CN115305106A - Device and method for treating styrene tar - Google Patents
Device and method for treating styrene tar Download PDFInfo
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- CN115305106A CN115305106A CN202210950045.XA CN202210950045A CN115305106A CN 115305106 A CN115305106 A CN 115305106A CN 202210950045 A CN202210950045 A CN 202210950045A CN 115305106 A CN115305106 A CN 115305106A
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- styrene tar
- tar
- styrene
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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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
- C10G11/182—Regeneration
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22G—SUPERHEATING OF STEAM
- F22G1/00—Steam superheating characterised by heating method
- F22G1/16—Steam superheating characterised by heating method by using a separate heat source independent from heat supply of the steam boiler, e.g. by electricity, by auxiliary combustion of fuel oil
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a device and a method for treating styrene tar, which comprises a tar storage tank and a styrene tar feeding main line connected with the tar storage tank, wherein the tail end of the styrene tar feeding main line is divided into a first styrene tar feeding branch line and a second styrene tar feeding branch line, the first styrene tar feeding branch line is communicated with a coking tank, and the second styrene tar feeding branch line is communicated with a main riser reactor.
Description
Technical Field
The invention relates to the technical field of styrene tar treatment, in particular to a device and a method for treating styrene tar.
Background
The styrene tar is the residual substance after the rectification of the styrene, has complex components, contains high-boiling-point byproducts, polymer residues, polymerization inhibitors and the like in the production process of the styrene, and generally can reach more than 1 percent of the yield of the styrene. Since styrene monomer has self-polymerizing property, in order to reduce the loss caused by polymerization of styrene monomer in the styrene rectification process, a polymerization inhibitor 2, 6-dinitro-4-sec-butylphenol (DNBP) must be added in the styrene rectification process. Finally, DNBP can remain in styrene tar, and DNBP has biotoxicity, and the direct discharge of unpurified styrene tar can cause adverse effects on the environment and the like, so that the national environmental protection department has listed the styrene tar in the national hazardous waste record as "heavy fraction produced in the process of producing styrene by catalytic dehydrogenation of ethylbenzene".
At present, enterprises producing styrene tar have the following ways to treat styrene tar: (1) The waste is treated by a professional hazardous waste treatment unit, and the treatment cost is higher in the mode. (2) As fuel oil type boiler fuel, the content of tar nitrogen is high, and nitrogen oxides in flue gas of a heating furnace exceed the standard during combustion, so that tar needs to be treated first, and the tar is removed as much as possible and then used as heating furnace fuel, a matched tar purification treatment device needs to be added, and waste water and waste residues can be generated in the treatment process. (3) The method is used as a feed of a coke tower to convert the styrene tar into the coker gasoline, the coker diesel and coke, but the additional value of products converted by processing the styrene tar in the mode is low.
In recent years, some new ways of recycling styrene tar have appeared, such as (1) preparing a cement water reducing agent, recovering DNBP in the tar, performing a sulfonation reaction on the residual tar, and then performing a condensation reaction by using formaldehyde as a condensing agent to prepare the cement water reducing agent. (2) The method is characterized in that a certain amount of trans-1, 2-stilbene (10-17%) can exist in tar, the substance is an organic synthetic raw material, diphenylacetylene can be prepared, the method is widely applied to the industries of medicines, foods, functional materials and dyes, the trans-stilbene in the tar can be recovered through the procedures of distillation, recrystallization, washing and the like, and a suitable treatment mode is required to be found for residual (80%) tar due to high investment of a newly-built treatment device. These new approaches can realize high value-added conversion of styrene tar, but all require removing DNBP from the styrene tar first, so that the styrene tar needs to be treated or utilized more well, harmless treatment is needed, and investment in new equipment is also needed to remove DNBP from the styrene tar.
Disclosure of Invention
In order to solve the technical defects in the prior art, the invention provides a device and a method for treating styrene tar, which can flexibly send the styrene tar into a coke burning tank to generate saturated vapor or into a riser reactor to be converted into components of gasoline and diesel oil according to the self requirements, thereby treating the styrene tar in an environment-friendly way and generating certain benefits. .
The technical solution adopted by the invention is as follows: the utility model provides a handle device of styrene tar, includes tar storage tank and the styrene tar feeding thread of being connected with the tar storage tank, the end of styrene tar feeding thread divide into first styrene tar feeding branch line and second styrene tar feeding branch line, first styrene tar feeding branch line intercommunication burning jar, second styrene tar feeding branch line intercommunication main riser reactor.
And one side of the main riser reactor is also provided with a secondary riser reactor, and the secondary riser reactor is communicated with the main riser reactor.
The upper end of the main riser reactor is provided with a settler, and the secondary riser reactor is communicated with the main riser reactor through the settler.
The upper part of the coke burning tank is provided with a regenerator, and the regenerator is communicated with the interior of the coke burning tank.
The coke burning tank is provided with a plurality of inclined pipes which are respectively communicated with the lower parts of the main riser reactor and the secondary riser reactor.
The coke burning tank is also provided with an external heat taking pipe which conducts heat and sends medium-pressure saturated steam generated after the steam-liquid separation of the deoxidized water to the waste heat boiler.
And flow control valves are arranged on the main styrene tar feeding line, the first styrene tar feeding branch line and the second styrene tar feeding branch line.
Flow control valves on the first styrene tar feeding branch line and the second styrene tar feeding branch line are respectively provided with a pilot shower valve and a pressure gauge in front.
A method for treating styrene tar adopts any one of the following modes:
(1) Closing the second styrene tar feeding branch line, and opening the first styrene tar feeding branch line to feed all styrene tar into the coke burning tank to generate heat and supply the waste heat boiler to generate superheated saturated steam after heat is extracted; or
(2) Closing the first styrene tar feeding branch line, and opening the second styrene tar feeding branch line to feed all styrene tar into the main riser reactor to be contacted with the catalyst, so that the styrene tar is converted into components of gasoline and diesel oil and a small amount of coke; or
(3) And simultaneously starting the first styrene tar feeding branch line and the second styrene tar feeding branch line, feeding a part of styrene tar into the main riser reactor to produce gasoline, diesel oil and coke, and feeding a part of styrene tar into the coke burning tank to produce superheated saturated steam.
The styrene tar is fed from the middle upper part of the main riser reactor.
The temperature of the styrene tar fed into the coke burning tank is 650-700 ℃, and the temperature of the styrene tar fed into the main riser reactor is 550-630 ℃.
The catalyst consists of a zeolite molecular sieve, a carrier and a binder, wherein the content of aluminum oxide in the zeolite molecular sieve is more than or equal to 55 percent, the pore volume is less than or equal to 0.3mL/g, and the specific surface area is more than or equal to 140m 2 /g。
In order to prevent the catalyst from flowing back to the first styrene tar feeding branch line and the second styrene tar feeding branch line, a pressure gauge arranged on a pipeline is observed or a pilot valve is opened slightly, when the pressure of the pressure gauge is increased to 0.4 to 0.6MPa or the styrene tar is seen at the pilot valve, flow control valves of the first styrene tar feeding branch line and the second styrene tar feeding branch line are opened.
Wherein the amount of the styrene tar fed into the coking tank is 0-10t/h, and the amount of the styrene tar fed into the riser reactor is 0-10t/h.
The invention has the beneficial effects that: the invention provides a device and a method for treating styrene tar, which comprises a tar storage tank and a styrene tar feeding main line connected with the tar storage tank, wherein the tail end of the styrene tar feeding main line is divided into a first styrene tar feeding branch line and a second styrene tar feeding branch line, the first styrene tar feeding branch line is communicated with a coking tank, and the second styrene tar feeding branch line is communicated with a main riser reactor.
Drawings
FIG. 1 is a schematic view showing the structure of an apparatus for treating styrene tar according to the present invention.
Wherein, the system comprises a tar storage tank 1, a styrene tar feeding main line 2, a coking tank 3, a main riser reactor 4, a waste heat boiler 5, a first styrene tar feeding branch line 21, a second styrene tar feeding branch line 22, a regenerator 31, a secondary riser reactor 41 and a settler 42.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The utility model provides a handle device of styrene tar, includes tar storage tank 1 and the styrene tar feeding thread 2 of being connected with tar storage tank 1, the end of styrene tar feeding thread 2 divide into first styrene tar feeding branch line 21 and second styrene tar feeding branch line 22, first styrene tar feeding branch line 21 intercommunication burnt jar 3, second styrene tar feeding branch line 22 intercommunication main riser reactor 4. And a secondary riser reactor 41 is arranged on one side of the main riser reactor 4, and the secondary riser reactor 41 is communicated with the main riser reactor 4. The invention can flexibly send the styrene tar into a coking tank to generate heat and generate saturated vapor or send the saturated vapor into a riser reactor to be converted into components of gasoline and diesel oil according to the self requirement, thereby disposing the styrene tar in an environment-friendly way and generating certain benefits.
The upper end of the main riser reactor 4 is provided with a settler 42, and the secondary riser reactor 41 is communicated with the main riser reactor 4 through the settler 42.
The upper part of the coking tank 3 is provided with a regenerator 31, and the regenerator 31 is communicated with the interior of the coking tank 3.
The coking tank 3 is provided with a plurality of inclined pipes which are respectively communicated with the lower parts of the main riser reactor 4 and the secondary riser reactor 41.
The coke burning tank 3 is also provided with an external heat taking pipe which conducts heat and sends medium-pressure saturated steam generated after the steam-liquid separation of the deoxidized water to the waste heat boiler 5.
The main styrene tar feeding line 2, the first styrene tar feeding branch line 21 and the second styrene tar feeding branch line 22 are all provided with flow control valves. And a pilot valve and a pressure gauge are arranged 10-30cm in front of the flow control valves on the first styrene tar feeding branch line 21 and the second styrene tar feeding branch line 22.
A method for flexibly treating styrene tar by using the device comprises the following two modes:
(1) Feeding styrene tar into a coking tank of the device to generate heat for a waste heat boiler to generate superheated saturated steam;
(2) Styrene tar is fed into a riser reactor of the device and contacts with a catalyst to react and be converted into gasoline, diesel oil components and coke.
The refinery can flexibly process the styrene tar by adopting one of the following modes according to the production requirements:
(1) The second styrene tar feeding branch line 22 is closed, the first styrene tar feeding branch line 21 is opened, all styrene tar is sent into the coke burning tank to generate heat, and the heat is supplied to the waste heat boiler to generate superheated saturated steam after heat is extracted;
(2) Closing the first styrene tar feeding branch line 21, and opening the second styrene tar feeding branch line 22 to completely feed the styrene tar into the main riser reactor 4 to contact with the catalyst, so that the styrene tar is converted into components of gasoline and diesel oil and a small amount of coke;
(3) Meanwhile, a first styrene tar feeding branch line 21 and a second styrene tar feeding branch line 22 are started, a part of styrene tar is fed into the main riser reactor 4 to produce gasoline, diesel oil and coke, and a part of styrene tar is fed into a coke burning tank to produce superheated saturated steam.
Wherein, the second styrene tar feeding branch line 22 can be connected with an oil slurry recycling line, styrene tar is fed into the main riser reactor 4 by sharing an oil slurry recycling nozzle, and can also be communicated with the middle upper part of the main riser reactor 4, and the styrene tar is fed into the middle upper part of the riser by the feeding nozzle alone.
In order to prevent the catalyst from flowing back to the first styrene tar feeding branch line and the second styrene tar feeding branch line, a pressure gauge arranged on a pipeline needs to be observed or a pilot valve needs to be opened slightly, when the pressure of the pressure gauge is increased to 0.4 to 0.6MPa or styrene tar is seen at the pilot valve, and then flow control valves of the first styrene tar feeding branch line and the second styrene tar feeding branch line are opened.
Wherein the amount of the styrene tar fed into the coking tank is 0-10t/h, and the amount of the styrene tar fed into the riser reactor is 0-10t/h.
Wherein the problem of feeding the styrene tar into the coke burning tank is 650-700 ℃, and the temperature of the part of the lift pipe, which is fed with the styrene tar, is 550-630 ℃.
Wherein the catalyst for the styrene tar to contact in the riser reactor consists of a zeolite molecular sieve, a carrier and a binder, the content of aluminum oxide in the zeolite molecular sieve is more than or equal to 55 percent, the pore volume is less than or equal to 0.3mL/g, and the specific surface area is more than or equal to 140m 2 /g。
Example 1
The main styrene tar feeding line 2 and the first styrene tar feeding branch line 21 are opened, the second styrene tar feeding branch line 22 is closed, the styrene tar is introduced into the coking tank, and the heat after combustion is used for the waste heat boiler to generate superheated steam at the temperature of 420 ℃ of 3.9MPa. The thermal efficiency of the boiler is 85%; the enthalpy value of water at 20 ℃ is 84kJ/kg, the enthalpy value of superheated steam at 3.9MPa 420 ℃ is 3264kJ/kg, and the calculation shows that 10 tons of superheated steam at 3.9MPa 420 ℃ can be generated by burning 1 ton of tar, and the product value is about 3000 yuan by using 1 ton of styrene tar according to the calculation of the steam price of 300 yuan/ton.
Example 2
The main feeding line 2 of the styrene tar and the branch feeding line 22 of the styrene tar are opened, the branch feeding line 21 of the first styrene tar is closed, the styrene tar is introduced into the main riser, the yield of light oil produced after the styrene tar is cracked in the main riser is 55%, the yield of heavy oil is 35%, and the yield of coke is 10%. The product value created by using 1 ton of styrene tar according to the method is about 4000 yuan by calculating the average price of light oil of 5700 yuan/ton and the average price of heavy oil of 3000 yuan/ton.
Example 3
Starting a main styrene tar feeding line 2, a first styrene tar feeding branch line 21 and a second styrene tar feeding branch line 22, and respectively introducing styrene tar into a coking tank and a main riser, wherein the feeding amount of the coking tank is 1t/h, and the feeding amount of the main riser is 2t/h. Thus, the styrene tar is treated, 10 tons of superheated saturated steam at the temperature of 420 ℃ of 3.9MPa is generated by taking heat from the coking tank and the waste heat boiler every hour, 1.1 ton of cracked light oil and 0.7 ton of cracked heavy oil are generated by the main riser every hour.
The skilled person should understand that: although the invention has been described in terms of the above specific embodiments, the inventive concept is not limited thereto and any modification applying the inventive concept is intended to be included within the scope of the patent claims.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above embodiments, and all technical solutions that belong to the idea of the present invention belong to the scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (10)
1. The utility model provides a handle device of styrene tar, includes tar storage tank (1) and styrene tar feeding thread (2) of being connected with tar storage tank (1), its characterized in that, the end of styrene tar feeding thread (2) divide into first styrene tar feeding branch line (21) and second styrene tar feeding branch line (22), first styrene tar feeding branch line (21) intercommunication burnt jar (3), second styrene tar feeding branch line (22) intercommunication main riser reactor (4).
2. The apparatus for treating styrene tar according to claim 1, wherein said primary riser reactor (4) is further provided with a secondary riser reactor (41) at one side thereof, said secondary riser reactor (41) being in communication with said primary riser reactor (4).
3. The apparatus for treating styrene tar according to claim 2, wherein said primary riser reactor (4) has a settler (42) at the upper end thereof, and said secondary riser reactor (41) is connected to said primary riser reactor (4) through said settler (42).
4. The apparatus for treating styrene tar according to claim 1, wherein a regenerator (31) is provided at an upper portion of said coking tank (3), and said regenerator (31) is communicated with the interior of said coking tank (3).
5. The apparatus for treating styrene tar according to claim 2, wherein said coke-burning tank (3) is provided with a plurality of inclined pipes, and said plurality of inclined pipes are respectively communicated with the lower portions of said primary riser reactor (4) and said secondary riser reactor (41).
6. The device for treating styrene tar according to claim 1, wherein the coke burning tank (3) is further provided with an external heat taking pipe, and the external heat taking pipe transfers heat and sends medium-pressure saturated steam generated after the steam-liquid separation of the deoxidized water to the waste heat boiler (5).
7. A method for treating styrene tar by using the apparatus according to any of claims 1 to 6, characterized in that the styrene tar is treated by any of the following means:
(1) Closing the second styrene tar feeding branch line, and opening the first styrene tar feeding branch line to feed all styrene tar into the coke burning tank to generate heat and supply the waste heat boiler to generate superheated saturated steam after heat is extracted; or
(2) Closing the first styrene tar feeding branch line, and opening the second styrene tar feeding branch line to feed all styrene tar into the main riser reactor to be contacted with the catalyst, so that the styrene tar is converted into components of gasoline and diesel oil and a small amount of coke; or
(3) And simultaneously starting the first styrene tar feeding branch line and the second styrene tar feeding branch line, feeding a part of styrene tar into the main riser reactor to produce gasoline, diesel oil and coke, and feeding a part of styrene tar into the coke burning tank to produce superheated saturated steam.
8. The method of processing styrene tar according to claim 7, wherein said styrene tar is fed from the middle-upper portion of the main riser reactor.
9. The method of claim 7, wherein the temperature of the styrene tar fed into the coke oven is 650 ℃ to 700 ℃ and the temperature of the styrene tar fed into the main riser reactor is 550 ℃ to 630 ℃.
10. The method for treating styrene tar according to claim 7, wherein the catalyst comprises zeolite molecular sieve, carrier and binder, the content of alumina in the zeolite molecular sieve is not less than 55%, the pore volume is not more than 0.3mL/g, and the specific surface area is not less than 140m 2 /g。
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210950045.XA CN115305106A (en) | 2022-08-09 | 2022-08-09 | Device and method for treating styrene tar |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210950045.XA CN115305106A (en) | 2022-08-09 | 2022-08-09 | Device and method for treating styrene tar |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5406010A (en) * | 1993-01-28 | 1995-04-11 | Ponsford; Thomas E. | Method of reclaiming styrene and other products from polystyrene based products |
| US5799626A (en) * | 1993-01-28 | 1998-09-01 | Ponsford; Thomas E. | Methods for using styrene oil (as heat transfer fluid, hydraulic fluid, lubricant) |
| CN202039032U (en) * | 2010-11-04 | 2011-11-16 | 中国石油天然气华东勘察设计研究院 | Propylene production device by using heavy oil |
| CN110511783A (en) * | 2019-09-30 | 2019-11-29 | 中国石油化工股份有限公司 | The device and method that styrene heavy distillate is comprehensively utilized |
| CN217895509U (en) * | 2022-08-09 | 2022-11-25 | 中海石油宁波大榭石化有限公司 | Device for treating styrene tar |
-
2022
- 2022-08-09 CN CN202210950045.XA patent/CN115305106A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5406010A (en) * | 1993-01-28 | 1995-04-11 | Ponsford; Thomas E. | Method of reclaiming styrene and other products from polystyrene based products |
| US5799626A (en) * | 1993-01-28 | 1998-09-01 | Ponsford; Thomas E. | Methods for using styrene oil (as heat transfer fluid, hydraulic fluid, lubricant) |
| CN202039032U (en) * | 2010-11-04 | 2011-11-16 | 中国石油天然气华东勘察设计研究院 | Propylene production device by using heavy oil |
| CN110511783A (en) * | 2019-09-30 | 2019-11-29 | 中国石油化工股份有限公司 | The device and method that styrene heavy distillate is comprehensively utilized |
| CN217895509U (en) * | 2022-08-09 | 2022-11-25 | 中海石油宁波大榭石化有限公司 | Device for treating styrene tar |
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