CN106701177B - A kind of production method of ultra-clean gasoline - Google Patents

Abstract

The invention discloses a kind of production methods of ultra-clean gasoline.This method includes the following steps: the hydrogenated absorption desulfurization of (1) bad gasoline, obtains absorption desulfurization product；(2) absorption desulfurization product is divided into light petrol, middle gasoline and heavy petrol；(3) gasoline enters aromatisation Olefin decrease reactor in, contacts with aromatized catalyst and carries out aromatization, obtains aromatisation gasoline；(4) the resulting light petrol of step (2) and heavy petrol are mixed with the resulting aromatisation gasoline of step (3), obtain ultra-clean gasoline product.This method can be produced sulfur content ≯ 10 μ g/g, olefin(e) centent ≯ 15.0v% clean gasoline by inferior patrol, while loss of octane number is few, and the side reactions such as cracking and polymerization are few, feed throughput is big, the requirement to the product end point of distillation is readily satisfied, aromatized catalyst stability is good, and service life is long.

Description

A kind of production method of ultra-clean gasoline

Technical field

The present invention relates to a kind of production methods of ultra-clean gasoline, specifically, the present invention relates to a kind of inferior patrols Produce super-low sulfur, the method for low-alkene gasoline.

Background technique

The discharge amount of harmful substance in vehicle exhaust can significantly be reduced by reducing content of sulfur in gasoline, and therefore, the world is each State's clean gasoline new standard proposes the limitation being increasingly stringenter to sulfur content.2014, the European VI class that European Union comes into effect It " no sulphur " gasoline standard (EURO VI/E5 standard) and gasoline standard (EURO VI/E15 standard) will be implemented within 2017 will require Sulfur content ≯ 10 μ g/g, olefin(e) centent 3.0v% ~ 13.0v%.U.S.EPA Tier 2-III standard provides that 2008 U.S. Nian Hou are clear The sulfur content of clean gasoline ≯ 30 μ g/g, olefin(e) centent ≯ 14.0v%.In China, whole nation state of enforcement IV on January 1st, 2014 discharge mark Quasi- (GB17930-2011), it is desirable that sulfur content ≯ 50 μ g/g, olefin(e) centent ≯ 28.0v%.Before and after 2017, China's whole nation gasoline " no sulphur " gasoline (ULSG) state's V standard (GB17930-2013) will be executed, it is desirable that sulfur content ≯ 10 μ g/g, olefin(e) centent ≯ 24.0v%.In particular, in view of in order to further improve atmospheric environment, Chinese relevant department is formulating stringenter cleaning vapour Oil standard (abbreviation state VI standard), it is desirable that sulfur content ≯ 10 μ g/g, olefin(e) centent ≯ 15.0v%, state's VI normal benzine will be not It takes the lead in remote future implementing in megalopolis such as Beijing, Shanghai.

Currently, catalytic cracking (FCC) is the important sources of gasoline, as shared by FCC gasoline in Chinese oil plant gasoline product Ratio be 80% or more, and sulfur content is generally 200~1000 μ g/g in FCC gasoline, olefin(e) centent be generally 20.0v% ~ 45.0v%.Therefore, sulphur and olefin(e) centent are higher in FCC gasoline, and the sulfur content and olefin(e) centent for reducing FCC gasoline are to meet more The key of stringent clean specification gasoline.

Hydrodesulfurization (HDS) technique is the important means of sulphur and mercaptan in effective removing FCC gasoline, still, using tradition Catalyst and technique, while FCC gasoline hydrodesulfurization, alkene significantly add hydrogen saturation will cause biggish octane number Loss.In order to reduce the loss of sulfur-free gasoline octane number, various countries develop many selective hydrodesulfurizations (HDS) raw catelyst and Technique, such as US 6692635, EP 1031622, CN 02133136.7, CN 02121594.4 etc., but still it is unable to satisfy oil refining Enterprise produces clean gasoline sulfur content ≯ 10 μ g/g technology and needs, and loss of octane number is still larger.

Currently, absorption desulfurization is also one of the effective ways for removing sulphur in FCC gasoline.

Gasoline modifying method disclosed in US6482314 and US7182918 is to be evaporated entirely using the method for absorption desulfurization to handle Divide FCC gasoline.The main chemical reactions of this method are desulphurization reaction.Therefore, the product of generation is compared with raw material, except sulfur content is big Outside width reduces, density, boiling range and other properties are basically unchanged, and alkene is slightly reduced, and alkane is increased slightly, and (RON+MON)/2 is damaged Lose less than 1.0 units.But the olefin(e) centent in gasoline products cannot be greatly lowered in this method, higher for olefin(e) centent FCC gasoline can not solve the problems, such as Olefin decrease.

CN 101492610B discloses a kind of method of deep desulfurization olefin hydrocarbon reduction of gasoline, successively by gasoline stocks and hydrogen It is contacted with hydrogen absorbing desulfurization catalyst, alkene aromatized catalyst is added, remove the sulphur in gasoline and reduces the olefin(e) centent of product. Olefin(e) centent is still in 15v% or more in the resulting gasoline products of this method, and full distillation gasoline progress aromatization, and first, The density of gasoline can be improved, dramatically increase the end point of distillation of gasoline, in this way for the requirement for meeting the end point of distillation, usually to reduce raw material The end point of distillation, such feed throughput greatly reduces；Second, the side reactions such as cracking and polymerization increase, and are not only easy catalyst Coking deactivation, influences operation cycle, and the liquid of gasoline products is incorporated low, and the indexs such as vapour pressure, benzene content are also impacted, and Three, loss of octane number is larger.To make olefin(e) centent satisfaction ≯ 15.0v% requirement, above-mentioned deficiency will be protruded more.

Summary of the invention

Aiming at the shortcomings in the prior art, the present invention provides a kind of production methods of ultra-clean gasoline.This method can be by Inferior patrol produces sulfur content ≯ 10 μ g/g, olefin(e) centent ≯ 15.0v% clean gasoline, while loss of octane number is few, cracking With polymerization etc. side reactions it is few, feed throughput is big, readily satisfies the requirement to the product end point of distillation, aromatized catalyst stability Good, service life is long.

The production method of ultra-clean gasoline provided by the invention, including the following steps:

(1) the hydrogenated absorption desulfurization of bad gasoline obtains absorption desulfurization product；

(2) the resulting absorption desulfurization product of step (1) enters fractionating column, is divided into light petrol, middle gasoline, heavy petrol；Gently The cutting temperature of gasoline and middle gasoline is 55~65 DEG C；The cutting temperature of middle gasoline and heavy petrol is 95~105 DEG C；

(3) the resulting middle gasoline of step (2) enters aromatisation Olefin decrease reactor, and progress virtue is contacted with aromatized catalyst Structureization reaction, obtains aromatisation gasoline；

(4) the resulting light petrol of step (2) and heavy petrol are mixed with the resulting aromatisation gasoline of step (3), are obtained super clear Clean gasoline products.

In the present invention, in the ultra-clean gasoline, sulfur content ≯ 10 μ g/g, olefin(e) centent ≯ 15v%, i.e. sulfur content are not Greater than 10 μ g/g, olefin(e) centent is not more than 15v%.

Step (1) is described plus hydrogen adsorbs desulfurization preferably with the method for fluidised bed adsorption desulfurization, which can use Commodity adsorbent can also be prepared by prior art preparation, such as by CN00808906.X.It is wherein sorbent used to use Carrier comprising aluminium oxide and zinc oxide can also contain one of silica, swelled ground or a variety of, the gold of load in carrier Belonging to is one of group VIB and group VIII metal or a variety of, preferably nickel, and on the basis of the weight of adsorbent, carrier contains Amount is 50%~95%, and the content of group VIB and/or group VIII metal based on the element is 5%~50%, wherein with the weight of carrier On the basis of, the content of zinc oxide is 15%~90%, and the content of aluminium oxide and/or silica is 10%~85%.

When in step (1) using fluidised bed adsorption desulfurization, preferably with desulfurizing agent circular regeneration technique, specific steps are such as Under: the first step, the sulphur atom of sulfur-containing compound is selectively adsorbed onto desulfurization in presence of hydrogen in desulfurization zone, gasoline stocks In agent；Second step, the absorption desulfurization product after being adsorbed desulfurization are separated with the adsorbent of absorption sulphur；Third step adsorbs sulphur Adsorbent burn sulphur with air in oxidation regeneration device and make charcoal activation；4th step, the adsorbent after activation with hydrogen reducing again It is raw；5th step, the adsorbent after regeneration return to desulfurization zone, are recycled next time.

In absorption desulfurization product obtained in step (1), sulfur content ≯ 10 μ g/g is substantially free of alkadienes.

Absorption desulfurization product described in step (2) is fractionated tower and is divided into light petrol, middle gasoline, heavy petrol, wherein light vapour Oily sulfur content ≯ 10 μ g/g, olefin(e) centent ≯ 40v%；Middle content of sulfur in gasoline ≯ 10 μ g/g, olefin(e) centent ≯ 60v%；Heavy petrol sulphur Content ≯ 10 μ g/g, olefin(e) centent ≯ 15.0v%.

In step (2), the absorption desulfurization product is fractionated tower and is divided into light petrol, middle gasoline, heavy petrol, wherein with weight Meter, light petrol typically constitute from the 10% ~ 20% of absorption desulfurization product；Middle gasoline typically constitutes from the 20% ~ 40% of absorption desulfurization product；Weight vapour Oil typically constitutes from the 40% ~ 70% of absorption desulfurization product.

In the present invention, in conjunction in obtained by step (2) the characteristics of gasoline, particularly preferred following aromatized catalysts, specifically As follows: catalyst composition includes molecular sieve, nickel and the binder of zinc and titanium same order elements, can also contain rare earth metal member Element, wherein the molecular sieve of zinc and titanium same order elements is Zn-Ti-HZSM-5, and grain size is 20nm~300nm, preferably 40nm ~200nm, SiO₂/Al₂O₃Molar ratio is 20 ~ 30.Thulium is selected from lanthanum and/or cerium.Using the weight of catalyst as base The molecular sieve content of standard, zinc and titanium same order elements be 50.0wt%~90.0wt%, nickel based on the element content be 0.1wt%~ 3.0wt%, preferably 0.5%~2.0%, rare earth metal based on the element content be 0wt%~4.0wt%, preferably 1.0%~3.0%, Surplus is binder.Wherein, in the molecular sieve of zinc and titanium same order elements, zinc and titanium account for point of zinc and titanium same order elements based on the element 0.5wt%~4.0wt% of son sieve weight, preferably 1.0%~3.0%, wherein the molar ratio of titanium and zinc is 1:2~1:9, preferably 1:4~1:8.The binder is the binder used in conventional catalyst preparation process, generally uses aluminium oxide and silica One of or it is a variety of.The preparation process of the catalyst is as follows: (1) preparing the molecular sieve of zinc and titanium same order elements, (2) zinc and titanium Catalyst carrier is made after the molecular sieves of same order elements and adhesive kneading and compacting, drying and roasting, (3) dip loading nickel and dilute Earth metal obtains aromatized catalyst after drying and roasting, wherein to the molecule of step (1) resulting zinc and titanium same order elements Sieve or the resulting catalyst carrier of step (2) carry out hydro-thermal process, and the condition of hydro-thermal process is as follows: 450~650 DEG C of temperature, place Reason 3~20 hours.Wherein in the molecular sieve of zinc and titanium same order elements, zinc and titanium elements are introduced into during system with molecular sieve for preparing is standby In framework of molecular sieve structure, it can be synthesized using hydro-thermal method.The method of dip loading nickel and rare earth metal can be used conventional Infusion process carries out, such as excessive infusion process, saturation infusion process, spray process etc..It is used dry when step (2) prepares carrier Dry and roasting condition is as follows: it is 3~15 hours dry at 90~140 DEG C, it is roasted 2~10 hours at 400~600 DEG C.In step (3) when preparing catalyst, used drying and roasting condition are as follows: dry 3~15 hours at 90~140 DEG C, 400~ It is roasted 2~10 hours at 600 DEG C.

In step (3), aromatisation is that used reaction condition is as follows: reaction pressure is generally 1.5MPa~4.5MPa, Reaction temperature is generally 360 DEG C ~ 460 DEG C, and volume space velocity is generally 1.0 h when total liquid^-1~5.0h^-1, hydrogen to oil volume ratio is generally 200:1~1000:1；Preferred reaction condition is as follows: reaction pressure is 2.5MPa~3.5MPa, and reaction temperature is 380 DEG C ~ 420 DEG C, volume space velocity is 2.0 h when total liquid^-1~4.0h^-1, hydrogen to oil volume ratio is 500 ~ 700:1.

The resulting aromatisation gasoline of step (3), sulfur content ≯ 10 μ g/g, olefin(e) centent ≯ 15.0v%, preferably ≯ 10.0v%, compared with middle gasoline, loss of octane number ≯ 3.0 unit.

Clean gasoline product obtained by step (4), sulfur content ≯ 10 μ g/g, olefin(e) centent ≯ 15.0v%, with inferior patrol original Material is compared, and loss of octane number ≯ 1.5 unit can be made.

In the method for the present invention, bad gasoline first passes around process for adsorption desulfuration, makes the sulfur-bearing chemical combination in inferior patrol Object, alkadienes are substantially achieved complete removing, and obtained absorption desulfurization product is fractionated tower and is divided into light petrol, middle gasoline, again Gasoline, wherein middle gasoline is free of alkadienes, and sulfur content is ultralow, and olefin(e) centent is high (especially C6 ~ C8 olefin(e) centent is high), not only Reduce the treating capacity of device, and uses preferred aromatized catalyst, the particularly suitable middle vapour of the invention of comprehensive performance On the one hand oily aromatisation can make the direct dehydrocyclization of most of C6 ~ C8 alkene in middle gasoline carry out aromatization, reduce alkene Hydrocarbon content reduces loss of octane number, and on the other hand during middle aromatization of gas, and it is secondary to significantly reduce cracking and polymerization etc. The generation of reaction reduces the coke content generated on catalyst, improves the stabilization service life of aromatized catalyst.In addition, light vapour Oil does not have to processing, can not only reduce the loss of yield of gasoline in this way, but also gasoline products vapour pressure can be made to touch the mark It is required that；Heavy petrol can reduce carbon deposit on catalyst without processing in this way, and compared with gasoline stocks, gasoline products are done It will not obviously increase.

Detailed description of the invention

Fig. 1 is the flow diagram of the method for the present invention.

Specific embodiment

Bad gasoline described in the method for the present invention is fluid catalytic cracking (FCC) gasoline, catalytic cracking gasoline, coke Change one of gasoline, pressure gasoline etc. or a variety of.Currently preferred raw material is FCC gasoline.The bad gasoline It can be full fraction FCC gasoline, wherein initial boiling point is 30~40 DEG C, and preferably 32~38 DEG C, the end point of distillation is 180~220 DEG C, Preferably 190~205 DEG C；General 200~1000 μ g/g of sulfur content, especially 300~800 μ g/g；Olefin(e) centent is general 20.0v%~45.0v%, especially 25.0v%~40.0v%；Diene content general 0.5~4.0gI/100g, especially 1.0~ 2.5gI/100g。

Present invention absorption desulfurization as described in step (1) uses fluidized-bed reactor, and operating condition is as follows: reaction pressure For 1.0MPa~4.5MPa, 350 DEG C~550 DEG C of reaction temperature, reactor inlet feeds hydrogen to oil volume ratio 50:1~200:1.It inhales Content of sulfur in gasoline after attached desulfurization process generally can achieve ≯ 10 μ g/g.

The adsorbent of absorption sulphur burns sulphur with air and activating and regenerating of making charcoal in oxidation regeneration device in step (1) of the present invention, Regeneration condition in regenerator is as follows: regeneration pressure is 0.5MPa~1.5MPa, gas agent volume ratio 500:1~1000:1,400 DEG C~550 DEG C at constant temperature 3.0~10.0 hours, regeneration gas is air.

The method of the present invention can produce sulfur content ≯ 10 μ in the case where research octane number (RON) (RON) loses ≯ 1.5 units G/g, olefin(e) centent ≯ 15v% clean gasoline technology need.

Further the method for the present invention process and effect with reference to the accompanying drawings and examples.Logistics and each unit operation are along arrow Direction carries out in order.

The method of the present invention is described in detail below with reference to Fig. 1.

Inferior patrol 1 carries out absorption desulfurization in absorption desulfurization unit A and generates absorption desulfurization product 2；Adsorb desulfurization product 2 into Enter fractionating column B, is divided into light petrol 3, middle gasoline 5, heavy petrol 4；Middle gasoline 5 is mixed into aromatization reactor C with new hydrogen 11 It carries out aromatization and generates product 6, product 6 generates aromatization products 7 after gas-liquid separation tower D；Aromatization products 7 and light Gasoline 3, heavy petrol 4 are mixed to get clean gasoline 12.The gas phase 8 isolated by gas-liquid separation tower D is after processing as circulation Hydrogen 9 and 10 enters aromatization reactor C.

The solution of the present invention and effect are further illustrated below by embodiment, but are not intended to limit the present invention.

Comparative example 1

This comparative example uses routine Ti, Zn infusion process, prepares aromatized catalyst DC-1, and form as follows: Zn content is 2.0wt%, Ti content are that 0.3wt%, Ni content are 1.6wt%, and nano-HZSM-5 zeolite content is 75 wt%, and surplus is oxidation Aluminium.

Weigh 229.6g Nano-sized HZSM-5 (SiO₂/Al₂O₃Molar ratio is 27, and grain size is 20nm~80nm) and 140.0g Al₂O₃, and their ground and mixeds is uniform, the dilute nitric acid solution that 150mL concentration is 5.6g/100mL is added, is ground into humidity conjunction Suitable muffin body.The item that diameter is 2.0mm is extruded on banded extruder.It is 10 hours dry at 120 DEG C after drying at room temperature, It is roasted 8 hours at 520 DEG C, is then down to room temperature, obtains shaping carrier.

Above-mentioned shaping carrier is put into vertical water heat-treatment furnace, saturated vapor is passed through at 550 DEG C and is handled 5 hours, system At hydro-thermal process carrier, referred to as S-1.

It weighs above-mentioned -1 100g of carrier S and is put into and spray in tank, start rotary pump.65mL is contained into Ti/Zn in 30 minutes Titanium sulfate/zinc nitrate solution that molar ratio is 1:5 is sprayed into catalyst carrier S-1.After drying at room temperature, done at 120 DEG C It dry 10 hours, is roasted 8 hours at 500 DEG C, the carrier containing Ti and Zn, number M-1 is made.

It weighs above-mentioned carrier M-1 50g and is put into and spray in tank, start rotary pump.52mL is contained into 1.0g in 30 minutes The nickel nitrate solution of NiO is sprayed into carrier M-1.It is 10 hours dry at 120 DEG C after drying at room temperature, it is roasted at 500 DEG C 8 hours, Ti-Zn-Ni/HZSM-5 aromatized catalyst, number DC-1 is made.The physico-chemical property of DC-1 catalyst is listed in table 1 In.

Comparative example 2

This comparative example uses same order elements Zn-HZSM-5, prepares aromatized catalyst DC-2, forms as follows: Zn content It is 1.6wt% for 2.0wt%, Ni content, nano-HZSM-5 zeolite content is 75 wt%, and surplus is aluminium oxide.

Weigh 229.6g nanometers of same order elements Zn-HZSM-5(SiO₂/Al₂O₃Molar ratio is 23, grain size be 20nm~ 80nm) with 140.0g Al₂O₃, and their ground and mixeds is uniform, it is molten that the dust technology that 150mL concentration is 5.6g/100mL is added Liquid is ground into the suitable muffin body of humidity.The item that diameter is 2.0mm is extruded on banded extruder.After drying at room temperature, at 120 DEG C Lower drying 10 hours roasts 8 hours at 520 DEG C, is then down to room temperature, obtains shaping carrier.

Above-mentioned shaping carrier is put into vertical water heat-treatment furnace, saturated vapor is passed through at 500 DEG C and is handled 3 hours, system At hydro-thermal process carrier S -2.

It weighs said catalyst carrier S-2 50g and is put into and spray in tank, start rotary pump.52mL is contained in 30 minutes The nickel nitrate solution of 1.0g NiO is sprayed into catalyst carrier S-2.It is 10 hours dry at 120 DEG C after drying at room temperature, It is roasted 8 hours at 480 DEG C, NiO/Zn-HZSM-5 aromatized catalyst, number DC-2 is made.The materialization of DC-2 catalyst Matter is listed in Table 1 below.

Embodiment 1

The present embodiment uses same order elements Zn-Ti-HZSM-5, prepares aromatized catalyst C-1, forms as follows: Ni Content is 1.6wt%, and Zn-Ti-HZSM-5 molecular sieve content is 77.5 wt %, and surplus is aluminium oxide, wherein with the weight of catalyst Meter, Zn content are that 2.0wt%, Ti content are 0.3wt%.

Weigh 229.6g nanometer Zn-Ti-HZSM-5(SiO₂/Al₂O₃Molar ratio is that 27, Ti/Zn molar ratio is 1:5, crystal grain Degree is 20nm~80nm), 140.0g Al₂O₃, and their ground and mixeds is uniform, it is 5.6g/100mL's that 150mL concentration, which is added, Dilute nitric acid solution is ground into the suitable muffin body of humidity.The item that diameter is 2.0mm is extruded on banded extruder.After drying at room temperature, It is 10 hours dry at 120 DEG C, it is roasted 8 hours at 520 DEG C, is then down to room temperature, obtains shaping carrier.

Above-mentioned shaping carrier is put into vertical water heat-treatment furnace, saturated vapor is passed through at 550 DEG C and is handled 5 hours, system At hydro-thermal process carrier S -3.

It weighs said catalyst carrier S-3 50g and is put into and spray in tank, start rotary pump.52mL is contained in 30 minutes The nickel nitrate solution of 1.0g NiO is sprayed into catalyst carrier S-3.It is 10 hours dry at 120 DEG C after drying at room temperature, It is roasted 8 hours at 500 DEG C, NiO/Zn-Ti-ZSM-5 aromatized catalyst, number C-1 is made.The materialization of C-1 catalyst Matter is listed in Table 1 below.

Embodiment 2

The present embodiment uses same order elements Zn-Ti-HZSM-5, prepares aromatized catalyst C-2, forms as follows: Ni Content is 1.0wt%, and Zn-Ti-HZSM-5 molecular sieve content is 83.0wt%, and surplus is aluminium oxide, wherein with the weight of catalyst Meter, Zn content is that 2.4wt%, Ti content are 0.3wt%.

Weigh 229.6g nanometer Zn-Ti-HZSM-5(SiO₂/Al₂O₃Molar ratio is that 27, Ti/Zn molar ratio is 1:7, crystal grain Degree is 20nm~80nm), 120.0g Al₂O₃, and their ground and mixeds is uniform, it is 5.6g/100mL's that 150mL concentration, which is added, Dilute nitric acid solution is ground into the suitable muffin body of humidity.The item that diameter is 2.0mm is extruded on banded extruder.After drying at room temperature, It is 10 hours dry at 120 DEG C, it is roasted 8 hours at 520 DEG C, is then down to room temperature, obtains shaping carrier.

Above-mentioned shaping carrier is put into vertical water heat-treatment furnace, saturated vapor is passed through at 550 DEG C and is handled 5 hours, system At hydro-thermal process carrier S -4.

It weighs said catalyst carrier S-450g and is put into and spray in tank, start rotary pump.52mL is contained in 30 minutes The nickel nitrate solution of 0.7g NiO is sprayed into catalyst carrier S-4.It is 10 hours dry at 120 DEG C after drying at room temperature, It is roasted 8 hours at 500 DEG C, NiO/Zn-Ti-ZSM-5 aromatized catalyst, number C-2 is made.The materialization of C-2 catalyst Matter is listed in Table 1 below.

1 aromatized catalyst physical property of table

Catalyst number	DC-1	DC-2	C-1	C-2
					BET method porous
Specific surface area, m2/g	310	320	330	334
					Kong Rong, mL/g	0.20	0.22	0.25	0.24
Average pore diameter, nm	1.83	1.88	1.95	1.94
					Hammett indicator method acid amount, mmol/g
H0≤+2.27 strong acid	0.13	0.12	0.07	0.08
					+2.27<H0≤+4.8 weak acid	0.51	0.50	0.50	0.50

Comparative example 3

This comparative example is to investigate catalyst performance and Coking Behavior using above-mentioned C-1 aromatized catalyst.

Test raw material FCC gasoline and the property for adsorbing desulfurization product through S Zorb are shown in Table 2.S Zorb is adsorbed used in desulfurization Hydrogen absorbent is added to prepare by 1 method of CN00808906.X embodiment.Using the method for fluidised bed adsorption desulfurization, desulfurization is adsorbed Process conditions are as follows: reaction pressure 2.0MPa, and 450 DEG C of reaction temperature, reactor feed liquid hydrogen to oil volume ratio 150:1.Wherein, Using desulfurizing agent circular regeneration technique, regeneration condition is as follows: regeneration pressure 1.0MPa, gas agent volume ratio 800:1, at 480 DEG C Lower constant temperature 5.0 hours, regeneration gas is air.

Test reactor is packed into C-1 aromatized catalyst 40mL, is diluted with the ratio of 2:1 with quartz sand.After airtight qualification, Presulfiding of catalyst is carried out first.Sulfurized oil is direct steaming gasoline, vulcanizing agent CS₂, CS₂Concentration is 1.0v%；Sulfide stress is 1.6MPa, temperature be 230 DEG C at 8 hours at 8 hours, 280 DEG C；Sulfurized oil volume space velocity is 2.0h^-1.It, will be anti-after vulcanization Pressure is answered to be increased to 2.0MPa.Continue to be warming up to 385 DEG C in 3 hours into sulfurized oil.Then the absorption of swap-in S Zorb device is de- Sulfur oil, reaction volume air speed are 2.0h^-1, hydrogen to oil volume ratio 600:1.Duration of runs control is into 500 hours after raw material, institute The property for obtaining product is shown in Table 2, then stops work, and draws off catalyst, measures catalyzer coke content.

Table 2 lists raw material and product characteristics in comparative example 3.

The property of FCC gasoline raw material used in 2 comparative example 3 of table and products therefrom

Project	FCC gasoline raw material	Adsorb desulfurization product	500h product
				Density, g/cm3	0.7300	0.7290	0.7305
Sulphur, μ g/g	350	7.3	5.5
				Diene value, gI/100g oil	1.67	Nothing	Nothing
RON	93.3	92.5	91.3
				Fluorescence method arene content, v%	23.9	23.7	30.0
Fluorescence method olefin(e) centent, v%	28.5	26.0	16.5
				Fluorescence method Determination of Alkane Content, v%	47.6	50.3	53.6
Boiling range, DEG C
				Initial boiling point	36.0	35.0	36.0
10%	57.0	57.0	58.0
				50%	105.0	104.0	107.0
90%	180.0	179.0	184.0
				The end point of distillation	198.0	197.0	204.0
Catalyst carbon deposition, wt%	/	/	7.5

Embodiment 3

The present embodiment is to investigate catalyst performance and carbon deposit to above-mentioned C-1 aromatized catalyst using the method for the present invention Energy.

FCC gasoline raw material and S Zorb absorbing process are the same as comparative example 3.

Absorption desulfurization product is fractionated in fractionating column, wherein the cut point of light petrol and middle gasoline is 60 DEG C, in The cut point of gasoline and heavy petrol is 100 DEG C.

Table 3 lists the main character of absorption desulfurization product, light petrol, middle gasoline and heavy petrol.

The property of the resulting desulfurization product of 3 embodiment of table 3, light petrol, middle gasoline and heavy petrol

Project	Adsorpting desulfurization device product	Light petrol	Middle gasoline	Heavy petrol
					Mass ratio, %	100	15	35	50
Density, g/cm3	0.7290	0.6550	0.6680	0.7850
					Sulphur, μ g/g	7.3	5.0	5.8	9.0
Diene value, gI/100g oil	0	0	0	0
					Research octane number (RON) RON	92.5	92.0	93.8	91.5
Fluorescence method arene content, v%	23.7	4.5	12.0	38.0
					Fluorescence method olefin(e) centent, v%	26.0	31.0	40.5	14.5
Fluorescence method Determination of Alkane Content, v%	50.3	64.5	47.5	47.5
					Fluorescence method benzene content, v%	1.5	0.0	4.3	0.2
Boiling range, DEG C
					Initial boiling point	35.0	30.0	63.0	91.0
10%	57.0	32.0	72.0	98.0
					50%	104.0	40.0	85.0	124.0
90%	179.0	50.0	92.0	175.0
					The end point of distillation	197.0	60.0	95.0	200.0

Middle aromatization of gas Olefin decrease: test reactor is packed into C-1 aromatized catalyst 40mL, with the ratio stone of 2:1 Ying Sha dilution.After airtight qualification, progress presulfiding of catalyst first.Sulfurized oil is direct steaming gasoline, vulcanizing agent CS₂, CS₂Concentration For 1.0v%；Sulfide stress is 1.6MPa, and temperature is at 230 DEG C 8 hours at 8 hours, 280 DEG C；Sulfurized oil volume space velocity is 2.0h^-1.After vulcanization, reaction pressure is increased to 2.0MPa, continues to be warming up to 390 DEG C in 3 hours into sulfurized oil.So Gasoline in swap-in afterwards, reaction volume air speed are 2.0h^-1, hydrogen to oil volume ratio 500:1.The steady running time, control was into middle gasoline 500 hours after raw material, products obtained therefrom property is shown in Table 4, then stops work, and draws off catalyst, measures catalyzer coke content.

Table 4 lists gasoline stocks, aromatization products property in 3 gained of embodiment.

The property that final products clean gasoline is obtained by light petrol, after gasoline and heavy petrol mix during treated is shown in Table 5.

Gasoline and aromatization products property in 4 embodiment of table, 3 gained

Project	Middle gasoline	500h product
			Density, g/cm3	0.6680	0.6685
Sulphur, μ g/g	5.8	3.8
			Diene value, gI/100g oil	0	0
Research octane number (RON) RON	93.8	90.8
			Fluorescence method arene content, v%	12.0	27.6
Fluorescence method olefin(e) centent, v%	40.5	6.4
			Fluorescence method Determination of Alkane Content, v%	47.5	66.0
Fluorescence method benzene content, v%	4.3	2.4
			Boiling range, DEG C
Initial boiling point	63.0	62.0
			10%	72.0	73.0
50%	85.0	88.0
			90%	92.0	94.0
The end point of distillation	95.0	99.0
			Catalyst carbon deposition, wt%	-	2.0

The property of 5 embodiment of table, 3 gained clean gasoline product

Project	FCC gasoline raw material	Adsorpting desulfurization device product	500h clean gasoline product
				Density, g/cm3	0.730	0.7290	0.7350
Sulphur, μ g/g	350	7.3	6.5
				Diene value, gI/100g oil	1.67	Nothing	Nothing
Research octane number (RON) RON	93.3	92.5	91.0
				Fluorescence method arene content, v%	23.9	23.7	29.3
Fluorescence method olefin(e) centent, v%	28.5	26.0	14.1
				Fluorescence method Determination of Alkane Content, v%	47.6	50.3	56.6
Fluorescence method benzene content, v%	1.5	1.5	1.0
				Boiling range, DEG C
Initial boiling point	36.0	35.0	35.0
				10%	57.0	57.0	58.0
50%	105.0	104.0	106.0
				90%	180.0	179.0	181.0
The end point of distillation	198.0	197.0	200.0

Embodiment 4

Compared with Example 3, the difference is that using catalyst C-2, and following aromatization conditions are used: reaction 400 DEG C of temperature, reaction pressure 1.6MPa, volume space velocity is 3.0h when liquid^-1, hydrogen to oil volume ratio 600:1.The property of gasoline in gained Matter is shown in Table 6, and the property of clean gasoline is shown in Table 7.

Gasoline and aromatization products property in 6 embodiment of table, 4 gained

Project	Middle gasoline	500h product
			Density, g/cm3	0.6680	0.6682
Sulphur, μ g/g	5.8	4.0
			Diene value, gI/100g oil	0	0
Research octane number (RON) RON	93.8	91.3
			Fluorescence method arene content, v%	12.0	28.5
Fluorescence method olefin(e) centent, v%	40.5	5.0
			Fluorescence method Determination of Alkane Content, v%	47.5	66.5
Fluorescence method benzene content, v%	4.3	2.2
			Boiling range, DEG C
Initial boiling point	63.0	63.0
			10%	72.0	72.2
50%	85.0	85.5
			90%	92.0	93.0
The end point of distillation	95.0	100.0
			Catalyst carbon deposition, wt%	-	3.0

7 embodiment of table, 4 FCC gasoline raw material and clean gasoline product property

Project	FCC gasoline raw material	Adsorpting desulfurization device product	500h clean gasoline product
				Density, g/cm3	0.730	0.7290	0.7350
Sulphur, μ g/g	350	7.3	6.6
				Diene value, gI/100g oil	1.67	Nothing	Nothing
Research octane number (RON) RON	93.3	92.5	91.2
				Fluorescence method arene content, v%	23.9	23.7	29.8
Fluorescence method olefin(e) centent, v%	28.5	26.0	13.0
				Fluorescence method Determination of Alkane Content, v%	47.6	50.3	57.2
Fluorescence method benzene content, v%	1.5	1.5	1.0
				Boiling range, DEG C
Initial boiling point	36.0	35.0	35.0
				10%	57.0	57.0	58.0
50%	105.0	104.0	106.0
				90%	180.0	179.0	181.0
The end point of distillation	198.0	197.0	200.0

Comparative example 4

Compared with Example 3, the difference is that using catalyst DC-1.The property of gasoline is shown in Table 8 in gained, cleans vapour The property of oil is shown in Table 9.

Gasoline and aromatization products property in 8 comparative example of table, 4 gained

Project	Middle gasoline	500h product
			Density, g/cm3	0.6680	0.6689
Sulphur, μ g/g	5.8	3.0
			Diene value, gI/100g oil	0	0
Research octane number (RON) RON	93.8	90.8
			Fluorescence method arene content, v%	12.0	25.5
Fluorescence method olefin(e) centent, v%	40.5	9.5
			Fluorescence method Determination of Alkane Content, v%	47.5	66.0
Fluorescence method benzene content, v%	4.3	2.8
			Boiling range, DEG C
Initial boiling point	63.0	63.8
			10%	72.0	73.2
50%	85.0	86.5
			90%	92.0	95.0
The end point of distillation	95.0	103.0
			Catalyst carbon deposition, wt%	-	6.8

9 comparative example of table, 4 FCC gasoline raw material and clean gasoline product property

Project	FCC gasoline raw material	Adsorpting desulfurization device product	500h clean gasoline product
				Density, g/cm3	0.730	0.7290	0.7310
Sulphur, μ g/g	350	7.3	5.6
				Diene value, gI/100g oil	1.67	Nothing	Nothing
Research octane number (RON) RON	93.3	92.5	90.7
				Fluorescence method arene content, v%	23.9	23.7	28.8
Fluorescence method olefin(e) centent, v%	28.5	26.0	16.0
				Fluorescence method Determination of Alkane Content, v%	47.6	50.3	55.2
Fluorescence method benzene content, v%	1.5	1.5	1.3
				Boiling range, DEG C
Initial boiling point	36.0	35.0	35.3
				10%	57.0	57.0	58.5
50%	105.0	104.0	106.5
				90%	180.0	179.0	182.0
The end point of distillation	198.0	197.0	201.5

Comparative example 5

Compared with Example 3, the difference is that using catalyst DC-2.The property of gasoline is shown in Table 10 in gained, cleaning The property of gasoline is shown in Table 11.

Gasoline and aromatization products property in 10 comparative example of table, 5 gained

Project	Middle gasoline	500h product
			Density, g/cm3	0.6680	0.6690
Sulphur, μ g/g	5.8	3.3
			Diene value, gI/100g oil	0	0
Research octane number (RON) RON	93.8	90.9
			Fluorescence method arene content, v%	12.0	25.2
Fluorescence method olefin(e) centent, v%	40.5	10.5
			Fluorescence method Determination of Alkane Content, v%	47.5	64.3
Fluorescence method benzene content, v%	4.3	2.5
			Boiling range, DEG C
Initial boiling point	63.0	63.5
			10%	72.0	73.1
50%	85.0	86.1
			90%	92.0	94.7
The end point of distillation	95.0	102.8
			Catalyst carbon deposition, wt%	-	6.0

11 comparative example of table, 5 FCC gasoline raw material and clean gasoline product property

Project	FCC gasoline raw material	Adsorpting desulfurization device product	500h clean gasoline product
				Density, g/cm3	0.730	0.7290	0.7308
Sulphur, μ g/g	350	7.3	6.0
				Diene value, gI/100g oil	1.67	Nothing	Nothing
Research octane number (RON) RON	93.3	92.5	90.8
				Fluorescence method arene content, v%	23.9	23.7	28.5
Fluorescence method olefin(e) centent, v%	28.5	26.0	16.8
				Fluorescence method Determination of Alkane Content, v%	47.6	50.3	54.7
Fluorescence method benzene content, v%	1.5	1.5	1.3
				Boiling range, DEG C
Initial boiling point	36.0	35.0	35.1
				10%	57.0	57.0	58.0
50%	105.0	104.0	106.0
				90%	180.0	179.0	181.5
The end point of distillation	198.0	197.0	201.3

Comparative example 6

Compared with Example 3, the difference is that using catalyst C-1, and absorption desulfurization product is fractionated into two components That is light petrol and heavy petrol, cut point are 100 DEG C, and property is shown in Table 12.

Light petrol carries out alkene aromatization using the method for embodiment 3, and acquired results are shown in Table 13.It will be light after reaction After gasoline and heavy petrol mixing, the property of resulting clean gasoline product is shown in Table 14.

The property of 12 comparative example of table, 6 gained light petrol, heavy petrol

Project	Adsorpting desulfurization device product	Light petrol	Heavy petrol
				Mass ratio, %	100	50	50
Density, g/cm3	0.7290	0.6650	0.7850
				Sulphur, μ g/g	7.3	5.6	9.0
Diene value, gI/100g oil	0	0	0
				Research octane number (RON) RON	92.5	93.2	91.5
Fluorescence method arene content, v%	23.7	9.4	38.0
				Fluorescence method olefin(e) centent, v%	26.0	38.0	14.5
Fluorescence method Determination of Alkane Content, v%	50.3	52.6	47.5
				Fluorescence method benzene content, v%	1.5	2.2	0.2
Boiling range, DEG C
				Initial boiling point	35.0	33.0	91.0
10%	57.0	40.0	98.0
				50%	104.0	48.0	124.0
90%	179.0	70.0	175.0
				The end point of distillation	197.0	89.0	200.0

13 comparative example of table, 6 gained light petrol and aromatization products property

Project	Light petrol	500h product
			Density, g/cm3	0.6650	0.6710
Sulphur, μ g/g	5.6	4.8
			Diene value, gI/100g oil	0	0
Research octane number (RON) RON	93.2	90.0
			Fluorescence method arene content, v%	9.4	19.5
Fluorescence method olefin(e) centent, v%	38.0	16.8
			Fluorescence method Determination of Alkane Content, v%	52.6	66.7
Fluorescence method benzene content, v%	2.2	1.5
			Boiling range, DEG C
Initial boiling point	33.0	33.5
			10%	40.0	42.0
50%	48.0	50.0
			90%	70.0	73.0
The end point of distillation	89.0	97.0
			Catalyst carbon deposition, wt%		4.0

The property of 14 comparative example of table, 6 gained clean gasoline product

Project	FCC gasoline raw material	Adsorpting desulfurization device product	500h clean gasoline product
				Density, g/cm3	0.7300	0.7290	0.7350
Sulphur, μ g/g	350	7.3	6.8
				Diene value, gI/100g oil	1.67	Nothing	Nothing
Research octane number (RON) RON	93.3	92.5	90.8
				Fluorescence method arene content, v%	23.9	23.7	28.7
Fluorescence method olefin(e) centent, v%	28.5	26.0	15.9
				Fluorescence method Determination of Alkane Content, v%	47.6	50.3	57.1
Fluorescence method benzene content, v%	1.5	1.5	1.1
				Boiling range, DEG C
Initial boiling point	36.0	35.0	35.2
				10%	57.0	57.0	58.5
50%	105.0	104.0	106.5
				90%	180.0	179.0	183.0
The end point of distillation	198.0	197.0	202.0

Claims (19)

1. a kind of production method of ultra-clean gasoline, including the following steps:

(1) the hydrogenated absorption desulfurization of bad gasoline obtains absorption desulfurization product；

(2) the resulting absorption desulfurization product of step (1) enters fractionating column, is divided into light petrol, middle gasoline, heavy petrol；Light petrol Cutting temperature with middle gasoline is 55~65 DEG C；The cutting temperature of middle gasoline and heavy petrol is 95~105 DEG C；

(3) the resulting middle gasoline of step (2) enters aromatisation Olefin decrease reactor, contacts with aromatized catalyst and carries out aromatisation Reaction, obtains aromatisation gasoline；

(4) the resulting light petrol of step (2) and heavy petrol are mixed with the resulting aromatisation gasoline of step (3), obtain ultra-clean vapour Oil product；

Wherein, step (3) the aromatized catalyst composition includes molecular sieve, nickel and the binder of zinc and titanium same order elements, is contained There is thulium or without thulium, wherein the molecular sieve of zinc and titanium same order elements be Zn-Ti-HZSM-5, Its grain size is 20nm~300nm, SiO₂/Al₂O₃Molar ratio is 20 ~ 30.

2. according to the method for claim 1, it is characterised in that: the bad gasoline is fluid catalytic cracking vapour One of oil, catalytic cracking gasoline, coker gasoline, pressure gasoline are a variety of, and property is as follows: initial boiling point is 30~40 DEG C, the end point of distillation is 180~220 DEG C, and sulfur content is 200~1000 μ g/g, and olefin(e) centent is 20.0v%~45.0v%, and alkadienes contains Amount is 0.5~4.0gI/100g.

3. according to the method for claim 1, it is characterised in that: the property of the bad gasoline is as follows: initial boiling point It is 32~38 DEG C, the end point of distillation is 190~205 DEG C, and sulfur content is 300~800 μ g/g, and olefin(e) centent is 25.0v%~40.0v%, Diene content is 1.0~2.5gI/100g.

4. according to the method for claim 1, it is characterised in that: step (1) is described plus hydrogen absorption desulfurization is inhaled using fluidized bed The method of attached desulfurization, used in adsorbent, on the basis of the weight of adsorbent, the content of carrier is 50%~95%, Section VI B The content of race and/or group VIII metal based on the element is 5%~50%, wherein zinc oxide contains on the basis of the weight of carrier Amount is 15%~90%, and the content of aluminium oxide and/or silica is 10%~85%.

5. according to the method for claim 1, it is characterised in that: the operating condition of absorption desulfurization as described in step (1) is such as Under: reaction pressure is 1.0MPa~4.5MPa, and reaction temperature is 350 DEG C~550 DEG C, and reactor inlet feeds hydrogen to oil volume ratio 50:1~200:1.

6. according to the method for claim 1, it is characterised in that: the method that absorption desulfurization uses fluidised bed adsorption desulfurization, and And desulfurizing agent circular regeneration, regeneration condition are as follows: regeneration pressure be 0.5MPa~1.5MPa, gas agent volume ratio 500:1~1000: 1, the constant temperature 3.0~10.0 hours at 400 DEG C~550 DEG C, regeneration gas is air.

7. according to the method for claim 1, it is characterised in that: gained content of sulfur in gasoline ≯ 10 μ g/g after absorption desulfurization, no Containing alkadienes.

8. according to any method of claim 1~7, it is characterised in that: in step (2), the absorption desulfurization product warp Fractionating column is divided into light petrol, middle gasoline, heavy petrol, wherein light petrol sulfur content ≯ 10 μ g/g, olefin(e) centent ≯ 40v%；Middle vapour Oily sulfur content ≯ 10 μ g/g, olefin(e) centent ≯ 60v%；Heavy petrol sulfur content ≯ 10 μ g/g, olefin(e) centent ≯ 15.0v%.

9. according to any method of claim 1~7, it is characterised in that: in step (2), the absorption desulfurization product warp Fractionating column is divided into light petrol, middle gasoline, heavy petrol, wherein by weight, light petrol accounts for the 10% ~ 20% of absorption desulfurization product； Middle gasoline accounts for the 20% ~ 40% of absorption desulfurization product；Heavy petrol accounts for the 40% ~ 70% of absorption desulfurization product.

10. according to the method for claim 1, it is characterised in that: the molecular sieve Zn- of zinc and titanium same order elements in step (3) The grain size of Ti-HZSM-5 is 40nm~200nm.

11. according to method described in claim 1 or 10, it is characterised in that: in the molecular sieve of the zinc and titanium same order elements, zinc Account for 0.5wt%~4.0wt% of the molecular sieve of zinc and titanium same order elements based on the element with titanium, wherein the molar ratio of titanium and zinc is 1:2~1:9.

12. according to the method for claim 11, it is characterised in that: in the molecular sieve of the zinc and titanium same order elements, zinc and Titanium accounts for the 1.0%~3.0% of the molecular sieve of zinc and titanium same order elements based on the element, wherein the molar ratio of titanium and zinc be 1:4~ 1:8.

13. according to the method for claim 11, it is characterised in that: the aromatized catalyst is with the weight of catalyst The molecular sieve content of benchmark, zinc and titanium same order elements be 50.0wt%~90.0wt%, nickel based on the element content be 0.1wt%~ 3.0wt%, content is 0wt%~4.0wt% to rare earth metal based on the element, and surplus is binder.

14. according to the method for claim 13, it is characterised in that: the aromatized catalyst is with the weight of catalyst Benchmark, content is 0.5%~2.0% to nickel based on the element, and content is 1.0%~3.0% to rare earth metal based on the element.

15. according to the method for claim 11, it is characterised in that: the preparation process of the aromatized catalyst is as follows: (1) The molecular sieve of zinc and titanium same order elements is prepared, the molecular sieve of (2) zinc and titanium same order elements and adhesive kneading and compacting, drying and roasting Catalyst carrier is made after burning, (3) dip loading nickel and rare earth metal obtain aromatized catalyst after drying and roasting, In to the resulting catalyst carrier of the molecular sieve or step (2) of the resulting zinc of step (1) and titanium same order elements carry out hydro-thermal process, The condition of hydro-thermal process is as follows: 450~650 DEG C of temperature, handling 3~20 hours.

16. according to the method for claim 1, it is characterised in that: in step (3), aromatization condition is as follows: reaction pressure Power is 1.5MPa~4.5MPa, and reaction temperature is 360 DEG C ~ 460 DEG C, and volume space velocity is 1.0 h when total liquid^-1~5.0h^-1, hydrogen oil body Product is than being 200:1 ~ 1000:1.

17. according to the method for claim 16, it is characterised in that: in step (3), aromatization condition is as follows: reaction Pressure is 2.5MPa~3.5MPa, and reaction temperature is 380 DEG C ~ 420 DEG C, and volume space velocity is 2.0 h when total liquid^-1~4.0h^-1, hydrogen oil Volume ratio is 500 ~ 700:1.

18. according to the method for claim 1, it is characterised in that: the resulting aromatisation gasoline of step (3), sulfur content ≯ 10 μ g/g, olefin(e) centent ≯ 15.0v%.

19. according to the method for claim 1, it is characterised in that: ultra-clean gasoline product obtained by step (4), sulfur content ≯ 10 μ g/g, olefin(e) centent ≯ 15.0v%.