CN103059965B - Catalytic gasoline deep hydrodesulfurizationmethod method - Google Patents
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Abstract
The invention discloses a kind of catalytic gasoline deep hydrodesulfurizationmethod method.The operational condition of adjustment catalytic unit separation column, increase a side line, take the cut point be suitable for, tower top goes out FCC gasoline lighting end, and side line goes out FCC last running; Alkali-free sweetening is carried out in FCC gasoline lighting end, then separates petroleum naphtha and middle gasoline by hydrogenation preliminary fractionator; Middle gasoline carries out the selective hydrogenation relaxed, and heavy petrol carries out the selective hydrogenation of the degree of depth, gained two portions refine after distillate mix with the petroleum naphtha of alkali-free sweetening, obtain clean gasoline product or blend component.Compared with existing catalyzed gasoline hydrogenation desulfurization technology, the inventive method plant energy consumption obviously reduces, and gasoline octane rating loss is little, and the specification of quality that gasoline product quality can be made to meet sulphur content be less than 10 μ g/g improves the economic benefit of oil refining enterprise.
Description
Technical field
The present invention relates to a kind of catalytic gasoline deep hydrodesulfurizationmethod method, is specifically that raw material hydrogenation production sulphur content is less than the clean gasoline of 10 μ g/g or the method for clean gasoline blend component with catalytic gasoline.
Background technology
Increasingly strict along with environmental regulation, the developed country such as American-European in succession makes laws and proposes more and more stricter regulation to sulphur in motor spirit and olefin(e) centent.From 2009, execution sulphur content is less than 10 μ g/g Europe V emission standards.China requires also more and more stricter to the sulphur content of motor spirit, from 1 day January in 2008, supply Pekinese gasoline starts to perform the specification being equivalent to Europe IV emission standard, and namely sulphur content is less than 50 μ g/g, and similar standard also will be carried out successively in the domestic big city such as Shanghai, Guangzhou.On July 1st, 2010, other areas started to perform the specification being equivalent to EuropeⅢ emission standard, and namely sulphur content is less than 150 μ g/g, and alkene percentage composition is not more than 18v%.As can be seen here, the requirement of following China to content of sulfur in gasoline and olefin(e) centent will be more and more stricter.Therefore, for the product structure of China's motor spirit, be necessary that a kind of new Technology of exploitation is less than the motor spirit of 10 μ g/g for the production of sulphur content, to meet the needs of future market.
Due to historical reasons, in China's motor spirit blend component, catalytically cracked gasoline accounts for about 75% ~ 80%, and has the advantages that sulphur content is higher and alkene is higher.Therefore, reducing China's sulfur content of catalytic cracking gasoline is the major issue faced present stage.
External prior art mainly comprises the SCANFining technique of ExxonMobil company, the Prime-G of Inst Francais Du Petrole
+hydrogenating desulfurization/octane value recovering the combination process of technique to be the selective hydrogenation desulfurization process of representative and the OCTGAIN technique of ExxonMobil company, the ISAL technique of Uop Inc. be representative.But because external catalytically cracked gasoline character difference compared with domestic is comparatively large, and proportion is less in gasoline blending component.Therefore, foreign technology is difficult to realize satisfactory results at the domestic catalytically cracked gasoline of processing.
The reducing olefins by hydrogen desulfurization of catalytic gasoline technology of domestic-developed has RSDS, RSDS-II, the RIDOS of Research Institute of Petro-Chemical Engineering and the OCT-M technology of Fushun Petrochemical Research Institute (FRIPP) and OCT-MD technology, these technology all achieve industrialization, but, when production sulphur content is less than the gasoline products of 10 μ g/g, all there is the comparatively large and shortcoming that energy consumption is higher of product loss of octane number.Such as RSDS-II technology of Research Institute of Petro-Chemical Engineering's exploitation, show in the situation of full scale plant running, want the clean gasoline that production sulphur content is less than 10 μ g/g, the loss of octane value will be very large.
CN101307255A discloses a kind of method of producing low sulfur gasoline by using by inferior gasoline fractions.Full cut bad gasoline is first fixed an oxidation deodorizing by the method, mercaptan sulfur is converted into disulphide, then fractionation is lighting end and last running, last running carries out selective hydrodesulfurization through high reactivity/low activity combined hydrogenation desulfurization catalyst, and desulfurization product and lighting end are mixed to get clean gasoline product.Although the method also can produce the gasoline products that sulphur content is less than 10 μ g/g, stock oil adaptability is poor, and loss of octane number is also comparatively large, and technical process and the present invention have very big difference.
CN101787307A discloses a kind of gasoline hydrodesulfurizationmethod method.Gasoline stocks is fractionated into lighting end gasoline and last running gasoline by the method, and wherein the mercaptan sulfur removed wherein refined by lighting end gasoline through alkali cleaning; Last running gasoline, successively through two hydrogenators, carries out hydrogenation and takes off diene, selective hydrodesulfurization and the reaction of selective hydrodesulfurization alcohol; The hydrogenation last running gasoline of gained with refining after lighting end gasoline mix after obtain the full distillation gasoline of super low sulfur.Although the method also can produce the gasoline products that sulphur content is less than 10 μ g/g, raw material has adaptability poor, and technical process is completely different from thinking of the present invention.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of catalytic gasoline deep hydrodesulfurizationmethod method, production sulphur content can be less than the clean gasoline blend component of 10 μ g/g, and energy consumption significantly reduces compared with existing apparatus.
Catalytic gasoline deep hydrodesulfurizationmethod method of the present invention comprises following content:
(1) adjust the operation of catalytic cracking unit separation column, in FCC separation column, carry out FCC gasoline pre-separation, obtain lighting end and last running; The segmentation temperature of described lighting end and last running is 110 DEG C ~ 130 DEG C;
(2) step (1) gained lighting end enters alkali-free sweetening unit, carries out mercaptan removal process;
(3) lighting end after step (2) gained deodorization enters gasoline hydrogenation preliminary fractionator, isolates petroleum naphtha and middle gasoline; The segmentation temperature of petroleum naphtha and middle gasoline is 60 DEG C ~ 75 DEG C;
(4), after in step (3) gained, gasoline mixes with hydrogen, successively by catalytic gasoline middle runnings pre-hydrogenator and hydrodesulphurisatioreactors reactors, gained reaction effluent enters separator and is separated; Enter catalytic gasoline heavy fractioning hydrogenation desulphurization reactor after the last running of step (1) gained catalytic gasoline mixes with hydrogen to react, reaction effluent enters separator and is separated; Gained two portions hydrogenated liquid product mixes with the petroleum naphtha of step (3) after air lift, obtains clean gasoline product or gasoline blending component.
According to catalytic gasoline deep hydrodesulfurizationmethod method of the present invention, wherein adjust the operation of catalytic cracking unit separation column described in step (1), can carry out in newly-built catalytic cracking unit, also can make full use of existing product fractionating system in catalytic cracking unit to transform, such as, can realize by increasing FCC gasoline last running side line and adjusting operational condition.Described in step (1), the segmentation temperature of lighting end and last running is generally 110 DEG C ~ 130 DEG C, preferably 115 DEG C ~ 130 DEG C.
Alkali-free sweetening described in step (2) can adopt routine techniques well known in the art.Used catalyst is the catalyzer that this area is commonly used, and can select commercial goods or be prepared according to the knowledge of this area.The condition of lighting end alkali-free sweetening is: reactor operating pressure is 0.1 ~ 1.0MPa, and temperature of reaction is 20 DEG C ~ 70 DEG C, Feed space velocities 0.5 ~ 2.0h
-1, air flow quantity/inlet amount volume ratio is 0.1 ~ 1.0.Lighting end is after alkali-free sweetening, and the mercaptan wherein contained and easily remove after sulfide is oxidized to the heavier sulfide such as disulphide (thioether), enters in heavier middle gasoline.
The segmentation temperature of the petroleum naphtha described in step (3) and middle gasoline is 60 DEG C ~ 75 DEG C, preferably 60 DEG C ~ 70 DEG C.After hydrogenation unit hydrogenation preliminary fractionator, what generate in step (2) removes gasoline in sulphur containing disulphide (thioether) etc. compared with heavy sulfide and part difficulty and is separated with the petroleum naphtha after deodorization.Petroleum naphtha after gained alkali-free sweetening enters product mediation tank field.
The last running of gasoline and the pre-separation of FCC separation column in gained in step (4), respectively as the charging of selective hydrogenation device.The catalyzer that described catalytic gasoline middle runnings pre-hydrogenator uses is Hydrobon catalyst conventional in this area, as being W-Mo-Ni series hydrocatalyst.The composition of W-Mo-Ni series hydrocatalyst generally includes: Tungsten oxide 99.999 8wt% ~ 15wt%, molybdenum oxide 6 wt% ~ 16 wt% and nickel oxide 2.0 wt% ~ 8.0 wt%.Catalytic gasoline middle runnings and heavy fractioning hydrogenation desulphurization reactor are built with desulfurization catalyst, and described desulfurization catalyst is also the Hydrobon catalyst that this area is conventional, as being Mo-Co series hydrocatalyst.The composition of Mo-Co series catalysts comprises: molybdenum oxide 6wt% ~ 16 wt%, cobalt oxide 2.0 wt% ~ 8.0 wt%.Two portions hydrogenation products is through gas-liquid separation and mix with step (3) gained petroleum naphtha after stripping tower, can obtain sulphur content lower than the clean gasoline product of 10 μ g/g or clean gasoline blend component.
In step (4), middle gasoline hydrodesulfurizationmethod reaction effluent and heavy fractioning hydrogenation desulphurization reaction effluent can enter two cover gas-liquid separation devices respectively and be separated, and also can share a set of gas-liquid separation device and carry out gas-liquid separation.
In the inventive method, in step (4), the operational condition of catalytic gasoline middle runnings pre-hydrogenator is: hydrogen dividing potential drop 0.8MPa ~ 4.0MPa, best 1.0MPa ~ 2.5MPa; Temperature of reaction is 150 DEG C ~ 250 DEG C, best 160 DEG C ~ 230 DEG C; Volume space velocity is 2.0h
-1~ 6.0h
-1, best 2.5h
-1~ 5.0h
-1; Hydrogen to oil volume ratio is 10 ~ 300, is preferably 50 ~ 200; The operational condition of catalytic gasoline middle distillate hydrodesulfurization reactor is: hydrogen dividing potential drop 1.0MPa ~ 4.0MPa, is preferably 1.0MPa ~ 3.0MPa; Temperature of reaction is 200 DEG C ~ 300 DEG C, is preferably 220 DEG C ~ 280 DEG C; Volume space velocity is 1.0 h
-1~ 6.0h
-1, be preferably 2.5 h
-1~ 4.0 h
-1; Hydrogen to oil volume ratio is 100 ~ 700, is preferably 200 ~ 500.
In step (4), the operational condition of catalytic gasoline heavy fractioning hydrogenation desulphurization reactor is: hydrogen dividing potential drop 1.2 MPa ~ 4.0 MPa, best 1.5MPa ~ 3.0MPa; Temperature of reaction is 220 DEG C ~ 340 DEG C, and best 250 DEG C ~ 320 DEG C, volume space velocity is 1.0 h
-1~ 6.0h
-1, be preferably 2.0 h
-1~ 4.0 h
-1; Hydrogen to oil volume ratio is 100 ~ 700, is preferably 200 ~ 500.
Because catalytic gasoline middle runnings (namely in gasoline) and last running (i.e. heavy petrol) can hydrogenating desulfurizations under different processing condition respectively, therefore under the condition reaching identical desulfurization depth, the loss of octane number of the inventive method products obtained therefrom is minimum; Two portions reaction effluent is after separator and stripping tower, and product liquid enters product mediation tank field, and the gas being rich in hydrogen returns reactor through desulfurization process Posterior circle to be continued to use.
Compared with existing catalyzed gasoline hydrogenation desulfurization technology, the inventive method has following outstanding technique effect:
1, in the inventive method, only need the operational condition adjusting catalytic cracking unit separation column, the pre-separation of light, the last running to catalytic gasoline can be realized in catalytic cracking unit, existing product fractionating system in catalytic cracking unit can be made full use of transform, be conducive to reducing plant modification investment and process cost, and technical scheme mature and reliable, simple.
2, in prior art, oil require that catalytic cracking unit is steamed is after cooling, gasoline hydrogenation device can be transported to by pipeline, and then the requirement of preliminary fractionator feeding temperature just can be reached by heat exchange or process furnace, catalytic gasoline needs the temperature variation that experience cooling, intensification etc. are larger, causes gasoline hydrogenation device to considerably increase unnecessary energy consumption.And in the inventive method, adopt the flow process of light, the last running direct hot feed of catalytic cracking pre-separation, eliminate the operation of cooling, intensification equitemperature fluctuation, the catalytic gasoline that can make full use of catalytic cracking pre-separation is light, the heat of last running, thus significantly reduce the energy consumption of gasoline hydrogenation preliminary fractionator and hydrogenation unit, reduce process cost simultaneously.
3, in the inventive method, first the lighting end of catalytic cracking pre-separation carries out alkali-free sweetening, remove mercaptan wherein and simple sulfide, then by hydrogenation preliminary fractionator, petroleum naphtha wherein can as product blend component, and the disulphide that deodorising process generates and a small amount of coke precursor enter heavier middle gasoline, can be removed by the selective hydrodesulfurization of pre-hydrogenation and mitigation, the more heavy petrol of sulfur-bearing then carries out depth-selectiveness hydrogenating desulfurization under comparatively exacting terms.Therefore, the inventive method is conducive to reducing the total sulfur content of the petroleum naphtha device, and product loss of octane number is minimum simultaneously, and the gasoline hydrogenation unitary reactor pressure drop can eliminating the initiations such as easy green coke precursor raises problem extremely fast.
4, the inventive method is for the feature of catalytic gasoline, is divided into different fractions and processes, and while realizing deep desulfuration, reduces product loss of octane number.Catalytic gasoline middle runnings pre-hydrogenator uses non-precious metal catalyst, at relatively low temperature by saturated for the diolefine in raw material, can slow down desulphurization reactor bed coking speed, the running period of assurance device.Because active metallic content is lower, therefore advantage of lower cost.Catalyzer in catalytic gasoline middle runnings and heavy fractioning hydrogenation desulphurization reactor, the while that main purpose being to reduce sulphur content, reduces loss of octane number.By the enforcement of several measure, the inventive method can realize the object of deep desulfuration, obtains technique effect more better than existing technique, significantly can also reduce plant energy consumption simultaneously.
Accompanying drawing explanation
Fig. 1 is the block diagram of catalytic gasoline deep hydrodesulfurizationmethod method of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the inventive method is done into detailed description.
As shown in Figure 1, in catalytic cracking unit (FCCU) separation column 1, pre-separation is carried out to gasoline, obtain lighting end (comprising petroleum naphtha and middle gasoline) and last running (heavy petrol).Gained lighting end enters lighting end surge tank 3 through pipeline 2, and enters in alkali-free sweetening reaction tower 5 through feedstock pump 4, and the lighting end after gained alkali-free sweetening enters hydrogenation unit preliminary fractionator 6, obtains petroleum naphtha and is drawn by pipeline 7, obtain middle gasoline at the bottom of tower at tower top.Middle gasoline through feedstock pump 8, pipeline 9, and enters middle gasoline pre-hydrogenator 10 after mixing with recycle hydrogen 21.The pre-hydrogenation effluent of gained, after interchanger 11 carries out heat exchange intensification, enters middle gasoline hydrodesulfurizationmethod reactor 12, and first gained hydrogenating desulfurization effluent enters process furnace 13 and heat, and then after interchanger 11 with pre-hydrogenation effluent heat exchange, enters separator 14.Separator 14 gained gas enters desulphurization of recycle hydrogen tower 17 through pipeline 15 and purifies, and the hydrogen-rich gas after desulfurization enters circulating hydrogen compressor 20 after pipeline 18 mixes with the new hydrogen introduced through pipeline 19.In separator 14 gained, gasoline product goes out device through pipeline 16, can enter product mediation tank field after gas stripping column.The last running of separation column 1 gained is after pipeline 23 and raw oil pump 24 and after mixing with the recycle hydrogen of pipeline 22, after process furnace 25, enter heavy fractioning hydrogenation desulphurization reactor 26, gained reaction effluent enters separator 27, gained gas enters desulphurization of recycle hydrogen tower 17, gained heavy petrol product is drawn through pipeline 28, can enter product mediation tank field after gas stripping column.Through the petroleum naphtha of pipeline 7, and through pipeline 16 and through gasoline in air lift with after mixing through pipeline 28 and through the last running of air lift, namely obtain clean gasoline product or clean gasoline product blend component.In FCC gasoline, cut fraction hydrogenation reaction effluent and heavy fractioning hydrogenation reaction effluent can share a set of tripping device and gas stripping column.
In the inventive method, the cutting temperature of the lighting end of the gasoline that catalytic cracking unit fractionator overhead fractionates out and the last running of lateral line withdrawal function is 110 DEG C ~ 130 DEG C, preferably 115 DEG C ~ 130 DEG C.Lighting end enters alkali-free sweetening device mercaptan removal, then enters gasoline hydrogenation device preliminary fractionator, and fractionation is petroleum naphtha and middle gasoline, and the segmentation temperature of petroleum naphtha and middle gasoline is 60 DEG C ~ 75 DEG C, preferably 60 DEG C ~ 70 DEG C.Lighting end after deodorization is directly as clean gasoline blend component, middle gasoline enters catalytic gasoline middle runnings hydrogenation unit pre-hydrogenator, the diolefine removed in raw material is contacted with W-Mo-Ni series hydrocatalyst, generation oil enters desulphurization reactor and contacts with Mo-Co series hydrocatalyst, remove sulphur, the heteroatomss such as nitrogen, heavy petrol enters catalytic gasoline last running desulphurization reactor and contacts with Mo-Co series hydrocatalyst, remove sulphur, the heteroatomss such as nitrogen, two portions treated oil mixes with the petroleum naphtha of deodorization after separator and stripping tower, obtain clean gasoline product or blend component.
Can use W-Mo-Ni series hydrocatalyst in catalytic gasoline pre-hydrogenator, the composition of this catalyzer comprises: Tungsten oxide 99.999 8wt% ~ 15wt%, molybdenum oxide 6wt% ~ 16wt%, nickel oxide 2.0wt% ~ 8.0wt%; In catalytic gasoline, in cut and last running desulphurization reactor, catalyzer can be Mo-Co series hydrocatalyst, and composition comprises: molybdenum oxide 6 wt% ~ 16wt%, cobalt oxide 2.0wt% ~ 8.0wt%.Support of the catalyst is generally refractory porous oxide, as aluminum oxide, silicon oxide, titanium oxide or zirconium white etc., can also contain other adjuvant component in carrier.Catalyzer can select existing goods catalyzer, also can prepare by method well known to those skilled in the art.According to the character of feed gasoline, can in the agent of pre-hydrogenator top filling part hydrogenation protecting, Intake Quantity is 5% ~ 20% of pre-hydrogenator hydrogenation catalyst volume, and protectant shape can be Raschig ring, Bird's Nest or abnormal shape etc.
Through the cat naphtha of the inventive method process, product can reach following character: sulphur content is lower than 10 μ g/g, product loss of octane number is less, is less than 1.5 units, and the product after process is applicable to clean gasoline product or blend component as meeting Europe V quality standard.If adopt existing processing method, when production sulphur content is less than the gasoline products of 10 μ g/g, product loss of octane number is comparatively large, and energy consumption is much higher than present method.
In the inventive method, in FCCU separation column, the final boiling point general requirement of gained catalytic gasoline last running is less than 205 DEG C, and sulphur content is less than 600 μ g/g, and olefin(e) centent is less than 28v%.The contents such as concrete technology condition can be determined by those skilled in the art according to material elementses such as the character of raw material, quality product requirements.
In the inventive method, catalytic gasoline carries out pre-separation in separation column, and lighting end enters hydrogenation preliminary fractionator after alkali-free sweetening, the mercaptan contained in petroleum naphtha be converted into disulphide (thioether) etc. comparatively heavy sulfide enter in middle gasoline; Middle gasoline contains the coking precursor such as more diolefine, carries out deep hydrodesulfurizationof after needing first to carry out hydrogenation presaturation again; And substantially containing diolefine coking precursor in last running, so can directly carry out hydrogenating desulfurization, to remove the sulfocompound wherein contained as far as possible under comparatively exacting terms.Two portions hydrogenation products, after air lift, mixes with the petroleum naphtha after deodorization and can obtain sulphur content lower than the clean gasoline product of 10 μ g/g or clean gasoline blend component.
The advantage of the inventive method is:
Combined with the FCC apparatus product fractionating section degree of depth by catalyzed gasoline hydrogenation desulfurization device, not only can ensure that petroleum naphtha removes mercaptan and removes the effect of total sulfur, by carrying out hydrotreatment respectively to cut in catalytic gasoline (middle gasoline) and last running (heavy petrol), product loss of octane number can be made minimum, and ensure that the smooth running of complete assembly long period, and be conducive to reducing plant modification investment, normal production run comprehensive energy consumption and process cost.
With Conventional catalytic gasoline hydrogenation device process CIMS, after process furnace is changed to desulphurization reactor, first centering cut fraction hydrogenation desulfurization effluent heats, and is promoted the temperature in entering hydrodesulphurisatioreactors reactors by heat exchange, can the speed of slowing device coking, prolong operating period.
The following examples illustrate the present invention further, but be not intended to limit the present invention.
Embodiment 1 ~ 3 adopts the block diagram of Fig. 1, petroleum naphtha through pipeline 7, middle gasoline through pipeline 17(and through air lift), heavy petrol is through pipeline 17(and through air lift) go out device and be in harmonious proportion, obtain product.The alkali-free sweetening II type technique that alkali-free sweetening adopts Chinese Petroleum Univ. to develop, catalyzer is the AFS-12 prefabrication type catalyzer of Chinese Petroleum Univ.'s research and development.Test uses Hydrobon catalyst A and B that catalyzer is industrial application, catalyst A is the FH-40C hydrogenation catalyst of Fushun Petrochemical Research Institute's development and production, catalyst B is the FGH-31 hydrogenation catalyst of Fushun Petrochemical Research Institute's development and production, wherein A is applied to cut pre-hydrogenator in catalytic gasoline, and B is applied to cut and heavy fractioning hydrogenation desulphurization reactor in catalytic gasoline.The character of not carrying out full distillation gasoline during pre-separation is listed in table 1.
Embodiment 1
Carry out pre-separation to gasoline in catalytic cracking unit separation column, obtain lighting end and last running, the segmentation temperature of described lighting end and last running is 125 DEG C; Alkali-free sweetening is carried out in lighting end, then enters hydrogenation preliminary fractionator and is separated, and the segmentation temperature of gained petroleum naphtha and middle gasoline is 65 DEG C.
Wherein alkali-free sweetening condition is: reactor operating pressure 0.6MPa, temperature of reaction 35 DEG C, Feed space velocities 0.9h
-1, air/input material volume ratio is 0.7.In catalytic gasoline, cut pre-hydrotreating reaction condition is: hydrogen pressure component 1.8MPa, volume space velocity 3.8 h
-1, temperature of reaction 178 DEG C; In catalytic gasoline, cut fraction hydrogenation desulphurization reaction condition is: hydrogen dividing potential drop 1.6MPa, volume space velocity 3.0h
-1, temperature of reaction 248 DEG C, total hydrogen to oil volume ratio be 350:1.Catalytic gasoline heavy fractioning hydrogenation desulphurization reaction condition is: hydrogen dividing potential drop 1.7MPa, volume space velocity 2.3h
-1, temperature of reaction 282 DEG C, hydrogen to oil volume ratio be 350:1.Operational condition and test-results list in table 2 and table 3 respectively.
From table 3, adopt this technology that product sulphur content can be made to be down to 10 below μ g/g, product octane value only loses 1.4 units.
Embodiment 2
In catalytic cracking unit separation column, pre-separation is carried out to gasoline, obtain lighting end and last running; The segmentation temperature of described lighting end and last running is 120 DEG C; Alkali-free sweetening is carried out in lighting end, then enters hydrogenation preliminary fractionator and is separated, and the segmentation temperature of gained petroleum naphtha and middle gasoline is 70 DEG C.
Wherein alkali-free sweetening condition is: reactor operating pressure 0.5MPa, temperature of reaction 45 DEG C, Feed space velocities 0.8 h
-1, air/input material volume ratio is 0.6.In catalytic gasoline, cut pre-hydrotreating reaction condition is: hydrogen pressure component 2.0MPa, volume space velocity 3.8h
-1, temperature of reaction 183 DEG C; In catalytic gasoline, cut fraction hydrogenation desulphurization reaction condition is: hydrogen dividing potential drop 1.8MPa, volume space velocity 3.2 h
-1, temperature of reaction 246 DEG C; Total hydrogen to oil volume ratio is 380:1; Catalytic gasoline heavy fractioning hydrogenation desulphurization reaction condition is: hydrogen dividing potential drop 1.7MPa, volume space velocity 2.5h
-1, temperature of reaction 285 DEG C, hydrogen to oil volume ratio be 360:1.Operational condition and test-results list in table 2 and table 3 respectively.
From table 3, adopt this technology that product sulphur content can be made to be down to 10 below μ g/g, product octane value only loses 1.5 units.
Embodiment 3
In catalytic cracking unit separation column, pre-separation is carried out to gasoline, obtain lighting end and last running; The segmentation temperature of described lighting end and last running is 130 DEG C; Alkali-free sweetening is carried out in lighting end, then enters cut fraction hydrogenation preliminary fractionator in catalytic gasoline and is separated, and the segmentation temperature of gained petroleum naphtha and middle gasoline is 68 DEG C.
Wherein alkali-free sweetening condition is: reactor operating pressure 0.5MPa, temperature of reaction 40 DEG C, Feed space velocities 1.1 h
-1, air/input material volume ratio is 1.0.In catalytic gasoline, cut pre-hydrotreating reaction condition is: hydrogen pressure component 1.8MPa, volume space velocity 4.2 h
-1, temperature of reaction 180 DEG C; In catalytic gasoline, cut fraction hydrogenation desulphurization reaction condition is: hydrogen dividing potential drop 1.6MPa, volume space velocity 3.2 h
-1, temperature of reaction 252 DEG C; Total hydrogen to oil volume ratio is 320:1; Catalytic gasoline heavy fractioning hydrogenation desulphurization reaction condition is: hydrogen dividing potential drop 1.6MPa, volume space velocity 2.7h
-1, temperature of reaction 278 DEG C, hydrogen to oil volume ratio be 360:1.Operational condition and test-results list in table 2 and table 3 respectively.
From table 3, adopt this technology that product sulphur content can be made to be down to 10 below μ g/g, product octane value only loses 1.2 units.
Comparative example 1
Ordinary method (OCT-MD technology) is adopted to carry out hydrotreatment.Technical process is, catalytic cracking full distillate gasoline, after alkali-free sweetening, enters hydrogenation preliminary fractionator and carries out prefractionation, obtains <65 DEG C of lighting end and is greater than the last running of 65 DEG C.Alkali-free sweetening is carried out in <65 DEG C of lighting end, is greater than 65 DEG C of last running and carries out selective hydrodesulfurization.Operational condition and test-results list in table 3.
As can be seen from Table 3, product sulphur content is reduced to 10 μ g/g, the product loss of octane number of present method is only 1.4 units, and ordinary method is 3.8 units simultaneously, and plant energy consumption is also marked oil/t by 18kg and dropped to 10.6kg mark oil/t.
Table 1 stock oil character
| Project | Catalytic gasoline 1 | Catalytic gasoline 2 | Catalytic gasoline 3 |
| Density, g/cm 3 | 0.7318 | 0.7386 | 0.7238 |
| Boiling range, DEG C | 42～193 | 42～196 | 42～188 |
| Sulphur content, μ g/g | 421 | 564 | 316 |
| Octane value | 93.2 | 92.4 | 92.8 |
Table 2 operational condition
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Alkali-free sweetening condition | ||||
| Reaction pressure, MPa | 0.6 | 0.5 | 0.5 | 0.6 |
| Temperature of reaction, DEG C | 35 | 45 | 40 | 35 |
| Feed space velocities, h -1 | 0.9 | 0.8 | 1.1 | 0.9 |
| Air flow quantity, m 3/h | 0.7 | 0.6 | 1.0 | 0.7 |
| Hydroconversion condition | ||||
| Reactor | 1-1/1-2/2 | 1-1/1-2/2 | 1-1/1-2/2 | 1/2 |
| Stock oil | Catalytic gasoline 1 | Catalytic gasoline 2 | Catalytic gasoline 3 | Catalytic gasoline 1 |
| Catalyzer | A/B/B | A/B/B | A/B/B | A/B |
| Temperature of reaction, DEG C | 178/248/282 | 183/246/285 | 180/252/278 | 178/296 |
| Hydrogen dividing potential drop, MPa | 1.8/1.6/1.7 | 2.0/1.8/1.7 | 1.8/1.6/1.6 | 1.8/1.7 |
| Volume space velocity, h -1 | 3.8/3.0/2.3 | 3.8/3.2/2.5 | 4.2/3.2/2.7 | 3.8/2.8 |
| Hydrogen-oil ratio (always), v/v | 350/350 | 380/360 | 320/360 | 350 |
note: gasoline pre-hydrogenator in 1-1 representative in table, gasoline desulfur reactor in 1-2 representative, 1 pre-hydrogenator representing conventional OCT-MD technology, 2 represent heavy petrol desulphurization reactor.
Table 3 test-results
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Density, g/cm 3 | 0.7305 | 0.7302 | 0.7268 | 0.7293 |
| Boiling range, DEG C | 38～189 | 40～195 | 36～187 | 39～187 |
| Sulphur content, μ g/g | 7.0 | 8.3 | 7.1 | 8.5 |
| Octane value | 91.8 | 90.9 | 91.6 | 89.4 |
| Loss of octane number | 1.4 | 1.5 | 1.2 | 3.8 |
| Plant energy consumption, kgEO/t | 10.6 | — | — | 18 |
Claims (12)
1. a catalytic gasoline deep hydrodesulfurizationmethod method, comprises following content:
(1) adjust the operation of catalytic cracking unit separation column, in FCC separation column, carry out FCC gasoline pre-separation, obtain lighting end and last running; The segmentation temperature of described lighting end and last running is 110 DEG C ~ 130 DEG C;
(2) step (1) gained lighting end enters alkali-free sweetening unit, carries out mercaptan removal process;
(3) lighting end after step (2) gained deodorization enters gasoline hydrogenation preliminary fractionator, isolates petroleum naphtha and middle gasoline; The segmentation temperature of petroleum naphtha and middle gasoline is 60 DEG C ~ 75 DEG C;
(4), after in step (3) gained, gasoline mixes with hydrogen, successively by catalytic gasoline middle runnings pre-hydrogenator and hydrodesulphurisatioreactors reactors, gained reaction effluent enters separator and is separated; Enter catalytic gasoline heavy fractioning hydrogenation desulphurization reactor after step (1) gained last running mixes with hydrogen to react, reaction effluent enters separator and is separated; Gained two portions hydrogenated liquid product mixes with the petroleum naphtha of step (3) after air lift, obtains clean gasoline product or gasoline blending component.
2. in accordance with the method for claim 1, it is characterized in that, the segmentation temperature of lighting end and last running described in step (1) 115 DEG C ~ 130 DEG C.
3. in accordance with the method for claim 1, it is characterized in that, the segmentation temperature of the petroleum naphtha described in step (3) and middle gasoline is 60 DEG C ~ 70 DEG C.
4. in accordance with the method for claim 1, it is characterized in that, in step (2), the condition of lighting end alkali-free sweetening is: reactor operating pressure is 0.1 ~ 1.0MPa, and temperature of reaction is 20 DEG C ~ 70 DEG C, Feed space velocities 0.5 ~ 2.0h
-1, air flow quantity/inlet amount volume ratio is 0.1 ~ 1.0.
5. in accordance with the method for claim 1, it is characterized in that, the catalyzer that described catalytic gasoline middle runnings pre-hydrogenator uses is W-Mo-Ni series hydrocatalyst, and the composition of W-Mo-Ni series hydrocatalyst comprises: Tungsten oxide 99.999 8wt% ~ 15wt%, molybdenum oxide 6wt% ~ 16wt% and nickel oxide 2.0wt% ~ 8.0wt%.
6. in accordance with the method for claim 1, it is characterized in that, described catalytic gasoline middle runnings and heavy fractioning hydrogenation desulphurization reactor are built with Mo-Co system Hydrobon catalyst, the composition of Mo-Co system Hydrobon catalyst comprises: molybdenum oxide 6wt% ~ 16 wt%, cobalt oxide 2.0 wt% ~ 8.0 wt%.
7. in accordance with the method for claim 1, it is characterized in that, two portions hydrogenation reaction effluent described in step (4) enters two cover gas-liquid separation devices respectively and is separated, or shared a set of gas-liquid separation device carries out gas-liquid separation.
8. in accordance with the method for claim 1, it is characterized in that, the operational condition of catalytic gasoline middle runnings pre-hydrogenator is: hydrogen dividing potential drop 0.8MPa ~ 4.0MPa, and temperature of reaction is 150 DEG C ~ 250 DEG C, and volume space velocity is 2.0h
-1~ 6.0h
-1, hydrogen to oil volume ratio is 10 ~ 300; The operational condition of catalytic gasoline middle distillate hydrodesulfurization reactor is: hydrogen dividing potential drop 1.0MPa ~ 4.0MPa, and temperature of reaction is 200 DEG C ~ 300 DEG C, and volume space velocity is 1.0 h
-1~ 6.0h
-1, hydrogen to oil volume ratio is 100 ~ 700.
9. in accordance with the method for claim 1, it is characterized in that, in step (4), the operational condition of catalytic gasoline heavy fractioning hydrogenation desulphurization reactor is: hydrogen dividing potential drop 1.2MPa ~ 4.0MPa, temperature of reaction is 220 DEG C ~ 340 DEG C, and volume space velocity is 1.0 h
-1~ 6.0h
-1, hydrogen to oil volume ratio is 100 ~ 700.
10. in accordance with the method for claim 1, it is characterized in that, in the agent of catalytic gasoline middle runnings pre-hydrogenator top filling hydrogenation protecting, hydrogenation protecting agent Intake Quantity is 5% ~ 20% of pre-hydrogenator hydrogenation catalyst volume.
11. in accordance with the method for claim 1, it is characterized in that, in FCC separation column, the final boiling point of gained catalytic gasoline last running is less than 205 DEG C, and sulphur content is less than 600 μ g/g, and olefin(e) centent is less than 28v%.
12. in accordance with the method for claim 1, it is characterized in that, the catalytic gasoline heavy fractioning hydrogenation desulphurization reactor described in step (4) adopts the mode of last running direct hot feed.
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