CN103131465A - Method for reducing benzene content in gasoline - Google Patents
Method for reducing benzene content in gasoline Download PDFInfo
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- CN103131465A CN103131465A CN2011103861884A CN201110386188A CN103131465A CN 103131465 A CN103131465 A CN 103131465A CN 2011103861884 A CN2011103861884 A CN 2011103861884A CN 201110386188 A CN201110386188 A CN 201110386188A CN 103131465 A CN103131465 A CN 103131465A
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Abstract
The invention relates to a method for reducing benzene content in gasoline. The method can be used for simultaneously removing light components in the gasoline and reducing benzene content in the gasoline. The method comprises a gasoline distillation process and an alkylate debenzolization process. The method includes the steps of leading out material flow from the gasoline distillation process into the alkylate debenzolization process, utilizing olefin carried by the gasoline to react with benzene to generate alkylate benzene, and enabling debenzolized material flow to return to the gasoline distillation process. Compared with the prior art, the method does not need extra material flow, does not need a new separation device, is capable of enabling the benzene content in the gasoline to be reduced to below 1% and enabling the octane value of the gasoline to be slightly improved, and is low in operation cost and low in investment.
Description
Technical field
The present invention relates to a kind of gasoline production method, especially relate to a kind of method that reduces benzene content in gasoline.
Background technology
Along with the pay attention to day by day of people to environment protection, more and more stricter to the restriction of the benzene content in gasoline.In Europe III and Europe IV standard, to being restricted to less than 1.0% of Benzene In Gasoline volume fraction, along with the upgrading of China's motor spirit standard, the content of Benzene In Gasoline also requires ≯ 1.0% (volume fraction).China's motor spirit is mainly from catalytically cracked gasoline, and benzene content in gasoline is often greater than 1% (volume fraction), thereby benzene content in gasoline is decreased, and just can meet the requirement of environmental regulation.
For when reducing the finished product gasoline olefin, keep and improve the octane value of gasoline product, need add reformed gasoline to be in harmonious proportion.And the benzene content of China's catalytically cracked gasoline is higher, and the incorporation of reformed gasoline is restricted, and often needing increases the benzene content that the benzene extraction plant reduces reformed gasoline, has increased the production cost of gasoline product.
The method that removes the benzene in gasoline has the benzene extraction technique, benzene hydrogenation saturation technique and benzene alkylation technology.Benzene extracting and benzene hydrogenation saturation technique are applicable to the cut that benzene content is high, olefin(e) centent is low, are not suitable for catalytically cracked gasoline.The benzene alkylation technology is to utilize benzene and olefine reaction to generate alkylated benzenes, thereby reduces the technology of the benzene content in gasoline.In recent years, adopt the method for benzene alkylation Techniques For Reducing Determination of Benzene In Gasoline that report is arranged repeatly.
CN 101362964A discloses a kind of catalysis conversion method that reduces benzene content in gasoline, and gasoline component contacts with catalyzer with the gas that contains small-numerator olefin, carries out alkylated reaction under certain reaction conditions.The method can reduce the content of gasoline component benzene more than 50%, and has improved octane value and the productive rate of gasoline.
CN 101440302A discloses a kind of method and catalyzer thereof that reduces benzene content in gasoline, utilizes catalytic cracking unit dry gas and gasoline component generation benzene alkylation reaction, reduces Determination of Benzene In Gasoline, increases simultaneously the yield of gasoline.
CN 1552811A discloses a kind of method that reduces Determination of Benzene In Gasoline, the method catalytically cracked gasoline or light fractions of FCC naphtha with after reformed gasoline mixes, carry out the alkylated reaction (catalytically cracked gasoline contains more alkene and reformed gasoline contains more benzene) of benzene on the ultrafine particle zeolite alkylated catalyst, can reduce simultaneously blended gasoline alkene and benzene content, and loss of octane number is little.
Adopt the benzene alkylation technology to take off benzene, can process the less catalytically cracked gasoline of benzene content, take off benzene satisfactory for result.The low-carbon alkene content of catalytically cracked gasoline is higher, and benzene content is lower, itself has the raw material basis of benzene alkylation.Yet, present benzene alkylation technology be all from the outside introduce the logistics contain alkene come with gasoline component benzene carry out alkylation, need complicated conversion unit and later separation equipment, investment greatly, complicated operation.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of extra logistics of need not adding in order to overcome the defective that above-mentioned prior art exists, and need not increase separating device, and rectifying and take off benzene and carry out simultaneously is simple to operate, invests the method for little reduction benzene content in gasoline.
Purpose of the present invention can be achieved through the following technical solutions: when removing the gasoline light constituent, reduce the benzene content in gasoline.It is characterized in that: the method comprises that gasoline rectifying and alkylation take off the benzene process, flow to into alkylation from gasoline rectifying derivated and take off the benzene process, utilize gasoline self with alkene and benzene reaction generate alkylated benzenes, the gasoline rectifying is returned in the logistics of taking off after benzene.
The present invention reduces the method for benzene content in gasoline, described gasoline is that olefin(e) centent is higher than 15%, benzene content is low lower than 3% gasoline, as the unpurified thick cut of catalytically cracked gasoline, coker gasoline, pressure gasoline and these gasoline, and preferred catalytic pressure gasoline and unpurified thick cut thereof.
The present invention reduces the method for benzene content in gasoline, and alkylation is taken off the benzene process and referred under the effect of special-purpose catalyst, and the alkene in gasoline and benzene generation alkylated reaction generate alkylated benzenes, reduces the process of benzene content.
The present invention reduces the method for benzene content in gasoline, and alkylation is taken off the benzene process and used special-purpose benzene alkylation catalyzer.
The present invention reduces the method for benzene content in gasoline, special-purpose catalyst can be obtained by one or more upgradings in hydrochloric acid, phosphoric acid, heteropolyacid or rare earth oxide by zeolite, zeolite can be selected from y-type zeolite, β zeolite, the one or more combination in ZSM-5 zeolite or H-Moderite zeolite.
The present invention reduces the method for benzene content in gasoline, and the gasoline rectifying can be gasoline desorption process or gasoline stabilization process.
The present invention reduces the method for benzene content in gasoline, can draw material from gasoline rectifying feed-pipe and enter alkylation and take off the benzene process, takes off material after benzene and returns to the gasoline rectifying and carry out rectifying.
The present invention reduces the method for benzene content in gasoline, and alkylation is taken off the benzene process and can in parallelly with the gasoline rectifying be carried out, and draws material from the rectifying tower side line of gasoline rectifying and enters alkylation and take off the benzene process, and the material that takes off after benzene returns to rectifying tower.
The present invention reduces the method for benzene content in gasoline, and the benzene process is taken off in alkylation can be used in separately the gasoline that the needs that contain alkene take off benzene, and need not to configure the gasoline rectifying.
The present invention reduces the method for benzene content in gasoline, and alkylation is taken off the benzene process and used fixed-bed reactor, loads special-purpose benzene alkylation catalyzer.
The present invention reduces the method for benzene content in gasoline, and the temperature of reaction that the benzene process is taken off in alkylation is 60 ℃～300 ℃, and volume space velocity is 1～10h
-1
Compared with prior art, the present invention has the following advantages:
(1) of the present inventionly take off the low-carbon alkene that the benzene process takes full advantage of gasoline self, do not need to introduce extra logistics, technical process is simple, easily operation;
(2) utilize the reaction of low-carbon alkene and benzene, generate the alkylated benzenes macromole, do not lose the octane value of gasoline when taking off benzene;
(3) the present invention can transform on existing gasoline production device, and not needing increases new separating device, has reduced the investment that gasoline takes off benzene.
Description of drawings
Fig. 1 is process flow diagram of the present invention in embodiment 1;
Fig. 2 is process flow diagram of the present invention in embodiment 2.
In figure: 1 for gasoline rectifying tower, 2 be that liquefied gas component, 7 be rectifying gasoline fraction, A for take off benzene reactor feed leading point, B for take off benzene after material reentry point for gasoline stocks, 4 takes off benzene reactor feed, 5 for alkylation for taking off material after benzene, 6 for taking off benzene reactor, 3.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
The present invention reduces the method for benzene content in gasoline, comprise that gasoline rectifying and alkylation take off the benzene process, flow to into alkylation from gasoline rectifying derivated and take off the benzene process, utilize gasoline self with alkene and benzene reaction generate alkylated benzenes, the gasoline rectifying is returned in the logistics of taking off after benzene.
The present invention reduces the method for benzene content in gasoline, and the reactor that the benzene process is taken off in alkylation adopts fixed-bed reactor, and the benzene alkylation catalyzer that filling is special-purpose according to the requirement of material temperature and reaction conditions, can use front preheating process device and aftercooler.
The present invention reduces the method for benzene content in gasoline, and the reaction conditions that the benzene process is taken off in alkylation is difference with the difference of feedstock property, processing target, and general temperature of reaction is 60 ℃～300 ℃, and volume space velocity is that volume space velocity is 1～10h
-1
The present invention reduces the method for benzene content in gasoline, according to the difference of processing target, can regulate entering the inventory that the benzene process is taken off in alkylation, reaches energy-saving and cost-reducing purpose.
Characteristics of the present invention be utilize gasoline self with alkene and benzene carry out alkylated reaction and take off benzene, utilize simultaneously the rectifying of former gasoline production flow process to carry out rectifying, do not need to add extra logistics, do not need to increase new separating device, can produce the catalytic gasoline of benzene content ≯ 1%, can alleviate the input that refinery gasoline takes off the benzene process to a certain extent, invest little, simple to operate.
Embodiment 1
For further illustrating technological process of the present invention, the below is described technical process of the present invention.As shown in Figure 1, gasoline stocks 3 enters and carries out rectifying in gasoline rectifying tower 1, is divided into liquefied gas component 6 and rectifying gasoline fraction 7.Simultaneously, take off A place, benzene reactor feed leading point draws and takes off benzene reactor feed 4 on gasoline rectifying tower 1 top, enter after pressurizeing by pump and take off benzene reactor 2, after taking off the interior generation benzene alkylation reaction of benzene reactor 2, take off after benzene material 5 and return to gasoline rectifying tower 1 and take off material reentry point B place after benzene.
Press the operating process of Fig. 1, take catalytically cracked gasoline as raw material, adopt special-purpose benzene alkylation catalyzer, result such as table 1～table 3.
Table 1 stock oil character
| Raw material | Catalytically cracked gasoline |
| Density (20 ℃), kg/m 3 | 715 |
| Benzene, V% | 1.20 |
| Alkene, V% | 20-40 |
| Boiling range, ℃ | |
| Initial boiling point | 34 |
| 10％ | 58 |
| 50％ | 105 |
| 90％ | 161 |
| Final boiling point | 187 |
Table 2 reaction conditions
| Reaction conditions |
| The benzene temperature of reaction is taken off in alkylation, ℃ | 80 |
| Benzene reaction pressure, MPa are taken off in alkylation | 1.4 |
| Liquid hourly space velocity, h -1 | 8 |
Table 3 quality product
| Rectifying gasoline | |
| Density (20 ℃), kg/m3 | 731 |
| Benzene, volume % | 0.47 |
| Boiling range, ℃ | |
| Initial boiling point | 40 |
| 10％ | 49 |
| 50％ | 67 |
| 90％ | 140 |
| Final boiling point | 175 |
Embodiment 2
Technical process and Fig. 1 shown in Figure 2 are basic identical, and after difference is to take off benzene reactor feed leading point and takes off benzene, the material reentry point is changed on gasoline rectifying tower feed-pipe by the rectifying tower side line.Gasoline stocks 3 enters and carries out rectifying in gasoline rectifying tower 1, is divided into liquefied gas component 6 and rectifying gasoline fraction 7.Simultaneously, taking off A place, benzene reactor feed leading point at gasoline rectifying tower 1 feed-pipe draws and takes off benzene reactor feed 4, enter after partly or entirely gasoline stocks pressurizes by pump and take off benzene reactor 2, after taking off the interior generation benzene alkylation reaction of benzene reactor 2, take off after benzene material 5 and return to gasoline rectifying tower 1 feed-pipe and take off material reentry point B place after benzene, then enter gasoline rectifying tower 1 and remove light constituent.
Press the operating process of Fig. 2, adopt raw material and the catalyzer identical with embodiment 1, the results are shown in Table 4～table 5.
Table 4 reaction conditions
| Reaction conditions | |
| The benzene temperature of reaction is taken off in alkylation, ℃ | 120 |
| Benzene reaction pressure, MPa are taken off in alkylation | 1.45 |
| Liquid hourly space velocity, h -1 | 6 |
Table 5 quality product
| Rectifying gasoline |
| Density (20 ℃), kg/m3 | 735.2 |
| Benzene, volume % | 0.63 |
| Boiling range, ℃ | |
| Initial boiling point | 40 |
| 10％ | 52 |
| 50％ | 73 |
| 90％ | 152 |
| Final boiling point | 179 |
Can find out from embodiment 1, embodiment 2, use present method, can in gasoline rectifying, the benzene content of rectifying gasoline be dropped to below 1%.Need not add extra logistics, need not increase separating device newly, productive rate and the octane value of gasoline are improved, and running cost is low, invest low.
Claims (10)
1. method that reduces benzene content in gasoline, it is characterized in that, the method comprises that gasoline rectifying and alkylation take off the benzene process, the logistics of drawing from the gasoline rectifying enters alkylation through feed-pipe and takes off the benzene process, utilize gasoline self with alkene and benzene reaction generate alkylated benzenes, the gasoline rectifying is returned in the logistics of taking off after benzene.
2. a kind of method that reduces benzene content in gasoline according to claim 1, it is characterized in that, the gasoline of processing is that olefin(e) centent is higher than 15%, benzene content is lower than 3% gasoline, the unpurified thick cut that comprises catalytically cracked gasoline, coker gasoline, pressure gasoline or these gasoline, preferred catalytic pressure gasoline and unpurified thick cut thereof.
3. a kind of method that reduces benzene content in gasoline according to claim 1, is characterized in that, described gasoline rectifying can be gasoline resolving or gasoline stabilization process.
4. a kind of method that reduces benzene content in gasoline according to claim 1, it is characterized in that, described alkylation is taken off the benzene process and is referred under the effect of special-purpose catalyst, and the alkene in gasoline and benzene generation alkylated reaction generate alkylated benzenes, reduces the process of benzene and olefin(e) centent.
5. a kind of method that reduces benzene content in gasoline according to claim 4, is characterized in that, described special-purpose catalyst is obtained by one or more upgradings in hydrochloric acid, phosphoric acid, heteropolyacid or rare earth oxide by zeolite.
6. a kind of method that reduces benzene content in gasoline according to claim 5, is characterized in that, described zeolite is selected from one or more in y-type zeolite, β zeolite, ZSM-5 zeolite or H-Moderite zeolite.
7. a kind of method that reduces benzene content in gasoline according to claim 1, is characterized in that, the benzene process is taken off in described alkylation, and can be used in separately olefin(e) centent high, and the gasoline that benzene content is low need not to configure the gasoline rectifying.
8. a kind of method that reduces benzene content in gasoline according to claim 1, it is characterized in that, described alkylation is taken off the benzene process and can in parallelly with the gasoline rectifying be carried out, flow to into described alkylation from the rectifying tower side line derivated of described gasoline rectifying and take off the benzene process, the gasoline that takes off after benzene returns to rectifying tower.
9. a kind of method that reduces benzene content in gasoline according to claim 1, is characterized in that, described alkylation is taken off the benzene process and used fixed-bed reactor, the filling special-purpose catalyst.
10. a kind of method that reduces benzene content in gasoline according to claim 1, is characterized in that, described alkylation is taken off the benzene process and adopted fixed-bed reactor, loads special-purpose benzene alkylation catalyzer, and temperature of reaction is 60 ℃～300 ℃, and volume space velocity is 1～10h
-1
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| CN2011103861884A CN103131465A (en) | 2011-11-28 | 2011-11-28 | Method for reducing benzene content in gasoline |
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| CN2011103861884A CN103131465A (en) | 2011-11-28 | 2011-11-28 | Method for reducing benzene content in gasoline |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115725325A (en) * | 2021-08-31 | 2023-03-03 | 中国石油化工股份有限公司 | Method for reducing benzene content in gasoline and phosphorus-containing catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210348A (en) * | 1991-05-23 | 1993-05-11 | Chevron Research And Technology Company | Process to remove benzene from refinery streams |
| CN1735675A (en) * | 2003-01-29 | 2006-02-15 | 催化蒸馏技术公司 | Process for the production of low benzene gasoline |
| CN1769388A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Hydrogenation and quality improvement method for reducing sulfur and olefin content of inferior gasoline |
| CN101440302A (en) * | 2008-12-22 | 2009-05-27 | 洛阳瑞泽石化工程有限公司 | Method for lowering benzene content in gasoline and catalyst thereof |
-
2011
- 2011-11-28 CN CN2011103861884A patent/CN103131465A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210348A (en) * | 1991-05-23 | 1993-05-11 | Chevron Research And Technology Company | Process to remove benzene from refinery streams |
| CN1735675A (en) * | 2003-01-29 | 2006-02-15 | 催化蒸馏技术公司 | Process for the production of low benzene gasoline |
| CN1769388A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Hydrogenation and quality improvement method for reducing sulfur and olefin content of inferior gasoline |
| CN101440302A (en) * | 2008-12-22 | 2009-05-27 | 洛阳瑞泽石化工程有限公司 | Method for lowering benzene content in gasoline and catalyst thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115725325A (en) * | 2021-08-31 | 2023-03-03 | 中国石油化工股份有限公司 | Method for reducing benzene content in gasoline and phosphorus-containing catalyst |
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Application publication date: 20130605 |