CN103031149A - Method for simultaneously removing sulfides in gasoline and liquefied gas through double reactors - Google Patents
Method for simultaneously removing sulfides in gasoline and liquefied gas through double reactors Download PDFInfo
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Abstract
A method for simultaneously removing sulfides in gasoline and a liquefied gas through double reactors is characterized in that a gasoline raw material and hydrogen enter a first adsorption reactor from the bottom, flow from bottom to top, and contact with a desulphurization adsorbent in the first adsorption reactor to adsorb and remove sulfides in gasoline; the reacted oil gas and the desulphurization adsorbent are separated at the upper portion of the first adsorption reactor, the separated desulphurization adsorbent undergoes pressure transition and is introduced into a second adsorption reactor, and a sulfur-containing liquefied gas enters the second adsorption reactor from the bottom and contacts with the low-activity desulphurization adsorbent in order to adsorb and remove sulfides in the liquefied gas; and the high-sulfur-content adsorbent to be regenerated reacted with the liquefied gas is separated from the oil gas, is leaded out of the second adsorption reactor, enters a fluidized bed regenerator, and is scorched and regenerated, and the regenerated adsorbent is reduced and is returned to the first adsorption reactor for cycle use. The method provided by the invention maximally utilizes the activity of the desulphurization adsorbent to deeply adsorb and remove the sulfides in the gasoline, and utilizes the residual desulphurization capability of the adsorbent to adsorb and remove the sulfides in the liquefied gas.
Description
Technical field
The present invention relates to remove the method for sulphur compound in the hydrocarbon fraction in a kind of situation that has hydrogen, more particularly, relate to the method that removes simultaneously sulphur compound in gasoline and the liquefied gas under a kind of condition that has hydrogen.
Background technology
In recent years, along with increasing of motor vehicle, vehicle exhaust has become the main source of atmospheric pollution, acid rain also so more frequent, buildings, soil and human living environment have been arrived in serious harm.Therefore, countries in the world have proposed higher oil quality standard one after another, further limit the sulphur content in the oil product.Mainly contain mercaptan, thioether, thiophene, thionaphthene sulfides in the light hydrocarbon oil, the method for traditional hydrogenating desulfurization is saturated with the hydrocarbon fraction in the gasoline when removing sulfide, causes the gasoline octane rating loss.
Disclosing among US7427581, US6869522 and the US6274533 under hydro condition, used sorbent material to remove for example method of the sulfide in the gasoline of light hydrocarbon oil, can the production sulphur content be the oil fuel below 30 microgram/grams.Sorbent used take zinc oxide, silica and alumina mixture as carrier, wherein zinc oxide accounts for that 10～90 heavy %, silica account for 5～85 heavy %, aluminum oxide accounts for 5～30 heavy %.Active ingredient is the as-reduced metal of load, is made of one or more that are carried in cobalt on the carrier, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin, vanadium etc.Carrier and metal component be through mixing, obtain sorbent material after the moulding, drying, roasting, is 0.5～50h at 0.1～10.3MPa, 37.7～537.7 ℃, weight hourly space velocity
-1Under the condition of facing hydrogen, the sulphur in the oil product is captured on the sorbent material, the hydrocarbon that generates after the sulfide cracking turns back in the reaction mass, contains sulfur absorbent and recycles by cyclic regeneration.The method can be removed to the sulphur in the catalytically cracked gasoline 10 micrograms/below the gram in practical application in industry, and the uprising index loss of product is no more than 0.6 unit.
The a large amount of liquefied gas of the rich product of refinery no matter liquefied gas is the sale that directly acts as a fuel, or all will remove a large amount of sulphur that wherein contain in advance as industrial chemicals.Sulfide in the liquefied gas is difficult to remove fully by traditional hydramine wet desulphurization mainly take hydrogen sulfide, mercaptan and thioether as organic sulfides such as main, the mercaptan that especially wherein contains, affects it as the application of industrial chemicals in downstream process.
CN 1775924A discloses a kind of method of liquefied gas desulfurizing and refining, may further comprise the steps: liquefied gas that will be to be made with extra care and iron content sweetening agent counter current contact in thionizer is carried out desulphurization reaction; Liquefied gas after the desulfurization enters separating tank and separates the smart filter of laggard sand tower; The rear sweetening agent of reaction advances the oxidation regeneration tower and carries out oxidation regeneration, the sweetening agent recycling use of activity recovery after the regeneration.The iron content sweetening agent is to the inorganic sulphide in the liquefied gas, better such as removal effects such as hydrogen sulfide, but, sweetening effectiveness to organic sulfide such as mercaptan etc. in the liquefied gas is not good, also need the further air sweetening of the liquefied gas after the desulfurization, enter the further air sweetening of air sweetening tower after adopting existing cobalt sulfonated phthalocyanine-alkali lye and air mixed.
Compare with the thiophene-type sulfide in the light hydrocarbon oil, the sulfide in the liquefied gas is take hydrogen sulfide, dithiocarbonic anhydride, mercaptan etc. as main, and these sulfide ratios are easier to remove.
Summary of the invention
A kind of double-reactor removes the method for hydrocarbon ils and liquefied gas medium sulphide content simultaneously, comprising: gasoline stocks and hydrogen enter the first adsorptive reactor from the bottom, flow from bottom to top, remove sulfide in the gasoline with desulfuration adsorbent Contact-sorption in the reactor; On the first adsorptive reactor top, reacted oil gas separates with more SA desulfuration adsorbent, oil gas after the separation is through further separating the gasoline products after obtaining desulfurization, isolated desulfuration adsorbent is behind transfer pressure, enter in the second adsorptive reactor, the sulfur-bearing liquefied gas enters the second adsorptive reactor from the bottom, contacts the sulfide that removes in the liquefied gas with more SA desulfuration adsorbent; After carrying sulfur content sorbent material to be generated and liquefied gas separates, reacted height draws reactor, enter coke burning regeneration in the fluid bed regenerator, sorbent material after the regeneration turns back in the first adsorptive reactor after reduction and recycles, isolated oil gas further separates and obtains liquefied gas product after the desulfurization in the second adsorptive reactor, and hydrogen uses with receiving.
The beneficial effect of method provided by the invention is:
Method provided by the invention adopts the sulfide in the desulfuration adsorbent adsorbing and removing gasoline, for reaching the purpose of deep desulfurization of gasoline, the sulfur content that carries of the reacted sorbent material of gasoline desulfur is controlled at theoretical below 60% of sulfur content that carries, and utilizes simultaneously the sulfide in the remaining sweetening power adsorbing and removing of the sorbent material liquefied gas.Under the prerequisite that does not affect the gasoline desulfur effect, maximizedly utilized the desulphurizing activated of sorbent material, effectively removed the sulfide in the liquefied gas, so that the requirement that the liquefied gas sulphur content meets subsequent treatment process of producing.
Description of drawings
Accompanying drawing is the method flow synoptic diagram that a kind of double-reactor provided by the invention removes gasoline and liquefied gas medium sulphide content simultaneously.
Wherein: 2-the first adsorptive reactor, 5-sorbent material pressure conversion tank, 8-the second adsorptive reactor, 11-reactor receptor, 13-locking hopper, 16-regenerator feed tank, the 19-fluid bed regenerator, 22-revivifier receptor, 25-sorbent material reducer, 1,3,4,6,7,9,10,12,14,15,17,18,20,21,23,24, the 26-pipeline.
Embodiment
The method of simultaneously desulfurization of hydrocarbon ils provided by the invention and liquefied gas is such implementation:
Desulfuration adsorbent is introduced the first adsorptive reactor, and the gasoline stocks and the hydrogen that are preheating to 100～500 ℃ enter the first adsorptive reactor from the bottom, flows from bottom to top, removes wherein sulfide with desulfuration adsorbent Contact-sorption in the reactor; The service temperature of the first adsorptive reactor is 200～550 ℃, preferred 300～500 ℃, and pressure is 0.5～5MPa, preferred 1.0～3.5MPa, and the weight hourly space velocity of gasoline stocks is 0.1～100h
-1, preferred 1～10h
-1
After gasoline desulfur reaction is finished, the desulfuration adsorbent load partial vulcanization thing, desulfuration adsorbent carry sulfur content be controlled at sorbent material theoretical carry sulfur content 15～60%, preferred 25～50%, adsorbent activity reduces.The oil gas of reaction after finishing carries out finish with desulfuration adsorbent in the first adsorptive reactor separates, and the oil gas after the desulfurization is sent to follow-up stable system and processes, and obtains the gasoline products after the desulfurization, the recover hydrogen recycle; Isolated more SA desulfuration adsorbent is introduced in the sorbent material pressure conversion tank, behind excess pressure conversion and stripping, be incorporated into again in the second adsorptive reactor, sulfur-bearing liquefied gas and hydrogen are introduced the second adsorptive reactor by the bottom, contact the sulfide that removes in the liquefied gas with low activity desulfuration adsorbent in the reactor; The operational condition of the second adsorptive reactor is: temperature is 100～550 ℃, preferred 200～500 ℃, and pressure is 0.1～5MPa, preferred 0.5～3.5MPa, and the weight hourly space velocity of liquefied gas is 0.1～100h
-1, preferred 1～20h
-1
After the desulfuration of liquefied gas reaction was finished, the sulfur content that carries on the desulfuration adsorbent was controlled at theoretical 25～95%, preferred 30～80% of the sulfur content that carries of sorbent material.Oil gas separates on the second adsorptive reactor top with sorbent material to be generated, and isolated oil gas is drawn the second adsorptive reactor by top, reclaims liquefied gas and the hydrogen obtain removing sulfide, and hydrogen can recycle; The sorbent material to be generated that isolated height carries sulfur content enters in the fluid bed regenerator and contacts coke burning regeneration with oxygen, and the sorbent material after the regeneration turns back in the fluidized-bed reactor after reduction and recycles.
In the method provided by the invention, described gasoline stocks is that boiling range is 35～250 ℃ hydrocarbon fraction, wherein, the sulphur content in the gasoline stocks greater than 50 μ g/g, be preferably greater than 100 μ g/g.The mixture of one or more in optional catalytic cracking gasoline, coker gasoline and the straight-run spirit.
Described liquefied gas refers to that wherein, the sulphur content in the liquefied gas is greater than 10 μ g/g take the C3-C4 lighter hydrocarbons as main hydrocarbon-fraction.Comprise catalytic cracking liquefied gas, coking liquefied gas etc.
In the method provided by the invention, the mol ratio of hydrogen and hydrocarbon oil crude material is 0.01～10 in described the first adsorptive reactor and the second adsorptive reactor: 1, preferred 0.1～3: 1.In the adsorption desulfurize reaction process, sulfide in hydrocarbon oil crude material, the liquefied gas at first is adsorbed on the desulfuration adsorbent, then facing under the condition of hydrogen, the sulfide of absorption changes into hydrogen sulfide, the hydrogen sulfide that generates and zinc oxide reaction generate zinc sulphide, sulphur in the hydrocarbon oil crude material is fixed on the sorbent material, to reach the purpose that the hydrocarbon oil crude material medium sulphide content is removed.
The hydrogen of introducing adsorptive reactor refers to the hydrogen-containing gas of various hydrogen richnesss, can be the hydrogen supply agent that can produce hydrogen also, and the present invention is not limited in this respect.Wherein, hydrogen volume content is more preferably greater than 30% in the described hydrogen-containing gas, can be selected from catalytic cracking process (FCC) and produce dry gas dry gas, coking dry gas, thermally splitting dry gas etc., described hydrogen supply agent is selected from one or more the mixture in naphthane, perhydronaphthalene, the indane.
In the method provided by the invention, described gasoline stocks and hydrogen are introduced the reactor from the first adsorptive reactor bottom, can introduce separately reactor, also can mix in the rear introducing reactor, preferably the mixture of gasoline stocks and hydrogen be introduced in the first adsorptive reactor.In the first adsorptive reactor bottom the charging distributing disc is set, the mixture of gasoline stocks and hydrogen is realized evenly distributing in reactor by the charging distributing disc, carries out good contact with desulfuration adsorbent in the reactor.
In the method provided by the invention, described the first adsorptive reactor, the second adsorptive reactor are fluidized-bed reactor, reproducing adsorbent after the highly active reduction at first enters into the first adsorptive reactor, contact with the mixture of the gasoline that enters from reactor bottom and hydrogen, preferentially remove the difficult thiophene-type sulfide that removes, the simultaneously activity decreased of desulfuration adsorbent in the gasoline.The desulfuration adsorbent of isolated activity decreased is transferred in the second reactor behind pressure conversion and stripping, contact with hydrogen mixture with the liquefied gas that enters from reactor bottom, remove the sulfide in the liquefied gas, because the activity decreased of sorbent material, the reservation of larger limit the olefin(e) centent in the liquefied gas.
In the method provided by the invention, the use of sorbent material pressure conversion tank is so that the first adsorptive reactor and the second adsorptive reactor are more independent, increase the handiness of device operation, can also effectively reduce the gasoline component that sorbent material carries when the second adsorptive reactor turns agent from the first adsorptive reactor.
In the method provided by the invention, described liquefied gas and hydrogen can be introduced reactor separately, also can mix in the rear introducing reactor, preferably the mixture of liquefied gas and hydrogen are introduced in the second adsorptive reactor.In the second adsorptive reactor bottom the charging distributing disc is set, the mixture of liquefied gas and hydrogen evenly distributes in reactor by the charging distributing disc, forms good contact with desulfuration adsorbent in the reactor.
In the method provided by the invention, desulfuration adsorbent is fluidized in reactor, difference according to the gasoline stocks sulphur content of processing in the first adsorptive reactor, press 0.1～20wt% of gasoline reaction zone sorbent material reserve/hour, preferred 1～10wt%/hour speed from reactor, draw off sorbent material to be generated and carry out reprocessing cycle.After sorbent material to be generated removed the hydro carbons of its absorption through stripping, lifting was delivered in the fluid bed regenerator.Desulfuration adsorbent to be generated is delivered in the revivifier, it is 300～800 ℃, preferred 350～600 ℃ in regeneration temperature, regeneration pressure is 0.1～3.0MPa, preferred 0.1～1.0MPa, the linear gas velocity of oxygen-containing gas is under the condition of 0.1～2.0m/s, contact coke burning regeneration with the oxygen-containing gas from the input of revivifier lower end.The volume content of oxygen is 5%～35% in the described oxygen-containing gas, the mixture of preferred air or air and nitrogen.
In the method provided by the invention, behind the impurity (such as the oxygen of absorption) of the desulfuration adsorbent after the regeneration of drawing from revivifier through removing its absorption behind the stripping, lifting is delivered in the reducer.The regenerative sulfur binding sorbent material that is delivered in the reducer contacts with reducing gas, it is 250～550 ℃, preferred 300～450 ℃ at reduction temperature, reduction pressure is 0.2～5.0MPa, preferred 0.5～3.5MPa, the linear gas velocity of reducing gas is under the condition of 0.05～1.0m/s and reducing gas carries out reduction reaction, and reducing gas is hydrogen or the gas that is rich in hydrogen.
Desulfuration adsorbent after the reduction is delivered in the first adsorptive reactor, realizes that the continuous circulation of adsorption desulfurize reaction-adsorbent reactivation-sorbent material reduction-adsorption desulfurize reaction carries out.
In the method provided by the invention, described desulfuration adsorbent is take zinc oxide, aluminum oxide and silica as carrier, load transition metal be the catalyzer of promoter metals active ingredient.Wherein, preferred desulfuration adsorbent is: described carrier contains the zinc oxide of 10～90wt%, the aluminum oxide of 5～30wt% and the silica of 5～85wt%, described promoter metals active ingredient is selected from one or more in cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin and the vanadium, and the promoter metals oxide content accounts for 5～30wt% of described desulfuration adsorbent gross weight.Described carrier obtains through making beating mixing, moulding, drying, roasting, and described promoter metals loads on the carrier by methods such as dipping, sprays, then carries out obtaining desulfuration adsorbent after drying, the roasting.Described desulfuration adsorbent is preferably microspheroidal for ease of fluidisation, and its median size is 20～200 μ m, preferred 40～100 μ m.
In the method provided by the invention, described sorbent material to be generated is the sorbent material that desulfuration adsorbent and gasoline and the reacted height of liquefied gas carry sulfur content, described reproducing adsorbent be sorbent material to be generated in fluid bed regenerator with regenerate sorbent material after burning of oxygen.
The present invention's advantage compared with prior art is:
1, after the highly active reproducing adsorbent reduction, at first contact with gasoline and carry out the adsorption desulfurize reaction, realization is carried out the purpose of deep desulfuration to the difficult thiophenic sulfur that removes in the gasoline, contacts with liquefied gas with the low activity sorbent material that is loaded with part sulphur after the gasoline reaction, removes the sulfide in the liquefied gas.Because the sulfide that removes easily take hydrogen sulfide, mercaptan etc. in the liquefied gas is as main, it is less that sorbent suspension carries the impact of sulfur content, can take full advantage of on the desulphurizing activated basis of sorbent material, reaches the purpose of desulfuration of liquefied gas.
2, with hydrocarbon ils adsorption desulfurize reaction after, the adsorbent activity of a certain amount of sulphur of load reduces, and under hydro condition, has reduced the saturability of sorbent material to alkene in the liquefied gas, has kept to greatest extent the olefin(e) centent in the liquefied gas.
3, with hydrocarbon ils reaction after be loaded with part sulphur the low activity sorbent material after the excess pressure changing device carries out pressure conversion and stripping, enter into the sulfide of the second adsorptive reactor adsorbing and removing liquefied gas, realized independently carrying out of desulfurization of hydrocarbon oil and desulfuration of liquefied gas reaction, made influencing each other between two reactions be reduced to minimum.
Below in conjunction with accompanying drawing method provided by the invention is further specified, but not thereby limiting the invention.
Accompanying drawing is the method flow synoptic diagram that a kind of double-reactor provided by the invention removes gasoline and liquefied gas medium sulphide content simultaneously.As shown in drawings, desulfuration adsorbent enters the first adsorptive reactor 2 from the bottom through pipeline 26, sour gasoline after the preheating and hydrogen enter from the bottom the first adsorptive reactor 2 through pipeline 1, contact with desulfuration adsorbent and to carry out desulphurization reaction, the sorbent material that reacted gasoline and adsorption activity reduce enters settlement separate section of reactor head, carry out finish and separate, reaction oil gas is sent to the subsequent disposal system through pipeline 3.Separation obtains the gasoline products after the desulfurization, hydrogen recovery utilization.Be sent in the sorbent material pressure conversion tank 5 through pipeline 4 from the first adsorptive reactor 2 with the low activity sorbent material of gasoline generation desulphurization reaction back loading part sulphur, carrying out pressure conversion and stripping in sorbent material pressure conversion tank 5 is delivered in the second adsorptive reactor 8 by pipeline 6, with contact with hydrogen through the liquefied gas that pipeline 7 enters from reactor bottom, remove the sulphur in the liquefied gas.Liquefied gas after the desulfurization with after sorbent material to be generated separates, is sent to subsequent disposal system through pipeline 9 on settlement separate section of the second adsorptive reactor 8 tops.Sorbent material to be generated is transported to reactor receptor 11 from the pipeline 10 on the second adsorptive reactor 8, in reactor receptor 11, be sent to locking hopper 13 through stripping by pipeline 12, change the nonactive atmosphere of low pressure into from hydrogen environment behind nitrogen replacement, displacement gas is sent to roasting kiln through pipeline 14 and burns.Then sorbent material is delivered to regenerator feed tank 16 by pipeline 15, and spent agent enters into fluid bed regenerator 19 through promoting the air lift liter by pipeline 17.Oxygen-containing gas enters into revivifier by pipeline 18 from regenerator bottoms, desulfuration adsorbent to be generated contacts with oxygen-containing gas in revivifier 19 and burns sulphur, desulfuration adsorbent after obtaining regenerating behind the burning carbon, sulfur-containing smoke gas separates with the regenerative sulfur binding sorbent material at the fluid bed regenerator top by pipeline 20 and is delivered to sulphur system processed or alkali cleaning removes SOx, the regenerative sulfur binding sorbent material is transported in the fluid bed regenerator receptor 22 through pipeline 21 from reactor, be delivered to locking hopper 13 with the nitrogen lifting through pipeline 23, in locking hopper 13, change hydrogen gas environment into the hydrogen stripped displacement and after boosting, in being delivered to sorbent material reducer 25, pipeline 24 reduces, regenerative sulfur binding sorbent material after the reduction is delivered in the first adsorptive reactor 2 by pipeline 26, realizes carrying out continuously of adsorption desulfurize reaction.
The following examples will be further described the present invention, but not thereby limiting the invention.Employed feedstock property is listed in table 1 among the embodiment, and desulfuration adsorbent is labeled as FCAS-LG, and take zinc oxide, silica and aluminum oxide as carrier, load Ni is as promotor.
Sorbent material FCAS-LG prepares by following steps: according to 10: 2: 3 ratios (weight) zinc oxide, aluminum oxide and silica (perlite) are mixed, then mix making beating with deionized water, obtain the slurries that solid content is 15wt%, the salpeter solution (volumetric concentration is 30%) that adds 2 parts under the stirring state, continue to stir, until form uniform colloidal sol, with this colloidal sol control exhaust temperature be 250～300 ℃, spray pressure is 50～60 normal atmosphere, spray drying forming makes the microspheroidal solid particulate.The microspheroidal solid particulate that makes after 2 hours, again 600 ℃ of lower roastings 2 hours, is obtained carrier granule 120 ℃ of lower dryings.Pre-configured quantitative nickel nitrate solution (quality solubility 20%) is sprayed uniformly to carrier granule, then after 2 hours, again 600 ℃ of lower roastings 2 hours, obtain desulfuration adsorbent through 120 ℃ of lower dryings.The main character of this sorbent material is as shown in table 2.
Wherein, zinc oxide is that chemical pure is produced by Pei County zinc oxide factory; Aluminum oxide is that chemical pure is produced by Shandong Zibo aluminium manufacturer; Silica is produced by Central Plains, Xinyang perlite factory, salpeter solution be chemical pure by Huantai County along prosperous chemical industry company limited produce, nickelous nitrate is that chemical pure is produced by Beijing Yili Fine Chemicals Co., Ltd..
Embodiment 1
Embodiment 1 explanation double-reactor provided by the invention removes the effect of the method for hydrocarbon ils and liquefied gas medium sulphide content simultaneously.
Use processing method shown in the accompanying drawing, adopt the first adsorptive reactor that gasoline stocks is carried out adsorption desulfurize, gasoline stocks and hydrogen enter from reactor bottom, and the regenerative sulfur binding sorbent material is introduced from reactor lower part, and coflow removes the sulfide in the gasoline.Adopt the second adsorptive reactor that the sulfur-bearing liquefied gas is carried out adsorption desulfurize.
Being that the catalytically cracked gasoline A of 573ppm carries out the adsorption desulfurize reaction to sulphur content at first, using hydrogen as for hydrogen medium, is 7h in 430 ℃ of temperature of reaction, reaction pressure 2.5MPa, weight hourly space velocity
-1, the hydrogen/oil mol ratio value is to react under 0.28 the reaction conditions, other concrete reaction conditions is listed in table 3.The result shows that the product gasoline sulphur content is 3.4ppm, and loss of octane number only has 0.4 unit, and product gasoline volume yield is 99.6%.
Through gasoline desulfur reacted sorbent material, with total sulfur content be 36.61ppm, mercaptan sulfur is that the liquefied gas raw material B of 30.50ppm contacts the sulfide that removes in the liquefied gas again, is 5.6h in 400 ℃ of temperature of reaction, reaction pressure 1.4MPa, weight hourly space velocity
-1, hydrogen hydrocarbon molar ratio is to react under 0.16 the reaction conditions, other concrete reaction conditions is listed in table 3.The result shows that the total sulfur content in the liquefied gas product has dropped to below the 0.2ppm, and less than the detectability of instrument, mercaptan sulfur does not then detect.The conversion of olefines rate is lower, is 4.37% such as propylene conversion, and just, isobutene conversion is 3.30%, and the transformation efficiency of butene-2 is 1.20%.
The sorbent material to be generated of sulfur loaded uses volume ratio under the condition of 530 ℃ of temperature of reaction, reaction pressure 0.5MPa be that 1: 1 air and the mixed gas of nitrogen are regenerated as regeneration gas, obtains reproducing adsorbent behind the sulphur on the burning-off sorbent material to be generated, the carbon.Reproducing adsorbent uses volume fraction under the condition of 430 ℃ of temperature of reaction, reaction pressure 2.5MPa be that 70% hydrogen reduces, to recover the desulphurizing activated of sorbent material.
Embodiment 2
The embodiment 2 explanations effect that removes simultaneously the method for gasoline and liquefied gas medium sulphide content provided by the invention.
Use processing method shown in the accompanying drawing, adopt the first adsorptive reactor that gasoline stocks is carried out adsorption desulfurize, gasoline stocks and hydrogen enter from reactor bottom, and the regenerative sulfur binding sorbent material is introduced from reactor lower part, and coflow removes the sulfide in the gasoline.Adopt the second adsorptive reactor that the sulfur-bearing liquefied gas is carried out adsorption desulfurize.
Being that the catalytically cracked gasoline A of 573ppm carries out the adsorption desulfurize reaction to sulphur content at first, using hydrogen as for hydrogen medium, is 4h in 400 ℃ of temperature of reaction, reaction pressure 1.4MPa, weight hourly space velocity
-1, the hydrogen/oil mol ratio value is to react under 1.24 the reaction conditions, other concrete reaction conditions is listed in table 3.The result shows that the product gasoline sulphur content only has 5.1ppm, and uprising index loss is 0.5 unit, product gasoline volume yield 99.7%.
Through the reacted sorbent material of gasoline desulfur, with total sulfur content be 6500ppm, mercaptan sulfur is that the liquefied gas raw material C of 450ppm contacts the sulfide that removes in the liquefied gas again, uses hydrogen as for hydrogen medium, is 1.4h in 430 ℃ of temperature of reaction, reaction pressure 0.6MPa, weight hourly space velocity
-1, hydrogen hydrocarbon molar ratio is to react under 0.44 the reaction conditions, other concrete reaction conditions is listed in table 3.The result shows that the total sulfur content in the liquefied gas product is less than 0.2ppm, and mercaptan sulfur does not then detect.Olefin conversion in the liquefied gas is lower, is 3.66% such as propylene conversion, and just, isobutene conversion is 2.43%, the transformation efficiency of butene-2 then is 0.48%.
The sorbent material to be generated of sulfur loaded uses air to regenerate as regeneration gas under the condition of 530 ℃ of temperature of reaction, reaction pressure 0.2MPa, obtains reproducing adsorbent behind the sulphur on the burning-off sorbent material to be generated, the carbon.Reproducing adsorbent uses volume fraction under the condition of 400 ℃ of temperature of reaction, reaction pressure 1.4MPa be that 90% hydrogen reduces, to recover the desulphurizing activated of sorbent material.
Table 1
Table 2
Table 3
Claims (18)
1. a double-reactor removes the method for hydrocarbon ils and liquefied gas medium sulphide content simultaneously, it is characterized in that, gasoline stocks and hydrogen enter the first adsorptive reactor from the bottom, flow from bottom to top, remove sulfide in the gasoline with desulfuration adsorbent Contact-sorption in the reactor; On the first adsorptive reactor top, reacted oil gas separates with more SA desulfuration adsorbent, oil gas after the separation is through further separating the gasoline products after obtaining desulfurization, isolated desulfuration adsorbent is behind transfer pressure, enter in the second adsorptive reactor, the sulfur-bearing liquefied gas enters the second adsorptive reactor from the bottom, contacts the sulfide that removes in the liquefied gas with more SA desulfuration adsorbent; After carrying sulfur content sorbent material to be generated and liquefied gas separates, reacted height draws reactor, enter coke burning regeneration in the fluid bed regenerator, sorbent material after the regeneration turns back in the first adsorptive reactor after reduction and recycles, isolated oil gas further separates and obtains liquefied gas product after the desulfurization in the second adsorptive reactor, and hydrogen recovery is used.
2. according to the method for claim 1, it is characterized in that the operational condition of described the first adsorptive reactor is: temperature is 200～550 ℃, and pressure is 0.5～5MPa, and the weight hourly space velocity of gasoline stocks is 0.1～100h
-1
3. according to the method for claim 1, it is characterized in that the operational condition of described the first adsorptive reactor is: temperature is 300～500 ℃, and pressure is 1.0～3.5MPa, and the weight hourly space velocity of gasoline stocks is 1～10h
-1。
4. according to any method among the claim 1-3, it is characterized in that the mol ratio of hydrogen and gasoline stocks is 0.01～10: 1 in described the first adsorptive reactor.
5. according to the method for claim 4, it is characterized in that the mol ratio of described hydrogen and gasoline stocks is 0.1～3: 1.
6. according to any method among the claim 1-3, it is characterized in that the operational condition of described the second adsorptive reactor is: temperature is 100～550 ℃, and pressure is 0.1～5MPa, and the weight hourly space velocity of liquefied gas is 0.1～100h
-1
7. according to any method in the claim 6, it is characterized in that the operational condition of described the second adsorptive reactor is: temperature is 200～500 ℃, and pressure is 0.5～3.5MPa, and the weight hourly space velocity of liquefied gas is 1～20h
-1
8. according to the method for claim 6 or 7, it is characterized in that in described the second adsorptive reactor, the mol ratio of hydrogen and liquefied gas is 0.01～10: 1.
9. according to the method for claim 8, it is characterized in that the mol ratio 0.1～3: 1 of described hydrogen and liquefied gas.
10. according to any method among the claim 1-3, it is characterized in that described gasoline stocks is that boiling range is 35～250 ℃ sulfur-bearing hydrocarbon fraction, sulphur content wherein is greater than 50 μ g/g.
11., it is characterized in that described liquefied gas is that wherein, the sulphur content in the liquefied gas is greater than 10 μ g/g take the C3-C4 lighter hydrocarbons as main fraction according to any method among the claim 1-3.
12. the method according to claim 1 is characterized in that, described desulfuration adsorbent draws off desulfuration adsorbent to be generated by the speed of 0.1～20wt%/h of sorbent material reserve in the first adsorptive reactor and carries out reprocessing cycle.
13. the method according to claim 12 is characterized in that, described desulfuration adsorbent draws off desulfuration adsorbent to be generated by the speed of 1～10wt%/h of sorbent material reserve in the first adsorptive reactor and carries out reprocessing cycle.
14. the method according to claim 1 is characterized in that, described desulfuration adsorbent to be generated and oxygen-containing gas are introduced in the fluid bed regenerator, it is 300～800 ℃ in temperature, pressure is 0.1～3.0MPa, and the linear gas velocity of oxygen-containing gas is to react coke burning regeneration under the condition of 0.1～2.0m/s.
15. the method according to claim 1, it is characterized in that, described regenerative sulfur binding sorbent material and reducing gas are introduced in the sorbent material reducer, are 250～550 ℃ in temperature, and pressure is that the linear gas velocity of 0.2～5.0MPa reducing gas is to react under the condition of 0.05～1.0m/s to reduce.
16. the method according to claim 15 is characterized in that, described regenerative sulfur binding sorbent material is 300～450 ℃ in temperature, and reduction pressure is to carry out reduction reaction with reducing gas under the condition of 0.5～3.5MPa.
17. the method according to claim 1 is characterized in that, described desulfuration adsorbent is take zinc oxide, aluminum oxide and silica as carrier, load transition metal be the catalyzer of promoter metals active ingredient.
18. the method according to claim 17, it is characterized in that, in the described desulfuration adsorbent, described carrier contains the zinc oxide of 10～90wt%, the aluminum oxide of 5～30wt% and the silica of 5～85wt%, described promoter metals active ingredient is selected from one or more in cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin and the vanadium, and the promoter metals oxide content accounts for 5～30wt% of described desulfuration adsorbent gross weight.
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