CN111996032A - System and method for removing olefin from reformate through hydrogenation - Google Patents
System and method for removing olefin from reformate through hydrogenation Download PDFInfo
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- CN111996032A CN111996032A CN202010815697.3A CN202010815697A CN111996032A CN 111996032 A CN111996032 A CN 111996032A CN 202010815697 A CN202010815697 A CN 202010815697A CN 111996032 A CN111996032 A CN 111996032A
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a system and a method for hydrogenation and olefin removal of reformate, wherein a contact tank, a dechlorination tank, a stabilizing tower feeding heat exchange device (1), a hydrogenation reactor (2), a stabilizing tower feeding heat exchanger (3), a stabilizing tower (4), a stabilizing tower top air cooler (5), a stabilizing tower top after cooler (6) and a stabilizing tower top reflux tank (7) are sequentially connected through pipelines; the invention directly carries out liquid phase hydrogenation treatment on the reformed oil obtained by separating from the reformate separating tank, not only makes full use of the dissolved hydrogen in the reformed oil, but also can remove the olefin in the reformed oil, and simultaneously eliminates the requirements on circulating hydrogen and circulating equipment thereof. The method obviously reduces the consumption of the argil, reduces the expense for replacing the argil and treating hazardous waste, avoids dangerous operation such as replacing the argil in the device, ensures the device to be produced in a quality and safe manner, and has obvious environmental protection benefit.
Description
Technical Field
The invention belongs to the technical field of reformate production, and relates to a system and a method for removing olefin from reformate through hydrogenation.
Background
The increase of the olefin content in the reformate of the refining and chemical separation company affects the acid-washing color comparison of aromatic hydrocarbon products and also affects the safe operation of downstream devices taking the aromatic hydrocarbon products as raw materials. On one hand, the olefin causes unqualified acid washing color of the aromatic hydrocarbon product, and on the other hand, the olefin can polymerize in the aromatic hydrocarbon extraction solvent to pollute the extraction solvent and cause corrosion of extraction system equipment.
In the prior art, the traditional clay refining process is used for removing olefin, although the technical cost is low, the clay has small specific surface area, short service cycle and low olefin removal rate. Particularly, when the content of olefin is high, the clay is frequently replaced, the discharge amount of solid waste is large, the solid waste treatment cost is increased, and the environmental pressure is large; meanwhile, the construction operation risk of replacing the argil is high, and the risk of parking the device is improved.
Disclosure of Invention
The invention provides a system and a method for removing olefin from reformate by hydrogenation, aiming at the defects of the technology.
The invention provides a system for hydrogenation and olefin removal of reformate, wherein a contact tank, a dechlorination tank, a stabilizing tower feeding heat exchange device, a hydrogenation reactor, a stabilizing tower feeding heat exchanger, a stabilizing tower top air cooler, a stabilizing tower top aftercooler and a stabilizing tower top reflux tank are sequentially connected through a pipeline;
wherein the stabilizing tower is connected with the stabilizing tower reboiler through a pipeline;
the PSA device is connected with a hydrogen heater through a pipeline, wherein the hydrogen heater is connected with a hydrogenation reactor through a pipeline.
Furthermore, the stabilizing tower feeding heat exchange device is formed by connecting three stabilizing tower feeding heat exchangers in series.
Furthermore, a filter is arranged between the PSA device and the hydrogen heater.
Furthermore, a first flow regulating valve is arranged on a pipeline between the hydrogen heater and the hydrogenation reactor, and a second flow regulating valve is arranged on an outlet pipeline of the hydrogen heater.
Further, the hydrogenation reactor is a tubular reactor.
Furthermore, a stabilizing tower reflux pump is arranged on a pipeline between the stabilizing tower top reflux tank and the stabilizing tower.
The invention also provides a method for removing olefin by hydrogenation of reformate, which comprises the following steps:
a. the reformed oil entering the re-contact tank and the dechlorination tank from each component device enters the bottom of the hydrogenation reactor after passing through a stabilizing tower feeding heat exchange device;
b. removing particle impurities from hydrogen conveyed by a PSA device through a filter, then feeding the hydrogen into the bottom of a hydrogenation reactor, adjusting a first flow regulating valve on a feeding line, and regulating the feeding amount of the hydrogen to ensure that the volume ratio of hydrogen to oil is 3: 1;
c. hydrogen and raw oil are efficiently mixed in a mixing section at the bottom of a hydrogenation reactor, and a mixed material flows through a catalyst bed layer in a tubular reactor from bottom to top to carry out hydrogenation reaction under the action of a catalyst to obtain a reaction product;
d. controlling the flow of the reaction product through a second flow regulating valve at the outlet of the hydrogenation reactor, and then further exchanging heat with a stabilizing tower feeding heat exchanger and then entering a stabilizing tower;
e. the excessive gas phase after hydrogenation reaction flows out from the top of the stabilizing tower, is condensed and cooled by an air cooler at the top of the stabilizing tower and a post cooler at the top of the stabilizing tower, is separated in a reflux tank at the top of the stabilizing tower, and enters a re-contact unit for hydrogen recovery;
f. and boosting the liquid phase after the hydrogenation reaction by a reflux pump of the stabilizing tower, returning most of the liquid phase after boosting to the stabilizing tower to be used as reflux, and sending the rest of the liquid phase to an aromatic device under the cascade control of liquid level and flow after heat exchange by a feed heat exchanger of the stabilizing tower.
The catalyst bed layer in the hydrogenation reactor is made of alumina carrier, and the specific surface area is more than or equal to 190m2Per gram, pore volume 0.6-0.7mL/g, containing 0.30% of active metals pt, pd; the loading density of the catalyst in the hydrogenation reactor is 0.6t/m3；
Furthermore, ceramic balls with the diameter of 6mm are filled in the upper part of the hydrogenation reactor, catalysts are filled in the middle part of the hydrogenation reactor, and ceramic balls with the diameter of 6mm and the diameter of 13mm are filled in the lower part of the hydrogenation reactor.
Further, after the reformed oil in the step a passes through a feeding heat exchanger device, heating to 130 ℃; and d, exchanging heat of the stabilizing tower feeding heat exchanger in the step d until the temperature is 170 ℃.
Further, in the step e, an air cooler and a post cooler at the top of the stabilizing tower are condensed and cooled to 40 ℃.
The invention has the beneficial effects that:
according to the method for hydrotreating reformate of the invention, the reformate separated from the reformate separation tank is directly subjected to liquid phase hydrotreating, which not only makes full use of the dissolved hydrogen in the reformate, but also can remove olefins in the reformate, and simultaneously eliminates the need for recycle hydrogen and recycle equipment thereof. The method obviously reduces the consumption of the argil, reduces the expense for replacing the argil and treating hazardous waste, avoids dangerous operation such as replacing the argil in the device, ensures the device to be produced in a quality and safe manner, and has obvious environmental protection benefit.
Drawings
In order to facilitate understanding for those skilled in the art, the present invention will be further described with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of a system for hydrodeolefination of reformate according to the present invention.
Detailed Description
The invention is illustrated in detail by the following examples in conjunction with fig. 1:
the increase of the olefin content in the reformate of the refining and chemical separation company affects the acid-washing color comparison of aromatic hydrocarbon products and also affects the safe operation of downstream devices taking the aromatic hydrocarbon products as raw materials. On one hand, the olefin causes unqualified acid washing color of the aromatic hydrocarbon product, and on the other hand, the olefin can polymerize in the aromatic hydrocarbon extraction solvent to pollute the extraction solvent and cause corrosion of extraction system equipment.
The traditional clay refining process is used before modification, although the technical cost is low, the clay has small specific surface area, short service cycle and low olefin removal rate. Particularly, when the content of olefin is high, the clay is frequently replaced, the discharge amount of solid waste is large, the solid waste treatment cost is increased, and the environmental pressure is large; meanwhile, the construction operation risk of replacing the argil is high, and the risk of parking the device is improved.
The embodiment provides a system for hydrogenation and olefin removal of reformate, wherein a contact tank, a dechlorination tank, a stabilizing tower feeding heat exchange device 1, a hydrogenation reactor 2, a stabilizing tower feeding heat exchanger 3, a stabilizing tower 4, a stabilizing tower top air cooler 5, a stabilizing tower top after cooler 6 and a stabilizing tower top reflux tank 7 are sequentially connected through pipelines;
wherein the stabilizer 4 is connected with the stabilizer reboiler 41 through a pipeline;
the PSA device is connected with a hydrogen heater 8 through a pipeline, wherein the hydrogen heater 8 is connected with the hydrogenation reactor 2 through a pipeline.
The stabilizing tower feeding heat exchange device 1 is formed by connecting three stabilizing tower feeding heat exchangers in series, and a plurality of stabilizing tower feeding heat exchangers are optionally selected to be opened according to needs;
a filter 81 is provided between the PSA apparatus and the hydrogen heater 8.
A first flow regulating valve 21 is arranged on a pipeline between the hydrogen heater 8 and the hydrogenation reactor 2, and a second flow regulating valve 22 is arranged on an outlet pipeline of the hydrogen heater 8.
Further, the hydrogenation reactor 2 is a tubular reactor.
Further, a stabilizing tower reflux pump 8 is arranged on a pipeline between the stabilizing tower top reflux tank 7 and the stabilizing tower 4. A stabilizer reboiler 9 is connected below the stabilizer 4, and the steam pressure in the stabilizer reboiler is 4 MPa.
A method for removing olefin by hydrogenation of reformate comprises the following specific steps:
a. the reformed oil entering the re-contact tank and the dechlorination tank from each component device enters the bottom of the hydrogenation reactor 2 after passing through the stabilizing tower feeding heat exchange device 1;
b. after removing particle impurities from the hydrogen conveyed by the PSA device through a filter 81, feeding the hydrogen into the bottom of a hydrogenation reactor 2, adjusting a first flow regulating valve 21 on a feeding line, and regulating the feeding amount of the hydrogen to ensure that the volume ratio of hydrogen to oil is 3: 1;
c. hydrogen and raw oil are efficiently mixed in a mixing section at the bottom of a hydrogenation reactor 2, the mixed material flows through a catalyst bed layer in a tubular reactor from bottom to top, and hydrogenation reaction is carried out under the action of a catalyst to obtain a reaction product;
d. the flow of the reaction product is controlled by a second flow regulating valve 22 at the outlet of the hydrogenation reactor 2, and the reaction product further exchanges heat with a stabilizing tower feeding heat exchanger 3 and then enters a stabilizing tower 4;
e. the excessive gas phase after hydrogenation reaction flows out from the top of the stabilizing tower 4, is condensed and cooled by an air cooler 5 and a post cooler 6 at the top of the stabilizing tower, is separated in a reflux tank 7 at the top of the stabilizing tower, and enters a re-contact unit for hydrogen recovery;
f. the liquid phase after hydrogenation reaction is boosted by a reflux pump 8 of the stabilizing tower, most of the liquid phase after boosting returns to the stabilizing tower 4 to be used as reflux, and the rest of the liquid phase is sent to an aromatic hydrocarbon device under the cascade control of liquid level and flow after heat exchange by a feed heat exchanger 3 of the stabilizing tower.
The catalyst bed layer in the hydrogenation reactor 2 is made of alumina carrier, and the specific surface area is more than or equal to 190m2Per gram, pore volume 0.6-0.7mL/g, containing 0.30% of active metals pt, pd; the loading density of the catalyst in the hydrogenation reactor 2 is 0.6t/m3；
Ceramic balls with the diameter of 6mm are filled in the upper part of the hydrogenation reactor 2, catalysts are filled in the middle part of the hydrogenation reactor, and ceramic balls with the diameter of 6mm and the diameter of 13mm are filled in the lower part of the hydrogenation reactor.
And d, exchanging heat in a stabilizing tower feeding heat exchanger 3 until the temperature is 170 ℃.
And (e) condensing and cooling the mixture to 40 ℃ by an air cooler 5 at the top of the stabilizing tower and a post cooler 6 at the top of the stabilizing tower.
In the embodiment, the hydrogenation process is used for removing the olefin in the reformate, so that the process flow is simple, the occupied area is small, the number of equipment is small, the process effect is good, and the stability is high. Meanwhile, the hydrogenation process can obviously improve the removal rate of olefin and reduce the generation of heavy aromatics. Further improving the product quality and improving the tail oil quality. The catalyst used in this embodiment is a high-activity high-selectivity noble metal catalyst, and the carrier is an alumina carrier with a special pore channel, so that the olefin produced after hydrogenation is not more than 0.1 w%.
Example 1
The reformed oil passes through a re-contact tank and a dechlorination tank, then passes through a stabilizing tower feeding heat exchanger 1 to exchange heat to the reaction temperature of 130 ℃ and 2.6MPa, and enters the bottom of a hydrogenation reactor 2. Hydrogen from a PSA device is filtered to remove particle impurities such as scrap iron and the like and then enters the bottom of the reactor, the hydrogen passes through an adjusting valve of a feeding line, the hydrogen-oil ratio is adjusted to be 3:1, the hydrogen and the raw oil are efficiently mixed in a mixing section at the bottom of the reactor, the mixed material flows through a catalyst bed layer in a tubular reactor from bottom to top, and hydrogenation reaction is carried out under the action of a catalyst. The reaction product is controlled by the flow rate of a reactor outlet regulating valve, and then is further subjected to heat exchange with a stabilizing tower feeding heat exchanger 4 to 170 ℃, and then enters a stabilizing tower, and the excessive reaction gas phase flows out of the top of the stabilizing tower, is condensed and cooled to 40 ℃ by a stabilizing tower top air cooler 5 and a stabilizing tower top aftercooler 6, is separated in a stabilizing tower top reflux tank 7, and enters a re-contact unit for hydrogen recovery. After the liquid phase is boosted by a reflux pump 71 of the stabilizing tower, most of the liquid phase returns to the stabilizing tower to be used as reflux, and the rest of the liquid phase is sent to an aromatic hydrocarbon device under the cascade control of liquid level and flow after heat exchange by a feed/tower bottom heat exchanger of the stabilizing tower.
Wherein the hydrogen heater 2 is used for providing purging hot hydrogen when the hydrogen heater is started and stopped, and the hydrogen heater is stopped under normal working conditions.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. A system for hydrogenation and olefin removal of reformate is characterized in that a contact tank, a dechlorination tank, a stabilizing tower feeding heat exchange device (1), a hydrogenation reactor (2), a stabilizing tower feeding heat exchanger (3), a stabilizing tower (4), a stabilizing tower top air cooler (5), a stabilizing tower top after cooler (6) and a stabilizing tower top reflux tank (7) are sequentially connected through pipelines;
wherein the stabilizer (4) is connected with the stabilizer reboiler (41) through a pipeline;
the PSA device is connected with a hydrogen heater (8) through a pipeline, wherein the hydrogen heater (8) is connected with the hydrogenation reactor (2) through a pipeline.
2. The reformate hydrodeolefm system according to claim 1, wherein the stabilizer feed heat exchanger (1) comprises three stabilizer feed heat exchangers connected in series.
3. The reformate hydrodeolefm system according to claim 1, wherein a filter (81) is disposed between the PSA device and the hydrogen heater (8).
4. The reformate hydrodeolefm system according to claim 1, wherein a first flow regulating valve (21) is arranged on a pipeline between the hydrogen heater (8) and the hydrogenation reactor (2), and a second flow regulating valve (22) is arranged on an outlet pipeline of the hydrogen heater (8).
5. The reformate hydrodeolefm system according to claim 1, wherein the hydrogenation reactor (2) is a tubular reactor.
6. The reformate hydrodeolefm system according to claim 1, wherein a stabilizer reflux pump (71) is disposed on the pipeline between the stabilizer overhead reflux drum (7) and the stabilizer (4).
7. The method for hydrodeolefination of reformate using the system of claim 1, comprising the steps of:
a. the reformed oil entering the re-contact tank and the dechlorination tank from each component device enters the bottom of the hydrogenation reactor (2) after passing through the stabilizing tower feeding heat exchange device (1);
b. after removing particle impurities from hydrogen conveyed from the PSA device through a filter (81), feeding the hydrogen into the bottom of a hydrogenation reactor (2), adjusting a first flow regulating valve 21 on a feeding line, and regulating the feeding amount of the hydrogen to ensure that the volume ratio of hydrogen to oil is 3: 1;
c. hydrogen and raw oil are efficiently mixed in a mixing section at the bottom of a hydrogenation reactor (2), and a mixed material flows through a catalyst bed layer in a tubular reactor from bottom to top to carry out hydrogenation reaction under the action of a catalyst to obtain a reaction product;
d. the flow of the reaction product is controlled by a second flow regulating valve (22) at the outlet of the hydrogenation reactor (2), and the reaction product further exchanges heat with a stabilizing tower feeding heat exchanger (3) and then enters a stabilizing tower (4);
e. the excessive gas phase after hydrogenation reaction flows out from the top of the stabilizing tower (4), is condensed and cooled by an air cooler (5) and a post cooler (6) at the top of the stabilizing tower, is separated in a reflux tank (7) at the top of the stabilizing tower, and enters a re-contact unit for hydrogen recovery;
f. and the liquid phase after the hydrogenation reaction is boosted by a reflux pump (8) of the stabilizing tower, most of the liquid phase after boosting returns to the stabilizing tower (4) to be used as reflux, and the rest of the liquid phase is sent to an aromatic hydrocarbon device under the cascade control of liquid level and flow after heat exchange by a feed heat exchanger (3) of the stabilizing tower.
8. The reformate hydrodeolefm as claimed in claim 7, wherein the catalyst bed in the hydrogenation reactor (2) is made of aluminaCarrier with specific surface area more than or equal to 190m2Per gram, pore volume 0.6-0.7mL/g, containing 0.30% of active metals pt, pd; the loading density of the catalyst in the hydrogenation reactor (2) is 0.6t/m3；
Ceramic balls with the diameter of 6mm are filled in the upper part of the hydrogenation reactor (2), catalysts are filled in the middle part of the hydrogenation reactor, and ceramic balls with the diameter of 6mm and the diameter of 13mm are filled in the lower part of the hydrogenation reactor.
9. The process of hydrodeolefm in reformate as claimed in claim 7, wherein the reformate in step a is heated to 130 ℃ after passing through the feed heat exchanger means;
and d, exchanging heat by a stabilizing tower feeding heat exchanger (3) in the step d until the temperature is 170 ℃.
10. The method for hydrodeolefination of reformate according to claim 7, characterized in that in step e the product is cooled to 40 ℃ by condensation in a stabilizer overhead air cooler (5), a stabilizer overhead aftercooler (6).
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010815697.3A CN111996032A (en) | 2020-08-14 | 2020-08-14 | System and method for removing olefin from reformate through hydrogenation |
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| CN202010815697.3A CN111996032A (en) | 2020-08-14 | 2020-08-14 | System and method for removing olefin from reformate through hydrogenation |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203878113U (en) * | 2014-05-25 | 2014-10-15 | 中国石油化工股份有限公司 | Reforming reaction liquid-phase product hydrogenation system |
| CN107304376A (en) * | 2016-04-22 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of reformed oil liquid-phase hydrogenatin processing method |
| CN107304371A (en) * | 2016-04-22 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of recapitalization generating oil hydrogenation processing method |
-
2020
- 2020-08-14 CN CN202010815697.3A patent/CN111996032A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203878113U (en) * | 2014-05-25 | 2014-10-15 | 中国石油化工股份有限公司 | Reforming reaction liquid-phase product hydrogenation system |
| CN107304376A (en) * | 2016-04-22 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of reformed oil liquid-phase hydrogenatin processing method |
| CN107304371A (en) * | 2016-04-22 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of recapitalization generating oil hydrogenation processing method |
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Application publication date: 20201127 |
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