CN107151564B - A kind of production method of super-low sulfur clean gasoline - Google Patents
A kind of production method of super-low sulfur clean gasoline Download PDFInfo
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- CN107151564B CN107151564B CN201610124810.7A CN201610124810A CN107151564B CN 107151564 B CN107151564 B CN 107151564B CN 201610124810 A CN201610124810 A CN 201610124810A CN 107151564 B CN107151564 B CN 107151564B
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
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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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- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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Abstract
The present invention provides a kind of production methods of super-low sulfur clean gasoline.The production method includes: that full distillation gasoline is made to contact generation orientation sulphur transfer reaction with low temperature sulfur transfer catalyst under hydro condition, then carries out oil product cutting, obtains light, heavy distillat gasoline；It mixes light fraction gasoline with organic acid and is contacted with esterification catalyst, esterification, the light fraction gasoline after being esterified occur for the C5-C7 alkene in light fraction gasoline；Make heavy distillat gasoline and catalyst for selectively hydrodesulfurizing and supplement desulfuration adsorbent haptoreaction, obtains the heavy distillat gasoline of super-low sulfur；By treated, light, heavy distillat gasoline is mixed, and obtains super-low sulfur clean gasoline.The present invention using hydrodesulfurization and absorption desulfurization group technology, can flexibly modulation process conditions to adjust the alkene range of decrease and desulfurization depth；Its octane number is substantially improved in the esterification of C5-C7 alkene in light fraction gasoline, so that the octane number of gasoline products is maintained or improves after making light, heavy distillat gasoline mixing.
Description
Technical field
The present invention relates to a kind of production method of super-low sulfur clean gasoline more particularly to a kind of catalytic cracking (FCC) gasoline
Refining field, the especially ultra-deep desulfurization of ultra-high-sulfur(UHS) FCC gasoline keep or propose high-octane method.
Background technique
With economic development, social progress, car ownership is continuously increased, and vehicle exhaust is polluted caused by atmospheric environment
It gets worse.For this purpose, more stringent quality of gasoline regulation has been put into effect in countries in the world in succession, advocates and use clean gasoline, reduce
Pollution to environment.Currently, 75% or so being FCC gasoline in China's gasoline product, but China's FCC content of olefin in gasoline is high, sulphur
Content is high, stability is poor, and gasoline product is caused to can not meet the requirement of new standard.Therefore, FCC gasoline hydro-upgrading technology is just
One of key technology as clean fuel for vehicle production.
US6,692,635 disclose a kind of low-sulphur oil production technology, its main feature is that: full fraction catalytic gasoline is first pre-
Alkadienes is removed in hydrogenator, mercaptan is made to be converted into higher boiling sulfur compound, while double-bond isomerism occurs for alkene；Then, in advance
Hydrogenation products carry out fraction cutting, obtain light, heavy distillat gasoline；Heavy distillat gasoline carries out hydrogenation reaction first, by unsaturated sulphur
Compound is converted into saturation sulfide, and hydrodesulfurization, the heavy distillat after obtaining desulfurization are then carried out under the action of desulphurization catalyst
Gasoline；Finally, light, heavy distillat gasoline mixing, obtains clean gasoline product.But lower (the 80.0%- of the desulfurization degree of this method
92%), product sulfur content is difficult near 50 μ g/g hereinafter, being unable to satisfy state IV and state's V clean gasoline standard.
CN104711018 A and CN103666559 A describe a kind of FCC gasoline ultra-deep desulfurization combined method, special
Point are as follows: FCC gasoline first takes off diene under hydro condition, then carries out fractionation cutting, obtains light, heavy distillat gasoline；Heavy distillat vapour
Oil carries out selective hydrodesulfurization reaction, and 100ppm or less is dropped in sulfur content；Then, light, heavy distillat gasoline mixing, carries out ultra-deep
Degree absorption desulfurization, obtains the super low-sulfur oil product that sulfur content is lower than 10ppm.But the technique is primarily directed to low-sulfur FCC vapour
Oil；In processing to high-sulfur FCC gasoline inferior, loss of octane number is excessive, is unable to reach ultra-deep desulfurization and keeps wanting for octane number
It asks.
CN103074107 A discloses a kind of production method of low-sulphur oil, this method first by gasoline cutting be divided into it is light,
In, weigh three kinds of gasoline fractions；Light fraction gasoline carries out caustic wash desulfuration alcohol；Midbarrel is obtained with after reformation processing through hydrogenated processing
High-octane midbarrel；Double distilled lease making takes off diene and selective hydrodesulfurization two-stage reaction, obtains low-sulfur heavy distillat gasoline；
Finally will it is light, in, heavy distillat gasoline mix, obtain low-sulfur, clean gasoline with high octane product.
CN101418234 A discloses a kind of low-sulphur oil production method similar with above-mentioned technique, unlike: the party
FCC gasoline is first carried out oxidation deodorizing by method, converts the mercaptans to high boiling disulphide, is then again divided FCC gasoline
Evaporate cutting, obtain it is light, in, heavy distillat gasoline；The heavy distillat gasoline of hydrogenated desulfurization, hydrogenated desulfurization and catalytic reforming centre
Distillation gasoline is mixed with light fraction gasoline, obtains clean gasoline product.
Above two method can be obtained clean gasoline product, and its octane number has been after catalytic reforming for midbarrel
It is promoted, obtains clean gasoline with high octane after mixing with light, heavy distillat gasoline；But its process flow is complicated, needs catalytic reforming
Reactor and hydrodesulphurisatioreactors reactors cooperate；And midbarrel gasoline generates liquefied gas and hydrogen after reforming, gasoline produces
Product liquid yield is lower.
CN102649914 A discloses a kind of side of catalytic gasoline hydrogenation of total effluent desulfurization production super-low sulfur clean gasoline
Method, feature are as follows: FCC gasoline first carries out de- diene processing, while isomerization reaction occurs for alkene, improves its octane number, so
Selective hydrodesulfurization reaction is carried out afterwards, obtains low-sulfur high octane gasoline products.But this method Olefin decrease ability is poor,
Alkene saturation factor is less than 20%；It is modified with FCC gasoline of this method to high olefin content, it is difficult to obtain meeting state's V standard
Gasoline products.
CN103450935 A discloses a kind of method for producing super low-sulfur oil, this method first by full distillation gasoline into
Row cutting, obtains light, heavy distillat gasoline；Heavy distillat gasoline after light fraction gasoline and selective hydrodesulfurization after oxidation deodorizing
Mixing, obtains super low-sulfur oil product.This method is when handling the gasoline that sulfur content is 450ppm, desulfurization degree 97.8%, but
Loss of octane number is larger (research octane number (RON) loses 3 units), reduces gasoline quality.
In conclusion being directed to the production of clean gasoline, existing many researchs all attempt to realize desulfurization drop by means of different
Alkene, while the octane number of oil product is kept and improved as far as possible.Above method has their own advantages, but its to the specific aim of oil product compared with
By force, it is difficult to the case where handling feedstock oil sulfur content, olefin(e) centent fluctuation.Therefore, developing one kind can be by modulation technique
Desulfurization degree and the alkene range of decrease is adjusted flexibly in condition, and can keep or mention high-octane gasoline modifying method and be of great significance.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of production methods of super-low sulfur clean gasoline.It should
Method using hydrodesulfurization and absorption desulfurization group technology, can flexibly modulation process conditions it is deep to adjust the alkene range of decrease and desulfurization
Degree, and light fraction gasoline carries out esterification, and gasoline products octane number while ultra-deep desulfurization is made to be maintained or mention
It is high.
In order to achieve the above objectives, the present invention provides a kind of production method of super-low sulfur clean gasoline, this method is mainly wrapped
Include following steps:
Full distillation gasoline is set to contact generation orientation sulphur transfer reaction with low temperature sulfur transfer catalyst under hydro condition, then
Oil product cutting is carried out, light fraction gasoline and heavy distillat gasoline are obtained；
Mix light fraction gasoline with organic acid, C5-C7 alkene under the action of esterification catalyst, in light fraction gasoline
Esterification occurs for hydrocarbon, then after rectifying separation system removes unreacted organic acid, the light fraction vapour that obtains that treated
Oil；
It contacts heavy distillat gasoline with catalyst for selectively hydrodesulfurizing and supplement desulfuration adsorbent, selective hydrogenation occurs
Desulphurization reaction and ultra-deep absorption desulfurization reaction, obtain the heavy distillat gasoline of super-low sulfur；
Will treated light fraction gasoline heavy distillat gasoline mix with treated, obtain described in super-low sulfur clean vapour
Oil.
In aforementioned production method, it is preferable that the reaction condition of the sulphur transfer reaction are as follows: reaction pressure 1.0-3.0
MPa, liquid volume air speed 2.0-8.0h-1, 100-200 DEG C of reaction temperature, hydrogen to oil volume ratio 5-15.
In aforementioned production method, it is preferable that on the basis of the total weight of catalyst, the low temperature sulfur transfer catalyst
Composition includes: transition metal oxide 2-30%, auxiliary agent 0.5-6%, zeolite 10-40%, and surplus is inorganic refractory oxide；Its
In, the transition-metal oxide may include NiO, CoO, ZnO, MoO3、WO3With the combination of one or more of CuO etc.；
The auxiliary agent may include K2O, MgO and La2O3Deng one or more of combination；The zeolite includes HZSM-5, H β and HY
Deng one or more of combination, also, the zeolite be by alkali process, ammonium exchange, hydro-thermal process zeolite；The nothing
Machine refractory oxide may include the combination of one or more of aluminium oxide, silica and silicon-containing alumina etc..
In aforementioned production method, it is preferable that the temperature of the oil product cutting is 50-100 DEG C, and the oil product is cut
It can be carried out in fractionating column.
In aforementioned production method, it is preferable that the reaction condition of the esterification are as follows: 80-200 DEG C of reaction temperature, instead
Answer pressure 0.1-4.0MPa, olefin weight ratio (sour alkene ratio) 0.5-2.5:1.0 in organic acid and light fraction gasoline, liquid volume sky
Fast 0.5-5.0h-1(in terms of organic acid).The process flow of the esterification may include: by light fraction gasoline and organic acid by
Certain proportion mixing be esterified by the fixed bed reactors equipped with esterification catalyst of one or several serial or parallel connections anti-
It answers, the light fraction gasoline after being esterified.After esterification, the light fraction gasoline after esterification is removed not through rectifying separation system
The organic acid of reaction, the light fraction gasoline that obtains that treated.
In aforementioned production method, it is preferable that the organic acid includes one had the following structure in the compound of general formula
Kind or several combinations:
In formula, R H, CH3、C2H5、C3H7In any one.
In aforementioned production method, it is preferable that the esterification catalyst has high secondary ester selectivity comprising metal oxidation
Object catalyst, zeolite molecular sieve catalyst, SO4 2-/MxOyOne of catalyst, strong acid cation exchange resin catalyst etc.
Or several combination；Wherein, the metal oxide catalyst may include in silica, molecular sieve and diatomite etc. extremely
It is few a kind of for carrier loaded ZnO, SnO and Al2O3Deng at least one of catalyst made by metal oxide, and it is described
Carrier can have conventional structure or meso-hole structure；
The zeolite molecular sieve catalyst may include aluminium phosphate molecular sieve, aluminium silicophosphate molecular sieve, H-type modenite,
The molecular sieve catalyst that one or more of HY zeolite, H- β zeolite and HZSM-5 zeolite etc. mix, and these are boiled
Stone molecular sieve can be conventional zeolite molecular sieve or step hole zeolite molecular sieve；
The SO4 2-/MxOyCatalyst may include by SO4 2-It is carried at least one of ZrO, ZnO and SnO etc. metal
Made SO on carrier made of oxide4 2-/MxOyCatalyst, and the metal oxide can aoxidize for common metal
Object or mesopore metal oxide；
The strong acid cation exchange resin catalyst includes containing strong acid reaction group (such as sulfonic group-SO3H
Deng) Jie-large pore macromolecular crosslink copolymer catalyst.
In aforementioned production method, the rectifying separation system includes at least two rectifying columns；Preferably, the rectifying point
It include four rectifying columns from system, respectively first rectifying column, Second distillation column, third distillation column and the 4th rectifying column, first
Rectifying column operating condition are as follows: number of plates 20-50, feedboard number 10-40,20-50 DEG C of tower top temperature, tower top pressure 1-5atm, tower
100-200 DEG C of kettle temperature degree, tower reactor pressure 1-10atm, reflux ratio are controlled in 0.1-10；After-fractionating tower operating condition are as follows: column plate
Number 20-100, feedboard number 10-80,100-150 DEG C of tower top temperature, tower top pressure 1-5atm, 100-200 DEG C of bottom temperature, tower
Kettle pressure 1-5atm, reflux ratio are controlled in 1-40；Third fractionating column operating condition are as follows: number of plates 20-70, feedboard number 10-60,
50-150 DEG C of tower top temperature, tower top pressure 1-5atm, 80-150 DEG C of bottom temperature, tower reactor pressure 1-5atm, reflux ratio control exists
1-30；4th fractionating column operating condition are as follows: number of plates 10-60, feedboard number 10-50,80-150 DEG C of tower top temperature, tower top pressure
1-5atm, 100-150 DEG C of bottom temperature, tower reactor pressure 1-5atm, reflux ratio is controlled in 1-30.
In aforementioned production method, connect heavy distillat gasoline with catalyst for selectively hydrodesulfurizing and supplement desulfuration adsorbent
Touching, is to contact heavy distillat gasoline successively with two kinds of catalyst, and selective hydrodesulfurization reaction and ultra-deep absorption successively occurs
Desulphurization reaction.
In aforementioned production method, it is preferable that the heavy distillat gasoline is contacted with the catalyst for selectively hydrodesulfurizing
Reaction condition are as follows: reaction pressure 1.0-3.0MPa, liquid volume air speed 1.5-6.0h-1, 200-300 DEG C of reaction temperature, hydrogen oil
Volume ratio 200-600.
In aforementioned production method, it is preferable that the ultra-deep absorption desulfurization reaction is in one or several dresses parallel with one another
It is carried out in the absorption desulfurization reactor for having supplement desulfuration adsorbent.It is highly preferred that two absorption desulfurization reactors of setting, wherein one
A when carrying out ultra-deep absorption desulfurization reaction, another carries out desulfuration adsorbent regeneration, and the two replaces.Preferably, described super
The reaction condition of deep absorption desulfurization reaction are as follows: pressure 0.1-2.0MPa, 30-60 DEG C of temperature, liquid volume air speed 1-5h-1；It is de-
The regeneration method of sulfur absorbent are as follows: at 0.1-2.0MPa, 150-250 DEG C, carry out N2Purging, N2Volume space velocity is 500-
3000h-1。
In aforementioned production method, it is preferable that on the basis of the total weight of catalyst, the selective hydrodesulfurization catalysis
The composition of agent includes: MoO310-18%, CoO2-6%, K2O1-7%, P2O52-6%, surplus are Al-Si-Mg composite oxides
Carrier；It is highly preferred that the weight composition of the Al-Si-Mg composite oxides in the catalyst includes (i.e. with the total of catalyst
On the basis of weight): Al2O360-75%, SiO25-15% and MgO3-10%.
In aforementioned production method, it is preferable that based on the total catalyst weight, the supplement desulfuration adsorbent is through over-voltage
Piece crosses the molding step hole HKUST-1 of 40-60 mesh.It is highly preferred that the step hole HKUST-1 is through the following steps that preparation
It obtains: lauryl sodium sulfate (SDS) being dissolved in deionized water, Cu (NO is then sequentially added3)2·3H2O, equal benzene three
Formic acid stirs evenly, and obtains colloidal sol, then in 80-150 DEG C of crystallization 12-36h, is filtered, washed, dries, later removed template method
(removed template method, extraction temperature can be able to be 30-80 DEG C by the way of ethyl alcohol extraction, extraction time can be 3-6h),
Tabletting, sieving obtain the step hole HKUST-1.Particularly preferably, SDS, deionized water, Cu (NO in the colloidal sol3)2·
3H2O, the molar ratio of trimesic acid is (1-2): (80-200): (1.5-2.5): 1.
Specific embodiment according to the present invention, it is preferable that aforementioned production method is further comprising the steps of: right before the reaction
The low temperature sulfur transfer catalyst, the catalyst for selectively hydrodesulfurizing are dried to be handled with presulfurization, to supplement desulfurization
Adsorbent is activated；Drying condition are as follows: 100-150 DEG C, N2Atmosphere, N2Air speed 200-2000h-1；The step of presulfurization
Are as follows: by N in catalyst bed2By H2Displacement completely, and keeps H2Air speed is 200-3000h-1, adjustment reaction bed temperature is extremely
120-180 DEG C, to catalyst bed with 1-5h-1Volume space velocity inject straight-run naphtha, adjustment hydrogen to oil volume ratio is to 200-
500:1；Catalyst bed is warming up to 150-200 DEG C with 10-30 DEG C/h, starts to inject vulcanizing agent (such as dimethyl disulfide
Ether), adjust the 1-5wt% of its injection rate to straight-run naphtha；It then proceedes to be warming up to 210- with the speed of 10-30 DEG C/h
250 DEG C, constant temperature 6-10h；It is warming up to 270-290 DEG C with the speed of 10-30 DEG C/h, constant temperature 6-10h；It is warming up to 10-30 DEG C/h
310-350 DEG C, constant temperature 6-10h；With each catalyst bed reaction temperature of 10-30 DEG C/h cooling；Finally, being replaced with reaction with oil product
Sulfurized oil in system, vulcanization terminate；The method of the activation processing are as follows: at 0.1-2MPa, 150-250 DEG C, carry out N2Purging,
N2Volume space velocity is 500-3000h-1。
In aforementioned production method, it is preferable that the sulfur content of the full distillation gasoline is 500-2000 μ gg-1, alkene contains
Amount is 30-50v% (with the total volume meter of the full distillation gasoline)；And the sulphur of the super-low sulfur clean gasoline produced contains
Measure≤10 μ gg-1, olefin(e) centent≤24v% (with the total volume meter of the super-low sulfur clean gasoline).
The present invention using hydrodesulfurization and absorption desulfurization group technology, can flexibly modulation process conditions to adjust the alkene range of decrease
And desulfurization depth；And its octane number is substantially improved in the esterification of C5-C7 alkene in light fraction gasoline, to make light, heavy distillat vapour
After oil mixing, the octane number of gasoline products is maintained or improves.Compared with prior art, super-low sulfur provided by the present invention is clear
Sulfur content can be 500-2000 μ gg by the production method of clean gasoline-1, olefin(e) centent 30-50v% gasoline upgrading be sulfur content
≤10μg·g-1, olefin(e) centent≤24v%, gasoline Research octane number (RON) lose≤0.5 unit premium, and
Product liquid yield >=99wt%.
Detailed description of the invention
Fig. 1 is the flow diagram for the super-low sulfur clean gasoline production method that embodiment 1,2,3 and 4 provides.
Primary clustering symbol description in Fig. 1:
Sulphur transfer reaction 101, fraction cutting 102, esterification 103, rectifying separation 104, selective hydrodesulfurization reaction
105, ultra-deep absorption desulfurization reaction 106, desulfuration adsorbent regeneration 107.
Rectifying separation system in the super-low sulfur clean gasoline production method that Fig. 2 provides for the embodiment of the present invention 1,2,3 and 4
Flow diagram；
Primary clustering symbol description in Fig. 2:
First rectifying column 201, Second distillation column 202, third distillation column 203, the 4th rectifying column 204.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
One kind is present embodiments provided with 823.1 μ gg of sulfur content-1, olefin(e) centent 35.2v% high-sulfur poor quality FCC vapour
Oily (feedstock oil 1) is the method that raw material carries out hydro-upgrading processing preparation super-low sulfur high-knock rating gasoline.
Wherein, on the basis of the total weight of each catalyst, the composition proportion of each catalyst is as follows:
Low temperature sulfur transfer catalyst: 12wt%NiO, 6wt%MoO3, 2wt%La2O3, 20wt%HZSM-5,60%
Al2O3-SiO2(silicon-containing alumina)；
Esterification catalyst: 40wt%HZSM-5,60%Al2O3-SiO2(silicon-containing alumina)；
Catalyst for selectively hydrodesulfurizing: 4wt%CoO, 12wt%MoO3, 3wt%K2O, 2wt%P2O5, 67wt%
Al2O3, 8wt%SiO2, 4wt%MgO；
Supplement desulfuration adsorbent: 100wt% step hole HKUST-1.
Specific preparation process is as follows for low temperature sulfur transfer catalyst:
First by HZSM-5 zeolite (SiO2/Al2O3Molar ratio is 30) to be placed in NaOH aqueous solution by the liquid-solid ratio of 10mL/g
In, pH value is adjusted to 13,4h is stirred at 75 DEG C, filtering washs the zeolite filtered out to neutrality, in 120 DEG C of dry 3h；It will
The HZSM-5 zeolite handled through NaOH aqueous solution is according to zeolite: ammonium nitrate: the ratio that the weight ratio of water is 1: 0.8: 10 mixes, and
In 80 DEG C of stirring 4h, then product is filtered, is washed, and in 120 DEG C of dryings, 480 DEG C of roasting 4h, obtains alkali process-ammonium
The HZSM-5 zeolite of exchange；The above-mentioned HZSM-5 zeolite exchanged through alkali process and ammonium is passed through steam treatment 20- at 600 DEG C
50min obtains modified HZSM-5 zeolite (i.e. alkali process-ammonium exchange-hydro-thermal process HZSM-5 zeolite)；
50.2g aluminum silicon powder is weighed (containing Al2O392.0wt%, SiO28.0wt%) and the HZSM-5 of the above-mentioned modification of 30.0g
Zeolite, 2.5g sesbania powder, its ground and mixed is uniform, 6mL concentration is added for the nitric acid solution of 65wt%, in crowded after abundant kneading
The cloverleaf pattern item that diameter is 2mm is squeezed out in machine, and molding catalyst is made after 120 DEG C of dry 4h, 520 DEG C of roasting 4h
Carrier；
It is prepared according to stoichiometric ratio and contains NiO, MoO3And La2O3Nickel nitrate, ammonium molybdate, lanthanum nitrate mixed solution, then
Maceration extract is dropped evenly in said catalyst carrier using equi-volume impregnating, through 120 DEG C of dry 4 h, 520 DEG C of roasting 4h
Afterwards, low temperature sulfur transfer catalyst is made.
Specific preparation process is as follows for esterification catalyst:
The ZSM-5 zeolite and 1mol/L NH for being 35 by silica alumina ratio4Cl solution is stirred with the mixing of 1:10 weight ratio in 80 DEG C
4h is filtered, washed, dries, 550 DEG C of roasting 5h；It repeats the above steps primary, obtains the HZSM-5 zeolite of ammonium exchange.
Weighing 30g takes aluminum silicon powder (containing Al2O392.0wt%, SiO 8.0wt%), the above-mentioned HZSM-5 zeolite of 20g and 1.9g
Sesbania powder, ground and mixed is uniform, and the nitric acid solution of 4.5mL65wt% is added, and abundant kneading is formed with banded extruder, dry through 120 DEG C
After dry 4h, 550 DEG C of roasting 5h, the cloverleaf pattern esterification catalyst of diameter 2mm is obtained.
Specific preparation process is as follows for catalyst for selectively hydrodesulfurizing:
Weigh Al-Si-Mg composite powder (aqueous 25wt%) and 2.0g that 70.0g has suitable Al/Si/Mg ratio
Sesbania powder, its ground and mixed is uniform, the nitric acid solution that 5mL concentration is 65wt% is added, is squeezed in banded extruder after abundant kneading
Item molding, after 120 DEG C of dry 3h, 520 DEG C of roasting 4h, is made molding catalyst carrier；
40.0g said catalyst carrier is impregnated in the mixed impregnant liquor of 35mL potassium nitrate and diammonium hydrogen phosphate, with oxygen
Compound meter contains 1.5g K in the maceration extract2O and 1.0g P2O5, then ripening 5h at room temperature, then in 120 DEG C of dryings
3h, 520 DEG C of roasting 4h, have been loaded the catalyst carrier of potassium and phosphorus；
It prepares 32.0mL and contains 2.0gCoO and 6.1g MoO3(content of each active component is counted in the form of an oxide, not
Active component in limitation mixed liquor exists in the form of an oxide) cobalt nitrate and ammonium molybdate mixed liquor, and it is dense that 3.0mL is added
Degree is the ammonium hydroxide of 17wt%, and sufficiently oscillation is until solid is completely dissolved maceration extract is made, then by above-mentioned potassium and the phosphorus of having loaded
Catalyst carrier is impregnated in the maceration extract, and room temperature is aged 5h, after 120 DEG C of drying process 3h, 520 DEG C of calcination process 5h, system
Obtain catalyst for selectively hydrodesulfurizing.
Supplementing desulfuration adsorbent, specific preparation process is as follows:
50.0g lauryl sodium sulfate (SDS) is dissolved in 750.0g deionized water at 55 DEG C, 55.0g is then added
Cu(NO3)2·3H2O is uniformly mixed；25.0g trimesic acid (H is added3BTC), 30min is stirred at 55 DEG C；Finally
The crystallization 12h at 120 DEG C, is filtered, washed, dries, and obtains step hole HKUST-1 original powder；By step hole HKUST-1 original powder point
(weight ratio 1:10) is dissipated in dehydrated alcohol, 6h, removed template method SDS are stirred at 80 DEG C, obtains step hole HKUST-1；It will
40-60 mesh is crossed in the HKUST-1 tabletting of step hole, obtains supplement desulfuration adsorbent.
The process for modifying production super-low sulfur high-knock rating gasoline using full feedstock oil is as follows, process flow such as Fig. 1
It is shown:
The property of feedstock oil 1 participates in table 1.Feedstock oil occurs orientation sulphur under the action of low temperature sulfur transfer catalyst first and turns
Move reaction 101, reaction condition are as follows: pressure 2.4MPa, 130 DEG C of temperature, liquid volume air speed 3h-1, hydrogen to oil volume ratio 7；
Then the gasoline after sulphur transfer reaction is entered into fractionating column, obtains light fraction gasoline and again by fraction cutting 102
Distillation gasoline, cutting temperature are 70 DEG C；
Light fraction gasoline enters in esterifier (the weight ratio of acetic acid and alkene in light fraction gasoline after mixing with acetic acid
For 1.2:1), under the action of esterification catalyst, esterification 103, reaction condition occur for the C5-C7 alkene in light fraction gasoline
Are as follows: pressure 2.0MPa, 110 DEG C of temperature, liquid volume air speed 2.5h-1(with Acetometer)；After esterification, product is subjected to rectifying
Separation 104, removes unreacted acetic acid, the light fraction gasoline that obtains that treated；
As shown in Fig. 2, the light fraction gasoline after esterification initially enters first rectifying column 201 in rectifying separation system,
Pass through the isolated overhead product of rectifying (light fraction gasoline) and tower reactor product (esters and unreacted acetic acid)；First rectifying column
Tower reactor product enters Second distillation column 202, is produced by the isolated overhead product of rectifying (low boiling point esters and acetic acid) and tower reactor
Product (higher boiling esters)；Second distillation column overhead product enters third distillation column 203, while introducing water into third distillation column and making
For entrainer, entrainer and Second distillation column overhead product molar ratio are 1:2.45, (low by the isolated overhead product of rectifying
Boiling point esters and water) and tower reactor product (acetic acid and water)；Third distillation column overhead product is layered to obtain oily phase and water phase, oily phase
With first rectifying column overhead product and Second distillation column tower reactor product mix, light fraction gasoline after the esterification of removing acetic acid is obtained；
Third distillation column tower reactor product enters the 4th rectifying column 204, passes through the isolated overhead product of rectifying (water) and tower reactor product
(acetic acid), tower reactor product are mixed with fresh acetic acid, continue esterification, the water of overhead product and third distillation column top product
Mutually and after fresh water mixing, continue to participate in rectifying as entrainer；First rectifying column 201, Second distillation column 202, third rectifying
Tower 203 and the 4th rectifying column 204 are all made of packed tower, and filler is the stainless steel θ ring of 2.5 × 2.5mm；
Rectifying separation system operating condition are as follows: first rectifying column operating condition are as follows: the number of plates 30, feedboard number 18, tower top
29 DEG C of temperature, tower top pressure 1atm, 141 DEG C of bottom temperature, tower reactor pressure 1.2atm, reflux ratio 2；After-fractionating tower operating condition
Are as follows: the number of plates 70, feedboard number 14,121 DEG C of tower top temperature, tower top pressure 1atm, 164 DEG C of bottom temperature, tower reactor pressure
1.5atm, reflux ratio 15；Third fractionating column operating condition are as follows: the number of plates 36, feedboard number 18,88 DEG C of tower top temperature, tower top pressure
Power 1atm, 114 DEG C of bottom temperature, tower reactor pressure 1.2atm, reflux ratio 10；4th fractionating column operating condition are as follows: the number of plates 40, into
Flitch number 24,100 DEG C of tower top temperature, tower top pressure 1atm, 126 DEG C of bottom temperature, tower reactor pressure 1.3atm, reflux ratio 7.
Heavy distillat gasoline is introduced into selective hydrodesulfurization reactor and contacts with catalyst for selectively hydrodesulfurizing, selects
Selecting property hydrodesulfurization reaction 105, reaction condition are as follows: pressure 1.5MPa, 250 DEG C of temperature, 3.5 h of liquid volume air speed-1, hydrogen oil body
Product compares 300:1；It is contacted subsequently into absorption desulfurization reactor with supplement desulfurization absorption, ultra-deep absorption desulfurization reaction occurs
106, reaction condition are as follows: pressure 1.5MPa, 35 DEG C of temperature, liquid volume air speed 1.5h-1；
The present embodiment be arranged two absorption desulfurization reactors, one carry out ultra-deep absorption desulfurization react 106 when, it is another
A progress desulfuration adsorbent regeneration 107, alternately；
Desulfuration adsorbent regeneration method are as follows: at 0.1MPa, 200 DEG C, carry out N2Purging, N2Volume space velocity is 1500h-1。
Above-mentioned by treated, light, heavy distillat gasoline is mixed after the reaction was completed, obtains blended gasoline product, i.e. super-low sulfur
Clean gasoline.
During the reaction, all catalyst are diluted with porcelain sand, also, in each reactor or the airtight qualification of reaction unit
Afterwards, low temperature sulfur transfer catalyst, catalyst for selectively hydrodesulfurizing are dried and presulfurization is handled, to supplement desulfurization absorption
Agent is activated；Drying condition are as follows: 120 DEG C, N2Atmosphere, N2Air speed 1000h-1；Pre-sulfiding step are as follows: by catalyst bed
Middle N2By H2Displacement completely, and keeps H2Air speed is 900h-1, adjust reaction bed temperature to 150 DEG C, to catalyst bed with
3h-1Volume space velocity inject straight-run naphtha, adjustment hydrogen to oil volume ratio is to 300:1；Catalyst bed is warming up to 20 DEG C/h
180 DEG C, starts to inject vulcanizing agent (dimethyl disulfide), adjust the 3wt% of its injection rate to straight-run naphtha, then proceed to
230 DEG C are warming up to the speed of 15 DEG C/h, constant temperature 8h；280 DEG C are warming up to the speed of 15 DEG C/h, constant temperature 8h；With 15 DEG C/h liter
Temperature is to 320 DEG C, constant temperature 8h；Each catalyst bed reaction temperature is cooled to 20 DEG C/h；Finally, with reaction oil product exchange system
Middle sulfurized oil, vulcanization terminate；The activating treatment method are as follows: at 0.1MPa, 200 DEG C, carry out N2Purging, N2Volume space velocity is
1500h-1.Air speed and hydrogen-oil ratio are adjusted, starts to be reacted, reaction 100h post-sampling analysis, table 1 gives reformulated gasoline product
Nature parameters.
As it can be seen from table 1 the method for modifying of the present embodiment can make the sulfur content of FCC gasoline from 823.1 μ gg-1Drop
To 8.5 μ gg-1, olefin(e) centent is down to 23.5v% by 35.2v%, simultaneously because light fraction gasoline esterification, makes full fraction
For feedstock oil while ultra-deep desulfurization, Olefin decrease content, product research method octane number only reduces by 0.2 unit, blended gasoline
Product yield is 99.3wt%, and product quality meets the requirement of state's V clean gasoline standard.
Light after the full feedstock of table 1 oil 1 and modification, heavy distillat gasoline reconciliation product nature parameters
| Project | Full feedstock oil 1 | Gently, heavy distillat gasoline reconciliation product |
| Yield (wt%) | - | 99.3 |
| Density (g/mL) | 0.732 | 0.735 |
| Boiling range | 34-205 | 33-208 |
| Typical hydrocarbon content (v%) | ||
| Aromatic hydrocarbons | 15.6 | 15.3 |
| Alkene | 35.2 | 23.5 |
| Sulphur (μ gg-1) | 823.1 | 8.5 |
| RON | 90.2 | 90.0 |
Embodiment 2
It present embodiments provides a kind of handle with feedstock oil 1 for raw material progress hydro-upgrading and prepares super-low sulfur clean gasoline
Method.
Wherein, low temperature sulfur transfer catalyst, catalyst for selectively hydrodesulfurizing, supplement desulfuration adsorbent preparation method and
Composition, gasoline upgrading process, Catalyst processing method are same as Example 1.
Specific preparation process is as follows for esterification catalyst:
50.0g zirconium chloride is dissolved in 250mL ethyl alcohol, be added 15.0g lauryl sodium sulfate (SDS), at 50 DEG C to
The ammonium hydroxide of 30wt% is wherein added dropwise, pH value of solution is adjusted to 6.0, obtains Zr (OH)4Colloidal sol；By the gelatinization at 80 DEG C of above-mentioned colloidal sol
12h obtains ZrO2Gel；By ZrO2Gel dry 12h at 90 DEG C, 500 DEG C of roasting 5h removing templates obtain mesoporous ZrO2；
120 meshes are crossed after tabletting, and sieving product is impregnated into 1h in 500mL2 mol/L ammonium sulfate, is filtered, washed, dries, 600
4h is roasted at DEG C, obtains SO4 2-/ZrO2Catalyst.
Specific reaction condition is as follows:
Sulphur transfer reaction condition is same as Example 1；
Fractionating column cutting temperature is same as Example 1；
Esterification condition are as follows: pressure 2.0MPa, 120 DEG C of temperature, liquid volume air speed 2.5h-1(with Acetometer)；
Rectifying separation system operating condition are as follows: first rectifying column operating condition are as follows: the number of plates 30, feedboard number 18, tower top
29 DEG C of temperature, tower top pressure 1atm, 143 DEG C of bottom temperature, tower reactor pressure 1.2atm, reflux ratio 2；After-fractionating tower operating condition
It is same as Example 1；Third fractionating column operating condition are as follows: the number of plates 36, feedboard number 18,88 DEG C of tower top temperature, tower top pressure
1atm, 109 DEG C of bottom temperature, tower reactor pressure 1.2atm, reflux ratio 10；4th fractionating column operating condition are as follows: the number of plates 40, charging
Plate number 24,97 DEG C of tower top temperature, tower top pressure 1atm, 126 DEG C of bottom temperature, tower reactor pressure 1.3atm, reflux ratio 8；
Selective hydrodesulfurization reaction condition is same as Example 1；
Ultra-deep absorption desulfurization reaction condition is same as Example 1；
Desulfuration adsorbent regeneration method is same as Example 1.
Above-mentioned by treated, light, heavy distillat gasoline is mixed after the reaction was completed, obtains blended gasoline product, i.e. super-low sulfur
Clean gasoline.
Table 2 gives the nature parameters of reformulated gasoline product.
From table 2 it can be seen that the method for modifying of the present embodiment can make the sulfur content of FCC gasoline from 823.1 μ gg-1Drop
To 8.6 μ gg-1, olefin(e) centent is down to 23.0v% by 35.2v%, simultaneously because light fraction gasoline esterification, makes full fraction
For feedstock oil while ultra-deep desulfurization, Olefin decrease content, product research method octane number improves 0.2 unit, blended gasoline
Product yield is 99.2wt%, and product quality meets the requirement of state's V clean gasoline standard.
Light, heavy distillat gasoline reconciliation product nature parameters after 1 modification of the full feedstock of table 2 oil
| Project | Gently, heavy distillat gasoline reconciliation product |
| Yield (wt%) | 99.2 |
| Density (g/mL) | 0.735 |
| Boiling range | 33-209 |
| Typical hydrocarbon content (v%) | |
| Aromatic hydrocarbons | 15.3 |
| Alkene | 23.0 |
| Sulphur (μ gg-1) | 9.0 |
| RON | 90.4 |
Embodiment 3
One kind is present embodiments provided with 1764.0 μ gg of sulfur content-1, olefin(e) centent 40.3v% high-sulfur FCC gasoline
(feedstock oil 2) is the method that raw material carries out hydro-upgrading processing preparation super-low sulfur clean gasoline.
Wherein, low temperature sulfur transfer catalyst, esterification catalyst, catalyst for selectively hydrodesulfurizing, supplement desulfuration adsorbent
Preparation method and composition, gasoline upgrading process, Catalyst processing method it is same as Example 1；
For the property of feedstock oil 2 referring to table 3, specific reaction condition is as follows:
Sulphur transfer reaction condition are as follows: reaction pressure 2.4MPa, 140 DEG C of reaction temperature, liquid volume air speed 3h-1, hydrogen oil body
Product ratio 7；
Fractionating column cutting temperature is 60 DEG C；
Esterification condition is same as Example 1；
Rectifying separation system operating condition are as follows: first rectifying column operating condition are as follows: the number of plates 30, feedboard number 18, tower top
29 DEG C of temperature, tower top pressure 1atm, 141 DEG C of bottom temperature, tower reactor pressure 1.2atm, reflux ratio 2；After-fractionating tower operating condition
It is same as Example 1；Third fractionating column operating condition is same as Example 2；4th fractionating column operating condition and 1 phase of embodiment
Together；
Selective hydrodesulfurization reaction condition are as follows: reaction pressure 1.5MPa, 260 DEG C of reaction temperature, liquid volume air speed
3.0h-1, hydrogen to oil volume ratio 300:1；
Ultra-deep absorption desulfurization reaction condition are as follows: reaction pressure 1.5MPa, 35 DEG C of reaction temperature, liquid volume air speed
1.0h-1。
Table 3 gives the nature parameters of reformulated gasoline product.
From table 3 it can be seen that the method for modifying of the present embodiment can make the sulfur content of FCC gasoline by 1764.0 μ gg-1Drop
To 9.5 μ gg-1, olefin(e) centent is down to 21.5v% by 40.3v%, simultaneously because the esterification of light fraction gasoline, makes to evaporate entirely
While ultra-deep desulfurization, research octane number (RON) only reduces by 0.3 unit for point feedstock oil 2, reconciles oil product yield 99.2wt%,
Product quality meets state's V clean gasoline standard requirements.
Light after the full feedstock of table 3 oil 2 and modification, heavy distillat gasoline reconciliation product nature parameters
| Project | Full feedstock oil 2 | Gently, heavy distillat gasoline reconciliation product |
| Yield (wt%) | - | 99.2 |
| Density (g/mL) | 0.735 | 0.740 |
| Boiling range | 38-204 | 37-207 |
| Typical hydrocarbon content (v%) | ||
| Aromatic hydrocarbons | 21.2 | 21.0 |
| Alkene | 40.3 | 21.5 |
| Sulphur (μ gg-1) | 1764.0 | 9.5 |
| RON | 90.3 | 90.0 |
Embodiment 4
It present embodiments provides a kind of handle with feedstock oil 2 for raw material progress hydro-upgrading and prepares super-low sulfur clean gasoline
Method.
Wherein, low temperature sulfur transfer catalyst, the preparation method of catalyst for selectively hydrodesulfurizing and composition, gasoline upgrading mistake
Journey, Catalyst processing method are same as Example 1；The composition and preparation method of esterification catalyst are identical as embodiment 2；
The specific preparation step for supplementing desulfuration adsorbent is substantially the same manner as Example 1, and difference is will be " by 50.0g ten
Sodium dialkyl sulfate (SDS) is dissolved in 750.0g deionized water at 55 DEG C " it is changed to " by 70.0g lauryl sodium sulfate (SDS)
It is dissolved at 55 DEG C in 750.0g deionized water ".
Specific reaction condition is as follows:
Sulphur transfer reaction condition, esterification condition and fractionating column cutting temperature are same as Example 3；
Rectifying separation system operating condition are as follows: first rectifying column operating condition are as follows: the number of plates 30, feedboard number 18, tower top
29 DEG C of temperature, tower top pressure 1atm, 141 DEG C of bottom temperature, tower reactor pressure 1.2atm, reflux ratio 2；After-fractionating tower operating condition
It is same as Example 1；Third fractionating column operating condition are as follows: the number of plates 36, feedboard number 18,88 DEG C of tower top temperature, tower top pressure
1atm, 110 DEG C of bottom temperature, tower reactor pressure 1.2atm, reflux ratio 10；4th fractionating column operating condition is same as Example 1；
Selective hydrodesulfurization reaction condition are as follows: reaction pressure 1.5MPa, 255 DEG C of reaction temperature, liquid volume air speed
3.0h-1, hydrogen to oil volume ratio 300:1；
Ultra-deep absorption desulfurization reaction condition are as follows: reaction pressure 1.5MPa, 35 DEG C of reaction temperature, liquid volume air speed
1.0h-1。
Table 4 gives the nature parameters of reformulated gasoline product.
From table 4, it can be seen that the method for modifying of the present embodiment can make the sulfur content of FCC gasoline by 1764.0 μ gg-1Drop
To 9.3 μ gg-1, olefin(e) centent is down to 22.6v% by 40.3v%, simultaneously because the esterification of light fraction gasoline, makes to evaporate entirely
While ultra-deep desulfurization, research octane number (RON) maintains 90.3 for point feedstock oil 2, reconciles oil product yield 99.2wt%, product
Quality meets state's V clean gasoline standard requirements.
Light, heavy distillat gasoline reconciliation product nature parameters after 2 modification of the full feedstock of table 4 oil
| Project | Gently, heavy distillat gasoline reconciliation product |
| Yield (wt%) | 99.2 |
| Density (g/mL) | 0.741 |
| Boiling range | 37-207 |
| Typical hydrocarbon content (v%) | |
| Aromatic hydrocarbons | 21.1 |
| Alkene | 22.6 |
| Sulphur (μ gg-1) | 9.3 |
| RON | 90.3 |
Above-mentioned two embodiment shows that the production method of super-low sulfur high-knock rating gasoline provided by the present invention can make height
Sulfur feedstock gasoline upgrading is sulfur content≤10 μ gg-1, olefin(e) centent≤24v%, gasoline Research octane number (RON) loss≤
State's V clean gasoline product of 0.5 unit；Simultaneously alkene saturation factor can be adjusted, product oil is made to exist by modulation process conditions
While meeting state's V standard, alkene is avoided to be saturated as far as possible, to keep its octane number；And esterification compensates for alkene saturation and makes
At loss of octane number；The method of the present invention has good hydro-upgrading effect to inferior patrol.
Specific embodiment described above further illustrates the purpose of the present invention, technical scheme and beneficial effects,
But it is not intended to limit the scope of protection of the present invention.
Claims (9)
1. a kind of production method of super-low sulfur clean gasoline, method includes the following steps:
So that full distillation gasoline is contacted generation orientation sulphur transfer reaction with low temperature sulfur transfer catalyst under hydro condition, then carries out
Oil product cutting, obtains light fraction gasoline and heavy distillat gasoline；The temperature of the oil product cutting is 50-100 DEG C；
Mix light fraction gasoline with organic acid, under the action of esterification catalyst, the C5-C7 alkene in light fraction gasoline occurs
Esterification, then after rectifying separation system removes unreacted organic acid, the light fraction gasoline that obtains that treated；Its
In, it is metal oxide catalyst, zeolite molecular sieve catalyst, SO that the esterification catalyst, which has high secondary ester selectivity,4 2-/
MxOyThe combination of one or more of catalyst, wherein the carrier of the metal oxide catalyst has meso-hole structure, institute
Stating zeolite molecular sieve catalyst is step hole zeolite molecular sieve, the SO4 2-/MxOyCatalyst includes by SO4 2-Be carried on ZrO,
Made SO on carrier made of at least one of ZnO and SnO metal oxide4 2-/MxOyCatalyst, and the metal
Oxide is mesopore metal oxide；
It contacts heavy distillat gasoline with catalyst for selectively hydrodesulfurizing and supplement desulfuration adsorbent, selective hydrodesulfurization occurs
Reaction and ultra-deep absorption desulfurization reaction, obtain the heavy distillat gasoline of super-low sulfur；Wherein, the supplement desulfuration adsorbent is to pass through
The molding step hole HKUST-1 of 40-60 mesh is crossed in tabletting；
Will treated light fraction gasoline heavy distillat gasoline mixes with treated, obtain described in super-low sulfur clean gasoline；
Wherein, on the basis of the total weight of catalyst, the composition of the low temperature sulfur transfer catalyst includes: transition metal oxide
2-30%, auxiliary agent 0.5-6%, zeolite 10-40%, surplus are inorganic refractory oxide；The transition metal oxide includes
NiO、CoO、ZnO、MoO3、WO3With the combination of one or more of CuO；The auxiliary agent includes K2O, MgO and La2O3In one
Kind or several combinations；The zeolite includes the combination of one or more of HZSM-5, H β and HY, also, the zeolite is
By the zeolite of alkali process, ammonium exchange, hydro-thermal process；The inorganic refractory oxide includes aluminium oxide, silica and siliceous oxygen
Change the combination of one or more of aluminium；
It is carrier loaded ZnO that the metal oxide catalyst, which includes at least one of silica, molecular sieve and diatomite,
SnO and Al2O3At least one of catalyst made by metal oxide；
The zeolite molecular sieve catalyst includes aluminium phosphate molecular sieve, aluminium silicophosphate molecular sieve, H-type modenite, HY zeolite, H-
The molecular sieve catalyst that one or more of β zeolite and HZSM-5 zeolite mix.
2. production method according to claim 1, wherein the reaction condition of the sulphur transfer reaction are as follows: reaction pressure
1.0-3.0MPa, liquid volume air speed 2.0-8.0h-1, 100-200 DEG C of reaction temperature, hydrogen to oil volume ratio 5-15；
The reaction condition of the selective hydrodesulfurization reaction are as follows: reaction pressure 1.0-3.0MPa, liquid volume air speed 1.5-
6.0h-1, 200-300 DEG C of reaction temperature, hydrogen to oil volume ratio 200-600；
The reaction condition of the ultra-deep absorption desulfurization reaction are as follows: pressure 0.1-2.0MPa, 30-60 DEG C of temperature, liquid volume is empty
Fast 1-5h-1。
3. production method according to claim 1, wherein the reaction condition of the esterification are as follows: reaction temperature 80-
200 DEG C, reaction pressure 0.1-4.0MPa, olefin weight ratio 0.5-2.5:1.0 in organic acid and light fraction gasoline, in terms of organic acid
Liquid volume air speed 0.5-5.0h-1。
4. production method according to claim 1 or 3, wherein the organic acid includes the change for having the following structure general formula
Close the combination of one or more of object:
In formula, R H, CH3、C2H5、C3H7In any one.
5. production method according to claim 1, wherein the rectifying separation system includes at least two rectifying columns.
6. production method according to claim 5, wherein the rectifying separation system includes four rectifying columns, respectively
First rectifying column, Second distillation column, third distillation column and the 4th rectifying column, first rectifying column operating condition are as follows: number of plates 20-
50, feedboard number 10-40,20-50 DEG C of tower top temperature, tower top pressure 1-5atm, 100-200 DEG C of bottom temperature, tower reactor pressure 1-
10atm, reflux ratio are controlled in 0.1-10；After-fractionating tower operating condition are as follows: number of plates 20-100, feedboard number 10-80, tower top
100-150 DEG C of temperature, tower top pressure 1-5atm, 100-200 DEG C of bottom temperature, tower reactor pressure 1-5atm, reflux ratio is controlled in 1-
40；Third fractionating column operating condition are as follows: number of plates 20-70, feedboard number 10-60,50-150 DEG C of tower top temperature, tower top pressure 1-
5atm, 80-150 DEG C of bottom temperature, tower reactor pressure 1-5atm, reflux ratio is controlled in 1-30；4th fractionating column operating condition are as follows: tower
Plate number 10-60, feedboard number 10-50,80-150 DEG C of tower top temperature, tower top pressure 1-5atm, 100-150 DEG C of bottom temperature, tower
Kettle pressure 1-5atm, reflux ratio are controlled in 1-30.
7. production method according to claim 1, wherein on the basis of the total weight of catalyst, the selective hydrogenation
The composition of desulphurization catalyst includes: MoO310-18%, CoO 2-6%, K2O 1-7%, P2O52-6%, surplus Al-Si-
Mg composite oxide carrier, and the weight composition of the Al-Si-Mg composite oxides in the catalyst includes: Al2O3 60-
75%, SiO25-15% and MgO 3-10%.
8. production method according to claim 1, wherein the step hole HKUST-1 is through the following steps that be prepared into
To: lauryl sodium sulfate is dissolved in deionized water, Cu (NO is then sequentially added3)2·3H2O, trimesic acid, stirring
Uniformly, colloidal sol is obtained, then in 80-150 DEG C of crystallization 12-36h, is filtered, washed, dries, later removed template method, tabletting, mistake
Sieve, obtains the step hole HKUST-1.
9. production method according to claim 8, wherein lauryl sodium sulfate, deionized water, Cu in the colloidal sol
(NO3)2·3H2O, the molar ratio of trimesic acid is (1-2): (80-200): (1.5-2.5): 1.
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