CN107151564A - 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 PDF

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CN107151564A
CN107151564A CN201610124810.7A CN201610124810A CN107151564A CN 107151564 A CN107151564 A CN 107151564A CN 201610124810 A CN201610124810 A CN 201610124810A CN 107151564 A CN107151564 A CN 107151564A
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gasoline
catalyst
reaction
temperature
production method
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CN107151564B (en
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范煜
王世华
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China University of Petroleum Beijing
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China University of Petroleum Beijing
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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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention provides a kind of production method of super-low sulfur clean gasoline.The production method includes：Full distillation gasoline is contacted generation orientation sulphur transfer reaction with low temperature sulfur transfer catalyst under hydro condition, then carry out oil product cutting, obtain light, heavy distillat gasoline；Light fraction gasoline is set to mix and be contacted with esterification catalyst with organic acid, 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, obtain the heavy distillat gasoline of super-low sulfur；Light, heavy distillat gasoline after processing is mixed, super-low sulfur clean gasoline is obtained.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 gently, heavy distillat gasoline mixing after, the octane number of gasoline products is maintained or improved.

Description

A kind of production method of super-low sulfur clean gasoline
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) vapour Oily refining field, the particularly ultra-deep desulfurization of ultra-high-sulfur(UHS) FCC gasoline, keep or put forward high-octane method.
Background technology
With economic development, social progress, car ownership is continuously increased, the dirt that vehicle exhaust is caused to atmospheric environment Dye is increasingly serious.Therefore, more strict quality of gasoline regulation has been put into effect in countries in the world in succession, advocate using cleaning vapour Oil, reduces the pollution to environment.At present, 75% or so it is FCC gasoline, but China FCC in China's gasoline product Content of olefin in gasoline is high, sulfur content is high, stability is poor, causes gasoline product to can not meet the requirement of new standard.Therefore, FCC gasoline hydro-upgrading technology just turns into one of key technology that clean fuel for vehicle is produced.
US6,692,635 disclose a kind of low-sulphur oil production technology, are characterized in：Full cut catalytic gasoline exists first Alkadienes is removed in pre-hydrogenator, mercaptan is converted into higher boiling sulfur compound, while double-bond isomerism occurs for alkene； Then, pre- hydrogenation products carry out cut cutting, obtain light, heavy distillat gasoline；Heavy distillat gasoline carries out being hydrogenated with instead first Should, unsaturated sulfide is converted into saturation sulfide, hydrodesulfurization is then carried out in the presence of desulphurization catalyst, Obtain the heavy distillat gasoline after desulfurization；Finally, light, heavy distillat gasoline mixing, obtains clean gasoline product.But the party The desulfurization degree of method is relatively low (80.0%-92%), and product sulfur content is difficult near below 50ug/g, it is impossible to meet state IV With state's V clean gasoline standard.
CN104711018 A and CN103666559 A describe a kind of FCC gasoline ultra-deep desulfurization combined method, Its feature is：FCC gasoline first takes off diene under hydro condition, then carries out fractionation cutting, obtains light, heavy distillat Gasoline；Heavy distillat gasoline carries out selective hydrodesulfurization reaction, and sulfur content is dropped into below 100ppm；Then, light, Heavy distillat gasoline is mixed, and carries out ultra-deep absorption desulfurization, obtains the super low-sulfur oil product that sulfur content is less than 10ppm. But the technique is primarily directed to low-sulfur FCC gasoline；In processing to high-sulfur FCC gasoline inferior, loss of octane number mistake Greatly, it is impossible to reach ultra-deep desulfurization and keep octane number requirement.
CN103074107 A disclose a kind of production method of low-sulphur oil, and gasoline cutting is divided into by this method first Gently, in, three kinds of gasoline fractions are weighed；Light fraction gasoline carries out caustic wash desulfuration alcohol；The hydrogenated processing of midbarrel and reformation High-octane midbarrel is obtained after processing；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 production Product.
CN101418234 A disclose a kind of low-sulphur oil production method similar with above-mentioned technique, unlike：Should FCC gasoline is first carried out oxidation deodorizing by method, converts the mercaptans to high boiling disulphide, then again by FCC Gasoline carries out fractionation cutting, obtain it is light, in, heavy distillat gasoline；It is the heavy distillat gasoline of hydrogenated desulfurization, hydrogenated de- The midbarrel gasoline of sulphur and catalytic reforming is mixed with light fraction gasoline, obtains clean gasoline product.
Above two method can obtain clean gasoline product, and its octane number has been after catalytic reforming for midbarrel Lifting, clean gasoline with high octane is obtained after being mixed with light, heavy distillat gasoline；But its technological process complexity is, it is necessary to urge Change reforming reactor and hydrodesulphurisatioreactors reactors cooperate；And midbarrel gasoline produces liquefied gas and hydrogen after reformation Gas, gasoline products liquid yield is relatively low.
CN102649914 A disclose the side that a kind of catalytic gasoline hydrogenation of total effluent desulfurization produces super-low sulfur clean gasoline Method, its feature is：FCC gasoline first carries out de- diene processing, while isomerization reaction occurs for alkene, makes its octane Value is improved, and is then carried out selective hydrodesulfurization reaction, is obtained low-sulfur high octane gasoline products.But, this method Olefin decrease ability is poor, and alkene saturation factor is less than 20%；The FCC gasoline of high olefin content is changed with this method Matter, it is difficult to be met the gasoline products of state's V standards.
CN103450935 A disclose a kind of method for producing super low-sulfur oil, and this method first enters full distillation gasoline Row cutting, obtains light, heavy distillat gasoline；Light fraction gasoline after oxidized deodorization and double distilled after selective hydrodesulfurization Divide gasoline mixing, obtain super low-sulfur oil product.This method takes off when handling the gasoline that sulfur content is 450ppm Sulphur rate is 97.8%, but loss of octane number is larger (research octane number (RON) loses 3 units), reduces gasoline quality.
In summary, for the production of clean gasoline, existing many researchs all attempt to realize that desulfurization is dropped by means of different Alkene, while keeping as far as possible and improving the octane number of oil product.Above method respectively has advantage, but its pin to oil product It is stronger to property, it is difficult to handle feedstock oil sulfur content, the situation of olefin(e) centent fluctuation.Therefore, exploitation one kind can be with By modulation process conditions, desulfurization degree and the alkene range of decrease is adjusted flexibly, and can keep or carry high-octane gasoline upgrading Method is significant.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of production method of super-low sulfur clean gasoline.Should Method using hydrodesulfurization and absorption desulfurization group technology, can flexibly modulation process conditions to adjust the alkene range of decrease and desulfurization Depth, and light fraction gasoline carries out esterification, gasoline products octane number while ultra-deep desulfurization is protected Hold or improve.
To reach above-mentioned purpose, the 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 is obtained；
Light fraction gasoline is set to be mixed with organic acid, in the presence of esterification catalyst, the C5-C7 in light fraction gasoline Esterification occurs for alkene, light after being handled then after rectifying piece-rate system removes unreacted organic acid Distillation gasoline；
Heavy distillat gasoline is contacted with catalyst for selectively hydrodesulfurizing and supplement desulfuration adsorbent, occur selective hydrogenation Desulphurization reaction and ultra-deep absorption desulfurization reaction, obtain the heavy distillat gasoline of super-low sulfur；
Light fraction gasoline after processing is mixed with the heavy distillat gasoline after processing, described super-low sulfur cleaning vapour is obtained Oil.
In aforementioned production method, it is preferable that the reaction condition of the sulphur transfer reaction is：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 gross weight of catalyst, the low temperature sulfur transfer catalyst Composition include：Transition metal oxide 2-30%, auxiliary agent 0.5-6%, zeolite 10-40%, surplus is inorganic refractory Oxide；Wherein, the transition-metal oxide can include NiO, CoO, ZnO, MoO3、WO3And CuO One or more of combinations in；The auxiliary agent can include K2O, MgO and La2O3One kind or several in The combination planted；The zeolite includes one or more of combinations in HZSM-5, H β and HY etc., also, institute It is the zeolite by alkali process, ammonium exchange, hydro-thermal process to state zeolite；The inorganic refractory oxide can include oxidation One or more of combinations in aluminium, 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 Cutting can be carried out in fractionating column.
In aforementioned production method, it is preferable that the reaction condition of the esterification is：80-200 DEG C of reaction temperature, Reaction pressure 0.1-4.0MPa, organic acid and olefin weight ratio (sour alkene ratio) 0.5-2.5 in light fraction gasoline:1.0, liquid Body volume space velocity 0.5-5.0h-1(in terms of organic acid).The technological process of the esterification can include：To gently it evaporate Divide gasoline to be mixed by a certain percentage with organic acid, pass through the consolidating equipped with esterification catalyst of one or several serial or parallel connections Fixed bed reactor carries out esterification, the light fraction gasoline after being esterified.After esterification, by gently evaporating after esterification Gasoline is divided to remove unreacted organic acid, the light fraction gasoline after being handled through rectifying piece-rate system.
In aforementioned production method, it is preferable that the organic acid includes one in the compound with following general structure Plant or several combinations：
In formula, R is H, CH3、C2H5、C3H7In any one.
In aforementioned production method, it is preferable that the esterification catalyst has high secondary ester selectivity, and it includes metal oxygen Compound catalyst, zeolite molecular sieve catalyst, SO4 2-/MxOyCatalyst, strong acid cation exchange resin catalyst One or more of combinations in；Wherein, the metal oxide catalyst can include with silica, molecular sieve It is carrier loaded ZnO, SnO and Al with least one of diatomite etc.2O3Deng at least one of metal oxide Made catalyst, and the carrier can have conventional structure or meso-hole structure；
The zeolite molecular sieve catalyst can include aluminium phosphate molecular sieve, aluminium silicophosphate molecular sieve, H types modenite, The molecular sieve catalyst that one or more in HY zeolites, H- β zeolites and HZSM-5 zeolites etc. are mixed, And these zeolite molecular sieves can be conventional zeolite molecular sieve or step hole zeolite molecular sieve；
The SO4 2-/MxOyCatalyst can be included SO4 2-It is carried at least one in ZrO, ZnO and SnO etc. Plant SO made on the carrier that metal oxide is made4 2-/MxOyCatalyst, and the metal oxide can be with For conventional metal oxides 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 piece-rate system includes at least two rectifying columns；Preferably, the rectifying Piece-rate system includes four rectifying columns, respectively first rectifying column, Second distillation column, third distillation column and the 4th rectifying Tower, first rectifying column operating condition is：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 is controlled in 0.1-10； After-fractionating tower operating condition is：Number of plates 20-100, feedboard number 10-80,100-150 DEG C of tower top temperature, tower Pressure on top surface 1-5atm, 100-200 DEG C of bottom temperature, tower reactor pressure 1-5atm, reflux ratio is controlled in 1-40；3rd Fractionating column operating condition is：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 is grasped It is as condition：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, heavy distillat gasoline is set to be connect with catalyst for selectively hydrodesulfurizing and supplement desulfuration adsorbent Touch, be heavy distillat gasoline is contacted successively with two kinds of catalyst, selective hydrodesulfurization reaction occurs successively and ultra-deep Adsorb desulphurization reaction.
In aforementioned production method, it is preferable that the heavy distillat gasoline is contacted with the catalyst for selectively hydrodesulfurizing Reaction condition be：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.
In aforementioned production method, it is preferable that the ultra-deep absorption desulfurization reaction is in one or several dresses parallel with one another Have in the absorption desulfurization reactor of supplement desulfuration adsorbent and carry out.It is highly preferred that two absorption desulfurization reactors are set, One of them is when carrying out ultra-deep absorption desulfurization reaction, and another carries out desulfuration adsorbent regeneration, the two alternating.It is excellent Selection of land, the reaction condition of ultra-deep absorption desulfurization reaction is：Pressure 0.1-2.0MPa, 30-60 DEG C of temperature, Liquid volume air speed 1-5h-1；The renovation process of desulfuration adsorbent is：At 0.1-2.0MPa, 150-250 DEG C, enter Row N2Purging, N2Volume space velocity is 500-3000h-1。
In aforementioned production method, it is preferable that on the basis of the gross weight of catalyst, the selective hydrodesulfurization is urged The composition of agent includes：MoO310-18%, CoO2-6%, K2O1-7%, P2O52-6%, surplus is Al-Si-Mg Composite oxide carrier；It is highly preferred that the weight composition of the Al-Si-Mg composite oxides in the catalyst includes (i.e. on the basis of the gross weight of catalyst)：Al2O360-75%, SiO25-15% and MgO3-10%.
In aforementioned production method, it is preferable that on the basis of total catalyst weight, the supplement desulfuration adsorbent is process The step hole HKUST-1 of 40-60 mesh sieves shaping is crossed in tabletting.It is highly preferred that the step hole HKUST-1 is to pass through What following steps were prepared：Lauryl sodium sulfate (SDS) is dissolved in deionized water, then sequentially added Cu(NO3)2·3H2O, trimesic acid, stir, and obtain colloidal sol, then in 80-150 DEG C of crystallization 12-36h, Filtering, washing, dry, afterwards removed template method (can be using removed template method by the way of ethanol extraction, extraction is warm Degree can be 30-80 DEG C, 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 mol ratio of trimesic acid are (1-2):(80-200):(1.5-2.5):1。
According to the embodiment of the present invention, it is preferable that aforementioned production method is further comprising the steps of：Before the reaction The low temperature sulfur transfer catalyst, the catalyst for selectively hydrodesulfurizing are dried and presulfurization processing, to mending Fill desulfuration adsorbent and carry out activation process；Drying condition is：100-150 DEG C, N2Atmosphere, N2Air speed 200-2000h-1； The step of presulfurization is：By N in beds2By H2Displacement is complete, and keeps H2Air speed is 200-3000h-1, Reaction bed temperature is adjusted to 120-180 DEG C, to beds with 1-5h-1Volume space velocity injection straight run stone Cerebrol, adjustment hydrogen to oil volume ratio to 200-500:1；Beds are warming up to 150-200 DEG C with 10-30 DEG C/h, Start injection vulcanizing agent (such as dimethyl disulfide), adjust its injection rate to the 1-5wt% of straight-run naphtha； Then proceed to be warming up to 210-250 DEG C, constant temperature 6-10h with 10-30 DEG C/h speed；With 10-30 DEG C/h speed Degree is warming up to 270-290 DEG C, constant temperature 6-10h；310-350 DEG C, constant temperature 6-10h are warming up to 10-30 DEG C/h； With each catalyst bed reaction temperature of 10-30 DEG C/h coolings；Finally, sulfurized oil in oil product exchange system is used to react, Vulcanization terminates；The method of the activation process is：At 0.1-2MPa, 150-250 DEG C, N is carried out2Purging, N2 Volume 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 Content is 30-50v% (with the total volume meter of the full distillation gasoline)；And produce obtained super-low sulfur cleaning The μ gg of the sulfur content of gasoline≤10-1, 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, so that gently, After the mixing of heavy distillat gasoline, the octane number of gasoline products is maintained or improved.Compared with prior art, institute of the present invention Sulfur content can be 500-2000 μ gg by the production method of the super-low sulfur clean gasoline of offer-1, olefin(e) centent 30-50v% Gasoline upgrading be the μ gg of sulfur content≤10-1, olefin(e) centent≤24v%, gasoline Research octane number (RON) loss The premium of≤0.5 unit, and product liquid yield >=99wt%.
Brief description of the drawings
Fig. 1 is the schematic flow sheet for the super-low sulfur clean gasoline production method that embodiment 1,2,3 and 4 is provided.
Primary clustering symbol description in Fig. 1：
Sulphur transfer reaction 101, cut cutting 102, esterification 103, rectifying separation 104, selective hydrodesulfurization Reaction 105, ultra-deep absorption desulfurization reaction 106, desulfuration adsorbent regeneration 107.
Fig. 2 is rectifying segregative line in the super-low sulfur clean gasoline production method that the embodiment of the present invention 1,2,3 and 4 is provided The schematic flow sheet of system；
Primary clustering symbol description in Fig. 2：
First rectifying column 201, Second distillation column 202, third distillation column 203, the 4th rectifying column 204.
Embodiment
In order to which technical characteristic, purpose and beneficial effect to the present invention are more clearly understood from, now to the skill of the present invention Art scheme carry out it is described further below, but it is not intended that to the present invention can practical range restriction.
Embodiment 1
One kind is present embodiments provided with the μ gg of sulfur content 823.1-1, olefin(e) centent 35.2v% high-sulfur poor quality FCC vapour Oily (feedstock oil 1) is that raw material carries out the method that hydro-upgrading processing prepares super-low sulfur high-knock rating gasoline.
Wherein, on the basis of the gross 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% steps hole HKUST-1.
The specific preparation process of low temperature sulfur transfer catalyst is as follows：
First by HZSM-5 zeolites (SiO2/Al2O3Mol ratio is 30) to be placed in NaOH by 10mL/g liquid-solid ratio In the aqueous solution, pH value is adjusted to 13, in stirring 4h at 75 DEG C, filters, wash the zeolite filtered out into Property, in 120 DEG C of dry 3h；By the HZSM-5 zeolites handled through the NaOH aqueous solution according to zeolite: ammonium nitrate: The weight ratio of water mixes for 1: 0.8: 10 ratio, and stirs 4h in 80 DEG C, then product is filtered, Washing, and in 120 DEG C of dryings, 480 DEG C of roasting 4h, obtain the HZSM-5 zeolites that alkali process-ammonium is exchanged；Will The above-mentioned HZSM-5 zeolites exchanged through alkali process and ammonium are passed through steam treatment 20-50min at 600 DEG C, obtain Modified HZSM-5 zeolites (i.e. the HZSM-5 zeolites of alkali process-ammonium exchange-hydro-thermal process)；
Weigh 50.2g aluminum silicon powders and (contain Al2O392.0wt%, SiO28.0wt%) with the above-mentioned modifications of 30.0g HZSM-5 zeolites, 2.5g sesbania powders, its ground and mixed is uniform, add the nitric acid that 6mL concentration is 65wt% Solution, abundant kneading after the cloverleaf pattern bar that a diameter of 2mm is extruded in banded extruder, through 120 DEG C of dry 4h, After 520 DEG C of roasting 4h, the catalyst carrier of shaping is made；
Prepared according to stoichiometric proportion and contain NiO, MoO3And La2O3Nickel nitrate, ammonium molybdate, lanthanum nitrate mixing it is molten Maceration extract, is then uniformly added drop-wise in said catalyst carrier by liquid using equi-volume impregnating, and 4 are dried through 120 DEG C After h, 520 DEG C of roasting 4h, low temperature sulfur transfer catalyst is made.
The specific preparation process of esterification catalyst is as follows：
By the ZSM-5 zeolite and 1mol/L NH that silica alumina ratio is 354Cl solution is with 1:10 weight are than mixing, in 80 DEG C Stir 4h, filtering, washing, dry, 550 DEG C of roasting 5h；Repeat the above steps once, obtain ammonium exchange HZSM-5 zeolites.
Weighing 30g takes aluminum silicon powder (to contain Al2O392.0wt%, SiO 8.0wt%), the above-mentioned HZSM-5 zeolites of 20g With 1.9g sesbania powders, ground and mixed uniformly, adds 4.5mL65wt% salpeter solution, and abundant kneading uses extrusion Machine is molded, and after 120 DEG C of dry 4h, 550 DEG C of roasting 5h, the cloverleaf pattern esterification for obtaining diameter 2mm is urged Agent.
The specific preparation process of catalyst for selectively hydrodesulfurizing is as follows：
Weigh 70.0g have suitable Al/Si/Mg ratios Al-Si-Mg composite powders (aqueous 25wt%) and 2.0g sesbania powders, its ground and mixed is uniform, add the salpeter solution that 5mL concentration is 65wt%, abundant kneading After extruded moulding in banded extruder, after 120 DEG C of dry 3h, 520 DEG C of roasting 4h, the catalyst of shaping is made Carrier；
In the mixed impregnant liquor that 40.0g said catalyst carriers are impregnated in 35mL potassium nitrate and diammonium hydrogen phosphate, In terms of oxide, 1.5g K are contained in the maceration extract2O and 1.0g P2O5, then ripening 5h at room temperature, Again in 120 DEG C of dry 3h, 520 DEG C of roasting 4h, the catalyst carrier of potassium and phosphorus has been loaded；
Prepare 32.0mL and contain 2.0gCoO and 6.1g MoO3(content of each active component is counted in the form of an oxide, Not the active component in limitation mixed liquor exists in the form of an oxide) cobalt nitrate and ammonium molybdate mixed liquor, and add 3.0mL concentration is 17wt% ammoniacal liquor, and maceration extract is made up to solid is completely dissolved in fully vibration, then will be above-mentioned The catalyst carrier for having loaded potassium and phosphorus is impregnated in the maceration extract, room temperature ageing 5h, through 120 DEG C of drying process 3h, After 520 DEG C of calcination process 5h, catalyst for selectively hydrodesulfurizing is made.
The specific preparation process for supplementing desulfuration adsorbent is as follows：
By 50.0g lauryl sodium sulfate (SDS) in being dissolved at 55 DEG C in 750.0g deionized waters, Ran Houjia Enter 55.0g Cu (NO3)2·3H2O, is uniformly mixed；Add 25.0g trimesic acids (H3BTC), at 55 DEG C Lower stirring 30min；Finally the crystallization 12h at 120 DEG C, filters, washs, dries, obtain step hole HKUST-1 Former powder；HKUST-1 former powder in step hole is scattered in absolute ethyl alcohol to (weight compares 1:10), in stirring 6h at 80 DEG C, Removed template method SDS, obtains step hole HKUST-1；By the HKUST-1 tablettings of step hole, 40-60 mesh sieves are crossed, Obtain supplementing desulfuration adsorbent.
Process using full feedstock oil modification production super-low sulfur high-knock rating gasoline is as follows, its technological process such as Fig. 1 It is shown：
The property of feedstock oil 1 participates in table 1.Feedstock oil occurs to orient sulphur first in the presence of low temperature sulfur transfer catalyst Transfer reaction 101, reaction condition is：Pressure 2.4MPa, 130 DEG C of temperature, liquid volume air speed 3h-1, hydrogen oil Volume ratio 7；
Then the gasoline after sulphur transfer reaction is entered into fractionating column, light fraction gasoline and again is obtained by cut cutting 102 Distillation gasoline, cutting temperature is 70 DEG C；
Light fraction gasoline enters in esterifier (the weight ratio of acetic acid and alkene in light fraction gasoline after being mixed with acetic acid For 1.2:1), in the presence of esterification catalyst, esterification 103 occurs for the C5-C7 alkene in light fraction gasoline, Reaction condition is：Pressure 2.0MPa, 110 DEG C of temperature, liquid volume air speed 2.5h-1(with Acetometer)；Esterification After reaction, product is subjected to rectifying separation 104, unreacted acetic acid, the light fraction gasoline after being handled is removed；
As shown in Fig. 2 in rectifying piece-rate system, the light fraction gasoline after esterification initially enters first rectifying column 201, Pass through the isolated overhead product of rectifying (light fraction gasoline) and tower reactor product (esters and unreacted acetic acid)；The One tower bottom of rectifying tower product enter Second distillation column 202, by the isolated overhead product of rectifying (low boiling esters and Acetic acid) and tower reactor product (higher boiling esters)；Second distillation column overhead product enters third distillation column 203, simultaneously Water is introduced into third distillation column as entrainer, entrainer is 1 with Second distillation column overhead product mol ratio:2.45, Pass through the isolated overhead product of rectifying (low boiling esters and water) and tower reactor product (acetic acid and water)；3rd rectifying Column overhead product is layered to obtain oil phase and aqueous phase, and oil phase is produced with first rectifying column overhead product and Second distillation column tower reactor Product are mixed, and obtain light fraction gasoline after the esterification of removing acetic acid；Third distillation column tower reactor product enters the 4th rectifying column 204, by the isolated overhead product of rectifying (water) and tower reactor product (acetic acid), tower reactor product and fresh acetic acid Mixing, proceeds esterification, after overhead product is mixed with the aqueous phase and fresh water of third distillation column top product, after It is continuous to participate in rectifying as entrainer；First rectifying column 201, Second distillation column 202, third distillation column 203 and the 4th Rectifying column 204 uses packed tower, and filler is 2.5 × 2.5mm stainless steel θ rings；
Rectifying piece-rate system operating condition is：First rectifying column operating condition is：The number of plates 30, feedboard number 18, 29 DEG C of tower top temperature, tower top pressure 1atm, 141 DEG C of bottom temperature, tower reactor pressure 1.2atm, reflux ratio 2； After-fractionating tower operating condition is：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；3rd fractionating column operating condition is：The number of plates 36, Feedboard number 18,88 DEG C of tower top temperature, tower top pressure 1atm, 114 DEG C of bottom temperature, tower reactor pressure 1.2atm, Reflux ratio 10；4th fractionating column operating condition is：The number of plates 40, feedboard number 24,100 DEG C of tower top temperature, tower Pressure on top surface 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 contacted with catalyst for selectively hydrodesulfurizing, selects Selecting property hydrodesulfurization reaction 105, reaction condition is：Pressure 1.5MPa, 250 DEG C of temperature, liquid volume air speed 3.5 h-1, hydrogen to oil volume ratio 300:1；Subsequently into being contacted in absorption desulfurization reactor with supplement desulfurization absorption, occurs ultra-deep Degree adsorbs desulphurization reaction 106, and reaction condition is：Pressure 1.5MPa, 35 DEG C of temperature, liquid volume air speed 1.5h-1；
The present embodiment set two absorption desulfurization reactors, one carry out ultra-deep absorption desulfurization reaction 106 when, separately One carries out desulfuration adsorbent regeneration 107, alternately；
Desulfuration adsorbent renovation process is：At 0.1MPa, 200 DEG C, N is carried out2Purging, N2Volume space velocity is 1500h-1。
After the completion of above-mentioned reaction, light, the heavy distillat gasoline after processing are mixed, blended gasoline product is obtained, i.e., it is ultralow Sulphur clean gasoline.
During the course of the reaction, all catalyst are diluted with porcelain sand, also, airtight qualified in each reactor or reaction unit Afterwards, low temperature sulfur transfer catalyst, catalyst for selectively hydrodesulfurizing are dried and presulfurization processing, it is de- to supplement Sulfur absorbent carries out activation process；Drying condition is：120 DEG C, N2Atmosphere, N2Air speed 1000h-1；Presulfurization is walked Suddenly it is：By N in beds2By H2Displacement is complete, and keeps H2Air speed is 900h-1, adjust catalyst bed Layer temperature is to 150 DEG C, to beds with 3h-1Volume space velocity injection straight-run naphtha, adjust hydrogen oil volume Than to 300:1；Beds are warming up to 180 DEG C with 20 DEG C/h, start injection vulcanizing agent (dimethyl disulfide), Its injection rate is adjusted to the 3wt% of straight-run naphtha, then proceedes to be warming up to 230 DEG C with 15 DEG C/h speed, Constant temperature 8h；280 DEG C, constant temperature 8h are warming up to 15 DEG C/h speed；320 DEG C, perseverance are warming up to 15 DEG C/h Warm 8h；Each catalyst bed reaction temperature is cooled to 20 DEG C/h；Finally, used with reacting in oil product exchange system Sulfurized oil, vulcanization terminates；The activating treatment method is：At 0.1MPa, 200 DEG C, N is carried out2Purging, N2Volume space velocity is 1500h-1.Air speed and hydrogen-oil ratio are adjusted, reaction is proceeded by, reaction 100h post-samplings are analyzed, Table 1 gives the nature parameters of reformulated gasoline product.
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-1 It is down to 8.5 μ gg-1, olefin(e) centent is down to 23.5v% by 35.2v%, simultaneously because light fraction gasoline esterification, Make full 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 mediation product nature parameters
Project Full feedstock oil 1 Gently, heavy distillat gasoline mediation 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 is that raw material carries out hydro-upgrading processing preparation super-low sulfur clean gasoline with feedstock oil 1 to present embodiments provide a kind of Method.
Wherein, low temperature sulfur transfer catalyst, catalyst for selectively hydrodesulfurizing, the preparation method for supplementing desulfuration adsorbent And composition, gasoline upgrading process, Catalyst processing method are same as Example 1.
The specific preparation process of esterification catalyst is as follows：
50.0g zirconium chlorides are dissolved in 250mL ethanol, 15.0g lauryl sodium sulfate (SDS) is added, in 30wt% ammoniacal liquor is added dropwise at 50 DEG C thereto, pH value of solution is adjusted to 6.0, Zr (OH) is obtained4Colloidal sol；Will be above-mentioned Colloidal sol gel 12h at 80 DEG C, obtains ZrO2Gel；By ZrO2Gel dries 12h, 500 DEG C at 90 DEG C It is calcined 5h and removes template, obtains mesoporous ZrO2；120 mesh sieves are crossed after tabletting, by sieving product in 500mL2 Impregnate 1h in mol/L ammonium sulfates, filtering, washing, dry, be calcined 4h at 600 DEG C, obtain SO4 2-/ZrO2 Catalyst.
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 is：Pressure 2.0MPa, 120 DEG C of temperature, liquid volume air speed 2.5h-1(with Acetometer)；
Rectifying piece-rate system operating condition is：First rectifying column operating condition is：The number of plates 30, feedboard number 18, 29 DEG C of tower top temperature, tower top pressure 1atm, 143 DEG C of bottom temperature, tower reactor pressure 1.2atm, reflux ratio 2； After-fractionating tower operating condition is same as Example 1；3rd fractionating column operating condition is：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, backflow Than 10；4th fractionating column operating condition is：The number of plates 40, feedboard number 24,97 DEG C of tower top temperature, tower top pressure Power 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 renovation process is same as Example 1.
After the completion of above-mentioned reaction, light, the heavy distillat gasoline after processing are mixed, blended gasoline product is obtained, i.e., it is ultralow Sulphur 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-1 It is down to 8.6 μ gg-1, olefin(e) centent is down to 23.0v% by 35.2v%, simultaneously because light fraction gasoline esterification, Make full 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 after the modification of the full feedstock of table 2 oil 1, heavy distillat gasoline mediation product nature parameters
Project Gently, heavy distillat gasoline mediation 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 the μ gg of sulfur content 1764.0-1, olefin(e) centent 40.3v% high-sulfur FCC gasoline (feedstock oil 2) is that raw material carries out the method that hydro-upgrading processing prepares super-low sulfur clean gasoline.
Wherein, low temperature sulfur transfer catalyst, esterification catalyst, catalyst for selectively hydrodesulfurizing, supplement desulfurization absorption Preparation method and composition, gasoline upgrading process, the Catalyst processing method of agent are same as Example 1；
The property of feedstock oil 2 is referring to table 3, and specific reaction condition is as follows：
Sulphur transfer reaction condition is：Reaction pressure 2.4MPa, 140 DEG C of reaction temperature, liquid volume air speed 3h-1, Hydrogen to oil volume ratio 7；
Fractionating column cutting temperature is 60 DEG C；
Esterification condition is same as Example 1；
Rectifying piece-rate system operating condition is：First rectifying column operating condition is：The number of plates 30, feedboard number 18, 29 DEG C of tower top temperature, tower top pressure 1atm, 141 DEG C of bottom temperature, tower reactor pressure 1.2atm, reflux ratio 2； After-fractionating tower operating condition is same as Example 1；3rd fractionating column operating condition is same as Example 2；4th point Evaporate tower operating condition same as Example 1；
Selective hydrodesulfurization reaction condition is：Reaction pressure 1.5MPa, 260 DEG C of reaction temperature, liquid volume is empty Fast 3.0h-1, hydrogen to oil volume ratio 300:1；
Ultra-deep absorption desulfurization reaction condition is：Reaction pressure 1.5MPa, 35 DEG C of reaction temperature, liquid volume is empty Fast 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-1 It is down 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, Make full feedstock oil 2 while ultra-deep desulfurization, research octane number (RON) only reduces by 0.3 unit, mediation oil product Yield 99.2wt%, product quality meets state's V clean gasoline standard requirement.
Light after the full feedstock of table 3 oil 2 and modification, heavy distillat gasoline mediation product nature parameters
Project Full feedstock oil 2 Gently, heavy distillat gasoline mediation 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 is that raw material carries out hydro-upgrading processing preparation super-low sulfur clean gasoline with feedstock oil 2 to present embodiments provide a kind of Method.
Wherein, low temperature sulfur transfer catalyst, the preparation method of catalyst for selectively hydrodesulfurizing and composition, gasoline upgrading Process, Catalyst processing method are same as Example 1；The composition and preparation method of esterification catalyst and embodiment 2 It is identical；
The specific preparation process for supplementing desulfuration adsorbent is substantially the same manner as Example 1, and difference is will be " by 50.0g Lauryl sodium sulfate (SDS) at 55 DEG C in being dissolved in 750.0g deionized waters " it is changed to " by 70.0g dodecanes Base sodium sulphate (SDS) at 55 DEG C in being dissolved in 750.0g deionized waters ".
Specific reaction condition is as follows：
Sulphur transfer reaction condition, esterification condition and fractionating column cutting temperature are same as Example 3；
Rectifying piece-rate system operating condition is：First rectifying column operating condition is：The number of plates 30, feedboard number 18, 29 DEG C of tower top temperature, tower top pressure 1atm, 141 DEG C of bottom temperature, tower reactor pressure 1.2atm, reflux ratio 2； After-fractionating tower operating condition is same as Example 1；3rd fractionating column operating condition is：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, backflow Than 10；4th fractionating column operating condition is same as Example 1；
Selective hydrodesulfurization reaction condition is：Reaction pressure 1.5MPa, 255 DEG C of reaction temperature, liquid volume is empty Fast 3.0h-1, hydrogen to oil volume ratio 300:1；
Ultra-deep absorption desulfurization reaction condition is：Reaction pressure 1.5MPa, 35 DEG C of reaction temperature, liquid volume is empty Fast 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-1 It is down 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, Make full feedstock oil 2 while ultra-deep desulfurization, research octane number (RON) maintains 90.3, mediation oil product yield 99.2wt%, product quality meets state's V clean gasoline standard requirement.
Light after the modification of the full feedstock of table 4 oil 2, heavy distillat gasoline mediation product nature parameters
Project Gently, heavy distillat gasoline mediation 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 the μ gg of sulfur content≤10-1, olefin(e) centent≤24v%, gasoline Research octane number (RON) Lose state's V clean gasoline product of≤0.5 unit；Alkene saturation can be adjusted by modulation process conditions simultaneously Rate, makes product oil while state's V standards are met, alkene saturation is avoided as far as possible, to keep its octane number；And ester Change reaction and compensate for the loss of octane number that alkene saturation is caused；The inventive method has to be hydrogenated with well to inferior patrol to be changed Matter effect.
Specific embodiment described above, is further illustrated to the purpose of the present invention, technical scheme and beneficial effect, But the protection domain being not intended to limit the present invention.

Claims (9)

1. a kind of production method of super-low sulfur clean gasoline, this method comprises the 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 is obtained；
Light fraction gasoline is set to be mixed with organic acid, in the presence of esterification catalyst, the C5-C7 in light fraction gasoline Esterification occurs for alkene, light after being handled then after rectifying piece-rate system removes unreacted organic acid Distillation gasoline；
Heavy distillat gasoline is contacted with catalyst for selectively hydrodesulfurizing and supplement desulfuration adsorbent, occur selective hydrogenation Desulphurization reaction and ultra-deep absorption desulfurization reaction, obtain the heavy distillat gasoline of super-low sulfur；
Light fraction gasoline after processing is mixed with the heavy distillat gasoline after processing, described super-low sulfur cleaning vapour is obtained Oil.
2. production method according to claim 1, wherein, the reaction condition of the sulphur transfer reaction is：Instead Answer 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 temperature of the oil product cutting is 50-100 DEG C；
The reaction condition of selective hydrodesulfurization reaction is：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 ultra-deep absorption desulfurization reaction is：Pressure 0.1-2.0MPa, 30-60 DEG C of temperature, liquid Body volume space velocity 1-5h-1。
3. production method according to claim 1, wherein, it is described low on the basis of the gross weight of catalyst The composition of warm sulfur transfer catalyst includes：Transition metal oxide 2-30%, auxiliary agent 0.5-6%, zeolite 10-40%, Surplus is inorganic refractory oxide；Preferably, the transition-metal oxide includes NiO, CoO, ZnO, MoO3、 WO3With one or more of combinations in CuO；The auxiliary agent includes K2O, MgO and La2O3In one kind or Several combinations；The zeolite includes one or more of combinations in HZSM-5, H β and HY, also, institute It is the zeolite by alkali process, ammonium exchange, hydro-thermal process to state zeolite；The inorganic refractory oxide include aluminum oxide, One or more of combinations in silica and silicon-containing alumina.
4. production method according to claim 1, wherein, the reaction condition of the esterification is：Reaction 80-200 DEG C of temperature, reaction pressure 0.1-4.0MPa, organic acid and olefin weight ratio in light fraction gasoline 0.5-2.5:1.0, the liquid volume air speed 0.5-5.0h in terms of organic acid-1。
5. the production method according to claim 1 or 4, wherein, the organic acid includes having following structure One or more of combinations in the compound of formula：
In formula, R is H, CH3、C2H5、C3H7In any one.
6. production method according to claim 1, wherein, the esterification catalyst is urged including metal oxide Agent, zeolite molecular sieve catalyst, SO4 2-/MxOyOne in catalyst, strong acid cation exchange resin catalyst Plant or several combinations；
Preferably, the metal oxide catalyst including being with least one of silica, molecular sieve and diatomite Carrier loaded ZnO, SnO and Al2O3At least one of catalyst made by metal oxide, and described carry Body has conventional structure or meso-hole structure；
The zeolite molecular sieve catalyst include aluminium phosphate molecular sieve, aluminium silicophosphate molecular sieve, H types modenite, The molecular sieve catalyst that one or more in HY zeolites, H- β zeolites and HZSM-5 zeolites are mixed, and And the zeolite molecular sieve is that conventional zeolite molecular is sieved or step hole zeolite molecular sieve；
The SO4 2-/MxOyCatalyst is included SO4 2-It is carried at least one of ZrO, ZnO and SnO metal Made SO on the carrier that oxide is made4 2-/MxOyCatalyst, and the metal oxide is common metal Oxide or mesopore metal oxide；
The strong acid cation exchange resin catalyst includes Jie containing strong acid reaction group-large pore macromolecular and handed over Linked polymer catalyst.
7. production method according to claim 1, wherein, the rectifying piece-rate system includes at least two essences Evaporate tower；Preferably, the rectifying piece-rate 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 is：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 is controlled in 0.1-10；After-fractionating tower operating condition is：Number of plates 20-100, feedboard number 10-80, tower 100-150 DEG C of temperature is pushed up, tower top pressure 1-5atm, 100-200 DEG C of bottom temperature, tower reactor pressure 1-5atm is returned Stream is than control in 1-40；3rd fractionating column operating condition is：Number of plates 20-70, feedboard number 10-60, tower top temperature 50-150 DEG C of degree, tower top pressure 1-5atm, 80-150 DEG C of bottom temperature, tower reactor pressure 1-5atm, reflux ratio control System is in 1-30；4th fractionating column operating condition is：Number of plates 10-60, feedboard number 10-50, tower top temperature 80-150 DEG C, tower top pressure 1-5atm, 100-150 DEG C of bottom temperature, tower reactor pressure 1-5atm, reflux ratio control In 1-30.
8. production method according to claim 1, wherein, on the basis of the gross weight of catalyst, the choosing The composition of selecting property Hydrobon catalyst includes：MoO310-18%, CoO 2-6%, K2O 1-7%, P2O52-6%, Surplus is Al-Si-Mg composite oxide carriers, and the weight of the Al-Si-Mg composite oxides in the catalyst Composition includes：Al2O360-75%, SiO25-15% and MgO 3-10%.
9. production method according to claim 1, wherein, the supplement desulfuration adsorbent is to pass through tabletting The step hole HKUST-1 of 40-60 mesh sieves shaping；Preferably, the step hole HKUST-1 through the following steps that Prepare：Lauryl sodium sulfate is dissolved in deionized water, Cu (NO are then sequentially added3)2·3H2O, Benzenetricarboxylic acid, stirs, and obtains colloidal sol, then in 80-150 DEG C of crystallization 12-36h, filters, washs, dries, Removed template method, tabletting, sieving afterwards, obtains the step hole HKUST-1；It is highly preferred that in the colloidal sol Lauryl sodium sulfate, deionized water, Cu (NO3)2·3H2O, the mol ratio of trimesic acid are (1-2):(80-200):(1.5-2.5):1。
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