieve Molecular Sieve and resin compounded catalyst, oxygen is carried out
Change desulphurization reaction, reaction temperature is 60 DEG C, reaction time 3h, removes sulfur-containing compound, obtains product oil C；
（5）By graphite and Cu (NO3)2·3H2O is added in the concentrated sulfuric acid, is then slowly added into potassium permanganate, stirs 1.5h, then add
Enter the attapulgite slurry of a concentration of 1.5g/L, ultrasonic disperse 1h；It is 12 to add in aqueous slkali to system pH, and composite suspension is made
Liquid adds in reducing agent solution under stirring condition into the composite dispersion liquid of gained, reacts 45min, filters, and washs, dry, is made
Compound desulfuration adsorbent；
（6）The product oil C carries out desulphurization reaction in the presence of compound desulfuration adsorbent in efficient mass transfer reactor, reaction
Temperature is 90 DEG C, liquid hourly space velocity (LHSV) 25h-1, desulfurization product oil is obtained by filtration after the completion of reaction.
Embodiment 4
A kind of high sour product sulfur removal technology, is as follows：
（1）High sulfur crude and hydrogen peroxide are mixed, 22min is stirred with the stir speed (S.S.) of 320r/min, merging is super after mixing
Acoustic frequency is 29kHz, the ultrasonic wave sound intensity is 0.48W/cm2Ultrasound reactor in, react 35min after take out it is quiet at room temperature
It puts, obtains product oil A；
（2）Air is passed through progress light provocative reaction in product oil A, diesel oil is promoted to generate active oxygen species in situ, obtains containing and live
The product oil B of property oxygen species；The light source power of the smooth provocative reaction be 750W, reaction time 7.5h, the stream of the air
Speed is 32min-1；
（3）Titanium Sieve Molecular Sieve powder, polymerized monomer polyenoid based compound and pore-foaming agent are sufficiently mixed, existed in initiator
Under, the addition of initiator for Titanium Sieve Molecular Sieve powder and polymerized monomer polyenoid based compound total weight 2.5%, 110 DEG C into
Row polymerisation 11h, obtains blocks of solid catalyst；Then catalyst solid particle is obtained through broken, above-mentioned catalyst is consolidated
Body particle is added in halogenated hydrocarbons after swelling 6.5h, is extracted activation 4.5h at 45 DEG C using extraction solvent, is obtained Titanium Sieve Molecular Sieve
With resin compounded catalyst；The Titanium Sieve Molecular Sieve and the specific surface area of resin compounded catalyst of obtaining is 190m2/ g, Kong Rongwei
0.28cm3/ g, side pressure strength 14N.mm-1；
（4）There is MoO by product oil B, in load3SiO2In the presence of Titanium Sieve Molecular Sieve and resin compounded catalyst, oxygen is carried out
Change desulphurization reaction, reaction temperature is 65 DEG C, reaction time 3.2h, removes sulfur-containing compound, obtains product oil C；
（5）By graphite and Cu (NO3)2·3H2O is added in the concentrated sulfuric acid, is then slowly added into potassium permanganate, is stirred 2h, is added
The attapulgite slurry of a concentration of 1.8g/L, ultrasonic disperse 1.1h；It is 12 to add in aqueous slkali to system pH, and composite suspension is made
Liquid adds in reducing agent solution under stirring condition into the composite dispersion liquid of gained, reacts 48min, filters, and washs, dry, is made
Compound desulfuration adsorbent；
（6）The product oil C carries out desulphurization reaction in the presence of compound desulfuration adsorbent in efficient mass transfer reactor, reaction
Temperature is 95 DEG C, liquid hourly space velocity (LHSV) 28h-1, desulfurization product oil is obtained by filtration after the completion of reaction.
Embodiment 5
A kind of high sour product sulfur removal technology, is as follows：
（1）High sulfur crude and hydrogen peroxide are mixed, 25min is stirred with the stir speed (S.S.) of 350r/min, merging is super after mixing
Acoustic frequency is 30kHz, the ultrasonic wave sound intensity is 0.5W/cm2Ultrasound reactor in, react 40min after take out it is quiet at room temperature
It puts, obtains product oil A；
（2）Air is passed through progress light provocative reaction in product oil A, diesel oil is promoted to generate active oxygen species in situ, obtains containing and live
The product oil B of property oxygen species；The light source power of the smooth provocative reaction be 800W, reaction time 8h, the flow velocity of the air
For 35min-1；
（3）Titanium Sieve Molecular Sieve powder, polymerized monomer polyenoid based compound and pore-foaming agent are sufficiently mixed, existed in initiator
Under, the addition of initiator is the 3% of Titanium Sieve Molecular Sieve powder and polymerized monomer polyenoid based compound total weight, in 120 DEG C of progress
Polymerisation 12h obtains blocks of solid catalyst；Then catalyst solid particle is obtained through broken, by above-mentioned catalyst solid
Particle is added in halogenated hydrocarbons after swelling 7h, is extracted activation 5h at 50 DEG C using extraction solvent, is obtained Titanium Sieve Molecular Sieve and resin
Composite catalyst；The Titanium Sieve Molecular Sieve and the specific surface area of resin compounded catalyst of obtaining is 200m2/ g, Kong Rongwei 0.3cm3/
G, side pressure strength 15N.mm-1；
（4）There is MoO by product oil B, in load3SiO2In the presence of Titanium Sieve Molecular Sieve and resin compounded catalyst, oxygen is carried out
Change desulphurization reaction, reaction temperature is 70 DEG C, reaction time 3.5h, removes sulfur-containing compound, obtains product oil C；
（5）By graphite and Cu (NO3)2·3H2O is added in the concentrated sulfuric acid, is then slowly added into potassium permanganate, stirs 2.5h, then add
Enter the attapulgite slurry of a concentration of 2g/L, ultrasonic disperse 1.2h；It is 13 to add in aqueous slkali to system pH, and composite suspension is made
Liquid adds in reducing agent solution under stirring condition into the composite dispersion liquid of gained, reacts 50min, filters, and washs, dry, is made
Compound desulfuration adsorbent；
（6）The product oil C carries out desulphurization reaction in the presence of compound desulfuration adsorbent in efficient mass transfer reactor, reaction
Temperature is 100 DEG C, liquid hourly space velocity (LHSV) 30h-1, desulfurization product oil is obtained by filtration after the completion of reaction.
The polymerized monomer polyenoid based compound be divinylbenzene, divinyl toluene and one kind in biethenyl-xylene or
It is a variety of.The pore-foaming agent is one or more in gasoline, C5-C13 n-alkanes, C4-C12 fatty alcohols.The initiation
Agent is two isobutanol of benzoyl peroxide and/or azo.The extraction solvent is benzene,toluene,xylene, ethyl acetate, acetic acid
It is one or more in butyl ester, ethyl alcohol and butanol.The aqueous slkali is sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide
Or one kind in ammonium bicarbonate soln.The reducing agent solution is formalin, acetaldehyde solution, glucose solution or hydrazine hydrate
In one kind.
The present invention carries out desulfurization using three-step approach, and oxidation selectivity and desulfurization degree are high, and used oxidant/catalyst is easy
Separation and following cycle use, and use air as indirect oxidation agent, at low cost, and in addition relatively low reaction temperature may be used in the present invention
Degree or shorter reaction time or less oxidizer, product quality and yield can improve, and low energy consumption, be its work
Industry application is laid a good foundation.
The better embodiment of this patent is explained in detail above, but this patent is not limited to above-mentioned embodiment party
Formula, can also be under the premise of this patent objective not be departed from the knowledge that one skilled in the relevant art has
Various changes can be made.
Claims (8)
1. a kind of high sour product sulfur removal technology, which is characterized in that be as follows：
(1) high sulfur crude and hydrogen peroxide are mixed, 15-25min is stirred with the stir speed (S.S.) of 250-350r/min, after mixing
It is 25-30kHz, in the ultrasound reactor that the ultrasonic wave sound intensity is 0.4-0.5W/cm2 to be placed in supersonic frequency, reacts 20-40min
After take out and stand at room temperature, obtain product oil A；
(2) air is passed through progress light provocative reaction in product oil A, diesel oil is promoted to generate active oxygen species in situ, obtained containing and live
The product oil B of property oxygen species；The light source power of the smooth provocative reaction be 600-800W, reaction time 6-8h, the air
Flow velocity be 25-35min-1；
(3) Titanium Sieve Molecular Sieve powder, polymerized monomer polyenoid based compound and pore-foaming agent are sufficiently mixed, existed in initiator
Under, the addition of initiator is Titanium Sieve Molecular Sieve powder and the 1-3% of polymerized monomer polyenoid based compound total weight, in 80-120
DEG C carry out polymerisation 8-12h, obtain blocks of solid catalyst；Then catalyst solid particle is obtained through broken, is urged above-mentioned
Agent solid particle is added in halogenated hydrocarbons after swelling 5-7h, is extracted activation 3-5h at 30-50 DEG C using extraction solvent, is obtained titanium
Si molecular sieves and resin compounded catalyst；
(4) by product oil B, in the presence of the load SiO2 of MoO3 and Titanium Sieve Molecular Sieve and resin compounded catalyst, oxygen is carried out
Change desulphurization reaction, reaction temperature is 50-70 DEG C, reaction time 2.5-3.5h, removes sulfur-containing compound, obtains product oil C；
(5) graphite and Cu (NO3) 23H2O are added in the concentrated sulfuric acid, are then slowly added into potassium permanganate, stir 0.5-
2.5h adds the attapulgite slurry of a concentration of 1-2g/L, ultrasonic disperse 0.8-1.2h；Adding in aqueous slkali to system pH is
10-13 is made composite suspension liquid, adds in reducing agent solution under stirring condition into the composite dispersion liquid of gained, reacts 40-
50min is filtered, and is washed, dry, and compound desulfuration adsorbent is made；
(6) the product oil C carries out desulphurization reaction in the presence of compound desulfuration adsorbent in efficient mass transfer reactor, reaction
Temperature is 80-100 DEG C, liquid hourly space velocity (LHSV) 20-30h-1, and desulfurization product oil is obtained by filtration after the completion of reaction.
2. high sour product sulfur removal technology according to claim 1, which is characterized in that the polymerized monomer polyene-based chemical combination
Object is one or more in divinylbenzene, divinyl toluene and biethenyl-xylene.
3. high sour product sulfur removal technology according to claim 1, which is characterized in that the pore-foaming agent is gasoline, C5-
It is one or more in C13 n-alkanes, C4-C12 fatty alcohols.
4. high sour product sulfur removal technology according to claim 1, which is characterized in that the initiator is benzoyl peroxide
Two isobutanol of formyl and/or azo.
5. high sour product sulfur removal technology according to claim 1, which is characterized in that the extraction solvent be benzene, toluene,
It is one or more in dimethylbenzene, ethyl acetate, butyl acetate, ethyl alcohol and butanol.
6. high sour product sulfur removal technology according to claim 1, which is characterized in that described to obtain Titanium Sieve Molecular Sieve and tree
The specific surface area of fat composite catalyst is 150-200m2/g, Kong Rongwei 0.2-0.3cm3/g, side pressure strength 10-15N.mm-1.
7. high sour product sulfur removal technology according to claim 1, which is characterized in that the aqueous slkali is hydroxide
One kind in sodium solution, potassium hydroxide solution, ammonium hydroxide or carbonic acid hydrogen ammonium salt solution.
8. high sour product sulfur removal technology according to claim 1, which is characterized in that the reducing agent solution is formaldehyde
One kind in solution, acetaldehyde solution, glucose solution or hydrazine hydrate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112705245A (en) * | 2020-12-28 | 2021-04-27 | 广东石油化工学院 | Method for removing sulfur-containing organic compounds in oil product by using three-dimensional ordered mesoporous molybdenum-based catalyst |
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