CN103059957A - Low-energy consumption catalytic gasoline hydrodesulfurization method - Google Patents
Low-energy consumption catalytic gasoline hydrodesulfurization method Download PDFInfo
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Abstract
The invention discloses a low-energy consumption catalytic gasoline hydrodesulfurization method. The method comprises: adjusting the operating conditions of a catalytic cracking device fractionating tower, and adopting an appropriate cutting point to perform pre-separation in an FCC (fluid catalytic cracking) fractionating tower so as to obtain light fractions and heavy fractions; subjecting the mercaptan in the light fractions to hydroconversion to form a heavy sulfide, making the treated light fractions enter a hydrogenation prefractionator to fractionate light gasoline and medium gasoline, mixing the medium gasoline with the heavy fractions generated by the FCC fractionating tower, letting the mixture enter a hydrodesulfurization reactor to undergo deep desulfurization, conducting steam stripping on the obtained refined heavy gasoline, and mixing it with the light gasoline, thus obtaining a clean gasoline product or a blending component. Compared with the existing catalytic gasoline hydrodesulfurization technologies, the method provided in the invention has the advantages that: the equipment energy consumption is significantly reduced, the gasoline octane number loss is small, the gasoline product quality can meet the quality requirement for a sulfur content of less than 10 micrograms/g, and the economic benefits of oil refining enterprises are improved.
Description
Technical field
The present invention relates to a kind of less energy-consumption process for catalyzed gasoline hydrogenation desulfurization, specifically take catalytic gasoline as the method for raw material hydrogenation production sulphur content less than the clean gasoline blend component of 10 μ g/g.
Background technology
Increasingly strict along with environmental regulation, the developed country such as American-European in succession makes laws sulphur in the motor spirit and olefin(e) centent has been proposed more and more stricter regulation.From 2009, will carry out sulphur content 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 begins to carry out the specification that is 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 cities such as Shanghai, Guangzhou.On July 1st, 2010, other areas began to carry out the specification that is equivalent to Europe III emission standard, and namely sulphur content is less than 150 μ g/g, and the alkene percentage composition is not more than 18v%.This shows, following China will be more and more stricter to the requirement of content of sulfur in gasoline and olefin(e) centent.Therefore, for the product structure of China's motor spirit, be necessary to develop a kind of new Technology for the production of the motor spirit of sulphur content less than 10 μ g/g, to satisfy the needs of future market.
Because historical reasons, catalytically cracked gasoline accounts for about 75% ~ 80% in China's motor spirit blend component, and has the higher and higher characteristics of alkene of sulphur content.Therefore, reducing China's sulfur content of catalytic cracking gasoline is the major issue that faces present stage.
External prior art mainly comprises the SCANFining technique of ExxonMobil company, the Prime-G of Inst Francais Du Petrole
+Technique is that the selective hydrogenation desulfurization process of representative and the OCTGAIN technique of ExxonMobil company, the ISAL technique of Uop Inc. are the hydrogenating desulfurization of representative/octane value recovering combination process.But because external catalytically cracked gasoline character is larger with the domestic difference of comparing, and proportion is less in the gasoline blend 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 OCT-M technology and the OCT-MD technology of RSDS, RSDS-II, RIDOS and the Fushun Petrochemical Research Institute (FRIPP) of Research Institute of Petro-Chemical Engineering, these technology have all realized industrialization, but, in the production sulphur content during less than the gasoline products of 10 μ g/g, all there is the large and higher shortcoming of energy consumption of product loss of octane number.The RSDS-II technology of Research Institute of Petro-Chemical Engineering exploitation for example shows that in the situation of full scale plant running want the production sulphur content less than the clean gasoline of 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.The method is fixed an oxidation deodorizing with full cut bad gasoline first, mercaptan sulfur is converted into disulphide, then fractionation is lighting end and last running, last running is carried out selective hydrodesulfurization through high reactivity/low activity combined hydrogenation desulfurization catalyst, and desulfurization product and lighting end are mixed to get the clean gasoline product.Although the method also can be produced sulphur content less than the gasoline products of 10 μ g/g, stock oil adaptability is relatively poor, and loss of octane number is also larger, and technical process and the present invention have very big difference.
CN101787307A discloses a kind of gasoline hydrodesulfurizationmethod method.The method is fractionated into lighting end gasoline and last running gasoline with gasoline stocks, and wherein lighting end gasoline is through the refining mercaptan sulfur that removes wherein of alkali cleaning; Last running gasoline carries out hydrogenation and takes off diene, selective hydrodesulfurization and the reaction of selective hydrodesulfurization alcohol successively through two hydrogenator; The hydrogenation last running gasoline of gained with refining after lighting end gasoline obtain the full distillation gasoline of super low sulfur after mixing.Although the method also can be produced sulphur content less than the gasoline products of 10 μ g/g, stock oil adaptability is relatively poor, and technical process is fully different from thinking of the present invention.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of less energy-consumption process for catalyzed gasoline hydrogenation desulfurization, can the production sulphur content less than the clean gasoline blend component of 10 μ g/g, and energy consumption is compared decrease with existing apparatus.
Less energy-consumption process for catalyzed gasoline hydrogenation desulfurization of the present invention comprises following content:
(1) pre-separation of FCC gasoline is carried out in the operation of adjustment catalytic cracking unit separation column in the FCC separation column, obtains lighting end and last running; The cut point temperature of described lighting end and last running is 70 ℃ ~ 85 ℃;
(2) step (1) gained lighting end enters and faces hydrogen mercaptan conversion reactor, carries out mercaptan and is converted into reaction than heavy sulfide;
(3) lighting end after step (2) gained mercaptan transforms enters catalytic gasoline hydrogenation preliminary fractionator, isolates petroleum naphtha and middle gasoline; The cut point temperature of petroleum naphtha and middle gasoline is 55 ℃ ~ 70 ℃;
(4) in step (3) gained gasoline with after the last running of step (1) mixes, with hydrogen by hydrodesulphurisatioreactors reactors, products therefrom mixes with the petroleum naphtha of step (2) after air lift, obtains clean gasoline product or gasoline blend component.
According to less energy-consumption process for catalyzed gasoline hydrogenation desulfurization of the present invention, wherein adjust the operation of catalytic cracking unit separation column described in the step (1), can carry out in newly-built catalytic cracking unit, also can take full advantage of the interior existing product fractionating system of catalytic cracking unit and transform, for example can realize by increasing catalytic gasoline last running (being a heavy petrol) side line and adjusting operation condition.The cut point temperature of the lighting end described in the step (1) and last running is generally 70 ℃ ~ 85 ℃, preferred 75 ℃ ~ 85 ℃.
Facing hydrogen mercaptan conversion process and can adopt prior art in this area described in the step (2).The processing condition of facing the conversion of hydrogen mercaptan are: hydrogen dividing potential drop 1.2 ~ 4.0MPa, 100 ℃ ~ 220 ℃ of temperature of reaction, charging air speed 4.0 ~ 8.0 h
-1, hydrogen to oil volume ratio is 5 ~ 100.After lighting end transformed through mercaptan, the lightweight mercaptan that wherein contains and diolefine generation thioetherification reaction were converted into the higher sulfide of boiling point, enter in the heavier middle gasoline.
The cut point temperature of the petroleum naphtha described in the step (3) and middle gasoline is 55 ℃ ~ 70 ℃, preferred 60 ℃ ~ 70 ℃.Behind the hydrogenation unit preliminary fractionator, the sulfide with higher that the middle mercaptan of step (2) faces hydrogen conversion generation enters in the heavier middle gasoline of cut, realizes separating with the refining petroleum naphtha after removing mercaptan.Refining petroleum naphtha behind the gained hydro-sweetening enters product mediation tank field.
In the step (4), after the last running that the middle gasoline that the hydrogenation preliminary fractionator obtains and FCC separation column come mixes, as the charging of hydrodesulphurisatioreactors reactors.Desulfurization catalyst is housed in the hydrodesulphurisatioreactors reactors, and described catalyzer is also for this area Hydrobon catalyst commonly used, as being the 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%.Hydrogenation products can obtain clean gasoline product or blend component that sulphur content is lower than 10 μ g/g through mixing with refining petroleum naphtha that the hydrogenation preliminary fractionator obtains behind the stripping tower.
In the inventive method, the operational condition of hydrodesulphurisatioreactors reactors is: hydrogen dividing potential drop 1.2 MPa ~ 4.0MPa are preferably 1.5MPa ~ 3.0MPa; Temperature of reaction is 220 ℃ ~ 340 ℃, is preferably in 250 ℃ ~ 320 ℃; Volume space velocity is 1.0 h
-1~ 6.0h
-1, be preferably 2.0 h
-1~ 4.0 h
-1Hydrogen to oil volume ratio is 100 ~ 700, is preferably in 200 ~ 500.Reaction product is through separator and stripping tower, and product liquid enters product and is in harmonious proportion the tank field, loops back reactor after the gas that is rich in hydrogen is processed through desulfurization and continues to use.
Compare with existing catalyzed gasoline hydrogenation desulfurization technology, the inventive method has following outstanding technique effect:
1, in the inventive method, only need adjust the operational condition of catalytic cracking unit separation column, can in catalytic cracking unit, realize the pre-separation to light, the last running of catalytic gasoline, can take full advantage of the interior existing product fractionating system of catalytic cracking unit transforms, be conducive to reduce plant modification investment and process cost, and the technical scheme mature and reliable, simple.
2, in the prior art, oil require that catalytic cracking unit is steamed is through after cooling, can transport to the catalytic gasoline hydrogenation unit by pipeline, and then just can reach the requirement of hydrogenation preliminary fractionator feeding temperature by heat exchange or process furnace, catalytic gasoline need to experience the larger temperature variation such as cooling, intensification, and unnecessary energy consumption increases greatly to cause the shortening device.And adopt the flow process of light, the last running direct hot feed of catalytic cracking pre-separation in the inventive method, reduced the operation of cooling, intensification equitemperature fluctuation, can take full advantage of the heat that catalytic gasoline is light, last running is carried of catalytic cracking pre-separation, thereby the energy consumption of decrease catalytic gasoline hydrogenation preliminary fractionator and hydrogenation unit reduces facility investment and process cost simultaneously.
3, in the inventive method, hydrogen mercaptan conversion reactor is at first faced in the lighting end of catalytic cracking pre-separation, the lightweight mercaptan that wherein contains and diolefine generation thioetherification reaction, be converted into heavier sulfide and enter middle gasoline fraction, then pass through the fractionation of hydrogenation preliminary fractionator, refining petroleum naphtha wherein can be used as the product blend component, and face that hydrogen mercaptan conversion process generates enter middle gasoline than heavy sulfide, and mix with the heavy petrol that contains most of sulfide, and in the selective hydrodesulfurization unit, removed.Therefore, the inventive method is conducive to reduce the total sulfur content that the device petroleum naphtha, and has slowed down the unusual quick rising problem of heavy petrol hydrogenation unit reactor pressure decrease of the initiations such as easy green coke precursor.
4, the inventive method is that different fractions is processed for the characteristics of catalytic gasoline with its cut point, when realizing deep desulfuration, has reduced the product loss of octane number.Face hydrogen mercaptan conversion reactor and use non-precious metal catalyst, can under relatively low temperature, the diolefine in the raw material and lightweight mercaptan be removed, slow down desulphurization reactor bed coking speed, assurance device running period.Therefore, compare with ordinary method, can not establish pre-hydrogenator, saved investment or the improvement expenses of device; And because the catalyst activity metal content is lower, so cost is relatively low.Catalyzer in the hydrodesulphurisatioreactors reactors, main purpose are when reducing sulphur content, reduce loss of octane number.By the enforcement of several measures, the inventive method can realize the purpose of deep desulfuration, obtain than the better technique effect of existing technique, and can the decrease plant energy consumption.
Description of drawings
Fig. 1 is the block diagram of less energy-consumption process for catalyzed gasoline hydrogenation desulfurization 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, gasoline is carried out pre-separation catalytic cracking unit (FCCU) separation column 1 is interior, obtain lighting end (comprising petroleum naphtha and middle gasoline) and last running (being heavy petrol).The gained lighting end enters lighting end surge tank 3 through pipeline 2, and face in the hydrogen mercaptan conversion reactor 5 with entering after the hydrogen of pipeline 22 mixes through feedstock pump 4, lighting end after gained mercaptan transforms enters hydrogenation unit preliminary fractionator 6, obtain refining petroleum naphtha at cat head and drawn by pipeline 7, obtain middle gasoline at the bottom of the tower and drawn by pipeline 9.Middle gasoline is with after last running through pipeline 8 mixes, through feedstock pump 10, after interchanger 11 carries out the heat exchange intensification, with mix through the hydrogen of pipeline 21 after enter hydrodesulphurisatioreactors reactors 12, the hydrogenating desulfurization effluent at first enters process furnace 13 and heats, and then enters separator 14 after interchanger 11 and the heat exchange of hydrogenating desulfurization raw material.Separator 14 gained gases enter desulphurization of recycle hydrogen tower 17 and purify, the hydrogen-rich gas after the desulfurization through pipeline 18 with enter recycle compressor 20 after the new hydrogen of introducing through pipeline 19 mixes.Separator 14 gained generate oil through stripping tower 15, and the refining heavy petrol of gained is drawn through pipeline 16, and namely obtain clean gasoline product or blend component after refining petroleum naphtha that pipeline 7 is drawn mixes.
In the methods of the invention, the cut point temperature of the lighting end of the FCC gasoline that the catalytic cracking unit fractionator overhead fractionates out and the last running of lateral line withdrawal function is 70 ℃ ~ 85 ℃, preferred 75 ℃ ~ 85 ℃.Lighting end enters faces hydrogen mercaptan conversion system and carries out mercaptan and transform, and then enters the hydrogenation preliminary fractionator, and fractionation is petroleum naphtha and middle gasoline, and the cut point temperature of petroleum naphtha and middle gasoline is 55 ℃ ~ 70 ℃, preferred 60 ℃ ~ 70 ℃.The petroleum naphtha that mercaptan conversion aftercut obtains is directly as the clean gasoline blend component, middle gasoline is then with after last running mixes, entering hydrodesulphurisatioreactors reactors contacts with Hydrobon catalyst, remove the heteroatomss such as sulphur, nitrogen, mix with petroleum naphtha behind treated oil process separator and the stripping tower, obtain clean gasoline product or blend component.
The catalyzer that faces filling in the hydrogen mercaptan conversion reactor can be the Mo-Ni series hydrocatalyst.The composition of Mo-Ni series hydrocatalyst comprises: molybdenum oxide 2 wt% ~ 12wt%, nickel oxide 8.0 wt% ~ 18.0 wt%.The catalyzer that hydrodesulphurisatioreactors reactors is used is to be the Mo-Co series hydrocatalyst, and composition comprises: molybdenum oxide 6 wt% ~ 16 wt%, cobalt oxide 2.0 wt% ~ 8.0 wt%.Support of the catalyst is generally the refractory porous oxide, such as aluminum oxide, silicon oxide, titanium oxide, zirconium white etc., can contain other adjuvant component.Catalyzer can be selected the existing goods catalyzer, also can be by method preparation well known to those skilled in the art.According to the character of feed gasoline, can face the top filling hydrogenation protecting agent of hydrogen mercaptan conversion reactor, Intake Quantity be mercaptan removal answer mercaptan-eliminating catalyst volume in the device 5%～20%, protectant shape can be Raschig ring, Bird's Nest or special-shaped etc.
Cat naphtha through the inventive method processing, product can reach following character: sulphur content is lower than 10 μ g/g, the product loss of octane number is less, and less than 1.8 units, the product after the processing is applicable to as the clean gasoline product or the blend component that satisfy Europe V quality standard.If adopt existing processing method, the production sulphur content is during less than the gasoline products of 10 μ g/g, and the product loss of octane number is larger, and energy consumption is much higher than present method.
In the methods of the invention, the final boiling point general requirement of gained catalytic gasoline last running is less than 205 ℃ in the FCCU separation column, and sulphur content is generally 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 raw material properties, quality product requirements.
The invention has the advantages that:
By catalyzed gasoline hydrogenation desulfurization device and the associating of FCC apparatus product fractionation partial depth, can guarantee that not only petroleum naphtha removes mercaptan, diolefine and removes the effect of total sulfur, and can guarantee the smooth running of complete assembly long period, and be conducive to reduce plant modification investment, normal production run comprehensive energy consumption and process cost.
Compare with conventional catalytic gasoline hydrogenation unit flow process, can not establish the raw material pre-hydrogenator, economy system investment or improvement expenses, after simultaneously process furnace being changed to desulphurization reactor, first the hydrogenating desulfurization effluent is heated, and promote the temperature in enter hydrodesulphurisatioreactors reactors by heat exchange, speed that can the 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, and petroleum naphtha goes out device through pipeline 7, hydrogenating desulfurization product through pipeline 17 and is in harmonious proportion, and obtains product.Facing the hydrogen thiols conversion catalyst is the catalytic hydroprocessing agent A of recent development, and Hydrobon catalyst is the catalyst B of industrial application.Catalyst A is the FST-1 hydrogenation conversion catalyst (containing molybdenum oxide 6.3wt%, nickel oxide 13.5wt%) that Fushun Petrochemical Research Institute develops, and catalyst B is the FGH-31 hydrogenation catalyst of Fushun Petrochemical Research Institute's development and production.Wherein A is applied to face hydrogen mercaptan conversion reactor, and B is used for hydrodesulphurisatioreactors reactors.The character of full distillation gasoline is not listed in the table 1 when carrying out pre-separation.
Embodiment 1
In the catalytic cracking unit separation column gasoline stocks 1 is carried out pre-separation, obtain lighting end and last running, the cut point temperature of described lighting end and last running is 80 ℃; Lighting end is faced hydrogen mercaptan and is transformed, and then enters the hydrogenation preliminary fractionator and separates, and the cut point temperature of gained petroleum naphtha and middle gasoline is 65 ℃.Wherein facing hydrogen mercaptan conversion reaction conditions is: hydrogen pressure component 2.0MPa, volume space velocity 4.8 h
-1, 148 ℃ of temperature of reaction, hydrogen to oil volume ratio is 12; The hydrodesulfurization reaction condition is: hydrogen dividing potential drop 1.6MPa, volume space velocity 2.8h
-1, 282 ℃ of temperature of reaction; Total hydrogen to oil volume ratio is 350.
Operational condition and test-results are listed in respectively table 2 and table 3.
By as seen from Table 3, adopt this technology that the product sulphur content is down to below the 10 μ g/g, the product octane value only loses 1.6 units.
Embodiment 2
In the catalytic cracking unit separation column gasoline stocks 2 is carried out pre-separation, obtain lighting end and last running; 78 ℃ of the cut point temperature of described lighting end and last running; Lighting end is faced hydrogen mercaptan and is transformed, and then enters the hydrogenation preliminary fractionator and separates, and the cut point temperature of gained petroleum naphtha and middle gasoline is 63 ℃.Wherein facing hydrogen mercaptan conversion reaction conditions is: hydrogen pressure component 2.2MPa, volume space velocity 5.4 h
-1, 157 ℃ of temperature of reaction, hydrogen to oil volume ratio be 18; The hydrodesulfurization reaction condition is: hydrogen dividing potential drop 1.8MPa, volume space velocity 3.0 h
-1, 288 ℃ of temperature of reaction; Total hydrogen to oil volume ratio is 380.
Operational condition and test-results are listed in respectively table 2 and table 3.
By as seen from Table 3, adopt this technology that the product sulphur content is down to below the 10 μ g/g, the product octane value only loses 1.8 units.
Embodiment 3
In the catalytic cracking unit separation column gasoline stocks 3 is carried out pre-separation, obtain lighting end and last running; The cut point temperature of described lighting end and last running is 85 ℃; Lighting end is faced hydrogen mercaptan and is transformed, and then enters the hydrogenation preliminary fractionator and separates, and the cut point temperature of gained petroleum naphtha and middle gasoline is 68 ℃.Wherein facing hydrogen mercaptan conversion reaction conditions is: hydrogen pressure component 1.8MPa, volume space velocity 4.5 h
-1, 152 ℃ of temperature of reaction, hydrogen to oil volume ratio be 26; The hydrodesulfurization reaction condition is: hydrogen dividing potential drop 1.6MPa, volume space velocity 3.2 h
-1, 277 ℃ of temperature of reaction; Total hydrogen to oil volume ratio is 320.
Operational condition and test-results are listed in respectively table 2 and table 3.
By as seen from Table 3, adopt this technology that the product sulphur content is down to below the 10 μ g/g, the product octane value only loses 1.2 units.
Comparative Examples 1
Adopt ordinary method to carry out hydrotreatment, stock oil is with embodiment 1.
Technical process is that catalytic cracking full distillate gasoline faces hydrogen mercaptan and transforms, and faces hydrogen mercaptan conversion condition and is: hydrogen pressure component 2.0Mpa, volume space velocity 4.8 h
-1, 148 ℃ of temperature of reaction, hydrogen to oil volume ratio is 12.Full cut entered the hydrogenation preliminary fractionator and carries out fractionation after mercaptan transformed, and obtained＜last running of 65 ℃ of lighting ends and＞65 ℃.Hydrogenating desulfurization is carried out in＞65 ℃ of last running.Operational condition and test-results are listed in respectively table 2 and table 3.
As can be seen from Table 3, simultaneously the product sulphur content is reduced to 10 μ g/g, the product loss of octane number of the embodiment of the invention 1 only is 1.6 units, and ordinary method is 3.0 units, and plant energy consumption also drops to 12.3kgEO/t by 18kgEO/t.
Table 1 stock oil character
| Project | Catalytic gasoline raw material 1 | Catalytic gasoline raw material 2 | Catalytic gasoline raw material 3 |
| Density, g/cm 3 | 0.7318 | 0.7386 | 0.7238 |
| Boiling range, ℃ | 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 Examples 1 |
| Stock oil | Catalytic gasoline 1 | Catalytic gasoline 2 | Catalytic gasoline 3 | Catalytic gasoline 1 |
| Face hydrogen mercaptan conversion condition | ? | ? | ? | ? |
| Catalyzer | A | A | A | A |
| The hydrogen dividing potential drop, MPa | 2.0 | 2.6 | 1.8 | 2.0 |
| Temperature of reaction, ℃ | 148 | 157 | 152 | 148 |
| The charging air speed, h -1 | 4.8 | 5.4 | 4.5 | 4.8 |
| Hydrogen to |
12 | 18 | 26 | 12 |
| Hydrodesulfurizationconditions conditions | ? | ? | ? | ? |
| Catalyzer | B | B | B | B |
| Temperature of reaction, ℃ | 282 | 288 | 277 | 296 |
| The hydrogen dividing potential drop, MPa | 1.6 | 1.8 | 1.6 | 1.6 |
| Volume space velocity, h -1 | 2.8 | 3.0 | 3.2 | 2.8 |
| Hydrogen-oil ratio (always), v/v | 350 | 380 | 320 | 350 |
Table 3 test-results
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Density, g/cm 3 | 0.7309 | 0.7328 | 0.7116 | 0.7309 |
| Boiling range, ℃ | 41～187 | 38～195 | 36～187 | 38～187 |
| Sulphur content, μ g/g | 8.0 | 9.0 | 7.6 | 8.0 |
| Octane value | 91.6 | 90.6 | 91.6 | 90.2 |
| Loss of octane number | 1.6 | 1.8 | 1.2 | 3.0 |
| Plant energy consumption, kgEO/t | 12.3 | — | — | 18 |
Claims (10)
1. less energy-consumption process for catalyzed gasoline hydrogenation desulfurization comprises following content:
(1) pre-separation of FCC gasoline is carried out in the operation of adjustment catalytic cracking unit separation column in the FCC separation column, obtains lighting end and last running; The cut point temperature of described lighting end and last running is 70 ℃ ~ 85 ℃;
(2) step (1) gained lighting end enters and faces hydrogen mercaptan conversion reactor, carries out mercaptan and is converted into reaction than heavy sulfide;
(3) lighting end after step (2) gained mercaptan transforms enters catalytic gasoline hydrogenation preliminary fractionator, isolates petroleum naphtha and middle gasoline; The cut point temperature of petroleum naphtha and middle gasoline is 55 ℃ ~ 70 ℃;
(4) in step (3) gained gasoline with after the last running of step (1) mixes, with hydrogen by hydrodesulphurisatioreactors reactors, products therefrom mixes with the petroleum naphtha of step (2) after air lift, obtains clean gasoline product or gasoline blend component.
2. in accordance with the method for claim 1, it is characterized in that, the cut point temperature of described lighting end and last running is 75 ℃ ~ 85 ℃.
3. in accordance with the method for claim 1, it is characterized in that, the cut point temperature of the petroleum naphtha described in the step (3) and middle gasoline is 55 ℃ ~ 70 ℃.
4. in accordance with the method for claim 1, it is characterized in that, face that lightweight mercaptan is converted into heavier sulfide in the hydrogen mercaptan conversion process described in the step (1), total sulfide content does not reduce.
5. in accordance with the method for claim 1, it is characterized in that, the operational condition that the conversion of hydrogen mercaptan is faced in lighting end described in the step (2) is: hydrogen dividing potential drop 1.0 ~ 4.0MPa, 100 ℃ ~ 220 ℃ of temperature of reaction, charging air speed 3.0 ~ 8.0h
-1, hydrogen to oil volume ratio is 5 ~ 100.
6. in accordance with the method for claim 1, it is characterized in that, the operational condition of hydrodesulphurisatioreactors reactors is described in the step (4): hydrogen dividing potential drop 1.2 MPa ~ 4.0MPa, and temperature of reaction is 220 ℃ ~ 340 ℃, volume space velocity is 1.0 h
-1~ 6.0h
-1, hydrogen to oil volume ratio is 100 ~ 700.
7. in accordance with the method for claim 1, it is characterized in that, describedly face that filling Mo-Ni is hydrogenation conversion catalyst in the hydrogen mercaptan conversion reactor, take the weight of catalyzer as benchmark, catalyzer comprises: molybdenum oxide 2 wt% ~ 12 wt% and nickel oxide 8.0 wt% ~ 18.0 wt%.
8. in accordance with the method for claim 1, it is characterized in that, filling Mo-Co series hydrocatalyst in the hydrodesulphurisatioreactors reactors, take the weight of catalyzer as benchmark, catalyzer comprises molybdenum oxide 6 wt% ~ 16 wt%, cobalt oxide 2.0 wt% ~ 8.0 wt%.
9. in accordance with the method for claim 1, it is characterized in that, the sulphur content when described catalytic gasoline does not carry out pre-separation is less than 600 μ g/g, and olefin(e) centent is less than 28v%, and final boiling point is less than 205 ℃.
10. in accordance with the method for claim 1, it is characterized in that, the operation of described adjustment catalytic cracking unit separation column refers to that catalytic cracking fractionating tower increases a catalytic gasoline last running side line.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5510568A (en) * | 1994-06-17 | 1996-04-23 | Chemical Research & Licensing Company | Process for the removal of mercaptans and hydrogen sulfide from hydrocarbon streams |
| CN1604956A (en) * | 2001-12-12 | 2005-04-06 | 催化蒸馏技术公司 | Process for sulfur reduction in naphtha streams |
| CN101469274A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Method for producing high-octane petrol |
| CN101787307A (en) * | 2009-01-22 | 2010-07-28 | 中国石油化工股份有限公司 | Gasoline hydrodesulfurization method |
-
2011
- 2011-10-21 CN CN201110321294.4A patent/CN103059957B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5510568A (en) * | 1994-06-17 | 1996-04-23 | Chemical Research & Licensing Company | Process for the removal of mercaptans and hydrogen sulfide from hydrocarbon streams |
| CN1604956A (en) * | 2001-12-12 | 2005-04-06 | 催化蒸馏技术公司 | Process for sulfur reduction in naphtha streams |
| CN101469274A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Method for producing high-octane petrol |
| CN101787307A (en) * | 2009-01-22 | 2010-07-28 | 中国石油化工股份有限公司 | Gasoline hydrodesulfurization method |
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| CN108026455A (en) * | 2015-09-18 | 2018-05-11 | 林德股份公司 | For separating the method and system of the mixture of substances comprising hydrocarbon and sulphur compound |
| US10570338B2 (en) | 2015-09-18 | 2020-02-25 | Linde Aktiengesellschaft | Method and system for processing a mixture of substances containing hydrocarbons and sulfur compounds by separation technology |
| CN108026455B (en) * | 2015-09-18 | 2020-10-30 | 林德股份公司 | Method and system for separating a mixture of substances comprising hydrocarbons and sulfur compounds |
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