CN102861540A - Slurry bed ft synthesis reactor - Google Patents
Slurry bed ft synthesis reactor Download PDFInfo
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- CN102861540A CN102861540A CN2011101840135A CN201110184013A CN102861540A CN 102861540 A CN102861540 A CN 102861540A CN 2011101840135 A CN2011101840135 A CN 2011101840135A CN 201110184013 A CN201110184013 A CN 201110184013A CN 102861540 A CN102861540 A CN 102861540A
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a slurry bed ft synthesis reactor, which comprises a reactor inlet, a reactor outlet, a reaction segment at the lower part of a reactor and a gas-liquid expansion section at the upper part of the reactor, and a demister capable of heating is arranged in the gas-liquid expansion section at the upper part of the reactor. The demister capable of heating is composed of a straight tube segment and a cone-shaped expansion section, and has an interlayer structure for circulating a heating medium. The reactor has good demisting effect, and can enhance the stability of the catalyst and the conversion rate of carbon monoxide, and can reduce the selectivity of carbon dioxide and methane.
Description
Technical field
The present invention relates to a kind of slurry bed ft synthetic reactor.
Background technology
Synthetic synthesis gas (the CO+H that refers to of Fischer-Tropsch
2) catalyze and synthesize the reaction of liquid hydrocarbon fuel at catalyst.Day by day exhaustion along with petroleum resources has been subject to the attention of countries in the world more with the Fischer-Tropsch synthesis prepare liquid fuel.
Be used for the synthetic reactor of F-T fixed bed, recirculating fluidized bed, fixed fluidized bed and slurry attitude bed are successively arranged.Fixed bed reactors have the shortcomings such as focus, obstruction and production capacity are low, and the fluid mapper process of recirculating fluidized bed is restive, and catalyst utilization hangs down serious wear, and production capacity is still on the low side.Fixed fluidized bed is the improved form of recirculating fluidized bed, easy operation simple in structure not only, has also solved the problem of the low and wearing and tearing of catalyst utilization, and production capacity improves greatly.The development of natural gas liquefaction has promoted the development of paste state bed reactor, and particularly in recent years, the syrup state bed Fischer Tropsch synthetic technology was greatly developed.
CN200810225473.6 discloses a kind of slurry attitude bed synthesis reactor, and this reactor comprises conversion zone, reactor inlet, reactor outlet and be arranged on the extension diameter section on slurry attitude bed top that described extension diameter section comprises settling section, washing section and foam removal section.CN03151109.0 discloses a kind of gas-liquid-solid three-phase slurry attitude bed industrial reactor that can continued operation, this reactor comprises the inlet gas distributed elements of carrying out even gas distribution that is comprised of the inlet gas distributor pipe, the heat exchanger tube parts that one or more layers heats/cool off bed, the liquid-solid separator parts that one or more layers can clean are automatically removed the outlet dedusting demister parts that liquid foam and solid are carried secretly.
In the syrup state bed Fischer Tropsch synthetic reaction process, the reaction consumption amounts of hydrogen that the reaction needed of generation carbon dioxide consumes carbon monoxide, generation methane is large, value of the product is low, they all are non-purpose products, and the methane and the carbon dioxide selectivity that therefore reduce in the Fischer-Tropsch building-up process are one of targets of this area pursuit.The activity stability of catalyst is the key factor that determines catalyst updating speed in addition, and the operating cost of Fischer-Tropsch building-up process is had obvious impact.In the syrup state bed Fischer Tropsch synthetic reaction process, methane and carbon dioxide selectivity and catalyst activity stability depend on the self performance of catalyst on the one hand, affected by the various factors in the course of reaction.In above-mentioned existing syrup state bed Fischer Tropsch building-up process and the consersion unit, not from course of reaction Optimum Operation process, to improve the selective and methane selectively of catalyst activity stability and reduction carbon dioxide.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of slurry bed ft synthetic reactor, this reactor not only foam removal is effective, and can improve the stability of conversion ratio and the fischer-tropsch synthetic catalyst of carbon monoxide, reduces methane selectively.
A kind of slurry bed ft synthetic reactor comprises the conversion zone of reactor inlet, reactor outlet, reactor lower part and the gas-liquid diffuser on reactor top, in the gas-liquid diffuser on described reactor top heatable demister is installed.
Heatable demister described in the present invention is made of direct tube section and taper diffuser, has the sandwich for the heat medium circulation.
The inwall of the bottom outer edge of the diffuser of taper described in the present invention and reactor top gas-liquid diffuser has certain interval, is generally the 1/10-1/15 of diffuser internal diameter.The cone line of taper diffuser and the angle of reactor axis are generally 45 ~ 60 degree.
The concrete size of the thickness of demister interlayer, import and outlet and position all can be determined by calculating or simple test according to requirements such as employed catalyst size, reactor for treatment amount, reaction condition and foam removal effect, heat medium situations by this area designer among the present invention.For example when selecting superheated steam to heat, the entrance of heat medium generally on the top of demister, outlet is in the bottom of demister, when selecting liquid heating medium, the entrance of heat medium is generally on the bottom of demister section, the outlet top at demister.
The internal diameter of reactor lower part conversion zone of the present invention can be identical with the internal diameter of reactor top gas-liquid diffuser, also can be less than the internal diameter less than reactor top gas-liquid diffuser, and can arrange as required the expansion linkage section this moment.
The lower end of described conversion zone is provided with gas distributor, sidewall is provided with liquid wax floss hole, is provided with cooling coil in the conversion zone.The gas distributor of described conversion zone lower end is one group of gas distribution tube, perforate and dispose nozzle on this gas distribution tube, this nozzle evenly distributes on reactor cross section, and be downwards or lateral openings, the size of nozzle inside diameter should guarantee that pressure drop that gas produces when passing through each nozzle is between 0.01MPa-0.1MPa.The steam that described cooling coil flows out can heat in the interlayer of rear inflow demister.The steam that described cooling coil flows out can be directly or after heating as the heat medium of demister interlayer.
Find after deliberation, the paste state bed reactor of available technology adopting, because slurry attitude phase hot melt is large, and the strenuous exercise of bubble makes reaction heat pass to easily cooling coil, make the slurry attitude isothermal that is close, but but there is thermograde in the upper gaseous phase space of paste state bed reactor, particularly in low temperature Fischer-Tropsch synthesis process, can cause the liquefaction of part steam to reflux, so that have a large amount of aqueous waters in starching mutually, water in starching mutually can cause the oxidation of catalyst under reaction condition, the salt of the difficulty reduction that generation can't be regenerated, in addition, the paste state bed reactor because steam and light hydrocarbon can not speed away can occupy a large amount of dividing potential drops (can up to 20%) when reaching vapor liquid equilibrium, the dividing potential drop that causes synthesis gas reduces, thereby affect carbon monoxide and the hydrogen mass transfer velocity in reaction system, cause the carbon monoxide conversion ratio to reduce, water gas shift reaction occurs and methane selectively increases.
On above-mentioned Research foundation, by adopting paste state bed reactor of the present invention, under the condition that catalyst need not change, reduced carbon dioxide and methane selectively, and improved the activity stability of catalyst.
Specifically, compared with prior art, slurry bed ft synthetic reactor of the present invention has following advantage:
1, by the demister with heating function is installed at the gas-liquid diffuser of slurry bed ft synthetic reactor, the liquid foam of carrying secretly is carried out double evaporation-cooling to be separated, improved the temperature of gas phase effluent in the Fischer-Tropsch synthesis process, reduced the backflow of light hydrocarbon and steam, accelerated the diffusion velocity of light hydrocarbon and steam, made light hydrocarbon and steam can leave fast reactor;
2, because the minimizing of steam in the reaction system has reduced water partial pressure, slow down the hydrothermal of catalyst, improved the stability of catalyst, reduced the selective of methane;
3, this slurry bed ft synthetic reactor can be accelerated the diffusion velocity of steam in the Fischer-Tropsch synthetic, makes its reactor that speeds away, and has reduced the steam reacting condition, has reduced the selective of carbon dioxide;
When 4, this slurry bed ft synthetic reactor plays efficient foam removal effect, can also improve hydrogen and the carbon monoxide mass transfer velocity in reaction dissolvent, improve the conversion ratio of carbon monoxide, reduce the content of light hydrocarbon in the Fischer-Tropsch synthesizing liquid product, improve production capacity.
Description of drawings
Fig. 1 is the structural representation of Fischer-Tropsch synthetic pulp state bed reactor used in the embodiment of the invention 1.
1 is reactor outlet, and 2 is heat exchanger tube, and 3 is the gas-liquid diffuser, and 4 is conversion zone, and 5 is cooling coil, and 6 is liquid wax floss hole, and 7 is gas distributor, and 8 is reactor inlet, and 9 is steam heater.
The specific embodiment
Further specify the effect of a kind of slurry bed ft synthetic reactor of the present invention below in conjunction with embodiment.
Hydrogen and carbon monoxide enter from the entrance 8 of slurry bed ft synthetic reactor among Fig. 1, enter reaction system by gas distributor 7, carry out Fischer-Tropsch synthesis at conversion zone 4 interior hydrogen and CO gas, the light hydrocarbon that generates in the Fischer-Tropsch synthetic after the reaction and steam are diffused into reactor from reaction system gas-liquid diffuser 3, enter piece-rate system from reactor outlet 1, the heavy hydrocarbon that generates is discharged by the liquid wax floss hole 6 on the conversion zone sidewall, cooling coil 5 is used for removing Fischer-Tropsch synthesis heat, the steam that cooling coil 5 flows out enters the interlayer of the demister 2 of gas-liquid diffuser 3 interior installations behind steam heater 9, to the liquid foam in the gas-liquid diffuser 3, light hydrocarbon and water heat.
Embodiment 1
Adopt slurry bed ft synthetic reactor shown in Figure 1, heat medium is the steam after heating that flows out in the conversion zone cooling coil, and used fischer-tropsch synthetic catalyst is 20%Co0.8%Pt/SiO
2(Wt.), reaction dissolvent is that paraffin, reaction temperature are that 220 ℃, reaction pressure are that 2.0MPa, air speed are 2.5Nm
3/ h/kg cat., H in the synthesis gas
2/ CO=2(mol ratio), liquid foam, light hydrocarbon and steam are heated to 230 ℃ at the gas-liquid diffuser.The conversion ratio of carbon monoxide, methane selectively, the results are shown in Table 1 for carbon dioxide selectivity and 200h stability test.
Table 1 result of the test.
Catalyst | Initial activity and selective, CO conversion ratio (%) | Initial activity and selective, CH 4Selectively (wt%) | Initial activity and selective, CO 2Selectively (wt%) | 100h, CO conversion ratio (%) | 100h, CH 4Selectively (wt%) | 100h, CO 2Selectively (wt%) | 200h, CO conversion ratio (%) | 200h, CH 4Selectively (wt%) | 200h, CO 2Selectively (wt%) |
Embodiment | 79.5 | 7.5 | 0.85 | 65.8 | 7.7 | 0.94 | 60.8 | 8.0 | 0.95 |
Comparative example | 78.2 | 7.6 | 0.9 | 55.5 | 8.4 | 1.3 | 40.5 | 9.4 | 2.0 |
Comparative example:
Adopt the described slurry bed ft synthetic reactor of CN200810225473.6, reaction condition is with embodiment 1.The conversion ratio of carbon monoxide, methane selectively, the results are shown in Table 1 for carbon dioxide selectivity and 200h stability test.
Claims (10)
1. slurry bed ft synthetic reactor, comprise the conversion zone of reactor inlet, reactor outlet, reactor lower part and the gas-liquid diffuser on reactor top, it is characterized in that: in the gas-liquid diffuser on described reactor top heatable demister is installed.
2. reactor according to claim 1, it is characterized in that: described heatable demister is made of direct tube section and taper diffuser, has the sandwich for the heat medium circulation.
3. reactor according to claim 2, it is characterized in that: the distance of the inwall of the bottom outer edge of described taper diffuser and reactor top gas-liquid diffuser is the 1/10-1/15 of reactor top gas-liquid diffuser internal diameter.
4. it is characterized in that according to claim 2 or 3 described reactors: the cone line of described taper diffuser and the angle of reactor axis are 45 ~ 60 degree.
5. reactor according to claim 2 is characterized in that: when described heat medium is steam, the entrance of heat medium on the top of demister, outlet is in the bottom of demister; When heat medium is liquid, the entrance of heat medium in the bottom of demister, outlet is on the top of demister.
6. reactor according to claim 1 is characterized in that: the internal diameter of the internal diameter of described reactor lower part conversion zone and reactor top gas-liquid diffuser is identical or less than the internal diameter of reactor top gas-liquid diffuser.
7. reactor according to claim 1, it is characterized in that: the lower end of described reactor lower part conversion zone is provided with gas distributor, sidewall is provided with liquid wax floss hole, is provided with cooling coil in the conversion zone.
8. reactor as claimed in claim 7, it is characterized in that: the steam that flows out in the described cooling coil is as the heat medium in the demister interlayer.
9. reactor as claimed in claim 7, it is characterized in that: described gas distributor is one group of gas distribution tube.
10. reactor as claimed in claim 9, it is characterized in that: perforate and dispose nozzle on the described gas distribution tube, this nozzle evenly distributes on reactor cross section, and be downwards or lateral openings, the size of nozzle inside diameter should guarantee that pressure drop that gas produces when passing through each nozzle is between 0.01MPa-0.1MPa.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105170036A (en) * | 2015-09-22 | 2015-12-23 | 太原理工大学 | Coal synthesis gas slurry bed reactor for producing oxygenated fuel |
CN105289423A (en) * | 2015-09-22 | 2016-02-03 | 太原理工大学 | Method for preparing oxygenous fuel by coal synthesis gas slurry bed |
CN107790073A (en) * | 2017-09-28 | 2018-03-13 | 北京中科诚毅科技发展有限公司 | A kind of reactor novel internal structure and its design method and purposes |
CN110407170A (en) * | 2018-04-28 | 2019-11-05 | 中国石油化工股份有限公司 | A kind of combined type F- T synthesis waste water treatment system and its method |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107254327B (en) * | 2017-06-05 | 2021-12-17 | 中石化宁波工程有限公司 | Fischer-Tropsch synthetic oil process |
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CN1600412A (en) * | 2003-09-22 | 2005-03-30 | 上海兖矿能源科技研发有限公司 | Contiuous industrial reactor of slurry state bed in gas, liquid and solid three phases |
US20080000623A1 (en) * | 2006-04-21 | 2008-01-03 | Francois Hugues | Novel internal exchanger for gas-liquid-solid reactor for fischer-tropsch synthesis |
CN201058854Y (en) * | 2007-06-13 | 2008-05-14 | 中国石油天然气集团公司 | Fixed bed device for F-T synthesis |
CN101391198A (en) * | 2008-10-31 | 2009-03-25 | 神华集团有限责任公司 | Slurry bed ft synthetic reactor and technique |
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2011
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1600412A (en) * | 2003-09-22 | 2005-03-30 | 上海兖矿能源科技研发有限公司 | Contiuous industrial reactor of slurry state bed in gas, liquid and solid three phases |
US20080000623A1 (en) * | 2006-04-21 | 2008-01-03 | Francois Hugues | Novel internal exchanger for gas-liquid-solid reactor for fischer-tropsch synthesis |
CN201058854Y (en) * | 2007-06-13 | 2008-05-14 | 中国石油天然气集团公司 | Fixed bed device for F-T synthesis |
CN101391198A (en) * | 2008-10-31 | 2009-03-25 | 神华集团有限责任公司 | Slurry bed ft synthetic reactor and technique |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105170036A (en) * | 2015-09-22 | 2015-12-23 | 太原理工大学 | Coal synthesis gas slurry bed reactor for producing oxygenated fuel |
CN105289423A (en) * | 2015-09-22 | 2016-02-03 | 太原理工大学 | Method for preparing oxygenous fuel by coal synthesis gas slurry bed |
CN105289423B (en) * | 2015-09-22 | 2017-10-10 | 太原理工大学 | A kind of coal synthesis gas slurry bed system oxygenated fuel method |
CN107790073A (en) * | 2017-09-28 | 2018-03-13 | 北京中科诚毅科技发展有限公司 | A kind of reactor novel internal structure and its design method and purposes |
CN110407170A (en) * | 2018-04-28 | 2019-11-05 | 中国石油化工股份有限公司 | A kind of combined type F- T synthesis waste water treatment system and its method |
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