CN108559010B - Production device for producing poly alpha olefin by Fischer-Tropsch synthesis olefin polymerization - Google Patents
Production device for producing poly alpha olefin by Fischer-Tropsch synthesis olefin polymerization Download PDFInfo
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- CN108559010B CN108559010B CN201810304521.4A CN201810304521A CN108559010B CN 108559010 B CN108559010 B CN 108559010B CN 201810304521 A CN201810304521 A CN 201810304521A CN 108559010 B CN108559010 B CN 108559010B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract
A production device for producing poly-alpha-olefin by Fischer-Tropsch synthesis olefin polymerization relates to a poly-alpha-olefin production device, and is characterized in that a carbon-ten-alkane rectifying tower (4), a carbon-ten-olefin rectifying tower (5), a polymerization reactor (6), a hydrogenation reactor (10), an oligomer rectifying tower (12), a molecular sieve refiner (15), a catalyst recovery tank (17) and a poly-alpha-olefin rectifying tower (20) are connected through a proper combination; the invention adopts a molecular sieve refiner to remove water from Fischer-Tropsch synthesis olefin, a carbon-decalin rectifying tower and a carbon-decalin rectifying tower are used for purifying the Fischer-Tropsch synthesis olefin to obtain the carbon-decalin, a catalyst boron trifluoride is added to convert the carbon-decalin into poly-alpha-olefin, a hydrogenation catalyst is added to react hydrogen with the poly-alpha-olefin to convert the poly-alpha-olefin into saturated poly-alpha-olefin, an oligomer is separated by an oligomer rectifying tower, and three poly-alpha-olefins with different viscosities are obtained by the poly-alpha-olefin rectifying tower.
Description
[ field of technology ]
The invention relates to a poly alpha olefin production device, in particular to a production device for producing poly alpha olefin by polymerizing Fischer-Tropsch synthesis olefin.
[ background Art ]
The Fischer-Tropsch synthesis olefin is a liquid coal-to-oil product which is prepared by indirectly liquefying coal and takes normal alkane and alpha olefin as main components. The main components of the Fischer-Tropsch synthesis olefin are 60% of alpha olefin with five to sixteen carbon atoms, 30% -35% of n-alkane with five to sixteen carbon atoms, a small amount of isoparaffin, naphthene and isoparaffin, and the impurity is a trace amount of water. With the development of coal-to-liquid technology, the production capacity of Fischer-Tropsch synthesized olefins in China is improved year by year, and the olefins are used as raw materials for preparing poly-alpha-olefins, so that the economic efficiency is good.
Polyalphaolefins (PAOs) are base oils for fully synthetic lubricating oils, widely used in the high end lubrication field, prepared from carbon-ten linear alpha olefins (1-decamethylene) by polymerization and hydrogenation processes; the imported alpha olefin which is commonly used internationally is prepared by an ethylene oligomerization method, and has higher price. The ethylene oligomerization technology is not known in China, alpha olefin is mainly produced by a wax cracking method, the normal structure content is low, and the product quality is poor.
[ invention ]
In order to overcome the defects in the background art, the invention discloses a production device for producing poly-alpha-olefins by polymerizing Fischer-Tropsch synthesis olefins.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a device for producing poly-alpha-olefin by Fischer-Tropsch synthesis olefin polymerization comprises a carbon-dodecyl-hydrocarbon rectifying tower, a polymerization reactor, a hydrogenation reactor, an oligomer rectifying tower, a molecular sieve refiner, a catalyst recovery tank and a poly-alpha-olefin rectifying tower, wherein the inlet of the Fischer-Tropsch synthesis olefin is positioned at the top end of the molecular sieve refiner, the outlet arranged at the bottom of the molecular sieve refiner is connected with the inlet arranged at the middle part of the carbon-dodecyl-hydrocarbon rectifying tower through a pipeline, the outlets of the carbon-dodecyl-hydrocarbon and lighter components are positioned at the top end of the carbon-dodecyl-hydrocarbon rectifying tower, the outlet arranged at the bottom of the carbon-dodecyl-hydrocarbon rectifying tower is connected with the inlet arranged at the middle part of the carbon-dodecyl-hydrocarbon rectifying tower through a pipeline, the outlet arranged at the top of the carbon-dodecyl-hydrocarbon rectifying tower is connected with the inlet arranged at the middle part of the polymerization reactor through a pipeline, the catalyst boron trifluoride inlet is positioned at the top of the polymerization reactor, the outlet arranged at the bottom of the polymerization reactor is connected with the inlet arranged at the middle part of the catalyst recovery tank through a pipeline, the catalyst boron trifluoride outlet is positioned at the top of the catalyst recovery tank, the outlet arranged at the bottom of the catalyst recovery tank is connected with the inlet arranged at the top of the hydrogenation reactor through a pipeline, the outlet arranged at the bottom of the hydrogenation reactor is connected with the inlet arranged at the middle part of the oligomer rectifying tower through a pipeline, the hydrogen inlet is positioned at the bottom of the hydrogenation reactor, the oligomer outlet is positioned at the top of the oligomer rectifying tower, the outlet arranged at the bottom of the oligomer rectifying tower is connected with the inlet arranged at the middle lower part of the polyalphaolefin rectifying tower through a pipeline, the polyalphaolefin four outlets are positioned at the top of the polyalphaolefin rectifying tower, the polyalphaolefin ten outlets are positioned at the middle part of the polyalphaolefin rectifying tower, the polyalphaolefin twenty outlet is located at the bottom of the polyalphaolefin rectifying column.
The device for producing the poly-alpha-olefin by polymerizing the Fischer-Tropsch synthesis olefin is characterized in that conveying pumps are respectively arranged on a pipeline between a molecular sieve refiner and a carbon-dodecyl-hydrocarbon rectifying tower, a pipeline between the carbon-dodecyl-hydrocarbon rectifying tower and the carbon-dodecyl-hydrocarbon rectifying tower, a pipeline between the carbon-dodecyl-hydrocarbon rectifying tower and a polymerization reactor, a pipeline between the polymerization reactor and a catalyst recovery tank, a pipeline between the catalyst recovery tank and a hydrogenation reactor, a pipeline between the hydrogenation reactor and an oligomer rectifying tower and a pipeline between the oligomer rectifying tower and the poly-alpha-olefin rectifying tower.
The device for producing poly alpha olefin by Fischer-Tropsch synthesis olefin polymerization is characterized in that a regulating valve is arranged on a pipeline of a Fischer-Tropsch synthesis olefin inlet, and a vacuum pump is arranged on a pipeline of a catalyst boron trifluoride outlet.
The device for producing poly alpha olefin by Fischer-Tropsch synthesis olefin polymerization has a molecular sieve refiner of 3A or 4A molecular sieve.
The device for producing the poly-alpha-olefin by polymerizing the Fischer-Tropsch synthesis olefin comprises a carbon-dodecyl-hydrocarbon rectifying tower, a carbon-dodecyl-hydrocarbon rectifying tower and a poly-alpha-olefin rectifying tower which are respectively regular stainless steel packed towers or tongue-shaped floating valve plate towers, and the effective plate number is 60-80.
The device for producing poly alpha olefin by Fischer-Tropsch synthesis olefin polymerization is characterized in that the polymerization reactor is a turbine blade type stirring kettle.
The catalyst recovery tank is a regular stainless steel pressure tank.
The hydrogenation reactor is a stainless steel kettle type fixed bed reactor, the middle part is filled with a hydrogenation catalyst, and the catalyst is platinum-based hydrogenation catalysis.
The device for producing poly alpha olefin by Fischer-Tropsch synthesis olefin polymerization is characterized in that the oligomer rectifying tower is a regular stainless steel packed tower or a tongue-shaped floating valve plate tower, and the effective plate number is 45-60.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
the invention relates to a production device for producing poly-alpha-olefins by Fischer-Tropsch synthesis olefin polymerization, which adopts a molecular sieve refiner to remove water from the Fischer-Tropsch synthesis olefin, a carbon-decalin rectifying tower and a carbon-decalin rectifying tower to purify the Fischer-Tropsch synthesis olefin to obtain carbon-decalin, adding a catalyst boron trifluoride to convert the carbon-decalin into poly-alpha-olefins, adding a hydrogenation catalyst to react hydrogen with the poly-alpha-olefins to convert the poly-alpha-olefins into saturated poly-alpha-olefins, separating oligomers by an oligomer rectifying tower, and obtaining three poly-alpha-olefins with different viscosities by the poly-alpha-olefin rectifying tower; the invention has the advantages of reasonable design, unique process, energy conservation, consumption reduction and environmental protection.
[ description of the drawings ]
Fig. l is a schematic structural diagram of the present invention.
In the figure: 1. a Fischer-Tropsch synthesis olefin inlet; 2. a regulating valve; 3. a carbon-ten alkane and lighter components outlet; 4. a carbon-ten alkane rectifying column; 5. a carbon decaolefin rectifying column; 6. a polymerization reactor; 7. catalyst boron trifluoride inlet; 8. catalyst boron trifluoride outlet; 9. a vacuum pump; 10. a hydrogenation reactor; 11. an oligomer outlet; 12. an oligomer rectifying column; 13. a polyalphaolefin four-way outlet; 14. a polyalphaolefin tenth outlet; 15. a molecular sieve refiner; 16. a carbon undecane and heavier component outlet; 17. a catalyst recovery tank; 18. a hydrogen inlet; 19. a transfer pump; 20. a polyalphaolefin rectifying column; 21. a poly alpha olefin twenty outlet.
[ detailed description ] of the invention
The invention will be explained in more detail by the following examples, which are not intended to limit the invention thereto, and the purpose of the present invention is to protect all changes and modifications within the scope of the invention;
the production device for producing poly-alpha-olefins by polymerizing Fischer-Tropsch synthesis olefins, which is shown in the attached figure 1, comprises a carbon-dodecyl-hydrocarbon rectifying tower 4, a carbon-dodecyl-hydrocarbon rectifying tower 5, a polymerization reactor 6, a hydrogenation reactor 10, an oligomer rectifying tower 12, a molecular sieve refiner 15, a catalyst recovery tank 17 and a poly-alpha-olefin rectifying tower 20, wherein a Fischer-Tropsch synthesis olefin inlet 1 is positioned at the top end of the molecular sieve refiner 15, an outlet arranged at the bottom of the molecular sieve refiner 15 is connected with an inlet arranged at the middle part of the carbon-dodecyl-hydrocarbon rectifying tower 4 through a pipeline, a carbon-dodecyl-hydrocarbon and lighter component outlet 3 is positioned at the top end of the carbon-dodecyl-hydrocarbon rectifying tower 4, an outlet arranged at the bottom of the carbon-dodecyl-hydrocarbon rectifying tower 4 is connected with an inlet arranged at the middle part of the carbon-dodecyl-hydrocarbon rectifying tower 5 through a pipeline, a carbon-undecane and heavier component outlet 16 is positioned at the bottom of the carbon-dodecyl-hydrocarbon rectifying tower 5, the outlet arranged at the top of the carbon decaolefin rectifying tower 5 is connected with the inlet arranged at the middle part of the polymerization reactor 6 through a pipeline, the catalyst boron trifluoride inlet 7 is positioned at the top of the polymerization reactor 6, the outlet arranged at the bottom of the polymerization reactor 6 is connected with the inlet arranged at the middle part of the catalyst recovery tank 17 through a pipeline, the catalyst boron trifluoride outlet 8 is positioned at the top of the catalyst recovery tank 17, the outlet arranged at the bottom of the catalyst recovery tank 17 is connected with the inlet arranged at the top of the hydrogenation reactor 10 through a pipeline, the outlet arranged at the bottom of the hydrogenation reactor 10 is connected with the inlet arranged at the middle part of the oligomer rectifying tower 12 through a pipeline, the hydrogen inlet 18 is positioned at the bottom of the hydrogenation reactor 10, the oligomer outlet 11 is positioned at the top of the oligomer rectifying tower 12, the outlet arranged at the bottom of the oligomer rectifying tower 12 is connected with the inlet arranged at the middle lower part of the polyalphaolefin rectifying tower 20 through a pipeline, the polyalphaolefin four outlets 13 are positioned at the top of the polyalphaolefin rectifying tower 20, the polyalphaolefin ten-outlet 14 is positioned at the middle part of the polyalphaolefin rectifying tower 20, the polyalphaolefin twenty-outlet 21 is positioned at the bottom of the polyalphaolefin rectifying tower 20, the molecular sieve refiner 15 is a 3A or 4A molecular sieve, the carbon dodecene rectifying tower 4, the carbon dodecene rectifying tower 5 and the polyalphaolefin rectifying tower 20 are respectively a regular stainless steel packed tower or a tongue-shaped floating valve plate type tower, the effective plate number is 60-80, the polymerization reactor 6 is a turbine blade type stirring kettle, the catalyst recovery tank 17 is a regular stainless steel pressure tank, the hydrogenation reactor 10 is a stainless steel kettle type fixed bed reactor, the middle part is filled with a hydrogenation catalyst, the catalyst is platinum-based hydrogenation catalyst, the oligomer rectifying tower 12 is a regular stainless steel packed tower or a tongue-shaped floating valve plate type tower, the effective tower plate number is 45-60, a conveying pump 19 is respectively arranged on a pipeline between the molecular sieve rectifier 15 and the carbon-dodecyl-hydrocarbon rectifying tower 4, a pipeline between the carbon-dodecyl-hydrocarbon rectifying tower 4 and the carbon-dodecyl-hydrocarbon rectifying tower 5, a pipeline between the carbon-dodecyl-hydrocarbon rectifying tower 5 and the polymerization reactor 6, a pipeline between the polymerization reactor 6 and the catalyst recovery tank 17, a pipeline between the catalyst recovery tank 17 and the hydrogenation reactor 10, a pipeline between the hydrogenation reactor 10 and the oligomer rectifying tower 12 and a pipeline between the oligomer rectifying tower 12 and the poly alpha-olefin rectifying tower 20, a regulating valve 2 is arranged on a pipeline of the Fischer-Tropsch synthesis olefin inlet 1, and a vacuum pump 9 is arranged on a pipeline of the catalyst boron trifluoride outlet 8.
When the production device for producing poly-alpha-olefin by Fischer-Tropsch synthesis olefin polymerization is used, fischer-Tropsch synthesis olefin enters a molecular sieve refiner 15 from a Fischer-Tropsch synthesis olefin inlet 1, and the moisture content in the Fischer-Tropsch synthesis olefin is reduced to below 10ppm at 25 ℃ and normal pressure;
the Fischer-Tropsch synthesis olefin comes out of the bottom of a molecular sieve refiner 15, and after entering from the middle part of a carbon-dodecyl-hydrocarbon rectifying tower 4, most of carbon-dodecyl-hydrocarbon and lighter components are separated from a carbon-dodecyl-hydrocarbon and lighter component outlet 3 arranged at the top of the tower, so that the carbon-dodecyl-hydrocarbon and heavier components with the purity of over 99.5 percent are obtained, and the content of the carbon-dodecyl-hydrocarbon and lighter components is lower than 0.5 percent;
the carbon dodecene with the purity of more than 99.5 percent and heavier components are discharged from the bottom of the carbon dodecene rectifying tower 4, and most of the carbon undecane and the heavier components are separated from a carbon undecane and heavier component outlet 16 arranged at the bottom of the tower after entering from the middle part of the carbon dodecene rectifying tower 5, so that the carbon dodecene with the purity of more than 99 percent is obtained, the content of the carbon dodecene and the lighter components is lower than 0.5 percent, and the content of the carbon undecane and the heavier components is lower than 0.5 percent;
introducing boron trifluoride from a catalyst boron trifluoride inlet 7 arranged at the top of a polymerization reactor 6 after the carbon dodecene with the purity of more than 99% comes out from the top of a carbon dodecene rectifying tower 5 and enters from the middle of the polymerization reactor 6, catalyzing the carbon dodecene by the catalyst boron trifluoride under the conditions of 50 ℃ and 0.2Mpa and stirring speed of 200 r/min, and reacting the carbon dodecene for 5 hours to obtain a mixture of poly alpha olefin with the purity of more than 95%, a small amount of poly alpha olefin oligomer, a small amount of unreacted carbon dodecene and trace boron trifluoride dissolved in a liquid phase;
the mixture of poly alpha olefin with the purity of more than 95 percent, a small amount of poly alpha olefin oligomer, a small amount of unreacted carbon dodecene and a trace amount of boron trifluoride dissolved in liquid phase is discharged from the bottom of a polymerization reactor 6, enters from the middle part of a catalyst recovery tank 17, starts a vacuum pump 9 arranged on a catalyst boron trifluoride outlet 8 arranged at the top of the catalyst recovery tank 17, the pressure in the tank is minus 0.2Mpa, the temperature is 50 ℃, and a small amount of boron trifluoride gas mixed in the poly alpha olefin is separated and recovered from the catalyst boron trifluoride outlet 8 to obtain the poly alpha olefin with the purity of more than 95 percent, a small amount of poly alpha olefin oligomer and a small amount of unreacted carbon dodecene mixture, and the boron trifluoride content is lower than 10ppm;
the poly alpha olefin with the purity of more than 95 percent, a small amount of poly alpha olefin oligomer and a small amount of unreacted carbon ten olefin mixture are discharged from the bottom of the catalyst recovery tank 17, after entering from the top of the hydrogenation reactor 10, hydrogen enters from a hydrogen inlet 18 arranged at the bottom of the hydrogenation reactor 10, the hydrogen reacts with the poly alpha olefin, the poly alpha olefin oligomer and the unreacted carbon ten olefin mixture, the reaction residence time is 2 hours, the hydrogen is continuously introduced, the pressure is kept at 5.0Mpa, the temperature is 300 ℃, and the hydrogen is completely consumed after the reaction, and the reaction products are saturated poly alpha olefin, a small amount of saturated poly alpha olefin oligomer and a small amount of carbon ten alkane;
saturated poly alpha olefin, a small amount of saturated poly alpha olefin oligomer and a small amount of carbon dodecene come out from the bottom of the hydrogenation reactor 10, enter from the middle part of the oligomer rectifying tower 12, are separated at the temperature of 200 ℃ and under normal pressure, and are separated from an oligomer outlet 11 arranged at the top of the oligomer rectifying tower 12, so that the product is the saturated poly alpha olefin with negligible impurity content;
saturated poly alpha olefin comes out from the bottom of the oligomer rectifying tower 12, enters from the middle lower part of the poly alpha olefin rectifying tower 20, separates poly alpha olefin four with the content of 30-40% from a poly alpha olefin four outlet 13 arranged at the top of the poly alpha olefin rectifying tower 20, separates poly alpha olefin ten with the content of 45-55% from a poly alpha olefin ten outlet 14 arranged at the middle part of the poly alpha olefin rectifying tower 20, and separates poly alpha olefin twenty with the content of 10-20% from a poly alpha olefin twenty outlet 21 arranged at the bottom of the poly alpha olefin rectifying tower 20 according to different distillation ranges.
The invention is not described in detail in the prior art.
Claims (7)
1. The utility model provides a production device of Fischer-Tropsch synthesis olefin polymerization production poly alpha olefin, includes carbon dodecene rectifying column (4), carbon dodecene rectifying column (5), polymerization ware (6), hydrogenation ware (10), oligomer rectifying column (12), molecular sieve refiner (15), catalyst recovery jar (17) and poly alpha olefin rectifying column (20), characterized by: the Fischer-Tropsch synthesis olefin inlet (1) is positioned at the top end of a molecular sieve refiner (15), an outlet arranged at the bottom of the molecular sieve refiner (15) is connected with an inlet arranged at the middle part of a carbon-decalin rectifying tower (4) through a pipeline, a carbon-decalin and lighter component outlet (3) is positioned at the top end of the carbon-decalin rectifying tower (4), an outlet arranged at the bottom of the carbon-decalin rectifying tower (4) is connected with an inlet arranged at the middle part of a carbon-decalin rectifying tower (5) through a pipeline, an outlet arranged at the top of the carbon-decalin rectifying tower (5) is connected with an inlet arranged at the middle part of a polymerization reactor (6) through a pipeline, a catalyst boron trifluoride inlet (7) is positioned at the top of the polymerization reactor (6), an outlet arranged at the bottom of the polymerization reactor (6) is connected with an inlet arranged at the middle part of a catalyst recovery tank (17) through a pipeline, a catalyst boron trifluoride outlet (8) is positioned at the top of the catalyst recovery tank (17), an outlet arranged at the bottom of the catalyst recovery tank (17) is connected with an inlet arranged at the bottom of the hydrogenation reactor (10) through a pipeline, an outlet arranged at the bottom of the catalyst recovery tank (17) is connected with an inlet (10) and is positioned at the bottom of the polymerization reactor (12) is positioned at the bottom of the polymerization reactor (12) through the low-concentration tower (12) and is positioned at the bottom of the low-concentration reactor (12) is arranged at the bottom of the low-concentration hydrogen reactor (12, an outlet arranged at the bottom of the oligomer rectifying tower (12) is connected with an inlet arranged at the middle lower part of the poly alpha olefin rectifying tower (20) through a pipeline, a poly alpha olefin four-outlet (13) is positioned at the top of the poly alpha olefin rectifying tower (20), a poly alpha olefin ten-outlet (14) is positioned at the middle part of the poly alpha olefin rectifying tower (20), and a poly alpha olefin twenty-outlet (21) is positioned at the bottom of the poly alpha olefin rectifying tower (20);
a transfer pump (19) is respectively arranged on a pipeline between the molecular sieve refiner (15) and the carbon-dodecyl hydrocarbon rectifying tower (4), a pipeline between the carbon-dodecyl hydrocarbon rectifying tower (4) and the carbon-dodecyl hydrocarbon rectifying tower (5), a pipeline between the carbon-dodecyl hydrocarbon rectifying tower (5) and the polymerization reactor (6), a pipeline between the polymerization reactor (6) and the catalyst recovery tank (17), a pipeline between the catalyst recovery tank (17) and the hydrogenation reactor (10), a pipeline between the hydrogenation reactor (10) and the oligomer rectifying tower (12) and a pipeline between the oligomer rectifying tower (12) and the poly alpha olefin rectifying tower (20);
a regulating valve (2) is arranged on a pipeline of the Fischer-Tropsch synthesis olefin inlet (1), and a vacuum pump (9) is arranged on a pipeline of the catalyst boron trifluoride outlet (8).
2. The apparatus for producing poly-alpha-olefin by polymerizing Fischer-Tropsch synthesis olefin according to claim 1, wherein: the molecular sieve refiner (15) is a 3A or 4A molecular sieve.
3. The apparatus for producing poly-alpha-olefin by polymerizing Fischer-Tropsch synthesis olefin according to claim 1, wherein: the carbon-ten alkane rectifying tower (4), the carbon-ten alkene rectifying tower (5) and the poly-alpha-olefin rectifying tower (20) are respectively regular stainless steel packed towers or tongue-shaped floating valve plate type towers, and the effective plate number is 60-80.
4. The apparatus for producing poly-alpha-olefin by polymerizing Fischer-Tropsch synthesis olefin according to claim 1, wherein: the polymerization reactor (6) is a turbine blade type stirring kettle.
5. The apparatus for producing poly-alpha-olefin by polymerizing Fischer-Tropsch synthesis olefin according to claim 1, wherein: the catalyst recovery tank (17) is a regular stainless steel pressure tank.
6. The apparatus for producing poly-alpha-olefin by polymerizing Fischer-Tropsch synthesis olefin according to claim 1, wherein: the hydrogenation reactor (10) is a stainless steel kettle type fixed bed reactor, the middle part is filled with a hydrogenation catalyst, and the catalyst is platinum-based hydrogenation catalyst.
7. The apparatus for producing poly-alpha-olefin by polymerizing Fischer-Tropsch synthesis olefin according to claim 1, wherein: the oligomer rectifying tower (12) is a regular stainless steel packed tower or a tongue-shaped floating valve plate tower, and the effective plate number is 45-6.
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| CN111892673A (en) * | 2020-06-17 | 2020-11-06 | 南京延长反应技术研究院有限公司 | Micro-interface enhanced reaction system and method for preparing polypropylene |
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