CN103059952A - Method for producing sulfur-free clean gasoline - Google Patents
Method for producing sulfur-free clean gasoline Download PDFInfo
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Abstract
The invention discloses a method for producing sulfur-free clean gasoline. The method adopts a dual-riser, dual-settler and dual-fractionating tower catalytic cracking technology to make heavy oil and gasoline react in different riser reactors respectively. Secondary catalytic cracking crude gasoline from an auxiliary fractionating tower separator undergoes a selective hydrodesulfurization reaction. The condensed oil from main fractionating tower and auxiliary fractionating tower tops undergoes a selective hydrogenation mercaptan removal reaction. The mercaptan removal product of the condensed oil and the hydrodesulfurization product of the secondary catalytic cracking crude gasoline are mixed to form the sulfur-free clean gasoline with a sulfur content of not more than 10 micrograms/g and an octane number loss of not greater than 1.0 unit. While realizing deep desulfurization, the method provided in the invention reduces the octane number loss of the product, and also can greatly reduce the equipment energy consumption.
Description
Technical field
The present invention relates to a kind of method of producing without the sulphur clean gasoline, specifically, the present invention relates to the combined technical method that adopts double lifting leg, two sedimentation pipe and two separation column catalytic cracking process technology and selective hydrodesulfurization.
Background technology
Reduce the quantity discharged that content of sulfur in gasoline can reduce objectionable impurities in the vehicle exhaust significantly, therefore, countries in the world clean gasoline new standard has proposed more and more stricter restriction to sulphur content.The sulphur content of Europe IV class automobile exhaust emission standard (EU2005 standard) regulation gasoline after 2005 ≯ 50 μ g/g, olefin(e) centent ≯ 18v% implements sulphur content less than 10 μ g/g " sweet gasoline (ULSG) " new standard after 2009.The sulphur content of U.S.'s U.S.EPA Tier 2-II standard code U.S.'s clean gasoline after 2006 ≯ 80 μ g/g, olefin(e) centent ≯ 14v%, the sulphur content of U.S.EPA Tier 2-III standard code U.S.'s clean gasoline after 2008 ≯ 30 μ g/g; China in 2005 national gasoline on July 1 is carried out European II emission standard (sulphur content ≯ 500 μ g/g), and European III emission standard (sulphur content ≯ 150 μ g/g) is carried out in the major area; On July 1st, 2007～2008, European III emission standard was carried out in the whole nation, and European IV emission standard (sulphur content ≯ 50 μ g/g) is carried out in the major area; On July 1st, 2010～2011, European IV emission standard was carried out in the whole nation.Before and after 2013, the big city clean gasolines such as Beijing, Shanghai will be carried out Europe V standard, require sulphur content ≯ 10 μ g/g.
At present, catalytic cracking (FCC) is the important sources of gasoline, be more than 80% such as the shared ratio of FCC gasoline in the Chinese refinery gasoline product, and some gasoline olefins and sulphur content that traditional catalytic cracking is produced are all higher, raw material becomes that heavily to become the bad quality of gasoline of its production that makes poorer.Although it is very low to utilize traditional hydrofining the alkene in the gasoline can be dropped to, and has significantly lost octane value.Therefore, domestic each research institution has developed various technology for reducing content of olefin in gasoline at present, Research Institute of Petro-Chemical Engineering of China Petrochemical Industry has developed the GOR catalyst series that reduces the catalytic gasoline olefin(e) centent (" refining of petroleum and chemical industry " 2002 7 phases the 5th～8 page), this catalyzer is by introducing y-type zeolite and the modification ZRP zeolite of oxide surface modification, have very high hydrogen transfer activity and higher isomerization activity, can make the FCC gasoline olefin reduce about 10 percentage points.Refining institute of Luoyang Petrochemical engineering corporation of China Petrochemical Industry has developed the LAP series auxiliary agent (the 23rd～27 page of " oil refining design " 9 phase of calendar year 2001) that reduces catalytic gasoline alkene, this auxiliary agent is selected the shape zeolite as main active component take the poly-metal deoxide modification, have very high gasoline olefin aromatization activity and higher cracking of olefins activity, when adding 5% LAP auxiliary agent in the catalyzer, can make the FCC gasoline olefin reduce about 10 percentage points.
On processing method, Research Institute of Petro-Chemical Engineering of China Petrochemical Industry has developed and has had the MGD technique that reduces the content of olefin in gasoline function (" refining of petroleum and chemical industry " 2002 2 phases the 19th～22 page), MGD technique is divided into two sections to conventional FCC master's riser reactor, hypomere is as the gasoline upgrading reaction zone, epimere is as FCC master's riser reaction zone, utilize large catalyzer and raw material weight ratio and high activated catalyst reformulated gasoline, this technique will be taken into account the reaction conditions of main riser tube heavy oil fluid catalytic cracking, the amount of gasoline upgrading is limited, it is also not ideal to fall the alkene amplitude, can make the FCC gasoline olefin reduce by 10～12 percentage points.China Petroleum Univ. (East-China) adopts two sections series connection riser tube Technologies (CN1302843A), reaction oil gas series connection, catalyzer relay operation, realize improving yield of light oil, improve the purpose of catalytic gasoline quality, but this technical matters flow process is complicated, the handiness of device operation is restricted, simultaneously because two-stage riser reaction oil gas serial operation, the gasoline upgrading reaction influences each other with other reaction, the purpose product selectivity is affected, the content of olefin in gasoline range of decrease is limited, can reduce about 15 percentage points.
CN 1401740A has introduced a kind of catalysis conversion method and device thereof of modifying inferior patrol.Inferior patrol mainly for high olefin content carries out upgrading.It is characterized in that comprising a conventional heavy oil catalytic cracking process, and an inferior patrol catalyzed conversion upgrading process.Heavy oil carries out conventional catalytic cracking reaction at the heavy oil riser reactor, and inferior patrol carries out the catalyzed conversion upgrading at the gasoline rising pipe reactor, and two processes share a catalyst regenerator, use the same catalytic cracking catalyst.The method can make the olefin(e) centent of inferior patrol reduce by 15～50 volume percentage points, and gasoline octane rating (RON) improves 0.2～2 unit; Content of sulfur in gasoline reduces by 5～30%.
In CN 1401740A patent, the reaction oil gas that raw material produces by the heavy oil riser tube, fractionate out rich gas and raw gasline by main fractionating tower, raw gasline enters gasoline rising pipe, in gasoline rising pipe, carry out the secondary reactions such as gasoline olefin cracking, aromizing, hydrogen transference, olefin(e) centent reduction, octane value are improved.Reaction product is isolated rich gas and raw gasline by secondary fractionator overhead separator.Because with gasoline component, then be dissolved with C in the raw gasline in the separator rich gas out
3, C
4Even C
2Component.So rich gas is entered absorption-stable system with raw gasline after pneumatic press boosts, cools off and tells condensed oil rich gas and raw gasline are separated into dry gas (≤C
2), liquefied gas (C
3, C
4) and the qualified stable gasoline of vapour pressure.The gasoline products olefin(e) centent that (referring to " petroleum refining engineering " second edition volume two P59 ~ 61) obtain like this is low, and octane value improves.This technique is the adaptable multieffect catalytic cracking series of processes (Flexible Dual-riser Fluid Catalytic Cracking is called for short FDFCC technique) of Luoyang petroleum chemical engineering company exploitation.
Utilize the main method of FDFCC gasoline production clean gasoline to comprise in the prior art: FDFCC gasoline or the FDFCC gasoline behind alkali-free sweetening are fractionated out lighting end and last running through the hydrogenation preliminary fractionator, last running gasoline is mixed to get the clean gasoline product with lighting end gasoline after carrying out the selective hydrodesulfurization reaction.
Summary of the invention
The purpose of this invention is to provide a kind of method of producing without the sulphur clean gasoline, specifically, just provide the combination process production of a kind of FDFCC technique and selective hydrodesulfurization technology without the method for sulphur clean gasoline, with simple flow, reduce plant energy consumption.
The method of production ultra-clean gasoline provided by the invention comprises the following steps:
(1) adjusts the operation of the catalytic cracking unit of a kind of double lifting leg, two settling vessel and two separation columns, obtain raw gasline, main fractionating tower and the compressed condensed oil that obtains of the isolated rich gas of secondary separation column from the separator of secondary fractionator overhead;
(2) step (1) gained raw gasline and hydrogen contact with Hydrobon catalyst by hydrodesulphurisatioreactors reactors, carry out the selective hydrodesulfurization reaction;
(3) step (1) gained condensed oil and hydrogen contact with the hydrogenating desulfurization alcohol catalyst by the hydro-sweetening reactor, carry out the hydro-sweetening reaction;
(4) step (2) gained reaction effluent and step (3) gained reaction effluent carry out gas-liquid separation, and the gained product liquid obtains the clean gasoline product through air lift.
The catalytic cracking unit of the described double lifting leg of step (1), two settling vessel and two separation columns, be a kind of catalytic unit that adopts the adaptable multieffect catalytic cracking series of processes (being called for short FDFCC technique) of duo-lift tube reactor common regenerator, heavy oil carries out at different riser reactors respectively from the reaction of raw gasline upgrading.
Step (1) is described, and to heat up in a steamer the raw gasline that tower fractionates out from pair be that olefin(e) centent is not more than 12v%, and preferred alkenes content is not more than the low-alkene gasoline of 10v%.
The reactive metal of the described catalyst for selectively hydrodesulfurizing of step (2) generally is selected from one or more among W, Mo, Ni and the Co, can contain conventional auxiliary agent, such as among K, Ca, P, Si, F, B, Ti and the Zr one or more.Active metal component content is counted 8.0wt%～20.0wt% with oxide compound in the described Hydrobon catalyst, is preferably 10.0wt%～18.0wt%; Auxiliary agent content is 1.0wt%～6.0wt%, particularly 1.5wt%～5.0wt%.
H in the hydrogen that the described hydrogenating desulfurization of step (2) is used
2S content ≯ 300 μ L/L, preferred ≯ 50 μ L/L, generally adopt recycle hydrogen de H
2S realizes that the control hydrodesulfurization process is used H in the hydrogen
2The content of S can effectively be controlled the generation of mercaptan in the hydrogenation products.CO in the employed hydrogen
2And/or CO content ≯ 50 μ L/L, preferred ≯ 10 μ L/L, the control hydrodesulfurization process is used CO in the hydrogen
2And/or the content of CO, can effectively control the hydrogenating desulfurization rate of catalyzer.
The described condensed oil of step (1) mainly contains＜C
4Hydrocarbon component and petroleum naphtha component, wherein mercaptan and thioether account for the 80wt%～90wt% of sulfocompound content in the condensed oil.
Wherein the described hydrogenating desulfurization alcohol catalyst of step (3) can be selected existing commodity hydrogenating desulfurization alcohol catalyst, perhaps can be prepared according to the technology general knowledge of this area.The hydrogenating desulfurization alcohol catalyst that preferably has following composition among the present invention, take the weight of catalyzer as benchmark, the content of cupric oxide is 5.0wt%～30.0wt%, be preferably 10wt%～20.0wt%, the content of zinc oxide is 3.0wt%～15.0wt%, be preferably 5.0wt%～10.0wt%, the content of auxiliary agent phosphorus is 0.5wt% ~ 3.0wt%, is preferably 1.0wt% ~ 2.0wt%; Wherein the weight ratio of cupric oxide and zinc oxide is 4:1～1:1, is preferably 2:1～1:1.The BET specific surface area of catalyzer is 200～300m
2/ g is preferably 230～260m
2/ g; Pore volume is 0.3～0.5cm
3/ g is preferably 0.4～0.5cm
3/ g.
This hydrogenating desulfurization alcohol catalyst needs to reduce before use.The reductive condition of catalyzer is: catalyzer is loaded in the reactor, and at reacting system pressure 0.5MPa～4.0MPa, hydrogen volume air speed (being that hydrogen flowing quantity/catalyst volume is than being) 100 h
-1～500 h
-1, reduction temperature is 160 ℃～300 ℃ lower constant temperature reduction 1～10 hour.
The processing condition of the condensed oil hydro-sweetening reaction described in the step (3) are: reaction pressure is 0.5MPa～4.0MPa, and hydrogen to oil volume ratio is 50: 1～500: 1, and temperature of reaction is 100 ℃～200 ℃, and volume space velocity is 0.5～10h during liquid
-1
Can reach ≯ 10 μ g/g through the condensed oil total sulfur content behind the hydro-sweetening in the step (3), octane value does not lose substantially; Total sulfur content in step (2) the selective hydrodesulfurization product also can reach ≯ 10 μ g/g, and loss of octane number ≯ 1.0 unit, the total sulfur content of mix products can reach ≯ 10 μ g/g, loss of octane number ≯ 1.5 unit.
Compare with existing FDFCC gasoline hydrodesulfurizationmethod technology, the inventive method has following outstanding technique effect:
1, contains alkene up to 80% in the inventive method in main fractionating tower and the secondary separation column gained condensed oil, contain simultaneously the mercaptan sulfur of high level, require catalyzer to have higher mercaptan removal activity and selectivity.The hydrogenating desulfurization alcohol catalyst of selecting in the inventive method, its active ingredient is different from Hydrobon catalyst active ingredient commonly used, such as W, Mo, Ni and Co etc., and the lower Cu of hydrogenation activity and Zn component have been adopted, add simultaneously auxiliary agent phosphorus, can stop loss and the establishment carbon deposit of Cu and Zn, thereby have higher hydro-sweetening selectivity and activity.Use this catalyzer that the condensed oil of main fractionating tower and secondary separation column gained is carried out hydro-sweetening, have that mercaptan removal is active high, active characteristics such as low of hydrogenation of olefins, liquid yield is high after the reaction, and loss of octane number seldom, and is long running period with timer.
2, in the prior art, FDFCC reformulated gasoline that device produces need to be through after cooling, can transport to the catalytic gasoline hydrogenation unit by pipeline, and then just can reach the requirement of hydrogenation preliminary fractionator feeding temperature by heat exchange or process furnace, catalytic gasoline need to experience repeatedly lower the temperature, the larger temperature variation such as intensification, unnecessary energy consumption increases greatly to cause the shortening device.And the flow process of the raw gasline direct hot feed of the secondary separation column pre-separation of employing in the inventive method, reduced the operation of cooling, intensification equitemperature fluctuation, can take full advantage of the heat that raw gasline carries in the secondary separation column, thereby the energy consumption of decrease catalytic gasoline hydrogenation unit reduces facility investment and process cost simultaneously.
3, in the inventive method, by adjusting the operation of FDFCC fractionation plant, directly separate and draw raw gasline and condensed oil from this fractionating system, and to directly the lower raw gasline of isolated olefin(e) centent being carried out selective hydrodesulfurization on the original device of FDFCC, and being carried out hydro-sweetening, the isolated condensed oil that is rich in mercaptan sulfur reacts.The present invention can take full advantage of the interior existing product fractionating system of existing FDFCC device and transform, and perhaps adopts at new device, is conducive to reduce plant modification investment and process cost, and the technical scheme mature and reliable is simple.
4, the inventive method is processed the different logistics of its gained respectively for technique and the catalytic gasoline compositing characteristic of FDFCC, when realizing deep desulfuration, has reduced the product loss of octane number.Thereby obtain than the better technique effect of existing technique, but also can the decrease plant energy consumption.
Description of drawings
Fig. 1 is the schematic flow sheet of the inventive method.
Embodiment
The catalytic cracking unit of the double lifting leg described in the inventive method, two settling vessel and two separation columns, be a kind of adaptable multieffect catalytic cracking equipment series that adopts the duo-lift tube reactor common regenerator, heavy oil carries out at different riser reactors respectively from the gasoline reaction.In many pieces of patent documentations, introduction was arranged about adaptable multieffect catalytic cracking series of processes, such as Chinese patent CN92105596.X, CN02139064.9, CN02139065.7, CN02139066.5, CN03126241.4, CN03126217.1, CN03126213.9, CN200520029793.6, CN 01212424.9 and CN 01128770.5.
In the inventive method, described to heat up in a steamer the raw gasline that tower fractionates out from pair be that olefin(e) centent is not more than 12v%, preferably is not more than the low-alkene gasoline of 10v%.The condensed oil that fractionates out from main fractionating tower and secondary separation column mainly contains＜C
4Hydrocarbon component and petroleum naphtha component, wherein mercaptan, thioether account for 80wt%～90wt% in the sulfocompound.Raw gasline can reach ≯ 10 μ g/g loss of octane number ≯ 1.5 unit through the total sulfur content in the selective hydrodesulfurization product.Total sulfur content behind the condensed oil hydro-sweetening can reach ≯ 10 μ g/g, and octane value does not lose substantially.The total sulfur content of mix products can reach ≯ 10 μ g/g, loss of octane number ≯ 1.5 unit.
Hydrogenation process uses the concentration of hydrogen sulfide in the hydrogen generally to pass through recycle hydrogen de H
2S control.Take off H
2The S recycle hydrogen is preferably controlled H
2S content ≯ 50 μ L/L, CO
2And/or CO content preferred ≯ 10 μ L/L.Recycle hydrogen de H
2The S method is generally conventional hydramine method.The flow process of hydramine method technique is generally: from the H that contains of reactive system
2S hydrogen stream and hydramine adsorption solvent (such as ethylene glycol amine) counter current contact in adsorption tower is taken off H
2The hydrogen of S is discharged from cat head, enters reactive system after recycle compressor boosts; The hydramine adsorption solvent of discharging from the adsorption tower bottom enters into solvent regeneration tower through after the manipulation of regeneration, returns and continues in the adsorption tower to use.The above-mentioned H that takes off
2The S method is this area general knowledge, and those skilled in the art can process according to existing method.
Hydrobon catalyst of the present invention can be conventional Hydrobon catalyst, in the periodic table of elements in group vib and/or the group VIII one or more base metals as active ingredient, in amorphous alumina, silicon-containing alumina and the titanium-contained aluminum oxide one or more are as carrier, can also contain auxiliary agent, such as in phosphorus, potassium, the fluorine one or more.
Take the weight of catalyzer as benchmark, in the described Hydrobon catalyst metal take the content of oxide compound as 8.0wt%～20.0wt%, 10.0wt%～18.0wt% particularly; The content of auxiliary agent is 1.0wt%～6.0wt%, particularly 1.5wt%～5.0wt%; Described reactive metal is preferably one or more in cobalt, molybdenum, nickel and the tungsten.Auxiliary agent is preferably one or more in phosphorus, potassium and the fluorine.This catalyzer can adopt the pickling process preparation, can adopt step impregnation method, also can adopt co-impregnation.Steeping fluid can wait the adsorptive capacity dipping, also can be the excessive dipping of steeping fluid.
The present invention adopts the selective hydrogenation desulfurization process condition to be: the hydrogen dividing potential drop is generally 0.5MPa～5.0MPa, and temperature of reaction is generally 230 ℃～330 ℃, and volume space velocity is generally 2.0h during liquid
-1～15.0h
-1, hydrogen to oil volume ratio is generally 200: 1～and 1000: 1; The hydrogen dividing potential drop is preferably 0.8MPa～3.0MPa, and temperature of reaction is preferably 250 ℃～280 ℃, and volume space velocity is preferably 4.0h during liquid
-1～10.0h
-1, hydrogen to oil volume ratio is preferably 200: 1～and 700: 1.
The hydrogenating desulfurization alcohol catalyst of recommendation is take copper and zinc as active ingredient among the present invention, and one or more in amorphous alumina, silicon-containing alumina and the titanium-contained aluminum oxide contain auxiliary agent phosphorus simultaneously as carrier.
The content of cupric oxide is 5.0wt%～30.0wt% in the described hydrogenating desulfurization alcohol catalyst, be preferably 10wt%～20.0wt%, the content of zinc oxide is 3.0wt%～15.0wt%, is preferably 5.0wt%～10.0wt%, the content of auxiliary agent phosphorus is 0.5wt% ~ 3.0wt%, is preferably 1.0wt% ~ 2.0wt%; Wherein cupric oxide and zinc oxide weight ratio are 4: 1～1: 1, are preferably 2: 1～1: 1.The BET specific surface area is 200～300m
2/ g is preferably 230～260m
2/ g; Pore volume is 0.3～0.5cm
3/ g is preferably 0.4～0.5cm
3/ g.
Described hydrogenating desulfurization alcohol catalyst be adopt contain active ingredient and adjuvant component co-impregnated solution once the mode of saturated total immersion load on the support of the catalyst and make, namely with the co-impregnated solution (being the Cu-Zn-P co-impregnated solution) that contains Cu, Zn and P support of the catalyst is carried out single-steeping and makes.
The preparation method of described hydrogenating desulfurization alcohol catalyst is: the aqueous solution of copper-containing compound, zinc compound and P contained compound is made stable co-impregnated solution through 60～100 ℃ of heating, with above-mentioned co-impregnated solution with the mode impregnated carrier of saturated dipping once, then through 80～150 ℃ of dryings 2～8 hours, 300～600 ℃ of roastings made in 5～10 hours.
In the inventive method, the preparation of amorphous alumina, silicon-containing alumina and titanium-contained aluminum oxide carrier that described Hydrobon catalyst, hydrogenating desulfurization alcohol catalyst are required can be that amorphous alumina, silicon-containing alumina or titanium-contained aluminum oxide are added peptizing agent and extrusion aid or silicon sol, extruded moulding after the kneading made through 2～8 hours, 500～650 ℃ roastings of 80～150 ℃ of dryings in 2～5 hours.Described amorphous alumina, silicon-containing alumina and titanium-contained aluminum oxide can be to adopt various existing methods to make, and make such as aluminum chloride-Ammonia Process, Tai-Ace S 150-sodium metaaluminate method, carborization and alkyl aluminum hydrolysis method etc.
Among the present invention, the compound method that contains the co-impregnated solution of Cu-Zn-P can be: copper-containing compound, zinc compound, P contained compound and deionized water are mixed simultaneously, and stirring makes stable co-impregnated solution by 60～100 ℃ of heating.The concentration of each component is in this co-impregnated solution: CuO is/100 milliliters of 8～50 grams, and ZnO is/100 milliliters of 5～30 grams, and P is/100 milliliters of 1.3～2.6 grams.
Above-mentioned copper-containing compound and zinc compound can be selected from one or more in water-soluble chlorination salt, vitriol, acetate, the nitrate, one or both in preferably sulfuric acid salt and the nitrate.Above-mentioned P contained compound can be selected from one or more in phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate, the ammonium phosphate, the preferably phosphoric acid ammonium dihydrogen.
Among the preparation method of catalyzer of the present invention, the condition of dipping: saturated dipping under the room temperature.Saturated dipping refers to that the consumption of dipping solution equals the water-intake rate of support of the catalyst.
Described extrusion aid is one or more that are selected from sesbania powder, citric acid, the acetic acid etc.Peptizing agent is one or more in nitric acid, hydrochloric acid and the deionized water etc.
Hydrogenating desulfurization alcohol catalyst described in the present invention need reduce before reaction, and reduction is adopted the method for capable territory routine and carried out.A kind of concrete catalyst reduction process and condition are: catalyzer is loaded in the reactor, at pure hydrogen or contain under the hydrogen and nitrogen gas, is generally 0.5MPa～4.0MPa at reacting system pressure, hydrogen volume air speed (being hydrogen flowing quantity/catalyst volume ratio) is 100 h
-1～500 h
-1, reduction temperature is generally 160 ℃～300 ℃ lower constant temperature reduction and is generally 1～10 hour.
The hydrogenating desulfurization alcohol catalyst is through after reducing, namely switch the condensed oil raw material to carry out hydro-sweetening reaction, reaction pressure is generally 0.5MPa～4.0MPa, and hydrogen to oil volume ratio is generally 100: 1～and 500: 1, temperature of reaction is generally 160 ℃～300 ℃, and volume space velocity is generally 0.5～10h during liquid
-1
Further specify the inventive method process and effect below in conjunction with drawings and Examples.Logistics and each unit operation carry out in order along the direction of arrow.
Below in conjunction with Fig. 1 the inventive method is elaborated.
The reaction oil gas 1 that comes from the FDFCC device fractionates out rich gas 2 and raw gasline 3 through secondary separation column A, after rich gas 2 compressed machine D compressions obtain condensed oil, be mixed into the hydro-sweetening reactor B with hydrogen 9 and carry out the hydro-sweetening reaction, mercaptan removal product 4 enters separator E.The raw gasline 3 that fractionates out from secondary separation column A enters hydrodesulphurisatioreactors reactors C, and desulfurization product 5 enters separator E, and isolated hydrogen 6 is washed tower F through amine and removed H
2Mix as recycle hydrogen 9 and new hydrogen 10 behind the S.Enter stripping tower G from the isolated blend gasoline 7 of separator, stripping goes out the gasoline products 11 that obtains behind the lighter hydrocarbons 8 and enters state V product Mixer pot H.
Further specify the solution of the present invention and effect below by embodiment, but therefore do not limit the present invention.
Example 1
This example prepares a kind of Hydrobon catalyst and the shared alumina supporter of hydrogenating desulfurization alcohol catalyst.
Take by weighing 1000g and intend thin water-aluminum hydroxide powder (Al
2O
3Contents on dry basis is 78wt%), adding accounts for Al
2O
3The sesbania powder extrusion aid of butt 5wt%, mass concentration are 10% aqueous nitric acid 200mL, mix and roll being mixed into plastic powder, prepare the cylindrical bars that diameter is 1.5mm with banded extruder, drying is 8 hours under 120 ℃, support of the catalyst T-1 is prepared in 500 ℃ of lower roastings 5 hours.
Example 2
This example adopts step impregnation method to prepare a kind of catalyst for selectively hydrodesulfurizing.
Press P on the catalyzer
2O
5Content is 1.5wt%, K
2O content is 2.0wt%, gets quantitative phosphoric acid, saltpetre, adds deionized water, is made into the 120mL steeping fluid, and then, spray is on the support of the catalyst of example 1 preparation of 160g.120 ℃ lower dry 10 hours, P is prepared in 500 ℃ of lower roastings 5 hours
2O
5(1.5wt%)-K
2O-(2.0wt%)/Al
2O
3Catalyst intermediate.
Press MoO on the catalyzer
3Content is that 13.0wt%, CoO content are 4.0wt%, gets quantitative molybdenum oxide, cobaltous dihydroxycarbonate, joins the deionized water of ammonia content 8%, is made into the 60mL steeping fluid, and then, spray is on the above-mentioned catalyst intermediate of 80g.120 ℃ lower dry 8 hours, catalyst for selectively hydrodesulfurizing is prepared in 490 ℃ of lower roastings 6 hours, is numbered ME-1.Nitrogen absorption under low temperature BET method is measured specific surface area of catalyst, pore volume character sees Table 1.
Example 3
This example adopts the standby a kind of hydrogenating desulfurization alcohol catalyst of total immersion legal system.
Cupric nitrate 60 grams, zinc nitrate 45 grams, Secondary ammonium phosphate 4.3 grams and 60 ml deionized water are mixed, in 60 ℃ of dissolvings 1 hour, obtain 65 milliliters of Cu-Zn-P co-impregnated solutions, carrier T-1 after the 100 gram roastings floods under room temperature with above-mentioned steeping fluid, through 120 ℃ of dryings 8 hours, 500 ℃ of roastings 8 hours make catalyzer ME-2.
ME-2 catalyzer physical property is listed in table 1.
The physical property of table 1 example 2 and example 3 catalyzer
| Project | Example 2 | Example 3 |
| The catalyzer numbering | ME-1 | ME-2 |
| MoO 3，wt% | 13.0 | — |
| CoO，wt% | 4.0 | — |
| K 2O，wt% | 2.0 | — |
| P 2O 5，wt% | 1.5 | 1.0 |
| CuO，wt% | — | 20.0 |
| ZnO，wt% | — | 12.2 |
| Specific surface area, m 2/g | 220 | 215 |
| Pore volume, cm 3/g | 0.40 | 0.36 |
Example 4
This example provides a kind of FDFCC gasoline desulfur effect.
(1) main fractionating tower and the secondary separation column from the FDFCC device obtains condensed oil and raw gasline.Stable FDFCC gasoline property after condensed oil, raw gasline and the mediation sees Table 2.
The condensed oil that fractionates out from FDFCC in table 2 example 4, raw gasline character
| Project | Condensed oil | Raw gasline | FDFCC gasoline |
| The cutting ratio, wt% | 20 | 80 | 100 |
| Density, g/mL | 0.6172 | 0.7682 | 0.7380 |
| Sulphur content, μ g/g | 385 | 295 | 313 |
| Mercaptans content, μ g/g | 130 | 10.0 | 34.0 |
| Research octane number (RON) | 92.9 | 95.9 | 95.3 |
| Stable hydrocarbon, v% | 20.0 | 48.9 | 46.0 |
| Olefin(e) centent, v% | 80.0 | 6.0 | 20.7 |
| Aromatic hydrocarbons, v% | 0 | 45.0 | 33.2 |
| Boiling range, ℃ | 40 ℃ (doing) | 37～198 | 36～195 |
(2) condensed oil hydro-sweetening reaction
Condensed oil carries out the hydro-sweetening reaction in a kind of hydro-sweetening reactor B.
30 milliliters of the ME-2 catalyzer that the example 3 of packing in the reactor B prepares.Lead to first hydrogen (hydrogen volume air speed 100h
-1), hydrogen pressure is 1.0MPa, rises to 260 ℃ by room temperature in 6 hours, then constant temperature reductase 12 hour.
Be cooled to 150 ℃ after the reduction, begin into condensed oil, the condensed oil volume space velocity is 2.0h
-1, the hydrogen dividing potential drop is 1.0MPa, hydrogen to oil volume ratio is 100: 1.After oil-feed is stablized 100 hours, sampling analysis.Table 3 has been listed the main character of raw material and product.
(3) raw gasline hydrogenating desulfurization
Evaluation test is that the device at fixed-bed reactor carries out, the ME-1 catalyzer of 50 milliliters of examples, 2 preparations of packing in the reactor.
Airtight qualified after, at first carry out catalyst vulcanization.Vulcanized oil is straight-run spirit, and vulcanizing agent is CS
2, CS
2Concentration is 1.0v%; Sulfide stress is 1.6MPa, and the circulation hydrogen to oil volume ratio is 300: 1, and the vulcanized oil volume space velocity is 2.0h
-1, be 230 ℃ of lower constant temperature 8 hours in temperature, 300 ℃ of lower constant temperature 8 hours.
After sulfuration finished, the switching raw gasline was stock oil, and the hydrogen dividing potential drop is 1.6MPa, uses not sulfide hydrogen and CO/CO
2Fresh hydrogen, volume space velocity is 3.0h
-1, in 2 hours, be cooled to 260 ℃.Steady running sampling analysis in 100 hours.Table 4 has been listed the character of raw material and desulfurization product.
The character of condensed oil raw material and product in table 3 example 4
| Project | Condensed oil | The hydro-sweetening product |
| Density, g/mL | 0.6172 | 0.6172 |
| Sulphur content, μ g/g | 385 | 8 |
| Mercaptans content, μ g/g | 130 | 5 |
| Research octane number (RON) | 92.9 | 92.8 |
| Stable hydrocarbon, v% | 20.0 | 20.3 |
| Olefin(e) centent, v% | 80.0 | 79.7 |
The character of table 4 example 4 raw gasline raw materials and product
| Project | Raw gasline | The hydrogenating desulfurization product |
| Density, g/mL | 0.7682 | 0.7680 |
| Sulphur content, μ g/g | 295 | 7.0 |
| Mercaptans content, μ g/g | 10.0 | 6.0 |
| Research octane number (RON) | 95.9 | 95.2 |
| Stable hydrocarbon, v% | 48.9 | 50.7 |
| Olefin(e) centent, v% | 6.0 | 4.0 |
| Aromatic hydrocarbons, v% | 45.0 | 45.3 |
(4) raw gasline hydrogenating desulfurization product mixes with condensed oil mercaptan removal product
Raw gasline hydrogenating desulfurization product mixes according to the cutting ratio with condensed oil mercaptan removal product.Table 5 has been listed the stable gasoline and the character of processing rear clean gasoline product before processing.
FDFCC gasoline before table 5 example 4 is processed and the character of processing rear clean gasoline product
| Project | FDFCC gasoline | Blended gasoline |
| Density, g/mL | 0.7380 | 0.7380 |
| Sulphur content, μ g/g | 313 | 7.2 |
| Mercaptans content, μ g/g | 34.0 | 5.8 |
| Research octane number (RON) | 95.3 | 94.4 |
| Stable hydrocarbon, v% | 46.0 | 51.9 |
| Olefin(e) centent, v% | 20.7 | 18.4 |
| Aromatic hydrocarbons, v% | 33.2 | 29.5 |
As can be seen from Table 5: method of the present invention can be reduced to 7.2 μ g/g by 313 μ g/g with the sulphur content of FDFCC gasoline, mercaptan sulfur content is reduced to 5.8 μ g/g by 34.0 μ g/g, olefin(e) centent is reduced to 18.4v% by 20.7v%, 0.9 unit of research octane number (RON) loss can be processed as inferior patrol sulphur content ≯ 10 μ g/g high-quality cleaning product.
Comparative Examples 1
Adopt prior art that identical FDFCC gasoline is carried out hydrogenating desulfurization.
(1), stock oil mercaptan removal
The stock oil mercaptan-eliminating catalyst adopts commodity AFS-12 catalyzer (buying from University of Petroleum), at pressure 0.5MPa, 35 ℃～45 ℃ of temperature, volume space velocity 2.0h
-1, carry out deodorization under gas-oil ratio (air/stock oil) the 1:1 condition.
(2), stock oil lighting end, last running cutting
Take 50 ℃ as the cut point temperature will be in harmonious proportion after FCC gasoline be separated into＜50 ℃ of lighting ends and 50 ℃ of last running, table 6 listed FDFCC gasoline,＜50 ℃ of lighting ends and the character of 50 ℃ of last running.
(3),〉50 ℃ of heavy fractioning hydrogenation desulfurization
Evaluation test is that the device at fixed-bed reactor carries out, the ME-1 catalyzer of 50mL example 2 preparations of packing in the reactor.
Airtight qualified after, at first carry out catalyst vulcanization.Vulcanized oil is straight-run spirit, and vulcanizing agent is CS
2, CS
2Concentration is 1.0v%; Sulfide stress is 1.6MPa, and the circulation hydrogen to oil volume ratio is 300: 1, and the vulcanized oil volume space velocity is 2.0h
-1, be 230 ℃ of lower constant temperature 8 hours in temperature, 300 ℃ of lower constant temperature 8 hours.
After sulfuration finishes, change 50 ℃ of double distilleds are divided into stock oil, the hydrogen dividing potential drop is 1.3MPa, uses not hydrogen sulfide containing fresh hydrogen, volume space velocity is 3.0h
-1, in 2 hours, be cooled to 260 ℃.Steady running sampling analysis in 100 hours.
The character of FDFCC gasoline, lighting end and last running in table 6 Comparative Examples 1
| Project | FDFCC gasoline | Sweet gasoline | ＜50 ℃ of lighting ends | 50 ℃ of last running |
| The cutting ratio, wt% | 100 | 100 | 25.8 | 74.2 |
| Density, g/mL | 0.7380 | 0.7380 | 0.6456 | 0.7550 |
| Sulphur content, μ g/g | 313 | 308 | 9.5 | 425 |
| Mercaptans content, μ g/g | 34.0 | 9.8 | 8.5 | 10.3 |
| Olefin(e) centent, v% | 20.7 | 20.7 | 35.0 | 16.0 |
| Research octane number (RON), RON | 95.3 | 95.3 | 97.2 | 94.6 |
| Boiling range, ℃ | 36～195 | 36～195 | 30～52 | 48～195 |
(4),〉50 ℃ of heavy fractioning hydrogenation desulfurization mix with＜50 ℃ of lighting ends
50 ℃ of heavy fractioning hydrogenation desulphurization reaction things go out with prefractionation＜50 ℃ of lighting ends mix according to the cutting ratio.Table 7 has been listed raw material FCC gasoline and the character of processing rear clean gasoline product.
The character of table 7 Comparative Examples 1 oil product
| Project | FCC gasoline | 50 ℃ of heavy fractioning hydrogenation products | Mixing oil |
| Density, g/mL | 0.7380 | 0.7551 | 0.7433 |
| Sulphur content, μ g/g | 313 | 10.5 | 9.8 |
| Mercaptan sulfur content, μ g/g | 34.0 | 8.0 | 8.1 |
| Olefin(e) centent, v% | 20.7 | 9.3 | 15.8 |
| Research octane number (RON) (RON) | 95.3 | 92.1 | 93.4 |
| C 5 +Yield, wt% | ? | 99.8 | 99.9 |
As can be seen from Table 7: adopt prior art to the FDFCC gasoline hydrodesulfurizationmethod, the sulphur content of FDFCC gasoline can be reduced to 9.8 μ g/g by 313 μ g/g, mercaptan sulfur content is reduced to 8.1 μ g/g by 34.0 μ g/g, olefin(e) centent is reduced to 15.8v% by 20.7v%, 1.9 units of research octane number (RON) loss.
Can find out that under identical processing condition, compare with comparative example 1, the desulfurization degree of the inventive method is higher, loss of octane number is less.
Example 5
(1) main fractionating tower and the secondary separation column from the FDFCC device obtains condensed oil and raw gasline.Stable FDFCC gasoline property after condensed oil, raw gasline and the mediation sees Table 8.
The condensed oil that fractionates out from FDFCC in table 8 example 5, raw gasline character
| Project | Condensed oil | Raw gasline | FDFCC gasoline |
| The cutting ratio, wt% | 20 | 80 | 100 |
| Density, g/mL | 0.6569 | 0.7644 | 0.7429 |
| Sulphur content, μ g/g | 298 | 448 | 418 |
| Mercaptans content, μ g/g | 129 | 4 | 29 |
| Research octane number (RON) | 94.1 | 95.6 | 95.3 |
| Stable hydrocarbon, v% | 20.0 | 49.2 | 43.5 |
| Olefin(e) centent, v% | 80.0 | 6.9 | 21.5 |
| Aromatic hydrocarbons, v% | 0 | 43.9 | 35.0 |
| Boiling range, ℃ | 30(does) | 34～200 | 36～195 |
(2) condensed oil hydro-sweetening reaction
Condensed oil carries out the hydro-sweetening reaction in a kind of hydro-sweetening reactor B.
30 milliliters of the ME-2 catalyzer that the example 3 of packing in the reactor B prepares.Lead to first hydrogen (hydrogen volume air speed 100h
-1), hydrogen pressure is 1.0MPa, rises to 260 ℃ by room temperature in 6 hours, then constant temperature reductase 12 hour.
Be cooled to 150 ℃ after the reduction, switch and advance condensed oil, volume space velocity is 2.0h
-1, the hydrogen dividing potential drop is 1.0MPa, hydrogen to oil volume ratio is 100: 1.After oil-feed is stablized 100 hours, sampling analysis.Table 9 has been listed the main character of raw material and product.
(3) raw gasline hydrogenating desulfurization
Evaluation test is that the device at fixed-bed reactor carries out, the ME-1 catalyzer of 50mL example 2 preparations of packing in the reactor.
The sulfuration of catalyzer is with embodiment 4.After sulfuration finished, the switching raw gasline was stock oil, and the hydrogen dividing potential drop is 1.6MPa, uses not sulfide hydrogen and CO/CO
2Fresh hydrogen, volume space velocity is 3.0h
-1, in 2 hours, be cooled to 270 ℃.Steady running sampling analysis in 100 hours.Table 10 has been listed the character of raw material and desulfurization product.
The character of condensed oil raw material and product in table 9 example 5
| Project | Condensed oil | The hydro-sweetening product |
| Density, g/mL | 0.6569 | 0.6569 |
| Sulphur content, μ g/g | 298 | 5 |
| Mercaptans content, μ g/g | 129 | 4 |
| Research octane number (RON) | 94.1 | 94.0 |
| Stable hydrocarbon, v% | 20.0 | 21.0 |
| Olefin(e) centent, v% | 80.0 | 79.0 |
(4) raw gasline hydrogenating desulfurization product mixes according to the cutting ratio with condensed oil mercaptan removal product with condensed oil mercaptan removal product mixing raw gasline hydrogenating desulfurization product.Table 11 has been listed the stable gasoline and the character of processing rear clean gasoline product before processing.
The character of table 10 example 5 raw gasline raw materials and product
| Project | Raw gasline | The hydrogenating desulfurization product |
| Density, g/mL | 0.7644 | 0.7644 |
| Sulphur content, μ g/g | 448 | 9.0 |
| Mercaptans content, μ g/g | 4.0 | 2.0 |
| Research octane number (RON) (RON) | 95.6 | 94.6 |
| Stable hydrocarbon, v% | 49.2 | 53.3 |
| Olefin(e) centent, v% | 6.9 | 3.4 |
| Aromatic hydrocarbons, v% | 43.9 | 43.3 |
Stable gasoline before table 11 example 5 is processed and the character of processing rear clean gasoline product
| Project | FDFCC gasoline | Blended gasoline |
| Density, g/mL | 0.7429 | 0.7429 |
| Sulphur content, μ g/g | 418 | 8.2 |
| Mercaptans content, μ g/g | 29 | 2.4 |
| Research octane number (RON) (RON) | 95.3 | 94.6 |
| Stable hydrocarbon, v% | 43.5 | 49.3 |
| Olefin(e) centent, v% | 21.5 | 20.0 |
| Aromatic hydrocarbons, v% | 35.0 | 31.7 |
| Boiling range, ℃ | 36～195 | 36～195 |
As can be seen from Table 11: method of the present invention can be reduced to 8.2 μ g/g by 418 μ g/g with the sulphur content of FDFCC gasoline, mercaptan sulfur content is reduced to 2.4 μ g/g by 29.0 μ g/g, olefin(e) centent is reduced to 20.0v% by 21.5v%, 0.7 unit of research octane number (RON) loss can be processed as inferior patrol sulphur content ≯ 10 μ g/g high-quality clean gasoline products.
Simultaneously, among embodiment 4 and the embodiment 5, owing to directly to the isolated hot raw gasline hydrotreatment of the secondary separation column of FDFCC, reduced the operation that intensification, cooling equitemperature fluctuate widely, the plant energy consumption of the inventive method is also lower.
Claims (11)
1. a method of producing without the sulphur clean gasoline comprises the following steps:
(1) adjusts the operation of the catalytic cracking unit of a kind of double lifting leg, two settling vessel and two separation columns, obtain raw gasline, main fractionating tower and the compressed condensed oil that obtains of the isolated rich gas of secondary separation column from the separator of secondary fractionator overhead;
(2) step (1) gained raw gasline and hydrogen contact with Hydrobon catalyst by hydrodesulphurisatioreactors reactors, carry out the selective hydrodesulfurization reaction;
(3) step (1) gained condensed oil and hydrogen contact with the hydrogenating desulfurization alcohol catalyst by the hydro-sweetening reactor, carry out the hydro-sweetening reaction;
(4) step (2) gained reaction effluent and step (3) gained reaction effluent carry out gas-liquid separation, and the gained product liquid obtains the clean gasoline product through air lift.
2. in accordance with the method for claim 1, it is characterized in that, the character of described hydrogenating desulfurization alcohol catalyst is, take the weight of catalyzer as benchmark, the content of cupric oxide is 5.0wt%～30.0wt%, and the content of zinc oxide is 3.0wt%～15.0wt%, and the content of auxiliary agent phosphorus is 0.5wt% ~ 3.0wt%, wherein the weight ratio of cupric oxide and zinc oxide is 4:1～1:1, and the BET specific surface area of catalyzer is 200～300m
2/ g, pore volume are 0.3～0.5cm
3/ g.
3. in accordance with the method for claim 2, it is characterized in that, take the weight of catalyzer as benchmark, the content of cupric oxide is 10wt%～20.0wt%, the content of zinc oxide is 5.0wt%～10.0wt%, and the content of auxiliary agent phosphorus is 1.0wt% ~ 2.0wt%, and the weight ratio of cupric oxide and zinc oxide is 2:1～1:1; The BET specific surface area of catalyzer is 230～260m
2/ g, pore volume are 0.4～0.5cm
3/ g.
4. in accordance with the method for claim 1, it is characterized in that, the processing condition of the described condensed oil hydro-sweetening reaction of step (3) are: reaction pressure is 0.5MPa～4.0MPa, hydrogen to oil volume ratio is 50: 1～500: 1, temperature of reaction is 100 ℃～200 ℃, and volume space velocity is 0.5～10h during liquid
-1
5. according to claim 2 or 3 described methods, it is characterized in that described hydrogenating desulfurization alcohol catalyst needs to reduce before use, reductive condition is: reaction pressure 0.5MPa～4.0MPa, hydrogen volume air speed 100 h
-1～500 h
-1, reduction temperature is 160 ℃～300 ℃, constant temperature reduction 1～10 hour.
6. in accordance with the method for claim 1, it is characterized in that, in amorphous alumina, silicon-containing alumina and the titanium-contained aluminum oxide one or more of described Hydrobon catalyst are as carrier, contain simultaneously auxiliary agent phosphorus, reactive metal is selected from one or more among W, Mo, Ni and the Co, active metal component content is counted 8.0wt%～20.0wt% with oxide compound, and auxiliary agent is one or more among K, Ca, P, Si, F, B, Ti and the Zr, and auxiliary agent content is 1.0wt%～6.0wt%.
7. in accordance with the method for claim 1, it is characterized in that the processing condition of the described selective hydrodesulfurization of step (2) are: the hydrogen dividing potential drop is 0.5MPa～5.0MPa, temperature of reaction is 230 ℃～330 ℃, and volume space velocity is 2.0h during liquid
-1～15.0h
-1, hydrogen to oil volume ratio is 200: 1～1000: 1.
8. according to claim 2 or 3 described methods, it is characterized in that, the preparation method of described hydrogenating desulfurization alcohol catalyst is: the aqueous solution of copper-containing compound and P contained compound is made stable co-impregnated solution through 60～100 ℃ of heating, with this co-impregnated solution with the mode impregnated carrier of saturated dipping once, then through 80～150 ℃ of dryings 2～8 hours, 300～600 ℃ of roastings made catalyzer in 5～10 hours.
9. in accordance with the method for claim 8, it is characterized in that, the compound method of described co-impregnated solution is: copper-containing compound, zinc compound and P contained compound and deionized water are mixed simultaneously, stir and make stable co-impregnated solution by 60～100 ℃ of heating, the concentration of each component is in this co-impregnated solution: CuO is/100 milliliters of 8～50 grams, ZnO is/100 milliliters of 5 ~ 30 grams, and P is/100 milliliters of 1.3～2.6 grams.
10. in accordance with the method for claim 1, it is characterized in that H in the hydrogen that the described hydrodesulfurization process of step (2) is used
2S content ≯ 300 μ L/L, CO
2And/or CO content ≯ 50 μ L/L.
11. in accordance with the method for claim 1, it is characterized in that the described raw gasline that fractionates out from secondary separation column of step (1) is the low-alkene gasoline that olefin(e) centent is not more than 12v%.
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|---|---|---|---|---|
| CN109207196A (en) * | 2018-10-25 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of FDFCC catalytic cracking modifies the processing flow of secondary raw gasoline |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5906730A (en) * | 1995-07-26 | 1999-05-25 | Mitsubishi Oil Co., Ltd. | Process for desulfurizing catalytically cracked gasoline |
| CN1401740A (en) * | 2002-09-16 | 2003-03-12 | 中国石油化工集团公司 | Catalytic conversion method and apparatus for upgrading poor gasoline |
| CN1465668A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline |
-
2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5906730A (en) * | 1995-07-26 | 1999-05-25 | Mitsubishi Oil Co., Ltd. | Process for desulfurizing catalytically cracked gasoline |
| CN1465668A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline |
| CN1401740A (en) * | 2002-09-16 | 2003-03-12 | 中国石油化工集团公司 | Catalytic conversion method and apparatus for upgrading poor gasoline |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109207196A (en) * | 2018-10-25 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of FDFCC catalytic cracking modifies the processing flow of secondary raw gasoline |
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