CN1283758C - Process for lowering sulfur content in gasoline through hydrogen supply agent - Google Patents
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- CN1283758C CN1283758C CN 200410060300 CN200410060300A CN1283758C CN 1283758 C CN1283758 C CN 1283758C CN 200410060300 CN200410060300 CN 200410060300 CN 200410060300 A CN200410060300 A CN 200410060300A CN 1283758 C CN1283758 C CN 1283758C
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Abstract
The present invention discloses a process for reducing the content of sulfur in gasoline by using a hydrogen supply agent. The method comprises the steps: raw material gasoline, a hydrogen supplying agent and a catalyst are thoroughly mixed and react in a reactor when steam exists or does not exist; reaction oil gas is sent to a follow up separation system; a catalyst of carbon deposition is circularly used after regeneration; the hydrogen supplying agent uses cyclane with 1 to 3 naphthene rings or cycloalkyl arene; and the reactor is a fixed bed reactor or a conveying pipe type reactor. The content of sulfur in gasoline can be greatly reduced at a low reaction temperature by using the method, the content of olefine in gasoline can also be reduced, and the yield of gas (dry gas and liquid gas) in products is low.
Description
Technical field
The present invention relates to a kind of hydrocarbon oil refining process, especially a kind of method that reduces content of sulfur in gasoline more particularly, is a kind of method of utilizing hydrogen supply agent to reduce content of sulfur in gasoline.
Background technology
In order to control the pollutant emission of vehicle exhaust, strict restriction has all been made to the sulphur content of motor spirit by the main developed country in the world.EPA is in the fuel II class standard regulation of promulgation on December 21st, 1999, and 2004 annual content of sulfur in gasoline are 120 μ g/g, and 2006 annual sulphur contents are reduced to 30 μ g/g; It is 150 μ g/g in the mean content of sulfur of the transitory stage on December 31st, 1 day 1 July in 2002 that Canada requires gasoline domestic production or import, and 2005 annual sulphur contents are reduced to 30 μ g/g; European Union member countries' low-sulphur oil with production sulphur content 50 μ g/g in 2005; Germany adopts the tax incentive policy to strive carrying out in 2003 the low-sulphur oil of use 10 μ g/g.World fuel standard II, III and IV class gasoline index request sulphur content are respectively less than 200 μ g/g, 30 μ g/g and 10 μ g/g.After the China joined WTO, the motor spirit quality index will be in line with international standards gradually, in December, 1999, the more preceding standard of unleaded gasoline for vehicle national standard of promulgation further reduced the sulphur content index, and requiring to rise on January 1st, 2003 in whole nation implementation New standard gasoline index is that sulphur content is not more than 800 μ g/g; By 2005, in Beijing, Shanghai, fringe three big cities were equivalent to the motor spirit of European III class emission standard with implementation, require sulphur content less than 150 μ g/g till that time.Constitute situation by China's motor spirit blend component in 2002, have more than 80% in China's motor spirit as can be seen from catalytic cracking process, because reformed gasoline, gasoline alkylate etc. are sulfur-bearing not substantially, 85～95% sulfide is from catalytically cracked gasoline in the motor spirit.Therefore, reducing sulfur content of catalytic cracking gasoline is the key point that solves vehicle gasoline and sulfur content in vehicle gasoline.
In recent years, " reduce the sulphur content of catalytically cracked gasoline " and become the focus and emphasis of insider's research.People have carried out extensive studies and exploration from aspects such as work flow, catalyzer, processing condition and device structures, and relevant bibliographical information is a lot.
A kind of method is that low-sulphur oil is produced in the pre-treatment of catalytically cracked stock hydrogenation, this method not only can reduce the sulphur content of catalytically cracked gasoline significantly, and can improve the yield of light oil of catalytic cracking unit, reduces coking yield, increase diesel-fuel cetane number, reduce SO in the flue gas
xAnd NO
xQuantity discharged.But the facility investment that this method need be higher and a large amount of hydrogen also cause the gasoline octane rating loss.Another kind method is the catalytic gasoline hydrogenation refining desulfurization, although this method is effective, the shortcoming that reduces gasoline octane rating is arranged equally.
U.S. Pat P5525210, USP5376280 disclose a kind of catalytically cracked gasoline sweetening additive, this additive is made by alumina load Lewis acid, can in the catalytic cracking reaction process, add at any time, also can be prepared in the catalytic cracking catalyst, can play the effect that reduces sulfur content of catalytic cracking gasoline.But this method does not obtain remarkable business success.
Chinese patent application CN1286291A, U.S. Pat P6036847 have disclosed a collection of catalytically cracked gasoline desulfurization catalyst, this catalyzer has stronger acidic components and the stronger hydrogen transfer activity and the function of selective absorption sulphide, can play the effect that reduces sulfur content of catalytic cracking gasoline.But this method does not obtain remarkable business success.
CN1401740A has disclosed a collection of effect inferior gasoline upgrading method preferably.This method adopts duo-lift tube reactor technology, and it is anti-and gasoline pipe is anti-that double lifting leg is called oil pipe, but both parallel operations also can be adopted series system.Oil pipe is counter to adopt conventional Hydrocarbon Content by Catalytic Cracking Operation pattern, and hydrocarbon molecule generates gas, gasoline and diesel oil under high temperature, short contact reaction conditions; Gasoline pipe is a raw material with the raw gasline that catalytic cracking reaction generates instead, adopts the low temperature, the long residence time operational condition that help hydrogen transfer reactions, and catalyzer is a regenerator.This method can significantly reduce the olefin(e) centent of catalytically cracked gasoline, but the desulfurization degree is limited, can only remove in the gasoline 20% sulphur.
CN1388219A has disclosed a kind of catalysis conversion method that reduces content of olefin in gasoline by means of hydrogen supply agent.This method is the proper site that hydrogen supply agents such as tetraline, perhydronaphthalene is joined catalytic cracking unit, plays the effect that reduces catalytic cracking gasoline olefine content.
In sum, reduce the method for sulfur content of catalytic cracking gasoline, also introduced some and in reducing catalytically cracked gasoline, added the method that hydrogen supply agent improves product distribution and product property though related to some in the prior art.But the relevant method of utilizing hydrogen supply agent to reduce sulfur content of catalytic cracking gasoline is not reported in existing documents and materials as yet.
Summary of the invention
The present invention be directed to the low and more high shortcoming of temperature of reaction of desulfurization degree in the prior art, and proposed a kind of method of utilizing hydrogen supply agent to reduce content of sulfur in gasoline.This method not only can reduce the sulphur content in the gasoline significantly under lower temperature of reaction, can also reduce olefin content in gasoline, and gas (dry gas and liquefied gas) productive rate is lower in the resultant.
The method of utilizing hydrogen supply agent to reduce content of sulfur in gasoline provided by the invention is: feed gasoline, hydrogen supply agent and catalyzer are in or be not in water vapor and have thorough mixing and reaction in reactor down, reaction oil gas is delivered to subsequent separation system, and the catalyzer of carbon deposit recycles after regeneration.
Reactor of the present invention is fixed-bed reactor or carries tubular reactor.
Hydrogen supply agent of the present invention is selected naphthenic hydrocarbon or the cycloalkyl aromatic hydrocarbons that contains 1～3 naphthenic ring for use, as C
6～C
8Naphthenic hydrocarbon, tetraline, perhydronaphthalene, anthracene dihydride, indane, tetrahydrochysene anthracene or octahydro anthracene etc.
The used catalyzer of the present invention is a catalytic cracking field catalyzer commonly used, can be acidic oxidation Al catalysts or the alumina silicate catalyst that active ingredient is selected from metal-modified or not modification, can be that active ingredient is selected from Y type or the HY type zeolite that contains or do not contain rare earth and/or phosphorus, contain or do not contain the ultrastable Y of rare earth and/or phosphorus, the supersiliceous zeolite of ZSM-5 type zeolite or tool five-membered ring structure, the β zeolite, the catalyzer of one or more in the ferrierite, it can be the catalyzer that active ingredient is selected from non-zeolite molecular sieve MeAPO-5 and/or MeAPSO-5, also can be the catalyzer that active ingredient is selected from mesopore crystalline material MCM-41 and/or MCM-48, these catalyzer all can buied on the market.
When adopting fixed-bed reactor, preferred catalyst is the acidic oxidation Al catalysts or the alumina silicate catalyst of metal-modified or not modification.Reaction conditions is: temperature of reaction arrives less than 450 ℃ for 200 ℃, and preferred 350 ℃ are arrived less than 450 ℃; Air speed 0.3～10h
-1, preferred 1.0～2.5h
-1Reaction pressure 0.1～0.8MPa, preferred 0.1～0.4Mpa; Quantity of steam accounts for 0～30 weight % of stock oil, is preferably 0～10 weight %.
When adopting the conveying tubular reactor, preferred catalyst is any molecular sieve catalyst that the catalytic cracking field is commonly used, and its active ingredient is one or more in the supersiliceous zeolite that contains or do not contain the Y type of rare earth and/or phosphorus or HY type zeolite, the ultrastable Y that contains or do not contain rare earth and/or phosphorus, ZSM-5 type zeolite or tool five-membered ring structure, β zeolite, the ferrierite.Reaction conditions is: temperature of reaction arrives less than 450 ℃ preferred 330～430 ℃ for 280 ℃; The weight ratio of catalyzer and feed gasoline is 2～35, preferred 3～20; Reaction pressure 0.1～0.5MPa, preferred 0.1～0.3MPa; Quantity of steam 0～30 weight %, preferred 1～5 weight %; 0.5～10 second reaction times, preferred 2～5 seconds.
When adopting the conveying tubular reactor, equipment therefor of the present invention comprises conventional catalytic cracking unit and deriving device thereof.Conventional catalytic cracking unit comprises riser fluid catalytic cracking, fluidized bed catalytic cracker, Desending catalytic cracking device etc.The described catalytic cracking unit of deriving is meant on the basis of above-mentioned conventional catalytic cracking unit transforms the resulting conventional catalytic cracking unit in back to reaction, regeneration, fractionation and/or absorption-steady component.For example, the related device of disclosed device in the patent application of CN1401740A, CN1388219A, riser tube+bed device etc.
Feed gasoline of the present invention can be selected from one or more the mixing oil in catalytically cracked gasoline, coker gasoline, the viscosity breaking gasoline, can be full cut, also can be the part narrow fraction.
Method provided by the invention can be implemented separately, also can install Joint Implementation with other.
The present invention is because hydrogen supply agent suppresses the further reaction of carbonium ion, reduce reaction transformation efficiency, the preferred hydrogen supply agent of the present invention only contacts with gasoline and the reaction process that do not contact with heavy oil.For example, process the fixed bed device of gasoline separately, the double lift pipe catalytic cracking device of gasoline rising pipe reactor etc. is arranged.
The present invention compared with prior art, (1) can significantly reduce the sulphur content of gasoline, the reduction amplitude can reach more than 40%, simultaneously other character of gasoline is improved.For example, the olefin(e) centent of gasoline descends, and increase inductive phase.And MON and RON for gasoline do not have detrimentally affect.(2) can improve the gasoline yield that has the double lift pipe catalytic cracking device now.The present invention introduces hydrogen supply agent in the catalytic conversion process of gasoline, thereby has strengthened hydrogen transfer reactions, has suppressed the further reaction of carbonium ion in the gasoline catalytic conversion process, and the cracking conversion rate of gasoline is reduced.(3) temperature of reaction of the present invention is less than 450 ℃, thereby can improve the retention rate of gasoline and promote hydrogen transfer reactions; Gas yield is lower, is not generally even producing gas below 5%.
Below in conjunction with accompanying drawing and enumerate several concrete embodiments so that the present invention is described further.But these embodiments do not limit the scope of the invention.
Accompanying drawing and description of drawings
Fig. 1 is the schematic flow sheet that the present invention implements separately on fixed-bed reactor.
Fig. 2 is that the present invention is carrying the schematic flow sheet of implementing separately on the tubular reactor.
Fig. 3 is that the present invention is having the schematic flow sheet of implementing on the double lift pipe catalytic cracking device of gasoline rising pipe reactor.
Enforcement mode one: the present invention implements separately on fixed bed reactors. As shown in Figure 1, the feed gasoline 1 after the preheating jointly enters in the fixed bed reactors 3 and with catalyst 4 with hydrogen supply agent 2 and contacts, and is in or be not under the water vapour existence to react, and reaction oil gas is delivered to subsequent separation system. For considering the regeneration of catalyst, set up two reactors and be used alternatingly.
Enforcement mode two: the present invention is carrying separately enforcement on the tubular reactor. As shown in Figure 2, jointly enter in the riser reactor 6 from feed gasoline 1 and the hydrogen supply agent 2 of regeneration catalyzing agent after preheating of regenerator 5, be in or be not in water vapour and react under existing; Reaction oil gas is separated with spent agent, and reaction oil gas enters subsequent separation system, further is separated into gasoline products and a small amount of dry gas, liquefied gas, diesel oil; Spent agent enters regenerator 5 behind the water vapour stripping, carry out coke burning regeneration in the presence of air; Catalyst Returning reactor 6 after the regeneration recycles. The heat that needs in the course of reaction can add fuel oil and replenish in regenerator.
Enforcement mode three: the present invention implements at the double lift pipe catalytic cracking device that gasoline riser reactor is arranged, and namely adopts reaction unit related in the CN1401740A patent to implement the present invention. Related reaction unit as shown in Figure 3 in the CN1401740A patent, this reaction unit comprises heavy oil riser reactor 13, the first settler 12, regenerator 15, gasoline riser reactor 7 and the second settler 9, heavy oil riser reactor 13 bottoms are connected with regenerator 15, top exit is connected with the first settler 12, and gasoline riser reactor 7 bottoms are connected with regenerator 15, top exit is connected with the second settler 9. Heavy oil 16 heavy oil riser reactor 13 bottoms be mixed into heavy oil riser reactor 13 from the high temperature catalyst 17 of regenerator 15 bottoms and under conventional catalytic cracking condition, react, enter the first settler 12 after the reaction and carry out catalyst and Oil-gas Separation, reaction oil gas 11 enters fractionating system to be separated, obtain comprising product and the unconverted oil of catalytically cracked gasoline, reclaimable catalyst stripping section 14 below the first settler enters regenerator 15 behind stripping, regenerator 15 is under conventional catalytic cracking catalyst regeneration condition, reclaimable catalyst is carried out coke burning regeneration, and general regeneration temperature is controlled at 650～750 ℃. Feed gasoline 1 and hydrogen supply agent 2 gasoline riser reactor 7 bottoms be mixed into gasoline riser reactor 7 from the high temperature catalyst 17 of regenerator 15 bottoms, carry out catalyst and transform Oil-gas Separation along being advanced into the second settler 9 on the gasoline riser reactor 7, conversion oil gas 10 enters fractionating system and carries out fractionation, obtains gasoline products and a small amount of dry gas, liquefied gas, diesel oil; Reclaimable catalyst stripping section 8 below the second settler 9 enters regenerator 15 behind stripping, carry out coke burning regeneration in the presence of air; Catalyst Returning reactor after the regeneration recycles.
Embodiment
In order to further specify method of the present invention, enumerate several specific embodiments below.But these embodiment do not limit the scope of the invention.
Present embodiment explanation: adopt fixed-bed reactor, with perhydronaphthalene as hydrogen supply agent, with ZnO/Al
2O
3Be catalyzer, reduce the sulphur content of gasoline.
The catalyzer loading amount is 10 the gram the small stationary bed bioreactors, with perhydronaphthalene as hydrogen supply agent, with ZnO/Al
2O
3Be catalyzer, test the catalytically cracked gasoline that raw materials used oil is produced for the SINOPEC Luoyang Company catalytic cracking unit, its character sees Table 1.It is as follows that main operational condition sees Table 2 testing sequences: add 3% perhydronaphthalene in catalytically cracked gasoline, contact with catalyzer in the fixed-bed reactor then and react, reaction oil gas is collected resulting reacted gas and product liquid after three grades of condensations are cooled off; It forms reacted gas by gas chromatographic analysis, C
5Above component counts in the gasoline fraction; Product liquid is measured the content of gasoline, diesel oil and heavy oil by the simulation distil device; Carry out deciding the carbon analysis after the catalyzer cooling, determine coke yield.Product distributes and gasoline property sees Table 2.
With embodiment 1, just in catalytically cracked gasoline, do not add hydrogen supply agent, the results are shown in table 2.
Two groups of data in the comparison sheet 2 as can be seen, adopt the present invention after, the desulfurization degree of gasoline rises to 50.3% by 32.9%.Simultaneously, the retention rate of gasoline improves, and the productive rate of dry gas, liquefied gas descends.
The present embodiment explanation: adopt lower temperature of reaction, the retention rate of gasoline improves, and can not produce gas, and shortcoming is that the octane value of gasoline descends.
Implementation method is with embodiment 1 and embodiment 2, and different is just temperature of reaction to be reduced to 200 ℃ from 380 ℃.The results are shown in table 3.
Embodiment 4
Present embodiment explanation: adopt testing laboratory's fixed fluidized-bed reactor, adopt conventional catalytic cracking catalyst, adopt the present invention, the sulphur content of gasoline is significantly reduced.
As hydrogen supply agent, is catalyzer with catalytic cracking catalyst LCS-7B poiser with methylcyclohexane, is the test of carrying out on testing laboratory's fixed-bed reactor of 100 grams in the catalyzer loading amount.Catalyst property sees Table 4.Test raw materials used oil with embodiment 1, main operational condition sees Table 5, testing sequence is as follows: the methylcyclohexane of adding 5% in catalytically cracked gasoline, pump in the fixed-bed reactor with pump then and contact and react with the catalyzer of heat, reaction oil gas is collected resulting reacted gas and product liquid after three grades of condensation coolings; It forms reacted gas by gas chromatographic analysis, C
5Above component counts in the gasoline fraction; Product liquid is measured the content of gasoline, diesel oil and heavy oil by the simulation distil device; Carry out deciding the carbon analysis after the catalyzer cooling, determine coke yield.Product distributes and gasoline property sees Table 5.
Embodiment 5
With embodiment 4, just in test raw material oil, do not add hydrogen supply agent, the results are shown in table 5.
Two groups of data in the comparison sheet 5 as can be seen, adopt the present invention after owing to strengthened hydrogen transfer reactions, the desulfurization degree of gasoline rises to 41.1% by 24.8%.Simultaneously, the retention rate of gasoline improves, and the productive rate of dry gas, liquefied gas descends.
Embodiment 6
The present embodiment explanation: the mixture that adopts two kinds of hydrogen supply agents adopts conventional catalytic cracking catalyst on testing laboratory's fixed fluidized-bed reactor, adopts the present invention, and the sulphur content of gasoline is significantly reduced.
As hydrogen supply agent, is catalyzer with catalytic cracking catalyst LCS-7B poiser with methylcyclohexane+tetraline, is the test of carrying out on testing laboratory's fixed-bed reactor of 100 grams in the catalyzer loading amount.Catalyst property sees Table 4.Test raw materials used oil with embodiment 1, main operational condition sees Table 6, and testing sequence just adds 2% methylcyclohexane+2% tetraline with embodiment 3 in catalytically cracked gasoline in stock oil.The product that obtains distributes and gasoline property sees Table 6.
With embodiment 6, just in test raw material oil, do not add hydrogen supply agent, the results are shown in table 6.
Present embodiment explanation: adopt the riser catalytic cracking middle-scale device, as hydrogen supply agent, use conventional catalytic cracking catalyst, adopt the present invention, the sulphur content of gasoline is significantly reduced with perhydronaphthalene.
This test is to be that the riser catalytic cracking middle-scale device of 5kg/h carries out in the raw material treatment capacity, and the test catalyst system therefor is conventional catalytic cracking catalyst LCS-7B poiser, and its character sees Table 4.Testing raw materials used oil is the catalytically cracked gasoline that Sinopec Chang Ling branch office catalytic cracking unit is produced, and its character sees Table 7.Main operational condition sees Table 8, testing sequence is as follows: the perhydronaphthalene of adding 2% in catalytically cracked gasoline, enter riser tube by the high-efficient atomizing nozzle that is arranged in the riser reactor bottom, contact with high temperature catalyst then and react from regenerator bottoms, reaction oil gas and mixture of catalysts are up and enter settling vessel along riser tube, catalyzer separates with reaction oil gas there, reaction oil gas enters and enters follow-up fractionating system through transfer line and separate, and obtains products such as reacted gas, gasoline, diesel oil.The spent agent of reaction back carbon deposit enters revivifier behind the water vapour stripping, carry out coke burning regeneration in the presence of air, and the catalyzer Returning reactor after the regeneration recycles.By flue gas table metering exhaust gas volumn, by exhaust gas volumn and forms definite coke yield.Product distributes and gasoline property sees Table 8.
With embodiment 8, just in test raw material oil, do not add hydrogen supply agent, the results are shown in table 8.
Two groups of data in the comparison sheet 8 as can be seen, adopt the present invention after, the desulfurization degree of gasoline rises to 43.6% by 22.3%.Simultaneously, the retention rate of gasoline improves, and the productive rate of dry gas, liquefied gas descends.
The present embodiment explanation: in the presence of hydrogen supply agent, adopt too high temperature of reaction, as 460 ℃ or higher, will reduce the hydrogen transfer reactions ability of reaction system, cause the gasoline loss to increase, sulphur reduction amplitude descends.
Test is carried out on the riser catalytic cracking middle-scale device, and the add-on of testing raw materials used oil, hydrogen supply agent, catalyzer and hydrogen supply agent is with embodiment 7.The main operational condition of test and the product that obtains distribute, gasoline property sees Table 9.
Data in comparison sheet 8, the table 9 as can be seen, temperature of reaction raises, because the competitive capacity of the hydrogen transfer reactions of heat release is reduced, the competitive capacity of the cracking reaction of heat absorption is improved, the desulfurization degree of gasoline reduces to 27.1% by 43.6%.Simultaneously, the retention rate of gasoline descends significantly, and gas yield, coke yield obviously increase.
Table 1 test Luoyang Company catalytically cracked gasoline character
| Project | Data |
| Density, 20 ℃, kg/m 3 | 720.7 |
| Boiling range, ℃ | |
| IBP | 37 |
| 10％ | 68 |
| 30％ | 94 |
| 50％ | 118 |
| 70％ | 153 |
| 90％ | 175 |
| FBP | 196 |
| Sulphur content, μ g/g | 1048 |
| Inductive phase, min | 676 |
| RON | 90.1 |
| RON | 80.6 |
| Group composition, v% | |
| Alkene | 48.0 |
| Aromatic hydrocarbons | 12.0 |
| Stable hydrocarbon | 40.0 |
Table 2 operational condition and refining result (fixed bed)
| Operational condition | ||
| Stock oil | Catalytically cracked gasoline | Catalytically cracked gasoline+3w% perhydronaphthalene |
| Temperature of reaction/℃ air speed/h -1Pressure/MPa | 380 2 0.3 | 380 2 0.3 |
| Product distributes, and w% dry gas liquefied gas gasoline, diesel heavy oil coke adds up to | 0.41 1.33 93.08 4.52 0 0.66 100 | 0.34 1.12 94.35 3.66 0 0.53 100 |
| Gasoline property density, 20 ℃, kg/m 3Sulphur content, μ g/g inductive phase, min RON MON group composition, v% alkene aromatic hydrocarbons stable hydrocarbon | 721.5 703 ＞1000 90.2 80.8 21.3 23.6 55.1 | 721.3 521 ＞1000 90.2 80.6 17.5 22.1 60.4 |
| Desulfurization degree, w% | 32.9 | 50.3 |
Table 3 temperature of reaction is to refining result's influence (fixed bed)
| Operational condition | ||
| Stock oil | Catalytically cracked gasoline | Catalytically cracked gasoline+3w% perhydronaphthalene |
| Temperature of reaction/℃ air speed/h -1Pressure/MPa | 200 2 0.3 | 200 2 0.3 |
| Product distributes, and % dry gas liquefied gas gasoline, diesel heavy oil coke adds up to | 0.00 0.00 95.31 4.20 0 0.49 100 | 0.00 0.00 96.03 3.54 0 0.43 100 |
| Gasoline property density, 20 ℃, kg/m 3Sulphur content, μ g/g inductive phase, min RON MON group composition, v% alkene aromatic hydrocarbons stable hydrocarbon | 720.8 688 ＞1000 89.3 78.6 18.3 21.9 59.8 | 720.7 517 ＞1000 89.3 78.6 17.1 18.1 64.8 |
| Desulfurization degree, w% | 34.4 | 50.7 |
The character of table 4LCS-7B poiser
| Tap density, g/cm 3The micro-activity carbon content, % specific surface area, m 2/ g pore volume, the mL/g lattice constant, nm Ni content, μ g/g V content, μ g/g Fe content, μ g/g Na content, μ g/g Cu content, μ g/g Ca content, μ g/g size composition, %＜20 μ m, 20～40 μ m, 40～80 μ m＞80 μ m | 0.84 64 0.04 135 0.36 2.428 4873 534 6070 2300 56 680 1.0 13 62 24 |
Table 5 operational condition and refining result (fixed fluidized bed)
| Operational condition | ||
| Stock oil | Catalytically cracked gasoline | Catalytically cracked gasoline+5w% methylcyclohexane |
| Temperature of reaction, ℃ agent-oil ratio air speed, h -1Steam water, weight % (accounting for raw material) | 420 4.5 10 5 | 420 4.5 10 5 |
| Product distributes, and w% dry gas liquefied gas gasoline, diesel heavy oil coke adds up to | 0.78 4.61 87.43 6.15 0 1.03 100 | 0.52 2.98 91.47 4.31 0 0.72 100 |
| Gasoline property density, 20 ℃, kg/m 3Sulphur content, μ g/g inductive phase, min RON MON group composition, v% alkene aromatic hydrocarbons stable hydrocarbon | 726.7 788 ＞1000 90.1 80.7 23.6 23.4 53.0 | 725.9 617 ＞1000 90.1 80.6 19.3 22.4 58.3 |
| The gasoline desulfur rate, weight % | 24.8 | 41.1 |
Table 6 operational condition and refining result (fixed fluidized bed)
| Operational condition | ||
| Stock oil | Catalytically cracked gasoline | Catalytically cracked gasoline+2w% methylcyclohexane+2w% tetraline |
| Temperature of reaction, ℃ agent-oil ratio air speed, h -1Steam water, weight % (accounting for raw material) | 440 5.5 10 5 | 440 5.5 10 5 |
| Product distributes, and w% dry gas liquefied gas gasoline, diesel heavy oil coke adds up to | 0.91 6.74 84.07 7.05 0 1.23 100 | 0.63 5.38 88.12 4.96 0 0.91 100 |
| Gasoline property density, 20 ℃, kg/m 3Sulphur content, μ g/g inductive phase, min RON MON group composition, v% alkene aromatic hydrocarbons stable hydrocarbon | 729.4 764 ＞1000 90.3 80.9 20.1 27.6 52.3 | 727.6 596 ＞1000 90.4 80.9 16.0 26.2 57.8 |
| The gasoline desulfur rate, weight % | 27.1 | 43.1 |
Table 7 test Chang Ling branch office catalytically cracked gasoline character
| Density, 20 ℃, kg/m 3 | 734.1 |
| Boiling range, ℃ | |
| IBP | 36 |
| 10％ | 71 |
| 30％ | 101 |
| 50％ | 123 |
| 70％ | 164 |
| 90％ | 186 |
| FBP | 201 |
| Sulphur content, μ g/g | 1314 |
| Inductive phase, min | 630 |
| RON | 91.1 |
| RON | 81.4 |
| Group composition, v% | |
| Alkene | 44.2 |
| Aromatic hydrocarbons | 22.9 |
| Stable hydrocarbon | 32.9 |
Table 8 hydrogen supply agent is to the influence (medium-sized riser tube) of reactivity worth
| Operational condition | ||
| Stock oil | Catalytically cracked gasoline | Catalytically cracked gasoline+2w% perhydronaphthalene |
| Temperature of reaction, ℃ agent-oil ratio reaction times, the s reaction pressure, the Mpa steam water, weight % (accounting for raw material) | 405 4.1 3.2 0.2 5 | 405 4.5 3.2 0.2 5 |
| Product distributes, and w% dry gas liquefied gas gasoline, diesel heavy oil coke adds up to | 0.72 4.37 88.97 5.06 0 0.88 100 | 0.48 3.02 92.44 3.43 0 0.63 100 |
| Gasoline property density, 20 ℃, kg/m 3Sulphur content, μ g/g inductive phase, min RON MON group composition, v% alkene aromatic hydrocarbons stable hydrocarbon | 735.5 1020 ＞1000 91.2 81.8 18.6 33.8 47.6 | 735.8 741 1000 91.2 80.6 16.7 32.1 51.2 |
| The gasoline desulfur rate, weight % | 22.3 | 43.6 |
Table 9 temperature of reaction is to the influence (medium-sized riser tube) of reactivity worth
| Operational condition | |
| Stock oil | Catalytically cracked gasoline+2w% perhydronaphthalene |
| Temperature of reaction, ℃ agent-oil ratio reaction times, the s reaction pressure, the Mpa steam water, weight % (accounting for raw material) | 460 5.5 3.2 0.2 5 |
| Product distributes, and w% dry gas liquefied gas gasoline, diesel heavy oil coke adds up to | 0.83 10.89 81.79 4.78 0 1.71 100 |
| Gasoline property density, 20 ℃, kg/m 3Sulphur content, μ g/g inductive phase, min RON MON group composition, v% alkene aromatic hydrocarbons stable hydrocarbon | 740.1 958.1 1000 91.8 81.1 12.3 41.8 45.9 |
| The gasoline desulfur rate, w% | 27.1 |
Claims (5)
1. method of utilizing hydrogen supply agent to reduce content of sulfur in gasoline, it is characterized in that: feed gasoline, hydrogen supply agent and catalyzer are in or be not in water vapor and have thorough mixing and reaction in reactor down, reaction oil gas is delivered to subsequent separation system, the catalyzer of carbon deposit recycles after regeneration, wherein said hydrogen supply agent is selected naphthenic hydrocarbon or the cycloalkyl aromatic hydrocarbons that contains 1～3 naphthenic ring for use, reactor is fixed-bed reactor or carries tubular reactor, when adopting fixed-bed reactor, temperature of reaction is 200 ℃ and arrives less than 450 ℃ that air speed is 0.3～10h
-1, reaction pressure is 0.1～0.8MPa, quantity of steam accounts for 0～30 weight % of stock oil; When adopting the conveying tubular reactor, temperature of reaction is 280 ℃ and arrives less than 450 ℃ that the weight ratio of catalyzer and feed gasoline is 2～35, and reaction pressure is 0.1～0.5MPa, and quantity of steam accounts for 0～30 weight % of stock oil, and the reaction times is 0.5～10 second.
2. it is characterized in that in accordance with the method for claim 1: described feed gasoline is selected from one or more the mixing oil in catalytically cracked gasoline, coker gasoline, the viscosity breaking gasoline.
3. it is characterized in that in accordance with the method for claim 1: described hydrogen supply agent is C
6～C
8Naphthenic hydrocarbon, tetraline, perhydronaphthalene, anthracene dihydride, indane, tetrahydrochysene anthracene or octahydro anthracene.
4. in accordance with the method for claim 1, it is characterized in that: when reactor was fixed-bed reactor, temperature of reaction was 350 to less than 450 ℃, and air speed is 1.0～2.5h
-1, reaction pressure is 0.1～0.4Mpa, quantity of steam accounts for 0～10 weight % of stock oil.
5. in accordance with the method for claim 1, it is characterized in that: when reactor was the conveying tubular reactor, temperature of reaction was 330～430 ℃, and agent-oil ratio is 3～20, and reaction pressure is 0.1～0.3Mpa, and quantity of steam accounts for 1～5 weight % of stock oil; Reaction times is 2～5 seconds.
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| CN101942337B (en) * | 2009-07-09 | 2013-08-28 | 中国石油化工股份有限公司 | Combined process for heavy oil modification |
| CN116162488A (en) * | 2021-11-25 | 2023-05-26 | 中国石化工程建设有限公司 | Method for treating ethylene cracking product gasoline |
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