CN102861540B - A kind of slurry bed ft synthetic reactor - Google Patents
A kind of slurry bed ft synthetic reactor Download PDFInfo
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- CN102861540B CN102861540B CN201110184013.5A CN201110184013A CN102861540B CN 102861540 B CN102861540 B CN 102861540B CN 201110184013 A CN201110184013 A CN 201110184013A CN 102861540 B CN102861540 B CN 102861540B
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Abstract
The present invention discloses a kind of slurry bed ft synthetic reactor, comprises reactor inlet, reactor outlet, the conversion zone of reactor lower part and the gas-liquid diffuser on reactor top, is provided with heatable demister in the gas-liquid diffuser on described reactor top.Described heatable demister is made up of direct tube section and taper diffuser, has the sandwich for heat medium circulation.This reactor not only foam removal is effective, and can improve the stability of catalyst and the conversion ratio of carbon monoxide, reduces the selective of carbon dioxide selectivity and methane.
Description
Technical field
The present invention relates to a kind of slurry bed ft synthetic reactor.
Background technology
F-T synthesis refers to synthesis gas (CO+H
2) catalyze and synthesize the reaction of liquid hydrocarbon fuel on a catalyst.Along with the exhaustion day by day of petroleum resources, prepare with Fischer-Tropsch synthesis the attention that liquid fuel receives countries in the world more.
Reactor for F-T synthesis successively has fixed bed, recirculating fluidized bed, fixed fluidized bed and slurry bed system.Fixed bed reactors have the shortcomings such as focus, blocking and production capacity are low, and the fluid mapper process of recirculating fluidized bed is restive, the low serious wear of catalyst utilization, and production capacity is still on the low side.Fixed fluidized bed is the improved form of recirculating fluidized bed, and not only structure simply easily operates, also solves the problem of the low and wearing and tearing of catalyst utilization, and production capacity improves greatly.The development of natural gas liquefaction facilitates the development of paste state bed reactor, and particularly in recent years, syrup state bed Fischer Tropsch synthetic technology is greatly developed.
CN200810225473.6 discloses a kind of slurry bed system synthesis reactor, and this reactor comprises conversion zone, reactor inlet, reactor outlet and is arranged on the extension diameter section on slurry bed system top, and described extension diameter section comprises settling section, washing section and foam removal section.CN03151109.0 disclose a kind of can the gas-liquid-solid three-phase slurry bed system industrial reactor of continued operation, this reactor comprises the inlet gas distributed elements of carrying out even gas distribution be made up of inlet gas distributor pipe, one or more layers heat exchanger tube parts that bed is heated/cooled, the liquid-solid separator parts that one or more layers can clean automatically, the outlet dedusting demister parts that removing liquid foam and solid are carried secretly.
In syrup state bed Fischer Tropsch synthetic reaction process, the reaction needed consumption carbon monoxide generating carbon dioxide, the reaction consumption amounts of hydrogen generating methane are large, value of the product is low, they are all non-object products, and the methane therefore in reduction Fischer-Tropsch synthesis and carbon dioxide selectivity are one of targets of this area pursuit.The activity stability of catalyst is the key factor determining catalyst updating speed in addition, has obvious impact to the operating cost of Fischer-Tropsch synthesis.In 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, also affect by the various factors in course of reaction on the other hand.In above-mentioned existing syrup state bed Fischer Tropsch building-up process and consersion unit, not from course of reaction Optimum Operation process, to improve catalyst activity stability and to reduce the selective and methane selectively of 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 conversion ratio of carbon monoxide and the stability of fischer-tropsch synthetic catalyst, reduces methane selectively.
Slurry bed ft synthetic reactor comprises reactor inlet, reactor outlet, the conversion zone of reactor lower part and the gas-liquid diffuser on reactor top, is provided with heatable demister in the gas-liquid diffuser on described reactor top.
Heatable demister described in the present invention is made up of direct tube section and taper diffuser, has the sandwich for heat medium circulation.
The bottom outer edge of the diffuser of taper described in the present invention and the inwall of reactor top gas-liquid diffuser have certain interval, are 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 in the present invention, import and outlet and position all can be required by calculate or simple test be determined according to used catalyst size, reactor for treatment amount, reaction condition and foam removal effect, heat medium situation etc. by this area designer.Such as when selecting superheated steam to heat, the entrance of heat medium generally on the top of demister, export bottom at demister, when selecting liquid heating medium, the entrance of heat medium generally in the bottom portion of demister, export 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 of reactor top gas-liquid diffuser, now can arrange expansion linkage section as required.
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 conversion zone.The gas distributor of described conversion zone lower end is one group of gas distribution tube, perforate on this gas distribution tube also configures nozzle, this nozzle is uniformly distributed in reactor cross section, and be downwards or lateral openings, the size of nozzle inside diameter should guarantee gas by the pressure drop that produces during each nozzle 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 as the heat medium of demister interlayer directly or after heating.
Find after deliberation, the paste state bed reactor adopted in prior art, because slurry phasd hot melt is large, and the strenuous exercise of bubble makes reaction heat easily pass to cooling coil, make slurry phasd close to isothermal, but but there is thermograde in the upper gaseous phase space of paste state bed reactor, particularly in Low Temperature Fischer Tropsch synthetic reaction process, part steam can be caused to liquefy reflux, make to starch mutually and there is a large amount of aqueous waters, the water starched mutually can cause the oxidation of catalyst at reaction conditions, the salt of the difficulty reduction that generation cannot regenerate, in addition, because steam and light hydrocarbon can not speed away paste state bed reactor, a large amount of dividing potential drop (can up to 20%) can be occupied when reaching vapor liquid equilibrium, the dividing potential drop of synthesis gas is caused to reduce, thus affect carbon monoxide and the mass transfer velocity of hydrogen in reaction system, CO conversion is caused 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, do not need the condition changed at catalyst under, reducing carbon dioxide and methane selectively, and improve the activity stability of catalyst.
Specifically, compared with prior art, slurry bed ft synthetic reactor of the present invention, tool has the following advantages:
1, by installing the demister with heating function at the gas-liquid diffuser of slurry bed ft synthetic reactor, double evaporation-cooling separation is carried out to the liquid foam carried secretly, improve the temperature of vapor phase stream effluent in Fischer-Tropsch synthesis process, reduce the backflow of light hydrocarbon and steam, accelerate the diffusion velocity of light hydrocarbon and steam, enable light hydrocarbon and steam leave reactor fast;
2, due to the minimizing of steam in reaction system, reduce water partial pressure, slow down the hydrothermal of catalyst, improve the stability of catalyst, reduce the selective of methane;
3, this slurry bed ft synthetic reactor can accelerate the diffusion velocity of steam in Fischer-Tropsch synthetic, makes its reactor that speeds away, reduces steam reacting condition, reduce the selective of carbon dioxide;
4, while this slurry bed ft synthetic reactor plays efficient foam removal effect, hydrogen and the mass transfer velocity of carbon monoxide in reaction dissolvent can also be improved, improve the conversion ratio of carbon monoxide, reduce the content of light hydrocarbon in F-T synthesis liquid product, improve production capacity.
Accompanying drawing explanation
Fig. 1 is the structural representation of F-T synthesis paste state bed reactor used in the embodiment of the present invention 1.
1 is reactor outlet, and 2 is heat exchanger tube, and 3 is 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.
Detailed description of the invention
The effect of a kind of slurry bed ft synthetic reactor of the present invention is further illustrated below in conjunction with embodiment.
In Fig. 1, hydrogen and carbon monoxide enter from the entrance 8 of slurry bed ft synthetic reactor, reaction system is entered by gas distributor 7, in conversion zone 4, hydrogen and CO gas carry out Fischer-Tropsch synthesis, the light hydrocarbon generated in Fischer-Tropsch synthetic after reaction and steam are diffused into the gas-liquid diffuser 3 of reactor from reaction system, piece-rate system is entered from reactor outlet 1, the heavy hydrocarbon generated is discharged by the liquid wax floss hole 6 on 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 installed in gas-liquid diffuser 3 after steam heater 9, to the liquid foam in gas-liquid diffuser 3, light hydrocarbon and water heat.
Embodiment 1
Adopt the slurry bed ft synthetic reactor shown in Fig. 1, heat medium is the steam after heating flowed out in conversion zone cooling coil, and fischer-tropsch synthetic catalyst used is 20%Co0.8%Pt/SiO
2(Wt.), reaction dissolvent is paraffin, reaction temperature is 220 DEG C, reaction pressure is 2.0MPa, air speed is 2.5Nm
3/ h/kgcat., H in synthesis gas
2/ CO=2(mol ratio), liquid foam, light hydrocarbon and steam are heated to 230 DEG C at 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 4Selective (wt%) | Initial activity and selective, CO 2Selective (wt%) | 100h, CO conversion ratio (%) | 100h, CH 4Selective (wt%) | 100h, CO 2Selective (wt%) | 200h, CO conversion ratio (%) | 200h, CH 4Selective (wt%) | 200h, CO 2Selective (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 slurry bed ft synthetic reactor described in 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. a slurry bed ft synthetic reactor, comprise reactor inlet, reactor outlet, the conversion zone of 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, is characterized in that: described heatable demister is made up of direct tube section and taper diffuser, has the sandwich for heat medium circulation.
3. reactor according to claim 2, is characterized in that: the distance of the bottom outer edge of described taper diffuser and the inwall of reactor top gas-liquid diffuser is the 1/10-1/15 of reactor top gas-liquid diffuser internal diameter.
4. the reactor according to Claims 2 or 3, is characterized in that: 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, export bottom at demister; When heat medium is liquid, the entrance of heat medium in the bottom of demister, export top at demister.
6. reactor according to claim 1, is characterized in that: the internal diameter of described reactor lower part conversion zone is identical with the internal diameter of reactor top gas-liquid diffuser or be less than the internal diameter of reactor top gas-liquid diffuser.
7. reactor according to claim 1, 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 conversion zone.
8. reactor as claimed in claim 7, is characterized in that: the steam flowed out in described cooling coil is as the heat medium in demister interlayer.
9. reactor as claimed in claim 7, 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 on described gas distribution tube also configures nozzle, this nozzle is uniformly distributed in reactor cross section, and be downwards or lateral openings, the size of nozzle inside diameter should guarantee gas by the pressure drop that produces during each nozzle between 0.01MPa-0.1MPa.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107254327A (en) * | 2017-06-05 | 2017-10-17 | 中石化宁波工程有限公司 | Fischer-Tropsch synthesis oil process system |
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| 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 |
| CN105170036B (en) * | 2015-09-22 | 2017-10-10 | 太原理工大学 | A kind of coal synthesis gas slurry bed system oxygenated fuel reactor |
| 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 |
| CN110407170B (en) * | 2018-04-28 | 2021-02-09 | 中国石油化工股份有限公司 | Combined Fischer-Tropsch synthesis wastewater treatment system and method |
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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 |
| 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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| FR2900065B1 (en) * | 2006-04-21 | 2008-05-30 | Inst Francais Du Petrole | NEW INTERNAL EXCHANGER FOR SOLID LIQUID GAS REACTOR FOR FISCHER TROPSCH SYNTHESIS. |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107254327A (en) * | 2017-06-05 | 2017-10-17 | 中石化宁波工程有限公司 | Fischer-Tropsch synthesis oil process system |
| 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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