CN103965941A - Method for producing clean diesel oil from synthetic gas - Google Patents
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Abstract
The invention provides a method for producing clean diesel oil from synthetic gas. The method comprises the following steps: allowing synthetic gas to enter a tubular fixed bed reactor and contact with a catalyst for a Fischer-Tropsch synthesis reaction, wherein the interior surface of a reaction tube is smooth, and the exterior surface of the reaction tube has a groove; separating heavy hydrocarbon and light hydrocarbon out from a synthetic product; mixing light hydrocarbon with hydrogen, allowing an obtained mixture to enter a hydrorefining reactor and contact with a catalyst for a hydrogenation saturation reaction and a hydrogenation deoxidation reaction; and allowing a hydrorefining reaction product to enter a separation system, mixing separated tail oil with heavy hydrocarbon, allowing an obtained mixture to enter a hydrogenation isocraking reactor and allowing a product to enter the separation system so as to obtain an intermediate distillate oil product. The method provided by the invention overcomes the problems of hardly controllable reaction heat and difficult heat transfer and hot spots of a reactor during the Fischer-Tropsch synthesis reaction and realizes economic and effective production of the clean diesel oil directed at the characteristic that hydrocarbons are produced in the process of production.
Description
Technical field
The present invention relates to a kind of method of being produced clean diesel by synthetic gas, more particularly, is a kind of hydro carbons obtaining by Fischer-Tropsch synthesis, then produces the method for diesel oil by multiple hydrotreatment processes.
Background technology
Synthesize (Fischer-Tropsch is synthetic) by hydrogen and carbon monoxide by Fischer-Tropsch and obtain hydrocarbon products, can obtain high-quality liquid fuel if gasoline, diesel oil and aviation kerosene and other industrial chemicals are as lubricant base, food grade wax etc. through deep processing, because hydrogen and carbon monoxide can come from coal, Sweet natural gas or Wood Adhesives from Biomass easily, this Technology Ways receives the very big concern of world energy sources chemical industry, and many international energies company has developed respectively the synthetic oil technique that synthesizes core with Fischer-Tropsch.The most successfully wherein South Africa Sasol company and Dutch Shell company.I, the II of Sasol, tri-factories of III, produce 7200000 tons of oil product and chemical per year.The common PetroSA project of building of Sasol and PetroSA, this project production capacity is 36000 barrels/day, and the liquid fuel in South Africa 7% is provided.Calendar year 2001 Sasol and Qatar Petroleum have set up Oryx co-partnership company, the Oryx Synthetic Oil Production from Natural Gas factory that builds together, 34000 barrels/day of throughput.Shell is constructed and put into operation in 1993 in Malay synthetic oil project, 62.5 ten thousand tons/year of throughput.Shell and Qatar Petroleum have built Pearl project jointly in 2007,140000 barrels/day of this project construction abilities, and part is constructed and put into operation at present.
Adopt calandria type fixed bed reactor carry out the synthetic technique of Fischer-Tropsch have simple to operate, the feature that flexible form is various, by many research institutions as first research and development technology.But many problems that fixed-bed reactor exist have limited it and have applied on a large scale, for example: fixed-bed reactor are because the reactor that affects being conducted heat exists focus; Per pass conversion is low, need to carry out compression cycle to a large amount of circulation gas, and energy consumption is high and reactor pressure decrease is large; The use of large granular catalyst is affected etc. catalyst performance.In order to improve the bad shortcoming of fixed-bed heat transfer performance, in prior art, liquid medium is imported to the method for reactor, because liquid has larger thermal capacitance, liquid medium adds the focus that can reduce beds.For example, CN1662476A discloses a kind of method, and the fluid medium of inertia is imported to reactor, and continuous liquid medium flows and can promote the transfer of heat, has obviously improved reactivity worth.But also there is limitation in this method, because adding of liquid increases the remarkable pressure drop of reactor, need in addition to increase separation and the recycle unit of circulatory mediator, increase the complicacy of technique.By also solving heat transfer problem to the improvement of reactor, for example CN1736574A discloses a kind of non-hot spot calandria type fixed bed reactors, this reactor is in reaction tubes, to increase a set of cooling inner tube, heat-eliminating medium can be in reaction tubes inner tube and reactor enclosure intrastratal flowage heat-obtaining, this scheme can increase heat exchange area, can reduce the radial temperature difference of beds, effectively solve heat transfer problem, but this improvement makes the very complicated of reactor change, and the reactor useful space inner tube that is cooled occupied very most ofly, economy is lower.
Synthesize by Fischer-Tropsch the product obtaining and be mainly straight-chain paraffin, there is the not component such as sulfur-bearing, nitrogen, aromatic hydrocarbons, but also there is certain limitation, for example comprise a small amount of alkene and oxygenatedchemicals, low temperature flowability is poor, zero pour is high, therefore Fischer-Tropsch synthetic need to just can obtain meeting the liquid fuel or the fuel blend component that use specification through corresponding hydrogenation upgrading process.US5378348 discloses a kind of method of producing intermediate oil by hydrocracking and hydroisomerisation process taking Fischer-Tropsch synthetic as raw material, the method is by being divided into Fischer-Tropsch synthesis product petroleum naphtha, lighting end and three cuts of last running, hydrocracking reaction is carried out in last running, and unconverted heavy ends loops back hydrocracking reactor and continues cracking.Used catalyst is noble metal catalyst or Ni+Co/Mo catalyzer, and conversion rate control is in 39～53 % by weight; The light constituent that lighting end and hydrocracking reaction obtain carries out hydrotreatment olefin saturation and hydrogenation deoxidation reaction mainly occurs after mixing, then kerosene carries out hydroisomerization.The method can increase the productive rate of the distillate of kerosene, diesel oil.But the method has increased many processing units, for example isomerization-visbreaking process, makes process complications; The water that unifining process generates has directly entered in isomerization-visbreaking reactor, affects catalyst performance; Intermediate oil yield is not high.US6296757 discloses a kind of method of producing diesel oil from Fischer-Tropsch synthesis oil, and the method is to fall Fischer-Tropsch synthesis oil to be cut into the last running of >371 DEG C and the lighting end of <371 DEG C; Last running enters hydroisomerization reactor, after then mixing with lighting end, enters fractionating system, obtains corresponding diesel oil distillate, oil circulation time hydroisomerization reactor of Fractionator Bottom.And the diesel quality that this method obtains is poor, and yield is not high.
Summary of the invention
The object of this invention is to provide a kind of method of being produced clean diesel by synthetic gas, both while having solved hydrogen and carbon monoxide generation Fischer-Tropsch synthesis, reaction heat is restive, there is the problem of conduct heat difficulty and focus in reactor, the method that produces the most economical effective production diesel oil of feature of hydro carbons for this process is provided again.
Method provided by the present invention comprises the following steps:
(1) material synthesis gas enters calandria type fixed bed reactor and carries out contacting with catalyzer Fischer-Tropsch synthesis occurs, and sintetics, through heat separator, cold separator, is isolated respectively heavy hydrocarbon and light hydrocarbon;
(2) light hydrocarbon and hydrogen are mixed into hydrofining reactor and contact with Hydrobon catalyst and carry out hydrogenation saturated reaction and hydrogenation deoxidation reaction;
(3) hydrofining reaction product enters separation system, the heavy hydrocarbon of isolated tail oil and step (1) gained is mixed into hydroisomerizing cracking case, under the effect of hydroisomerizing cracking catalyst, react, products therefrom obtains middle runnings oil production after separating;
The reaction tubes of described calandria type fixed bed reactor respectively by reactor upper tubesheet and reactor lower tubesheet stationary arrangement in reactor shell, the internal surface of described reaction tubes is smooth, outside surface has groove.
Described reaction tubes is structural carbon steel or austenitic stainless steel, and internal surface is smooth, and outside surface is formed with the spiral type groove of certain rule through hot and cold mechanical workout.Catalyst loading is in reaction tubes, and heat-eliminating medium flows through reactor enclosure journey, contacts with the outside surface of reaction tubes, and the heat that reaction is produced is taken reactor out of, and traverse baffle is distributed in the middle of reactor according to a determining deviation.
The characteristic parameter of described reaction tubes outer surface groove is: every meter has 200～2000 grooves, groove depth 0.5～1.5mm, and groove width 0.2～1.0mm, lead angle is 3 ~ 5 °.Preferably, every meter has 300～800 grooves, groove depth 1.0～1.2mm, groove width 0.5～0.8mm.Groove cross section can be T shape, rectangle, trapezoidal, trilateral, zig-zag, and in the time that groove cross section is non-rectangular shape, described groove width refers to the width average of groove.
The two ends up and down of described reaction tubes have the light pipe part of 200～500mm.On reactor, lower tubesheet is connected with the light pipe part at the two ends up and down of reaction tubes.
Described shell and tube reactor housing is made up of reactor upper cover, reactor shell, reactor lower cover, reactor feed mouth and feed distributor are set on reactor upper cover, reactor discharge port is set on reactor lower cover, heat-eliminating medium outlet is set on the top of reactor shell, in the bottom of reactor shell, heat-eliminating medium entrance is set.
Described calandria type fixed bed reactor, the heat-eliminating medium of employing can be pure water, oil, melt salt, water vapor, conventional gas etc.
Described in step (1), calandria type fixed bed reactor can adopt various ways, for example multiple reactor series winding series combination or upflowing.
Described fischer-tropsch synthetic catalyst is Co based Fischer-Tropsch synthesis catalyst, and in oxide compound, cobalt metal component mass content is 1%～60%, and granularity is 0.2～3.0mm.Preferably, cobalt metal component mass content is 5%～50%, and granularity is 0.5～2.0mm.In described Co based Fischer-Tropsch synthesis catalyst, can contain one or more auxiliary agents of metal and non-metallic element.Co based Fischer-Tropsch synthesis catalyst can, with precipitation, impregnating preparation method preparation, need to be processed certain hour under suitable dry and roasting condition.The shape of catalyzer can be column, spherical, hollow ball, ring-type, saddle, trilobal cross bar, four blade profile bars etc.
Described in step (1), reaction conditions is: pressure 1.0～5.0MPa, 150～300 DEG C of temperature, unstripped gas gas hourly space velocity 500～6000h
-1, H
2with CO ratio 1～3, be preferably: reaction pressure 2.0～4.0MPa, temperature is 180～230 DEG C, gas hourly space velocity 1000～3000h
-1, H
2with CO ratio 1.8～2.5.
In step (1), the Fischer-Tropsch synthetic that fixed-bed reactor obtain, through heat separator, cold separator, is isolated respectively gaseous stream, heavy hydrocarbon and light hydrocarbon, and the boiling range of gained heavy hydrocarbon is 50 ~ 700 DEG C, and the boiling range of light hydrocarbon is 30 ~ 300 DEG C.
In gaseous stream described in step (1), contain the complete CO of unreacted and H
2and the CO of reaction generation
2and C
1~ C
5hydro carbons mixed gas.Portion gas returns to Fischer-Tropsch synthesis device entrance.The described carburet hydrogen series products that returns to Fischer-Tropsch synthesis device entrance and the volume ratio of fresh feed gas are 0.1～8, preferably 0.5～5.
The described Hydrobon catalyst of step (2) is a kind of metal load type catalyst, and carrier is unformed aluminum oxide, and metal component is VIB or/and VIII family base metal, and wherein group vib metal is Mo or/and W, and VIII family is that Co is or/and Ni metal.Taking catalyzer as benchmark, in oxide compound, the content of described group vib metal is 5 ~ 40 % by weight, and the content of described VIII family metal is 1 ~ 8 % by weight.
The described hydrofining reaction condition of step (2) is: hydrogen dividing potential drop 2.0～15.0MPa, 250 DEG C～420 DEG C of temperature of reaction, volume space velocity 0.5～10.0h
-1, hydrogen to oil volume ratio is 100～1000v/v.
In step (3), hydrofining reaction product enters separation system, separates and obtains gas, naphtha fraction and tail oil, and the heavy hydrocarbon of isolated tail oil and step (1) gained is mixed into hydroisomerizing cracking case.The boiling range of described refining reaction tail oil is >150 DEG C.In hydroisomerizing cracking case, under hydrogen-rich gas and the effect of hydroisomerizing cracking catalyst, the generation conversion reaction of highly selective, products obtained therefrom, after separation and separation column, obtains gas phase hydrocarbon, naphtha fraction, diesel oil distillate and unconverted heavy oil fraction.The boiling range of described unconverted heavy oil fraction is >370 DEG C, and capable of circulation time hydroisomerizing cracking case proceeded cracking reaction.
The described hydroisomerizing cracking catalyst of step (3) is the noble metal catalyst of amorphous silicon aluminium load, and noble metal catalyst metal component is that Pt is or/and Pd; Or the non-precious metal catalyst of amorphous silicon aluminium load, the metal component of non-precious metal catalyst is VIB or/and VIII family base metal, and wherein group vib metal is Mo or/and W, and VIII family is that Co is or/and Ni metal.Preferably, described amorphous silicon aluminium contains aluminum oxide, silica-alumina, and taking amorphous silicon aluminium as benchmark, the content of described aluminum oxide is 5-95 % by weight, and the content of silica-alumina is 5-95 % by weight.When described hydrogenation active metals component is platinum and/or palladium, in element and taking catalyzer as benchmark, the content of described hydrogenation active metals component is 0.05-5 % by weight.When the described hydrogenation active metals component cobalt that is group VIII and/or the combination of nickel and group vib molybdenum and/or tungsten, in oxide compound and taking catalyzer as benchmark, the content of cobalt and/or nickel is 1-10 % by weight, and the content of molybdenum and/or tungsten is 5-40 % by weight.
The described hydroisomerizing cracking reaction condition of step (3) is: hydrogen dividing potential drop 2.0～15.0MPa, 300 DEG C～450 DEG C of temperature of reaction, volume space velocity 0.5～5.0h
-1, hydrogen to oil volume ratio is 100～1500v/v.
The present invention compared with prior art, has the following advantages:
(1), owing to having adopted outside surface to there is the calandria type fixed bed Fischer-Tropsch synthesis device of groove reaction tubes, tube side-shell side conducts heat and has obtained strengthening, has solved the problem that existing fixed bed synthesis reactor is axial, radial symmetry gradient is large; Less circulation of tail gas ratio be can adopt, reactor inner transmission matter and reaction process improved; Improve product composition, yield of heavy hydrocarbons increase, alkene and oxygenates level are reduced.
(2), according to the feature of this process Fischer-Tropsch synthetic, by light hydrocarbon and heavy hydrocarbon hydrogenation upgrading respectively, both alkene and the impact of oxygenatedchemicals on hydroisomerizing cracking catalyst in synthetic oil had been solved, greatly reduce again hydrotreated feedstock amount, reduce hydrotreating reactor volume and catalyst levels.
(3), the method that proposes of the present invention, be conducive to reduce the secondary cracking of light constituent, improve the yield of intermediate oil, intermediate oil quality product is high.
(4), method of the present invention has good production handiness, by controlling hydrofining and the depth of conversion of hydrocracking reaction and the cut point of separation column, the product that can obtain different demands distributes.
Brief description of the drawings
Fig. 1 is calandria type fixed bed reactor structural representation of the present invention.
Fig. 2 is the reaction tubes diagrammatic cross-section of calandria type fixed bed reactor of the present invention.
Fig. 3 is the method flow schematic diagram that synthetic gas provided by the invention is produced clean diesel.
Embodiment
Below in conjunction with accompanying drawing, method provided by the present invention is further described, but therefore the present invention is not subject to any restriction.
Fig. 1 is calandria type fixed bed reactor structural representation of the present invention.As shown in Figure 1, described calandria type fixed bed reactor comprises lower tubesheet on reactor shell, reactor (4,8), reaction tubes 5, traverse baffle 7, described reaction tubes 5 respectively by reactor upper tubesheet 4 and reactor lower tubesheet 8 stationary arrangement in reactor shell 6, the internal surface of described reaction tubes 5 is smooth, and outside surface has groove.Described reactor shell is made up of reactor upper cover 3, reactor shell 6, reactor lower cover 9, reactor feed mouth 1 and feed distributor 2 are set on reactor upper cover 3, reactor discharge port 10 is set on reactor lower cover 9, heat-eliminating medium outlet 12 is set on the top of reactor shell, in the bottom of reactor shell, heat-eliminating medium entrance 11 is set.
Reaction mass is introduced from reactor feed mouth 1, after feed distributor 2, enter in the reaction tubes 5 that catalyzer is housed, reaction raw materials reacts after contacting with catalyzer, the reaction raw materials not ruing out of and reaction product flow out from reaction tubes 5 lower ends, derive through reactor discharge port 10.Heat-eliminating medium enters reactor shell side from heat-eliminating medium entrance 11, under the restriction of traverse baffle 7, form horizontal and vertical flowing, the heat that reaction produces passes to heat-eliminating medium through reaction tubes 5 tube walls, and the heat-eliminating medium after heat absorption is derived reactor from heat-eliminating medium outlet 12.
Fig. 2 is the diagrammatic cross-section of reaction tubes, and D is reaction tubes external diameter, and d is tube inner diameter, outside surface helical groove.
Fig. 3 is the method flow schematic diagram that synthetic gas provided by the invention is produced clean diesel.As shown in Figure 3, the synthetic gas 1(hydrogen and the carbon monoxide that purify) enter fixed-bed reactor 2, after contacting with Co based Fischer-Tropsch synthesis catalyst, carry out Fischer-Tropsch synthesis, derive the complete synthetic gas of reaction product and unreacted 3 autoreactor bottoms, enters heat separator system 4, and isolated heavy hydrocarbon 30 enters hydroisomerizing cracking case 31, isolated light hydrocarbon and gas phase 5 enter cold separator system 6, are separated into gas phase 7, light hydrocarbon 21, product water 11.Gaseous stream 7 major parts enter circulation of tail gas compression system 8 and are circulated to reactor inlet 9, enter on a small quantity exhaust treatment system 10.Product water 11 enters oxygenatedchemicals recovery system.Light hydrocarbon 21 enters hydrofining reactor 22 after mixing with hydrogen; contact with Hydrobon catalyst with protective material; there is olefin saturation and hydrogenation deoxidation reaction; product introduction gas-liquid separator 23; isolate hydrogen 24 and enter hydrogen gas circulating system; liquid phase 25 enters separation column 26 carries out fractionation and is cut into gas phase hydrocarbon 27, petroleum naphtha 28 and tail oil 25, and wherein gas phase hydrocarbon 27, petroleum naphtha 28 are through pipeline caterpillar.Tail oil 25 enters hydroisomerizing cracking case 31 after pipeline 29 and heavy hydrocarbon 30 mixing, under hydrogen-rich gas and the effect of hydroisomerizing cracking catalyst, the generation conversion reaction of highly selective, product introduction gas-liquid separator 32, isolate hydrogen 33 and enter hydrogen gas circulating system, liquid phase 34 enters separation column 35 and carries out fractionation and be cut into gas phase hydrocarbon 36, petroleum naphtha 37, diesel oil 38, unconverted heavy oil fraction 39.Unconverted heavy oil fraction loops back hydroisomerizing cracking case through pipeline 39 and proceeds cracking.
Below in conjunction with embodiment, method of the present invention is illustrated further, but not thereby limiting the invention.
Embodiment
In embodiment, the preparation process of fischer-tropsch synthetic catalyst used is as follows: get aluminum oxide powder, drip distilled water to just wetting, write down the volume that consumes water, then calculate by Co content (oxide compound) 27 % by weight, make Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES steeping fluid.Then with this solution impregnation aluminum oxide to just wetting, leave standstill 8 hours, then in 120 DEG C dry 4 hours, in muffle furnace, 450 DEG C of roastings make catalyzer for 4 hours.Size range 1.2～the 1.6mm of gained Co based Fischer-Tropsch synthesis catalyst.
The present embodiment adopts technical process shown in Fig. 3,300 reaction tubess are wherein set in calandria type fixed bed synthesis reactor, its reaction tubes adopts external diameter 38mm, wall thickness 3mm austenitic stainless steel pipe material, outside surface adopts cold working to form groove structure, every mitron length comprises 500 grooves, groove depth 1.2mm, groove width average 0.6mm, lead angle is 4 °.
Fischer-Tropsch synthesis process condition is: material synthesis gas volume space velocity 800h
-1, hydrogen and carbon monoxide mol ratio be 2.0, reaction pressure 3.0MPa, circulation gas with feed gas volume than 2.0.
Hydrofining reactor top filling hydrofining protective material, bottom filling Hydrobon catalyst.Hydroisomerizing cracking case filling hydroisomerizing cracking catalyst; the protectant trade names of hydrofining are RGF-1; the trade names of Hydrobon catalyst are RTF-1, and the trade names of hydroisomerizing cracking catalyst are RCF-1, are Sinopec catalyzer branch office and produce.
Fischer-Tropsch synthetic obtains light hydrocarbon and heavy hydrocarbon after separating, and described light hydrocarbon enters hydrofining reactor, and hydrofining reaction condition is: hydrogen dividing potential drop 6.4MPa, 300 DEG C of temperature of reaction, volume space velocity 3.0h
-1, hydrogen to oil volume ratio 300v/v.The product of hydrofining reactor is isolated to naphtha fraction I and tail oil, and wherein the boiling range of tail oil is >150 DEG C.
Heavy hydrocarbon and tail oil enter hydroisomerizing cracking case, and reaction conditions is: hydrogen dividing potential drop 6.4MPa, 375 DEG C of temperature of reaction, volume space velocity 1.6h
-1, hydrogen to oil volume ratio 800v/v.The product of hydroisomerizing cracking case obtains naphtha fraction II, diesel oil distillate and unconverted heavy oil fraction after separating.Naphtha product character, diesel product character that character, naphtha fraction I and the naphtha fraction II of Fischer-Tropsch synthetic are mixed to get are listed in subordinate list.
Fischer-Tropsch synthesizes in the time reaching CO transformation efficiency 95% as can be seen from the table, and C5+ yield reaches 185g/m
3synthetic gas, light hydrocarbon and heavy hydrocarbon quality product ratio reach 1:2.5, and in light hydrocarbon, oxygen level is 0.85 % by weight, and in heavy hydrocarbon, oxygen level only has 0.5 % by weight.From hydrogenation, product data are known, and diesel yield reaches 85.5 % by weight, and cetane value reaches 79.
Table 1 Fischer-Tropsch synthesizing section general data
| CO transformation efficiency, % | 95.0 |
| H 2Transformation efficiency, % | 95.0 |
| C 5 +Oil yield, g/m 3Synthetic gas | 185 |
| Light hydrocarbon and heavy hydrocarbon ratio | 1:2.5 |
| Light hydrocarbon character | |
| Density (20 DEG C), g/cm 3 | 0.7120 |
| Oxygen level, quality % | 0.85 |
| Boiling range (ASTM D-86), DEG C | |
| IBP/10％ | 51/66 |
| 30％/50％ | 110/151 |
| 90％/95％ | 234/267 |
| Heavy hydrocarbon character | |
| Density (20 DEG C), g/cm 3 | 0.8635 |
| Oxygen level, quality % | 0.5 |
| Boiling range (ASTM D-86), DEG C | |
| IBP/10％ | 159/271 |
| 30％/50％ | 376/450 |
| 90％/95％ | 544/638 |
The character of table 2 naphtha product
| Project | |
| Boiling range | <150℃ |
| Total recovery, quality % | 14.25 |
| Density (20 DEG C), g/cm 3 | 0.7015 |
| Composition, quality % | |
| Normal paraffin | 45.48 |
| Isoparaffin | 51.97 |
The character of table 3 diesel product
| Project | |
| Boiling range | 150-370℃ |
| Yield, quality % | 85.5 |
| Density (20 DEG C), g/cm 3 | 0.7729 |
| Condensation point | -10 |
| Cetane value | 79 |
| Sulphur content, μ g/g | <5 |
| Nitrogen content, μ g/g | <5 |
| Aromaticity content, μ g/g | <1.0 |
Claims (15)
1. a method of being produced clean diesel by synthetic gas, comprises the following steps:
(1) material synthesis gas enters calandria type fixed bed reactor and carries out contacting with catalyzer Fischer-Tropsch synthesis occurs, and sintetics, through heat separator, cold separator, is isolated respectively heavy hydrocarbon and light hydrocarbon;
(2) light hydrocarbon and hydrogen are mixed into hydrofining reactor and contact with Hydrobon catalyst and carry out hydrogenation saturated reaction and hydrogenation deoxidation reaction;
(3) hydrofining reaction product enters separation system, the heavy hydrocarbon of isolated tail oil and step (1) gained is mixed into hydroisomerizing cracking case, under the effect of hydroisomerizing cracking catalyst, react, products therefrom obtains middle runnings oil production after separating;
The reaction tubes of described calandria type fixed bed reactor respectively by reactor upper tubesheet and reactor lower tubesheet stationary arrangement in reactor shell, the internal surface of described reaction tubes is smooth, outside surface has groove.
2. in accordance with the method for claim 1, it is characterized in that, the characteristic parameter of described reaction tubes outer surface groove is: every meter has 200～2000 grooves, groove depth 0.5～1.5mm, and groove width 0.2～1.0mm, lead angle is 3 ~ 5 °.
3. in accordance with the method for claim 2, it is characterized in that, the characteristic parameter of described reaction tubes outer surface groove is: every meter has 300～800 grooves, groove depth 1.0～1.2mm, groove width 0.5～0.8mm.
4. in accordance with the method for claim 1, it is characterized in that, in described calandria type fixed bed reactor, be arranged with 100～10000 reaction tubess, the interior diameter of every reaction tubes is 20～60mm, and length is 4～15m.
5. in accordance with the method for claim 4, it is characterized in that, the interior diameter of described reaction tubes is 25～50mm, and length is 6～12m.
6. in accordance with the method for claim 1, it is characterized in that, the thickness of pipe of described reaction tubes is 1 ~ 8mm.
7. in accordance with the method for claim 1, it is characterized in that, the two ends up and down of described reaction tubes have the light pipe part of 200～500mm; On reactor, lower tubesheet is connected with the light pipe part at the two ends up and down of reaction tubes.
8. in accordance with the method for claim 1, it is characterized in that, in described step (1), fischer-tropsch synthetic catalyst is Co based Fischer-Tropsch synthesis catalyst, and in oxide compound, cobalt metal component mass content is 1%～60%, and granularity is 0.2～3mm.
9. in accordance with the method for claim 8, it is characterized in that, described Co based Fischer-Tropsch synthesis catalyst, in oxide compound, cobalt metal component mass content is 5%～50%, granularity is 0.5～2.0mm.
10. in accordance with the method for claim 1, it is characterized in that, in described step (1), Fischer-Tropsch synthesis condition is: pressure 1～5MPa, 150～300 DEG C of temperature, unstripped gas gas hourly space velocity 500～6000h
-1, H
2with CO ratio 1～3.
11. in accordance with the method for claim 1, it is characterized in that, in described step (1), Fischer-Tropsch synthesis condition is: reaction pressure 2～4MPa, temperature is 180～230 DEG C, gas hourly space velocity 1000～3000h
-1, H
2with CO ratio 1.8～2.5.
12. in accordance with the method for claim 1, it is characterized in that, the Hydrobon catalyst of described step (2) is a kind of metal load type catalyst, carrier is unformed aluminum oxide, metal component is that VIB is or/and VIII family base metal, wherein group vib metal is Mo or/and W, and VIII family is that Co is or/and Ni metal.
13. in accordance with the method for claim 1, it is characterized in that, the described hydrofining reaction condition of step (2) is: hydrogen dividing potential drop 2.0～15.0MPa, 250 DEG C～420 DEG C of temperature of reaction, volume space velocity 0.5～10.0h
-1, hydrogen to oil volume ratio is 100～1000v/v.
14. in accordance with the method for claim 1, it is characterized in that, the described hydroisomerizing cracking catalyst of step (3) is the noble metal catalyst of amorphous silicon aluminium load, and noble metal catalyst metal component is that Pt is or/and Pd; Or the non-precious metal catalyst of amorphous silicon aluminium load, the metal component of non-precious metal catalyst is VIB or/and VIII family base metal, and wherein group vib metal is Mo or/and W, and VIII family is that Co is or/and Ni metal.
15. in accordance with the method for claim 1, it is characterized in that, the described hydroisomerizing cracking reaction condition of step (3) is: hydrogen dividing potential drop 2.0～15.0MPa, 300 DEG C～450 DEG C of temperature of reaction, volume space velocity 0.5～5.0h
-1, hydrogen to oil volume ratio is 100～1500v/v.
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| CN107001943A (en) * | 2014-12-22 | 2017-08-01 | 埃克森美孚研究工程公司 | Organic oxygen-containing compound to hydrocarbon conversion |
| CN108003940A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of system and method that biomass material is converted into cleaning diesel oil |
| CN109679689A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of liquid phase hydrogenation reactor and process for selective hydrogenation and reaction system |
| CN110016363A (en) * | 2018-01-08 | 2019-07-16 | 神华集团有限责任公司 | Fischer-Tropsch synthesis oil processing produces the method and system of diesel oil and lube base oil |
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| CN108003940B (en) * | 2016-10-28 | 2020-10-27 | 中国石油化工股份有限公司 | System and method for converting biomass raw material into clean diesel oil |
| CN109679689A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of liquid phase hydrogenation reactor and process for selective hydrogenation and reaction system |
| CN109679689B (en) * | 2017-10-19 | 2021-03-05 | 中国石油化工股份有限公司 | Liquid-phase hydrogenation reactor, hydrogenation reaction method and reaction system |
| CN110016363A (en) * | 2018-01-08 | 2019-07-16 | 神华集团有限责任公司 | Fischer-Tropsch synthesis oil processing produces the method and system of diesel oil and lube base oil |
| CN110016363B (en) * | 2018-01-08 | 2020-12-18 | 神华集团有限责任公司 | Method and system for producing diesel oil and lubricant base oil by processing Fischer-Tropsch synthetic oil |
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