CN1952060A - Production process of producing cleaning gasoline - Google Patents
Production process of producing cleaning gasoline Download PDFInfo
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- CN1952060A CN1952060A CN 200510047461 CN200510047461A CN1952060A CN 1952060 A CN1952060 A CN 1952060A CN 200510047461 CN200510047461 CN 200510047461 CN 200510047461 A CN200510047461 A CN 200510047461A CN 1952060 A CN1952060 A CN 1952060A
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Abstract
The invention disclosed a way to produce clean gasoline by poor-quality gasoline distillate. It adopts fluidized bed successive regenerating method to handle poor-quality gasoline distillate. The processing procedure comprises the following steps: the poor-quality gasoline and hydrogen contacting with the thermic de-sulphur and hydrogenating catalyst in the lifting pipes and reacting up on the fluidized bed; separating the hydrogenated product, the catalyst and the gas which contains hydrogen sulfide, after air lifting, transferring the catalyst into the regenerator; burning the carbon with air to regenerate the catalyst; returning the catalyst to the fluidized bed. Compared to the present technologies, the invention can substantially decrease the sulphur content, alkenes content and benzene content in the poor-quality gasoline; besides, the clean gasoline's antidetonate index doesn't decrease at all.
Description
1, technical field
The present invention relates to a kind of method of producing clean gasoline, particularly the inferior patrol cut fraction hydrogenation is produced the method for clean gasoline.
2, background technology
In order to control topsoil, various countries make laws in succession the sulphur in the gasoline, olefin(e) centent have been proposed more and more stricter restriction.Before and after 2005, the U.S.EPA Tier2 that the European IV emission standard (EN228-2004) that European Union works out, the U.S. work out etc. requires content of sulfur in gasoline ≯ 50 μ g/g, even to have proposed sulphur content be the suggestion of 5 μ g/g～10 μ g/g " sweet gasoline ", and olefin(e) centent will be reduced to about 10.0v% by ≯ 20.0v%.China will be on July 1st, 2005, and gasoline requires sulphur content ≯ 500 μ g/g, olefin(e) centent ≯ 30.0v%.The gasoline in supply capital, Shanghai is equivalent to the specification gasoline of European III class emission standard with execution, and its leading indicator is: sulphur content ≯ 150 μ g/g, olefin(e) centent ≯ 18.0v%.Therefore, reduce the megatrend that sulphur and olefin(e) centent are the development of clean gasoline quality.
Though adopt traditional hydrofining technology can remove sulfide and olefin(e) compound in the catalytically cracked gasoline effectively, but because the higher low-octane alkane of the saturated generation of hydrogenation of olefins of octane value, so, adopt traditional Hydrobon catalyst and technology when desulfurization and reducing olefin(e) centent, must follow the rapid decline of gasoline octane rating.Generally, when the desulfurization degree of catalytic gasoline is 90wt%, 5.0～8.0 units of anti-knock index ((R+M)/2) loss.Consume a large amount of hydrogen simultaneously.How reducing the saturated loss of octane number that causes of alkene is the difficult point of catalytic gasoline in hydrogenating desulfurization and reduction olefin(e) centent problem.
US5,362,376 technologies of having introduced a kind of FCC gasoline hydrodesulfurizationmethod and having selected shape hydrocracking two-stage catalytic agent combination.The catalytically cracked gasoline last running that is characterized in prefractionation is after hydrogenating desulfurization, pass through mesopore, tart NiO/HZSM-5 molecular sieve catalyst shape slective cracking again, thereby part is recovered because of the saturated loss of octane number that causes of hydrogenation of olefins in the hydrodesulfurization process, and then is in harmonious proportion with lighting end.The shortcoming of this technology is that the sweet gasoline octane value has certain loss, and yield generally will lose 5wt%～10wt%, and the hydrogen consumption is higher.
Chinese patent ZL 98117812.x discloses a kind of method of catalytic aromatization of gasoline fraction.Stock oil and water vapor contact with the microspherical catalyst that contains five yuan of supersiliceous zeolites of heat in fluidized-bed reactor, carry out aromatization under 500 ℃～650 ℃ of temperature.The characteristics of this method are to adopt the successive reaction-reprocessing cycle operating method of fluidized-bed reactor and the conveying of catalyzer fluidised form to carry out aromizing.The shortcoming of this method is the non-hydrogen operation, therefore, can not reduce the sulphur content of gasoline fraction.
US6,656,877 have introduced a kind of FCC gasoline adsorbing and desulfurizing agent.This sweetening agent is loaded on the carrier that contains zinc oxide, swelling soil and aluminum oxide by the nickel auxiliary agent.S-ZORB gasoline desulfur technology based on above-mentioned sweetening agent exploitation adopts sweetening agent cyclic regeneration technology.At first, at desulfurization zone, the sulphur atom of sulfur-bearing hydrocarbonylation thing optionally is adsorbed onto on the sweetening agent in the presence of hydrogen; Second the step, desulfurization hydrocarbonylation thing with contain separating of desulfurizing agent of sulfur; The 3rd, the inactivation sweetening agent burns sulphur and burns the carbon activation with air in the oxidation regeneration device; The 4th, the activation sweetening agent in reducer with regenerating behind the hydrogen reducing; The 5th, recycling desulfurizer turns back to desulfurization zone, circulates next time.The S-ZORB engineering test is the result show, in 2 hours, the sulphur of FCC gasoline can be reduced to 5 μ g/g by 1400 μ g/g, (R+M)/2) 1.8 units of loss; In 6 hours, be reduced to 146 μ g/g, (R+M)/2) 0.5 unit of loss.But for the higher catalytic cracking of olefin(e) centent (FCC) gasoline, the requirement that still can not satisfy under the situation of alkene in the clean gasoline specification alkene can not fall in S-ZORB technology only desulfurization.
3, summary of the invention
The objective of the invention is to propose a kind of method of producing clean gasoline by the inferior patrol cut, this method can reduce the sulphur content and the olefin(e) centent of inferior patrol significantly, simultaneously, the anti-knock index of the clean gasoline of being produced ((R+M)/2) does not lose substantially.
The inventive method is to adopt the method for fluidized-bed cyclic regeneration to handle the inferior patrol cut, and specific operation process comprises:
(1), bad gasoline and hydrogen after the preheating enters the riser tube from the bottom, contact with the desulfurization-olefine lowering catalyst of the heat that enters riser tube, and rise in the fluidized-bed reactor and react; Then, desulfurating and reducing olefinic hydrocarbon product and hydrogen sulfide containing gas and reclaimable catalyst carry out gas solid separation, and wherein desulfurating and reducing olefinic hydrocarbon product and hydrogen sulfide containing gas are discharged from reactor head, and reclaimable catalyst is transported to revivifier after gas is carried;
(2), in revivifier, reclaimable catalyst is coke-burning regeneration in the presence of air;
(3), the regenerated catalyst of step (2) gained returns fluidized-bed reactor and recycles.
Described inferior patrol cut is one or more mixture, especially catalytic cracking (FCC) gasoline fraction of catalytic cracking (FCC) gasoline, catalytic cracking gasoline, pressure gasoline and coker gasoline.
In the above-mentioned steps (1), the operational condition in the fluidized-bed reactor is as follows: reaction pressure is 1.0MPa～4.5MPa, 350 ℃～450 ℃ of temperature of reaction, feed volume air speed 0.5h
-1～3.0h
-1With hydrogen to oil volume ratio 200: 1～800: 1; Preferred operational condition is as follows: reaction pressure is 2.0～4.0MPa, 380～420 ℃ of temperature of reaction, feed volume air speed 1.0～3.0h
-1With hydrogen to oil volume ratio 400: 1～600: 1.Described gas solid separation can adopt any device of used separable solid in this area and gas, such as cyclone separator, settlement separate etc.
Desulfurization described in the above-mentioned steps (1)/fall olefin product and hydrogen sulfide containing gas carry out gas-liquid separation after discharging from reactor head in gas-liquid separator.Liquid product is low-sulfur, low alkene and low benzene content clean gasoline, discharges from the gas-liquid separator bottom, and gaseous product is discharged from gas-liquid separator top.Wherein contain hydrogen sulfide in the gas, after depriving hydrogen sulphide was handled, the hydrogen-rich gas of gained can promote gas and/or promote gas in advance and recycle.
In the above-mentioned steps (2), the regeneration condition in the revivifier is as follows: regeneration pressure is 0.5MPa～1.5MPa, and gas agent volume ratio 500: 1～1000: 1 was 400 ℃～550 ℃ following constant temperature 3.0～10.0 hours.Resurgent gases is an air.
Used desulfurization-the olefine lowering catalyst of the inventive method is as follows: the weight with catalyzer is benchmark, transition metal oxide content is 1.0wt%～10.0wt%, the lanthanide rare metal oxide content is 0.5wt%～3.0wt%, the ultrafine particle zeolite content is 50.0wt%～90.0wt%, and surplus is an inorganic oxide adhesive; The grain fineness number of ultrafine particle zeolite is 20nm～800nm.
Described transition group metallic oxide is one or more in zinc oxide, ferric oxide, manganese oxide, nickel oxide, cobalt oxide, molybdenum oxide and the Tungsten oxide 99.999, one or more of nickel oxide, molybdenum oxide and zinc oxide particularly, the lanthanide rare metal oxide is lanthanum trioxide and/or cerium oxide, particularly lanthanum trioxide.
Described ultrafine particle zeolite is one or more among HZSM-5, HL, HBeta, HM, HMCM-41, HSAPO-5, HSAPO-11, HSAPO-31 and the HSAPO-41, particularly HZSM-5 and/or HBeta, preferably HZSM-5 and HBeta.
Described binding agent is titanium oxide, aluminum oxide, silicon oxide or aluminium oxide-silicon oxide.
The preferred physico-chemical property of described desulfurization-olefine lowering catalyst is as follows: specific surface area is 300m
2/ g～550m
2/ g, pore volume are 0.15ml/g～0.45ml/g, average pore diameter 1.5nm～3.5nm.The B acid of used desulfurization/olefine lowering catalyst, L acid and total acid content are respectively: 0.020mmol/g～0.080mmol/g, 0.100mmol/g～0.250mmol/g, 0.120mmol/g～0.330mmol/g.Wherein specific surface area, pore volume and average pore diameter adopt the U.S. Micromeritics Instrument ASAP2400 of company type low temperature liquid nitrogen physical adsorption appearance to measure.The acid amount of catalyzer is measured on the IR instrument among the present invention, is adsorbate with the pyridine, measures 400 ℃ of pyridines in the acid amount of chemisorbed on catalyst amount as catalyzer on recording quartz spring weight absorption instrument.
Used desulfurization-the olefine lowering catalyst of the inventive method preferably adopts micro-spherical catalyst, and wherein diameter is 60wt%～95wt% that 20～80 microns microballoon accounts for total particulate, preferably accounts for 80wt%～95wt%.
The used desulfurating and reducing olefinic hydrocarbon Preparation of catalysts of the inventive method method can adopt method preparation provided by the invention, also can adopt the additive method preparation.
Desulfurating and reducing olefinic hydrocarbon Preparation of catalysts method provided by the invention may further comprise the steps:
A, ultrafine particle zeolite and binding agent are mixed, grind evenly, add aqueous nitric acid and form slurries, after spray-dried, the roasting, prepare microspheroidal carrier intermediate;
After b, above-mentioned carrier intermediate carried out hydrothermal treatment consists, adding equivalent concentration according to the ratio of liquid/solid volume than 1.5: 1.0～5.0: 1.0 was the dilute inorganic acid solution rinsing of 0.1N～2.0N, after drying, the roasting, prepares carrier;
C, the aqueous solution spray that will contain transition metal and lanthanide rare metal are impregnated in the above-mentioned carrier, after drying, the roasting, obtain the used micro-spherical catalyst of the inventive method.
Among the above-mentioned steps a in the spray-drying process, drying tower hot air inlet temperature is that 300～400 ℃, temperature out are 120～200 ℃, the microballoon that the process cyclonic separator obtains is after under 100～140 ℃ dry 2～8 hours, 400～600 ℃ of following roastings 3～10 hours.
Hydrothermal treatment consists process described in the above-mentioned steps b is to adopt method of the prior art, and the preferably water thermal treatment temp is 500～600 ℃, and the treatment time is 3～15 hours; Described diluted mineral acid is dilute hydrochloric acid, rare nitric acid, dilute phosphoric acid or rare carbonic acid; Described drying and roasting process were to descend dry 8～15 hours at 100～140 ℃, 400～600 ℃ of following roastings 3～10 hours.
The aqueous solution that contains transition metal and lanthanide rare metal among the above-mentioned steps c is preferably formulated by its nitrate or vitriol or ammonium salt; Described drying and roasting process were to descend dry 8～15 hours at 100～140 ℃, 400～600 ℃ of following roastings 3～10 hours.
The used catalyzer of the inventive method is to adopt the preparation of ultrafine particle zeolite, the ultrafine particle zeolite has bigger specific surface area and short duct on the one hand, fast reaction speed is reacted in the active centre that is diffused rapidly on the catalyzer that helps reactant; On the other hand, the rapid diffusion that also is beneficial to product is left the catalyst body phase, has reduced the degree that product carries out secondary side reactions such as cracking, polymerization again, improves C
5 +The coke content of gasoline product liquid and minimizing catalyzer.
The present invention adopts the ultrafine particle zeolite to prepare micro-spherical catalyst, can carry out the fluidized conveying operations.
Compared with prior art, the inventive method can reduce sulphur content, olefin(e) centent and the benzene content of FCC gasoline significantly, and simultaneously, the anti-knock index of the clean gasoline of being produced ((R+M)/2) does not lose substantially.
4, description of drawings
Fig. 1 is a method flow synoptic diagram provided by the invention.
1,2,5,7,9,10,11,13,15,17,19,20 all represent pipeline among Fig. 1,3 is riser tube, 4 is fluidized-bed reactor, 6 is gas-liquid separator, 8 is de-hydrogen sulfide column, and 12 is the reclaimable catalyst collector, and 14 is locking hopper, 16 is revivifier, and 18 are regeneration rear catalyst collector.
Fig. 1 illustrates that it is the flow process of clean gasoline that the present invention adopts the method for fluidized-bed cyclic regeneration to handle inferior patrol, and the shape and size of equipment and pipeline are not subjected to the restriction of accompanying drawing, but determine as the case may be.
5, embodiment
Below in conjunction with Fig. 1 method provided by the present invention is given further instruction.
The pre-gas that promotes enters riser tube 3 through pipeline 10 from the bottom, stock oil through the heating vaporization enters riser tube 3 through pipeline 1 and pipeline 2 respectively with hydrogen make-up from the middle and lower part, heat regenerative sulfur binding/olefine lowering catalyst through pipeline 20 from the middle part or the middle and lower part enter riser tube 3, and be thus lifted in the fluidized-bed reactor 4, carry out hydrogenation reaction under certain condition and come desulfurating and reducing olefinic hydrocarbon.Reaction product enters gas-liquid separator 6 through pipeline 5 and separates, low-sulfur, low alkene clean gasoline are got rid of from separator 6 bottoms, enter de-hydrogen sulfide column 8 from separator 6 top expellant gas products through pipeline 7, as promoting gas, another part is through the pre-gas that promotes of pipeline 10 conducts through pipeline 9 for a depriving hydrogen sulphide gaseous product part.Desulfurization/the olefine lowering catalyst of reaction back carbon deposit enters reclaimable catalyst collector 12 through pipeline 11, enters revivifier 16 after pipeline 13 enters locking hopper 14 through pipeline 15 with nitrogen with hydrogen exchange is clean, carries out coke-burning regeneration with air.The regeneration rear catalyst enters regeneration rear catalyst collector 18 through pipeline 17, enters locking hopper 14 through pipeline 19, enters riser tube 3 through pipeline 20, recycles.
The following examples will give further instruction to ten thousand methods provided by the invention, but not thereby limiting the invention.
Example 1
This examples preparation 2.0wt%NiO-0.50wt%ZnO-1.50wt%La
2O
3The alkene catalyzer falls in/nanometer HZSM-5 desulfurization.
Take by weighing 229.6g HZSM-5 (SiO
2/ Al
2O
3Mol ratio is 27, and grain fineness number is 30nm～100nm) and 140.0g Al
2O
3, and their ground and mixed is even, adding 150ml concentration is dilute nitric acid solution and the deionized water of 5.6g/100ml, is mixed with the slurries of 1000ml.
Above-mentioned slurries are carried out spraying drying, and the drying tower inlet temperature is 350 ℃, and air outlet temperature is 150 ℃.550 ℃ following roastings 5 hour, make nanometer HZSM-5 support of the catalyst intermediate in drying under 120 ℃ after 6 hours through the microballoon that cyclonic separator obtains.Resulting diameter is the 93wt% that 40～100 microns microspheroidal accounts for total particulate.
100ml said catalyst carrier intermediate is packed in the vertical activation furnace, under the atmosphere of water flowing 150ml/ hour water vapor, be warming up to 540 ℃, and thermostat(t)ed water thermal treatment 6 hours under this temperature.Then, stop into water steam, swap-in contains the nitrogen oxygen atmosphere of nitrogen 90wt%, and the wet steam displacement of adsorbing on the catalyzer is clean, after control is cooled to room temperature, draws off.
Get the sample of the above-mentioned hydrothermal treatment consists of 60g again and put into beaker, adding equivalent concentration according to the ratio of liquid/solid volume than 1.5: 1.0 is that the dilute hydrochloric acid solution of 0.30N carries out rinsing.Then, 120 ℃ of dry down 8 hours, 520 ℃ following roastings 6 hours.Take out after reducing to room temperature, prepare nanometer HZSM-5 zeolite catalysis agent carrier.
Take by weighing said catalyst carrier 50g and put into and spray jar, start rotor pump.In 30 minutes, 37.5ml contained 1.0g NiO, 0.25g ZnO and 0.75g La
2O
3Nickelous nitrate, zinc nitrate and lanthanum nitrate hexahydrate spray in the support of the catalyst.After drying under the room temperature, 120 ℃ dry 10 hours down, 550 ℃ of following roastings 6 hours, make the nanometer HZSM-5 catalyzer of nickeliferous, zinc and lanthanum, be numbered NZ.This catalyzer rerum natura is listed in the table 1.
Example 2
This examples preparation 4.0wt%MoO
3-1.0wt%ZnO-3.0wt%La
2O
3/ ultrafine particle HBeta desulfurating and reducing olefinic hydrocarbon catalyzer.
Take by weighing 239.6g HBeta (SiO
2/ Al
2O
3Mol ratio is 33, and grain fineness number is 70nm～300nm), 140.0g Al
2O
3, and their ground and mixed is even, adding 180ml concentration is dilute nitric acid solution and the deionized water of 3.6g/100ml, is mixed with the slurries of 1000ml.
Above-mentioned slurries are carried out spraying drying, and the drying tower inlet temperature is 320 ℃, and air outlet temperature is 170 ℃.The microballoon that the process cyclonic separator obtains is after under 110 ℃ dry 8 hours, 570 ℃ of following roastings 3 hours.Resulting diameter is the 92wt% that 40～100 microns microspheric accounts for total particulate.Make ultrafine particle HBeta desulfurating and reducing olefinic hydrocarbon support of the catalyst intermediate.
120ml said catalyst carrier intermediate is packed in the vertical activation furnace, under the atmosphere of water flowing 200ml/ hour water vapor, be warming up to 550 ℃, and thermostat(t)ed water thermal treatment 7 hours under this temperature.Then, stop into water steam, swap-in contains the nitrogen oxygen atmosphere of nitrogen 90wt%, and the wet steam displacement of adsorbing on the catalyzer is clean, after control is cooled to room temperature, draws off.
Get the sample of the above-mentioned hydrothermal treatment consists of 80g again and put into beaker, adding equivalent concentration according to the ratio of liquid/solid volume than 3.5: 1.0 is that the dilute hydrochloric acid solution of 0.80N carries out rinsing.Then, 130 ℃ of dry down 7 hours, 550 ℃ following roastings 5 hours.Take out after reducing to room temperature, prepare nanometer HBeta zeolite desulfurating and reducing olefinic hydrocarbon support of the catalyst.
Take by weighing said catalyst carrier 50g and put into and spray jar, start rotor pump.In 30 minutes, 40ml contained 2.0g MoO
3, 0.50g ZnO and 1.5g La
2O
3The aqueous solution of ammonium molybdate, zinc nitrate and lanthanum nitrate spray in the support of the catalyst.After drying under the room temperature, 140 ℃ dry 5 hours down, 530 ℃ of following roastings 8 hours, make the ultrafine particle HBeta zeolite desulfurating and reducing olefinic hydrocarbon catalyzer of nickeliferous, zinc and lanthanum, be numbered UB.This catalyzer rerum natura is listed in the table 1.
The rerum natura of table 1 zeolite desulfurating and reducing olefinic hydrocarbon catalyzer
| Project | Example 1 | Example 2 |
| The catalyzer numbering | NZ | UB |
| Chemical constitution, wt% | ||
| NiO | 2.0 | - |
| MoO 3 | - | 4.0 |
| ZnO | 0.5 | 1.0 |
| La 2O 3 | 1.5 | 3.0 |
| Physical properties | ||
| Specific surface area, m 2/g | 330 | 480 |
| Pore volume, ml/g | 0.25 | 0.40 |
| Average pore diameter, nm | 1.90 | 3.50 |
| Abrasion index, wt%/hour | 1.2 | 1.5 |
| The acid matter of IR | ||
| B acid, mmol/g | 0.031 | 0.047 |
| L acid, mmol/g | 0.126 | 0.175 |
| Total acid content, mmol/g | 0.157 | 0.222 |
| Size composition, wt% | ||
| 0～20 micron | 5.3 | 5.4 |
| 20～40 microns | 25.5 | 25.2 |
| 40～80 microns | 64.5 | 64.0 |
| ＞80 microns | 4.7 | 5.4 |
*Acid matter is to measure on the IR instrument, is adsorbate with the pyridine, measures 400 ℃ of pyridines in the acid amount of chemisorbed on catalyst amount as catalyzer on recording quartz spring weight absorption instrument.
Example 3
The catalytic performance of NZ catalyzer in this example test case 1.
With A
#FCC gasoline is raw material, uses the NZ catalyzer, and flow process is seen Fig. 1.
The operational condition of fluidized-bed reactor is as follows: reaction pressure is 3.0MPa, 400 ℃ of temperature of reaction, feed volume air speed 2.5h
-1With hydrogen to oil volume ratio 400: 1.
Regeneration condition is as follows: regeneration pressure is 0.8MPa, gas agent volume ratio 700: 1, and 530 ℃ of following constant temperature 5.0 hours, resurgent gases is an air.
The sampling analysis in 300 hours of turning round.Table 2 has been listed raw material and product material balance data, and table 3 has been listed the analytical results of product liquid.
Table 2 example 3 raw materials and product material balance
| The side of going into, wt% | |
| Raw material | 100.00 |
| Hydrogen | 0.35 |
| Add up to | 100.35 |
| The side of going out, wt% | |
| Hydrogen sulfide | 0.05 |
| Ammonia | 0.01 |
| C1 | 0.18 |
| C2 | 0.70 |
| C3 | 1.07 |
| i-C4 | 0.65 |
| n-C4 | 0.51 |
| C2 | 0.06 |
| C3＝ | 1.09 |
| C4＝ | 0.79 |
| C5 +Yield of gasoline | 95.24 |
| Add up to | 100.35 |
The analytical results of table 3 example 3 product liquids
| Project | A #FCC gasoline | 300 hours products | |
| Sulphur content, μ g/g | 1264 | 45.3 | |
| Fluorescent method is formed, v% | Alkane content | 35.2 | 59.0 |
| Olefin(e) centent | 42.8 | 9.5 | |
| Aromaticity content | 22.0 | 31.5 | |
| Chromatography | Benzene content, wt% | 2.21 | 1.25 |
| Isoparaffin and normal paraffin weight ratio | 2.96 | 5.99 | |
| Anti-knock index, (R+M)/2 | 85.8 | 85.1 | |
Example 4
The catalytic performance of UB catalyzer in this example test case 2.
The evaluation raw material is: B
#FCC gasoline, the UB catalyzer.Evaluation method and example 3 are identical.The operational condition of fluidized-bed reactor is as follows: reaction pressure is 1.8MPa, 430 ℃ of temperature of reaction, feed volume air speed 1.0h
-1Carry out for 600: 1 times with hydrogen to oil volume ratio.
Regeneration condition is as follows: regeneration pressure is 1.2MPa, gas agent volume ratio 900: 1, and 480 ℃ of following constant temperature 8.0 hours, resurgent gases was an air.
The sampling analysis in 300 hours of turning round.Table 4 has been listed raw material and product material balance data, and table 5 has been listed the analytical results of product liquid.
Table 4 example 4 raw materials and product material balance
| The side of going into, wt% | |
| Raw material | 100.00 |
| Hydrogen | 0.21 |
| Add up to | 100.21 |
| The side of going out, wt% | |
| Hydrogen sulfide | 0.02 |
| Ammonia | 0.01 |
| C1 | 0.11 |
| C2 | 0.26 |
| C3 | 0.79 |
| i-C4 | 0.32 |
| n-C4 | 0.17 |
| C2＝ | 0.02 |
| C3＝ | 0.42 |
| C4＝ | 0.24 |
| C5 +Yield of gasoline | 97.85 |
| Add up to | 100.21 |
The analytical results of table 5 example 4 product liquids
| Project | B #FCC gasoline | 300 hours products | |
| Sulphur content, μ g/g | 765 | 15.3 | |
| Fluorescent method is formed, v% | Alkane content | 30.7 | 54.3 |
| Olefin(e) centent | 49.8 | 13.5 | |
| Aromaticity content | 19.5 | 32.2 | |
| Chromatography | Benzene content, wt% | 1.80 | 0.92 |
| Isoparaffin and normal paraffin weight ratio | 4.13 | 6.90 | |
| Anti-knock index, (R+M)/2 | 85.2 | 84.8 | |
From table 2 and table 3 as can be seen, the NZ catalyzer can be reduced to 45.3 μ g/g and 9.5v% respectively with the sulphur content 1264 μ g/g and the olefin(e) centent 42.8v% of FCC gasoline, and benzene content has reduced by 43%, 0.7 unit of anti-knock index ((R+M)/2) loss.C5
+Yield of gasoline is 95.24wt%, and the hydrogen consumption is 0.35wt%.
From table 4 and table 5 as can be seen, the UB catalyzer can be reduced to 15.3 μ g/g and 13.5wt% respectively with the sulphur content 765 μ g/g and the olefin(e) centent 49.8v% of FCC gasoline, and benzene content has reduced by 49%, 0.4 unit of anti-knock index ((R+M)/2) loss.C5
+Yield of gasoline is 97.85wt%, and the hydrogen consumption is 0.21wt%.
Therefore, adopt desulfurization/olefine lowering catalyst of the present invention and fluidized-bed process technology the sulphur content of inferior patrol can be reduced to ≯ 50.0 μ g/g, olefin(e) centent is reduced to ≯ 15.0v%, and benzene content reduces about 45v%, ≯ 0.7 unit of anti-knock index ((R+M)/2) loss, C5
+Yield of gasoline is ≮ 95wt% hydrogen consumption ≯ 0.35wt%.
Claims (14)
1, a kind of method of producing clean gasoline is characterized in that adopting the method for fluidized-bed cyclic regeneration to handle the inferior patrol cut, and its operating process comprises:
(1), bad gasoline and hydrogen after the preheating enters the riser tube from the bottom, contact with the desulfurization-olefine lowering catalyst of the heat that enters riser tube, and rise in the fluidized-bed reactor and react; Then, desulfurating and reducing olefinic hydrocarbon product and hydrogen sulfide containing gas and reclaimable catalyst carry out gas solid separation, and wherein desulfurating and reducing olefinic hydrocarbon product and hydrogen sulfide containing gas are discharged from reactor head, and reclaimable catalyst is transported to revivifier after gas is carried;
(2), in revivifier, reclaimable catalyst is coke-burning regeneration in the presence of air;
(3), the regenerated catalyst of step (2) gained returns fluidized-bed reactor and recycles.
2, in accordance with the method for claim 1, the mixture of one or more that it is characterized in that described inferior patrol cut is catalytically cracked gasoline, catalytic cracking gasoline, pressure gasoline and coker gasoline.
3, in accordance with the method for claim 1, it is characterized in that the operational condition of fluidized-bed reactor is as follows in the step (1): reaction pressure is 1.0MPa～4.5MPa, 350 ℃～450 ℃ of temperature of reaction, feed volume air speed 0.5h
-1～3.0h
-1With hydrogen to oil volume ratio 200: 1～800: 1.
4, in accordance with the method for claim 1, it is characterized in that the operational condition of fluidized-bed reactor is as follows: reaction pressure is 2.0～4.0MPa, 380～420 ℃ of temperature of reaction, feed volume air speed 1.0～3.0h
-1With hydrogen to oil volume ratio 400: 1～600: 1.
5, in accordance with the method for claim 1, it is characterized in that desulfurating and reducing olefinic hydrocarbon product described in the step (1) and hydrogen sulfide containing gas after the reactor head discharge, carry out gas-liquid separation in gas-liquid separator; Wherein liquid product is a clean gasoline, discharges from the gas-liquid separator bottom, and gaseous product is discharged from gas-liquid separator top; Gas is after depriving hydrogen sulphide is handled, and the hydrogen-rich gas of gained is done to promote gas and/or promote gas in advance to recycle.
6, in accordance with the method for claim 1, it is characterized in that the regeneration condition in the revivifier is as follows in the step (2): regeneration pressure is 0.5MPa～1.5MPa, gas agent volume ratio 500: 1～1000: 1,400 ℃～550 ℃ following constant temperature 3.0～10.0 hours, resurgent gases was an air.
7, in accordance with the method for claim 1, it is characterized in that used desulfurization-olefine lowering catalyst is as follows: the weight with catalyzer is benchmark, transition metal oxide content is 1.0wt%～10.0wt%, the lanthanide rare metal oxide content is 0.5wt%～3.0wt%, the ultrafine particle zeolite content is 50.0wt%～90.0wt%, and surplus is an inorganic oxide adhesive; The grain fineness number of ultrafine particle zeolite is 20nm～800nm.
8, in accordance with the method for claim 7, the specific surface area that it is characterized in that described desulfurization-olefine lowering catalyst is 300m
2/ g～550m
2/ g, pore volume are 0.15ml/g～0.45ml/g, average pore diameter 1.5nm～3.5nm, and B acid amount is 0.020mmol/g～0.080mmol/g, and L acid amount is 0.100mmol/g～0.250mmol/g, and total acid content is 0.120mmol/g～0.330mmol/g.
9, in accordance with the method for claim 7, it is characterized in that described transition group metallic oxide is one or more in zinc oxide, ferric oxide, manganese oxide, nickel oxide, cobalt oxide, molybdenum oxide and the Tungsten oxide 99.999.
10, in accordance with the method for claim 7, it is characterized in that described transition group metallic oxide is one or more in nickel oxide, molybdenum oxide and the zinc oxide, the lanthanide rare metal oxide is lanthanum trioxide and/or cerium oxide.
11, in accordance with the method for claim 7, it is characterized in that described ultrafine particle zeolite is one or more among HZSM-5, HL, HBeta, HM, HMCM-41, HSAPO-5, HSAPO-11, HSAPO-31 and the HSAPO-41.
12, in accordance with the method for claim 7, it is characterized in that described ultrafine particle zeolite is HZSM-5 and/or HBeta.
13, in accordance with the method for claim 7, it is characterized in that used desulfurating and reducing olefinic hydrocarbon catalyzer adopts micro-spherical catalyst, wherein diameter is 60wt%～95wt% that 20～80 microns microballoon accounts for total particulate.
14, in accordance with the method for claim 13, it is characterized in that described microspheroidal desulfurating and reducing olefinic hydrocarbon catalyzer, diameter is 80wt%～95wt% that 20～80 microns microballoon accounts for total particulate.
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