CN111909724A - Process method for etherifying mercaptan - Google Patents
Process method for etherifying mercaptan Download PDFInfo
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- CN111909724A CN111909724A CN202010680524.5A CN202010680524A CN111909724A CN 111909724 A CN111909724 A CN 111909724A CN 202010680524 A CN202010680524 A CN 202010680524A CN 111909724 A CN111909724 A CN 111909724A
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- mercaptan
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
Abstract
The invention discloses a process method for etherifying mercaptan, catalytic cracking gasoline enters a pre-reactor, mercaptan and olefin are firstly subjected to etherification reaction to generate macromolecular thioether, the product of the pre-reactor enters a hydrogenation catalytic distillation tower, unreacted mercaptan and olefin are continuously reacted to generate macromolecular thioether, then a heavy component containing thioether is discharged from the bottom of the hydrogenation catalytic distillation tower, and a light component after the mercaptan and the olefin are removed is discharged from the top of the hydrogenation catalytic distillation tower. In the invention, the pre-reactor firstly etherifies mercaptan with larger molecular weight and higher boiling point and dialkene, thereby improving the mercaptan removal rate; the diolefins are already consumed by reaction in the prereactor, H being present during hydrogenation2The consumption is reduced, and simultaneously, the olefin hydrogenation saturation rate is low, so the octane number loss of the product is reduced; the pre-reactor is arranged, so that the removal efficiency is improved, the consumption of a catalyst in the hydrogenation catalytic distillation tower is reduced, and the service life of the hydrogenation catalytic distillation tower is prolonged; the reaction in the pre-reactor is mild, and catalytic cracking is not easy to occur, so that the product yield is high.
Description
Technical Field
The invention relates to a process method for etherifying mercaptan, belonging to the technical field of chemical processes.
Background
Along with the increasing attention of people on environmental protection, the requirements on the quality of light oil products are higher and higher. At present, the quality standards of light oil products are measured by lead-free, low-sulfur, low-aromatic hydrocarbon, low-olefin and high-octane number. At present, the market of catalytic cracking light oil in China occupies about 75%, mercaptan contained in the catalytic cracking light oil has great influence on the quality of the light oil, particularly, when the content of the mercaptan is high, the light oil has unpleasant smell, the light oil is easy to generate oxidation reaction to generate colloid, and the effects of an anti-knock agent, an antioxidant and the like are weakened. Besides mercaptan, the olefins produced during catalytic cracking also have a great influence on the quality of light oil, and the olefins can react with other impurities under an acidic catalyst to generate colloid to block the acidic catalyst, so that the activity of the catalyst is seriously influenced, and the hydrogenation effect of the light gasoline is influenced.
The prior art only removes mercaptan or olefin separately, so the equipment cost and the operation cost are higher. In order to remove mercaptan and olefin in light oil simultaneously, a new mercaptan etherification technology is developed, and the relevant technology and corresponding catalyst are utilized to carry out etherification reaction on mercaptan and olefin to generate heavy component thioether, and then the thioether is removed from the light oil through distillation, so that the mercaptan in the light oil can be removed and the olefin can be removed. And the heavy component thioether and other heavy components in the light oil are desulfurized together in a hydrogenation mode, so that the octane number loss can be reduced, and the hydrogen consumption and the operation cost can be reduced.
However, the mercaptan etherification technology still has the defects of low mercaptan removal rate, great octane number loss and the like although octane number loss can be reduced, and the hydrogen consumption and the operation cost still have great space saving.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a process method for mercaptan etherification, which has the advantages of simple process, easy operation, long service life of catalyst, high mercaptan removal rate, further reduction of octane number loss, and great reduction of hydrogen consumption and operation cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process method for etherifying mercaptan comprises the following steps:
(1) and (3) etherification reaction: the catalytic cracking gasoline is used as a reaction raw material, after the catalytic cracking gasoline enters a pre-reactor, mercaptan and olefin in the catalytic cracking gasoline are subjected to etherification reaction under the catalytic action of a catalyst I in the pre-reactor, and products are macromolecular thioether generated by the reaction, a small amount of unreacted mercaptan, unreacted olefin and light oil components;
(2) hydrogenation catalytic distillation reaction: feeding the product generated in the step (1) into a hydrogenation catalytic distillation tower, and simultaneously introducing hydrogen into the hydrogenation catalytic distillation tower; a small amount of unreacted mercaptan and part of unreacted olefin continue to carry out etherification reaction under the catalytic action of a catalyst II in the hydrogenation catalytic distillation tower to continue generate macromolecular thioether, and heavy components containing the thioether are discharged from the bottom of the tower; and partial unreacted olefin and hydrogen are subjected to hydrogenation reaction under the catalytic action of a catalyst II in the hydrogenation catalytic distillation tower, so that the content of the olefin in the product is reduced, and the product light oil after the mercaptan and the olefin are removed is discharged from the top of the hydrogenation catalytic distillation tower and then is collected.
In the above technical scheme, in the step (1), the pre-reactor is a fixed bed reactor.
In the above technical solution, in the step (1), the operation conditions of the pre-reactor are as follows: the temperature is 45-75 ℃ and the pressure is 0.1-10 MPa.
In the above technical solution, in the step (1), the catalyst I in the pre-reactor is an ion exchange resin catalyst, preferably a resin catalyst KC115 produced by the kelvin environmental protection technology limited company.
In the technical scheme, in the step (1), the catalytic cracking gasoline is used as a reaction raw material to enter a pre-reactorThe space velocity is 0.1-15 h-1。
In the above technical scheme, in the step (2), the operation conditions of the hydrocatalytic distillation column are as follows: the temperature at the top of the tower is 50-80 ℃, and the pressure is-0.2-10 MPa; the temperature of the tower kettle is 70-90 ℃, and the pressure is-0.1-11 MPa.
In the above technical solution, in the step (2), the catalyst II in the hydrocatalytic distillation column is an ion exchange resin catalyst, preferably a resin catalyst KC115 produced by keley environmental protection technologies ltd.
In the technical scheme, in the step (2), the space velocity of the product generated in the step (1) entering the hydrogenation catalytic distillation tower is 0.1-15 h-1(ii) a The volume ratio of the hydrogen to the product is 100-400: 1.
The technical scheme of the invention has the advantages that:
(1) the pre-reactor can ensure that mercaptan with larger molecular weight and higher boiling point and dialkene are etherified in advance, thereby improving the mercaptan removal rate.
(2) H in the hydrocatalytic distillation column because the diolefins are already consumed by reaction in the prereactor2The gas consumption is greatly reduced, and the olefin hydrogenation saturation rate is low, so the octane number loss of the product is greatly reduced.
(3) The pre-reactor improves the removal efficiency, reduces the consumption of the catalyst in the hydrogenation catalytic distillation tower and prolongs the service life of the hydrogenation catalytic distillation tower.
(4) The reaction in the pre-reactor is mild, and catalytic cracking is not easy to occur, so that the product yield is high.
Drawings
FIG. 1: the process flow of the process method is shown schematically;
wherein, 1, a pre-reactor; 2. a hydrogenation catalytic distillation tower.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but the present invention is not limited to the following descriptions:
example 1:
a process method for etherifying mercaptan comprises the following steps:
(1) and (3) etherification reaction: the catalytic cracking gasoline is used as a reaction raw material and takes 0.1h-1After entering a pre-reactor (fixed bed reactor) at a space velocity, mercaptan and olefin in the catalytically cracked gasoline are subjected to etherification reaction under the catalytic action of a resin catalyst KC115 of a Kery environmental protection technology Limited company in the pre-reactor 1, wherein the reaction conditions are as follows: the temperature is 45 ℃ and the pressure is 0.1 MPa; the products are macromolecular thioether generated by the reaction, unreacted mercaptan, unreacted olefin and light oil components;
(2) hydrogenation catalytic distillation reaction: the product generated in the step (1) is used for 0.1h-1The space velocity enters a hydrogenation catalytic distillation tower 2, and hydrogen is introduced into the hydrogenation catalytic distillation tower at the same time, wherein the volume ratio of the hydrogen to the product is 100: 1; the unreacted mercaptan and part of the unreacted olefin continuously carry out etherification reaction under the catalytic action of a resin catalyst KC115 of a Kery environmental protection technology Limited company in a hydrogenation catalytic distillation tower to continuously generate macromolecular thioether, and heavy components containing the thioether are discharged from the bottom of the tower; partial unreacted olefin and hydrogen are subjected to hydrogenation reaction under the catalytic action of a catalyst II in the hydrogenation catalytic distillation tower, so that the content of the olefin in the product is reduced, and the product light oil after the mercaptan and the olefin are removed is discharged from the top of the hydrogenation catalytic distillation tower; the hydrogenation catalytic distillation tower has the operating conditions that: the temperature at the top of the tower is 50 ℃ and the pressure is-0.2 MPa; the temperature of the tower bottom is 70 ℃, and the pressure is-0.1 MPa.
In this example, the mercaptan removal rate was 99.8 wt% or more.
Example 2:
a process method for etherifying mercaptan comprises the following steps:
(1) and (3) etherification reaction: the catalytic cracking gasoline is used as a reaction raw material and takes 5 hours-1After entering a pre-reactor 1 (fixed bed reactor) at a space velocity, mercaptan and olefin in the catalytically cracked gasoline are subjected to etherification reaction under the catalytic action of a resin catalyst KC115 of a Kery environmental protection technology Limited company in the pre-reactor, wherein the reaction conditions are as follows: the temperature is 60 ℃ and the pressure is 5 MPa; the products are macromolecular thioether generated by the reaction, unreacted mercaptan, unreacted olefin and light oil components;
(2) Hydrogenation catalytic distillation reaction: the product generated in the step (1) is used for 5h-1The space velocity enters a hydrogenation catalytic distillation tower 2, and hydrogen is introduced into the hydrogenation catalytic distillation tower at the same time, wherein the volume ratio of the hydrogen to the product is 200: 1; the unreacted mercaptan and part of the unreacted olefin continuously carry out etherification reaction under the catalytic action of a resin catalyst KC115 of a Kery environmental protection technology Limited company in a hydrogenation catalytic distillation tower to continuously generate macromolecular thioether, and heavy components containing the thioether are discharged from the bottom of the tower; partial unreacted olefin and hydrogen are subjected to hydrogenation reaction under the catalytic action of a catalyst II in the hydrogenation catalytic distillation tower, so that the content of the olefin in the product is reduced, and the product light oil after the mercaptan and the olefin are removed is discharged from the top of the hydrogenation catalytic distillation tower; the hydrogenation catalytic distillation tower has the operating conditions that: the temperature at the top of the tower is 70 ℃ and the pressure is 1 MPa; the temperature of the tower bottom is 80 ℃ and the pressure is 3 MPa.
In this example, the mercaptan removal rate was 99.9 wt% or more.
Example 3:
a process method for etherifying mercaptan comprises the following steps:
(1) and (3) etherification reaction: the catalytic cracking gasoline is used as a reaction raw material, and the catalytic cracking gasoline takes 15 hours-1After entering a pre-reactor 1 (fixed bed reactor) at a space velocity, mercaptan and olefin in the catalytically cracked gasoline are subjected to etherification reaction under the catalytic action of a resin catalyst KC115 of a Kery environmental protection technology Limited company in the pre-reactor, wherein the reaction conditions are as follows: the temperature is 75 ℃ and the pressure is 10 MPa; the products are macromolecular thioether generated by the reaction, unreacted mercaptan, unreacted olefin and light oil components;
(2) hydrogenation catalytic distillation reaction: the product generated in the step (1) is used for 15h-1The space velocity enters a hydrogenation catalytic distillation tower 2, and hydrogen is introduced into the hydrogenation catalytic distillation tower at the same time, wherein the volume ratio of the hydrogen to the product is 400: 1; the unreacted mercaptan and part of the unreacted olefin continuously carry out etherification reaction under the catalytic action of a resin catalyst KC115 of a Kery environmental protection technology Limited company in a hydrogenation catalytic distillation tower to continuously generate macromolecular thioether, and heavy components containing the thioether are discharged from the bottom of the tower; catalyst for partial unreacted olefin and hydrogen in hydrogenation catalytic distillation towerII, carrying out hydrogenation reaction under the catalytic action of II so as to reduce the content of olefin in the product, and discharging the product light oil from the top of the hydrogenation catalytic distillation tower after removing the mercaptan and the olefin; the hydrogenation catalytic distillation tower has the operating conditions that: the temperature at the top of the tower is 80 ℃ and the pressure is 10 MPa; the temperature of the tower bottom is 90 ℃ and the pressure is 11 MPa.
In this example, the mercaptan removal rate was 99.9 wt% or more.
The above examples are only for illustrating the technical concept and features of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A process method for etherifying mercaptan is characterized by comprising the following steps:
(1) and (3) etherification reaction: the catalytic cracking gasoline is used as a reaction raw material, after the catalytic cracking gasoline enters a pre-reactor (1), mercaptan and olefin in the catalytic cracking gasoline are subjected to etherification reaction under the catalytic action of a catalyst I in the pre-reactor, and the products are macromolecular thioether generated by the reaction, a small amount of unreacted mercaptan, unreacted olefin and light oil components;
(2) hydrogenation catalytic distillation reaction: feeding the product generated in the step (1) into a hydrogenation catalytic distillation tower (2), and simultaneously introducing hydrogen into the hydrogenation catalytic distillation tower; a small amount of unreacted mercaptan and part of unreacted olefin continue to carry out etherification reaction under the catalytic action of a catalyst II in the hydrogenation catalytic distillation tower to continue generate macromolecular thioether, and heavy components containing the thioether are discharged from the bottom of the tower; and partial unreacted olefin and hydrogen are subjected to hydrogenation reaction under the catalytic action of a catalyst II in the hydrogenation catalytic distillation tower, so that the content of the olefin in the product is reduced, and the product light oil after the mercaptan and the olefin are removed is discharged from the top of the hydrogenation catalytic distillation tower and then is collected.
2. The process of claim 1, wherein in step (1), the pre-reactor is a fixed bed reactor.
3. The process of claim 1, wherein in step (1), the prereactor is operated under the following conditions: the temperature is 45-75 ℃ and the pressure is 0.1-10 MPa.
4. The process of claim 1, wherein in step (1), the catalyst I in the pre-reactor is an ion exchange resin catalyst.
5. The process of claim 1, wherein in step (1), the space velocity of the catalytically cracked gasoline as the reaction raw material entering the pre-reactor is 0.1-15 h-1。
6. The process of claim 1, wherein in step (2), the hydrocatalytic distillation column is operated under the following conditions: the temperature at the top of the tower is 50-80 ℃, and the pressure is-0.2-10 MPa; the temperature of the tower kettle is 70-90 ℃, and the pressure is-0.1-11 MPa.
7. The process of claim 1, wherein in step (2), the catalyst II in the hydrocatalytic distillation column is an ion exchange resin catalyst.
8. The process of claim 1, wherein in step (2), the space velocity of the product generated in step (1) entering the hydrocatalytic distillation column is 0.1-15 h-1(ii) a The volume ratio of the hydrogen to the product is 100-400: 1.
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Citations (4)
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|---|---|---|---|---|
| CN101343562A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Hydrodesulphurization, olefin reduction method for gasoline |
| CN102453533A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline by using by inferior gasoline fractions |
| CN104471036A (en) * | 2012-07-17 | 2015-03-25 | Ifp新能源公司 | Method for producing a light petrol with a low sulphur content |
| CN106554839A (en) * | 2015-09-29 | 2017-04-05 | 中国石油化工股份有限公司 | The method for removing hydrogen sulfide and mercaptan in liquefied petroleum gas using fixed bed reactors simultaneously |
-
2020
- 2020-07-15 CN CN202010680524.5A patent/CN111909724A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343562A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Hydrodesulphurization, olefin reduction method for gasoline |
| CN102453533A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline by using by inferior gasoline fractions |
| CN104471036A (en) * | 2012-07-17 | 2015-03-25 | Ifp新能源公司 | Method for producing a light petrol with a low sulphur content |
| CN106554839A (en) * | 2015-09-29 | 2017-04-05 | 中国石油化工股份有限公司 | The method for removing hydrogen sulfide and mercaptan in liquefied petroleum gas using fixed bed reactors simultaneously |
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Application publication date: 20201110 |