CN1854265A - Production of intermediate fractional oil from Fischer-Tropsch synthetic oil - Google Patents
Production of intermediate fractional oil from Fischer-Tropsch synthetic oil Download PDFInfo
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Abstract
A kind of integrated hydrogenation improving quality method for the oil fractions from Fishcher-Tropsch synthesis process, it is used to gain high quality middle fraction oil. The all fractions and hydrogen contact with hydrofining catalyst, the middle fraction oil gained after isolation, naphtha and tail oil will be mixed by the reactant liquor of hydrofining and the reactant liquor of hydrocracking reactant liquor, the tail oil and hydrogen will be mixed and then circulate to isocracking reacktor and contact with hydrocracking and isocracking catalyst. The yield of the diesel oil is higher than 80% by the method, and the cetane number will be as high as 80, The water produced by hydrofining process can be prevented to go into the isocracking reacktor by this method, the availability and using periodic can also be improved. Moreover, the technological process of this method is high integrated; the equipment needed is fewer, so the cost of investment and operation can be decreased.
Description
Technical field
The invention belongs to a plurality of hydrogenation processes of a kind of usefulness and handle the method for hydrocarbon ils, more particularly, being hydroprocessing technique of a kind of usefulness and one exists cracking process under the situation of hydrogen to handle the method for Fischer-Tropsch synthesis oil.
Technical background
The employed fuel main source of the various vehicles is an oil on the our times, and the various derivatives of oil provide powerful motivation for development economic and society.But oil is as the non-renewable energy; be faced with exhausted day by day crisis; and; the quality of crude oil also worse and worse; undesirable components content such as condensed-nuclei aromatics, sulphur, nitrogen increase day by day in the composition of its derivative; cause the course of processing that before becoming the fuel commodity, needs through increasingly sophisticated, remove the component that influences environment, cause the process for processing cost significantly to increase.Therefore, the exploitation novel sustainable energy that can satisfy environmental protection and liquid fuel specification demand simultaneously utilizes technology and system to become the research power that solves energy dilemma and ecocrisis.
Coal or Sweet natural gas etc. comprise through the production technique principle process of oil from Fischer-Tropsch synthesis: coal or gas material are converted into hydro carbons and synthetic oil processing such as straight-chain paraffin, alkene through gasification generation raw gas, refining synthetic gas, the synthetic gas of obtaining of raw gas purifying through the Fischer-Tropsch building-up reactions.
Just with impurity removals such as sulphur, nitrogen, this following process to product is very favourable on the source for the production purifying step of synthetic gas (being made up of hydrogen and carbon monoxide); Fischer-Tropsch synthesis is found in nineteen twenty-three by Germanization scholar FFischer and HTropsch, Fischer-Tropsch synthesis is to be raw material with synthetic gas (being made up of hydrogen and carbon monoxide), under the synthetic catalyst effect, generate the reaction of hydro carbons, have in synthetic gas wide material sources, the product advantages such as undesirable components content such as sulphur, nitrogen, aromatic hydrocarbons are extremely low.The synthetic oil that adopts the Fischer-Tropsch synthetic technology to obtain, comparing with the conventional oil derivative with each side such as main character at hydrocarbon composition has bigger difference, is a kind of material of high content of wax composition, mainly is made of alkane and alkene, and sulphur, nitrogen content are extremely low, but contain a certain amount of oxygen.Gasoline fraction is not sulfur-bearing and nitrogen substantially, but because its alkene and alkane overwhelming majority in forming is a straight chain, so its octane value is very low; Diesel oil distillate sulphur, nitrogen and aromaticity content are extremely low, and cetane value is very high, but its low temperature flowability is also very poor, and condensation point etc. are higher.Therefore, each cut that is obtained by the Fischer-Tropsch synthesis product need pass through corresponding hydrogenation upgrading, just can obtain meeting the liquid fuel that uses specification.
Because the introducing of oxygen has determined wherein to contain a certain amount of oxygenatedchemicals in its synthetic gas production process, as alcohol, acid etc., can a certain amount of water of generation in the follow-up course of processing, can produce adverse influence to the use of catalyzer; The olefin(e) centent height is because the reaction mechanism of this production process is produced alkane by generating the alkene intermediate product.Oxidation not only himself takes place and superimposedly waits reaction in the existence of a large amount of alkene easily, but also can promote the oxidizing reaction of other hydro carbons, and generation has a strong impact on the products such as colloid of oil product use properties.Fischer-Tropsch synthesis oil need pass through corresponding hydrogenation upgrading, just can obtain meeting the liquid fuel that uses specification.
It is raw material is produced intermediate oil by hydrocracking and hydroisomerisation process method with the Fischer-Tropsch synthetic that US5378348 discloses a kind of, this method is by being divided into the Fischer-Tropsch synthesis product petroleum naphtha (C5-160 ℃), lighting end (160-260 ℃) and three cuts of last running (＞260 ℃), hydrocracking reaction is carried out in＞260 ℃ last running, and unconverted＞370 a ℃ heavy ends loops back hydrocracking reactor and continues cracking.Catalyst system therefor is noble metal catalyst or Ni+Co/Mo catalyzer, and transformation efficiency is controlled at the heavy % of 39-53; Lighting end with carry out hydrotreatment after the light constituent product that hydrocracking reaction obtains mixes olefin saturation and hydrogenation deoxidation reaction mainly take place, kerosene carries out hygrogenating isomerization reaction then, improves the different direct ratio (ratio of isomery hydro carbons and positive structure hydro carbons) in the hydrocarbon composition.This method can increase the productive rate of distillates such as kerosene, diesel oil, and these products have good low temperature flowability, and the kerosene freezing point can reach-43 ℃, and diesel oil (260-370 ℃) pour point can reach about 27 ℃.Because this method has increased isomerization-visbreaking catalytic reaction process and separation column, make its technical process comparatively complicated; Increased the isomerization-visbreaking section, catalyst levels also significantly increases; Unifining process generates water and directly enters into the isomerization-visbreaking reactor, for the isomerization-visbreaking catalyzer certain influence is arranged; The intermediate oil yield is not high yet.
US6656342 discloses a kind of method of hydrogenation upgrading Fischer-Tropsch synthetic, this method with the Fischer-Tropsch synthesis product be divided into light, weigh two cuts, cut point is about 371 ℃, two cuts of weight carry out hydrogenation reaction at two reaction zones respectively.Last running enters reactor upper catalyst bed layer, passes through different protective material bed of particle diameter and hydrocracking catalyst bed successively; Lighting end enters in the reactor middle and lower part, with after the reaction product of coming autoreactor top bed layer is mixed through entering later separation and fractionating system behind the hydrotreating catalyst bed, unconverted last running can loop back reactor and continue conversion reaction.In this method, lighting end has improved the yield of light oil distillate without the cracking catalyst bed, but two reaction zones are in same reactor, reaction conditions advolutions such as pressure; The reactor structure complexity, internal units such as thermal exchange and logistics mixing, reallocation are many, and the reactor practical efficiency is low; Complicated operation, two reaction zone operations are difficult to realize independent regulation.
US6309432 discloses a kind of method of producing rocket engine fuel from Fischer-Tropsch synthesis oil, this method is cut into two cuts of weight with Fischer-Tropsch synthesis oil earlier under 371 ℃,＜371 ℃ lighting end successively separates with cold branch through overheated branch and obtains 246 ℃ of-371 ℃ of cuts and C5-246 ℃ of cut, 246 ℃ of-371 ℃ of cuts and＞371 ℃ of last running are through the hydroisomerizing cracking case, saturated at alkene, in the time of the oxygenatedchemicals hydrogenation, normal paraffin generation hydroisomerizing and hydrocracking reaction, isomerized products is mainly monomethyl branching hydro carbons, and cracking conversion rate is about 30-50%; C5-246 ℃ of cut is without hydrotreatment, to keep oxygenatedchemicals wherein to the effect of being significantly improved of rocket engine fuel lubricity, it mainly is C7-C12 straight chain alcohols, remove separation column after this cut and hydrocracking reactor product are mixed together, cutting obtains cuts such as corresponding rocket engine fuel.Owing to contain the alkene and the nitrogen content of high level in the Fischer-Tropsch oil, directly contact with the isocracking catalyzer, stable and disadvantageous effect is arranged running period to it, and quality product is relatively poor.
US6296757 discloses a kind of method of producing diesel oil fuel from Fischer-Tropsch synthesis oil, and this method will be cut into from the reaction product of Fischer-Tropsch synthesis reactor＞371 ℃ last running and＜371 ℃ lighting end;＞371 ℃ last running enters hydroisomerization reactor, carry out that alkene is saturated, the oxygenatedchemicals hydrogenation reaction time, normal paraffin generation hydroisomerizing and hydrocracking reaction, the hydroisomerization reactor reaction product with enter the product fractionating system after＜371 ℃ lighting end mixes, obtain corresponding diesel oil distillate etc., the tail oil cut that obtains at the bottom of the separation column loops back hydroisomerization reactor and continues the reaction conversion.But owing to contain the alkene and the oxygen of high level in the Fischer-Tropsch synthesis oil, directly contact with the isocracking catalyzer, stable and disadvantageous effect is arranged running period to it, and quality product is relatively poor.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method, with the high-quality middle runnings oil production of fecund from Fischer-Tropsch synthesis oil fecund intermediate oil.
Method provided by the invention comprises:
The full cut of Fischer-Tropsch synthesis oil, hydrogen contact with Hydrobon catalyst, the hydrofining reaction logistics obtains intermediate oil product, petroleum naphtha and heavy oil through separation, wherein heavy oil contacts with hydrogen, isomery hydrocracking catalyst, and the hydrocracking reaction logistics obtains the intermediate oil product through separation.
This method diesel product yield up to 85 heavy % about, its cetane value and does not have sulphur, nitrogen and aromatic hydrocarbons substantially about 80.
Description of drawings
Accompanying drawing is the method flow synoptic diagram from Fischer-Tropsch synthesis oil fecund intermediate oil provided by the present invention.
Embodiment
Method provided by the invention is so concrete enforcement:
The present invention at first carries out hydrotreatment with the full cut of Fischer-Tropsch synthesis product; under hydrogen atmosphere and catalyst action, carry out hydrogenation deoxidation, olefin saturation; simultaneously can be with the trace impurity hydrogenation and removings such as sulphur, nitrogen and metal that may be present in the oil product; used catalyzer in the protection following process process avoids poisoning as noble metal hydrogenation isocracking catalyzer.Reaction product after hydrogenation of total effluent is handled enters separation column and is cut into naphtha fraction, diesel oil distillate and heavy oil fraction.
The cut point of naphtha fraction and diesel oil distillate should move forward under the prerequisite that guarantees diesel oil distillate character as far as possible, to guarantee the productive rate of diesel oil distillate; If require to produce the low-coagulation diesel oil cut in the hydrotreatment products, then the cut point of diesel oil distillate and heavy oil fraction may produce 0 if require in the hydrotreatment products about 280 ℃
#Diesel oil distillate, then the cut point of diesel oil distillate and heavy oil fraction may be about 330 ℃, the selection of cut point will be decided on the property requirements of purpose product, if it is but harsh to requirements such as hydrotreatment diesel oil distillate low-temperature performancies herein, can cause part of fraction of fuel-oil to enter the subsequent machining technology flow process, inevitably can cause the diesel oil overall yield in the whole course of processing the finished product distribution to descend.
The heavy oil fraction that hydrotreatment reaction product cutting obtains contacts with the hydroisomerizing cracking catalyst under hydrogen atmosphere, cracking be in, micromolecular hydro carbons, isomerization reaction takes place simultaneously.The isocracking reaction product enters separation column and distills, be cut into naphtha fraction, diesel oil distillate and tail oil cut, the selection of cut point is identical with the cut point selection principle of hydrotreatment reaction product, the tail oil cut can loop back the isomery hydrocracking reactor and continue cracking reaction, also can be used as the raw material of producing lubricant base.
Because the olefin(e) centent in the coal Fischer-Tropsch synthesis oil is very high, especially olefin(e) centent is higher in the lighting end, can reach more than 50%, and its structure mostly is straight chain hydrocarbon.If these alkene directly contact with hydrogenation catalyst, violent strong heat release hydrogenation saturated reaction can take place, on catalyzer, generate a large amount of coke and cause catalyst activity reduction; On the other hand, a large amount of hydrogenation of olefins saturated reactions reaction heat of being emitted can cause the bigger temperature rise of beds.
The Fischer-Tropsch synthesis product especially acid number in the lighting end is very high, and generally all greater than 5.0mg/g, high person even reach more than the 10.0mgKOH/g has stronger corrodibility to pipeline and equipment.Elder generation's hydrogenation aftercut all has positive effect to equipment and operation running.
Trace metal from the Fischer-Tropsch synthesis catalyzer very easily is deposited on the Hydrobon catalyst top with the metal ion that corrosion generates; cause the living piece of fouling of catalyst, reactor pressure reduction to occur; be deposited on metal on the catalyzer simultaneously and can cause the permanent deactivation of hydrogenation catalyst; therefore all adopted the protective material technology at hydrofining reactor and hydrocracking reactor; be seated in the Hydrobon catalyst top with protective material, thereby avoid the generation of above-mentioned phenomenon.
According to the different demands of purpose product, the lighting end after the hydrofining can cut out the steam crack material with high olefin productive rate, the diesel oil distillate with different low temperature flowabilities and need carry out the different fractions such as heavy oil fraction of hydrocracking reaction through separation column.The heavier heavy oil of boiling range is as greater than 350 ℃ of cuts, can be separately or with enter hydrocracking reactor after last running, tail oil or conventional oil heavy ends from the fischer tropsch process flow process mixes, the hydroisomerizing cracking reaction takes place.Like this, do not enter hydrocracking reactor, reduced the volume and the catalyst levels of hydrocracking reactor on the one hand, thereby reduced facility investment, running expense and catalyst costs through the light ends after the hydrofining; Also reduced lighting end on the other hand the generation that overcracking reacts has taken place under the hydrocracking catalyst effect, reduce the generation of gaseous product and small molecules undesirable components, guaranteed the yield of ideal composition such as middle runningss such as rocket engine fuel, diesel oil to greatest extent.The present invention has avoided unifining process to generate water and has entered into the isocracking reactor, can improve the utilization ratio and the life cycle of catalyzer.
In the isomery hydrocracking reactor, for to greatest extent the heavy hydrocarbon highly selective being converted into the middle runnings oil production, the diesel oil distillate that particularly has excellent low temperature flowability, adopt the isocracking catalyzer of high purpose product selectivity, the control transformation efficiency is at the preferred 40%-60% of 30%-80%, to guarantee that the selectivity that diesel oil distillate generates reaches higher level, the diesel oil distillate selectivity can reach 80 heavy % preferably, more excellent can reach more than the 85 heavy %, preferably can reach more than 90%, the production diesel oil distillate of maximum reduces the generation of naphtha fraction to greatest extent; Strengthen hygrogenating isomerization reaction simultaneously, make the different direct ratio (ratio of isomery hydro carbons and positive structure hydrocarbon content) in the purpose product significantly improve, guaranteeing the low-temperature performance of purpose product, can be good at meeting the requirement of harsh standard of currently available products as character such as the freezing point of boat coal and the condensation points of diesel oil.
Substantially do not contain sulphur, nitrogen in the Fischer-Tropsch synthesis oil, therefore react and do not contain gases such as hydrogen sulfide and ammonia in the gas phase substantially yet.Therefore, in the present invention, shared reaction hydrogen of hydrofining reaction and hydrocracking reaction and cold hydrogen are supplied with and the recycle system, can save the facility investment expense.
In the present invention, hydrofining hydrogen dividing potential drop is 2.0-15.0MPa, and temperature of reaction 250-400 ℃, hydrogen to oil volume ratio is 100-1000v/v, volume space velocity 0.5-10.0h
-1Hydroisomerizing cracking hydrogen dividing potential drop is 2.0-15.0MPa, and temperature of reaction is 300-450 ℃, volume space velocity 0.5-5.0h
-1, hydrogen to oil volume ratio 100-1500v/v.
In the present invention, used Hydrobon catalyst 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 the group vib metal is Mo or/and W, and VIII family metal is that Co is or/and Ni.
In the present invention, used isomery hydrocracking catalyst is the noble metal catalyst or the non-precious metal catalyst of amorphous aluminum silicide load.The metal component of non-precious metal catalyst is VIB or/and VIII family base metal, and wherein the group vib metal is Mo or/and W, and VIII family metal is that Co is or/and Ni; The metal component of noble metal catalyst is that Pt is or/and Pd.
Because the olefin(e) centent in the coal Fischer-Tropsch synthesis oil is very high,, can on catalyzer, generate a large amount of coke and cause catalyst activity reduction by vigorous reaction if alkene is direct and the Hydrobon catalyst contact reacts; Generally contain a certain amount of metal in the Fischer-Tropsch synthesis oil; these metals very easily are deposited on the Hydrobon catalyst top; cause reactor pressure reduction to occur; be deposited on metal on the catalyzer simultaneously and can cause the permanent deactivation of hydrogenation catalyst; for guaranteeing the long-term operation of full scale plant; preferably the hydrogenation protecting agent is seated in the Hydrobon catalyst top, thereby avoids the generation of above-mentioned phenomenon.Described protective material is to load on VIB on unformed aluminum oxide or the silica-alumina supports or/and VIII family non-precious metal catalyst, and wherein the group vib metal is Mo or/and W, and VIII family metal is Co or/and Ni, and this protective material has bigger pore volume and specific surface area.The volume ratio of protective material and Hydrobon catalyst is 0-30: 100 preferred 5-15: 100.
In addition, because the isomery hydrocracking reaction has a spot of alkene to generate, for guaranteeing constant product quality, should load a spot of back catalyst for refining in the bottom of isomery hydrocracking reactor, the volume ratio of back finishing agent and isocracking catalyzer is 0-15: 100 preferred 5-10: 100.
Below in conjunction with accompanying drawing method provided by the present invention is further detailed.
Accompanying drawing is the method flow synoptic diagram from Fischer-Tropsch synthesis oil fecund intermediate oil provided by the present invention, has omitted equipment such as hydrogen gas compressor and pipeline thereof, process furnace, interchanger, pump and valve among the figure.
This flow process describes in detail as follows:
Coal synthetic gas after the purification enters 14 reactions of Fischer-Tropsch synthesis device through pipeline 1; the logistics of the full cut product of the Fischer-Tropsch synthesis that obtains mixes with hydrogen-rich gas after heat exchange and process furnace enter hydrofining reactor 15 after heating up through pipeline 2; by with protective material and Hydrobon catalyst contact reacts; remove oxygen, metal impurities in the oil on the one hand, make a large amount of alkene generation saturated reactions in the oil on the other hand.Waiting hydrofining reaction owing to alkene is saturated is strong exothermal reaction, has cold hydrogen to inject between each beds of refining reaction device, with control reaction temperature, prevents out of control situation generations such as overtemperature.The effluent of hydrofining reactor 15 enters separation column 16 through pipeline 3 to carry out fractionation and is cut into naphtha fraction, diesel oil distillate and heavy oil fraction, naphtha fraction wherein, diesel oil distillate is respectively through pipeline 4,5 caterpillars, heavy oil fraction then through pipeline 6 with after tail oil from pipeline 12 mixes, enter hydroisomerizing cracking case 17 through pipeline 7, at hydrogen-rich gas, hydrocracking reaction takes place down in the effect of isomery hydrocracking catalyst, highly selective be converted into the purpose product, reaction product enters separation column 18 cuttings through pipeline 8 and obtains gas, naphtha fraction, diesel oil distillate and tail oil cut, gas wherein, naphtha fraction, diesel oil distillate is respectively through pipeline 9,10,11 caterpillars, the tail oil cut is then successively through pipeline 19,12 loop back hydroisomerizing cracking case 17 proceeds cracking, also can be successively through pipeline 19,13 caterpillars are as producing the lubricant base raw material.Hydrogen-rich stream loops back hydrofining reactor 15, hydroisomerizing cracking case 17 after the circulating hydrogen compressor compression.
The invention has the advantages that:
1, the relatively independent technical process of hydrotreatment and isomery hydrocracking can obtain the purpose product that has different performance, satisfy the variant production specification respectively.
2, the isomery hydrocracking reactor is because charging is the heavy ends in the hydrotreatment products, and basic is no sulphur, no nitrogen raw material, can adopt noble metal catalyst or cheap non-precious metal catalyst.
3, the petroleum naphtha after the hydrofining can be used as fine preparing ethylene by steam cracking raw material, and its total triolefin yield can reach more than the 60 heavy %.
4, the diesel oil after the hydrofining has does not have sulphur substantially, do not have nitrogen and do not have characteristics such as aromatic hydrocarbons, and cetane value reaches about 80, is the fine diesel oil blending component.
5, have production handiness preferably, by the adjustment of operating parameters, as control hydrofining reaction and the depth of conversion of hydrocracking reaction and the cut point of separation column etc., the product that can obtain different demands distributes.
6, the technical process that proposes of the present invention helps improving the yield of intermediate oil, can reduce the secondary cracking of light constituent; Help reducing the volume and the loaded catalyst of isomery hydrocracking reactor.
The following examples will give further instruction to present method, but therefore not limit present method.
With the full cut of Fischer-Tropsch synthesis oil is raw material, and its character sees Table 1.The trade names of Hydrobon catalyst are RTF-1, and the trade names of isomery hydrocracking catalyst are RCF-1, RCF-2, and wherein RCF-1 is the precious metal molecular sieve type catalyst, and RCF-2 is the base metal amorphous catalyst.Test is carried out according to technical process provided by the present invention on medium-sized fixed bed hydrogenation device.
The full cut of Fischer-Tropsch synthesis oil enters hydrofining reactor, under Hydrobon catalyst RTF-1 effect, carry out alkene saturated with reaction such as hydrogenation deoxidation, the reaction product after refining is cut into naphtha fraction, diesel oil distillate and heavy oil fraction through separation column; After mixing, the tail oil cut of heavy oil fraction with the hydrocracking separation column enter the isomery hydrocracking reactor, the reaction product that generates under isomery hydrocracking catalyst RCF-1 effect enters separation column and is cut into naphtha fraction, diesel oil distillate and tail oil cut, and it is lightweight purpose product that the tail oil cut loops back isomery hydrocracking reactor continuation cracking.Operational condition and product distribute as shown in table 2, and the naphtha fraction product property is listed in table 3, and the diesel oil distillate product property is listed in table 4.
From the table data as can be seen, diesel cetane-number is 80, can concoct with the low cetane number diesel cut; Naphtha fraction mainly is made of alkane, is preparing ethylene by steam cracking, propylene feedstocks preferably.
The full cut of Fischer-Tropsch synthesis oil enters hydrofining reactor, under Hydrobon catalyst RTF-1 effect, carry out alkene saturated with reaction such as hydrogenation deoxidation, the reaction product after refining is cut into naphtha fraction, diesel oil distillate and heavy oil fraction through separation column; After mixing, the tail oil cut of heavy oil fraction with the hydrocracking separation column enter the isomery hydrocracking reactor, the reaction product that generates under isomery hydrocracking catalyst RCF-2 effect enters separation column and is cut into naphtha fraction, diesel oil distillate and tail oil cut, and it is lightweight purpose product that the tail oil cut loops back isomery hydrocracking reactor continuation cracking.Operational condition and product distribute as shown in table 2, and the naphtha fraction product property is listed in table 3, and the diesel oil distillate product property is listed in table 4.
From table data as can be seen, the diesel product total recovery surpasses 81 heavy %, the diesel product cetane value is 79, can concoct with the low cetane number diesel cut; Naphtha fraction mainly is made of alkane, is preparing ethylene by steam cracking, propylene feedstocks preferably.
Table 1, the synthetic full distillate oil main character of Fischer-Tropsch
| Project | Data |
| Density (20 ℃), g/cm 3 | 0.7990 |
| Boiling range (ASTM D-1160), ℃ | |
| IBP/10％ | 68/205 |
| 30％/50％ | 331/369 |
| 90％/95％ | 553/637 |
| Oxygen level, heavy % | 0.75 |
Table 2, operational condition and product distribute
| Embodiment |
| 1 | 2 | |
| Hydrofining reactor: | ||
| Catalyzer | RTF-1 | RTF-1 |
| Operational condition | ||
| The hydrogen dividing potential drop, MPa | 6.4 | 6.4 |
| Temperature of reaction, ℃ | 300 | 300 |
| Volume space velocity, h -1 | 3.0 | 3.0 |
| Hydrogen to oil volume ratio, v/v | 300 | 300 |
| Hydrocracking reactor: | ||
| Catalyzer | RCF-1 | RCF-2 |
| Operational condition | ||
| The hydrogen dividing potential drop, MPa | 6.4 | 6.4 |
| Temperature of reaction, ℃ | 353 | 365 |
| Volume space velocity, h -1 | 2.0 | 2.0 |
| Hydrogen to oil volume ratio, v/v | 800 | 800 |
Table 3, naphtha fraction product property
| Embodiment |
| 1 | 2 | |
| The boiling range scope | ||
| Total recovery, heavy % | 19.86 | 18.65 |
| Density (20 ℃), g/cm 3 | 0.701 | 0.708 |
| Form heavy % | ||
| Normal paraffin | 90.95 | 88.12 |
| Isoparaffin | 6.49 | 9.95 |
Table 4, diesel oil distillate product property
| Embodiment |
| 1 | 2 | |
| The boiling range scope | ||
| Total recovery, heavy % | 79.72 | 81.02 |
| Density (20 ℃), g/cm 3 | 0.776 | 0.782 |
| Condensation point, ℃ | -12 | -15 |
| Cetane value | 80 | 79 |
| Sulphur content, heavy % | ＜5 | ＜5 |
| Nitrogen content, heavy % | ＜5 | ＜5 |
| Aromaticity content, heavy % | ＜1 | ＜1 |
Claims (6)
1, a kind of Fischer-Tropsch synthetic oil hydrogenation purification, it is characterized in that the full cut of Fischer-Tropsch synthesis oil, hydrogen contact with Hydrobon catalyst, the hydrofining reaction logistics obtains intermediate oil product, petroleum naphtha and heavy oil through separation, wherein heavy oil contacts with hydrogen, isomery hydrocracking catalyst, and the hydrocracking reaction logistics obtains the intermediate oil product through separation.
2,, it is characterized in that the hydrocracking reaction logistics loops back the hydroisomerizing cracking case through the tail oil cut that separation obtains according to the method for claim 1.
3, according to the method for claim 1, it is characterized in that hydrofining hydrogen dividing potential drop is 2.0-15.0MPa, temperature of reaction 250-400 ℃, hydrogen to oil volume ratio is 100-1000v/v, volume space velocity 0.5-10.0h
-1Hydroisomerizing cracking hydrogen dividing potential drop is 2.0-15.0MPa, and temperature of reaction is 300-450 ℃, volume space velocity 0.5-5.0h
-1, hydrogen to oil volume ratio 100-1500v/v.
4, according to the method for claim 1, it is characterized in that described Hydrobon catalyst is a kind of metal load type catalyst, carrier is unformed aluminum oxide, and metal component is that VIB is or/and VIII family base metal, wherein the group vib metal is Mo or/and W, and VIII family metal is that Co is or/and Ni.
5, according to the method for claim 1 or 4; it is characterized in that the hydrogenation protecting agent is seated in the Hydrobon catalyst top; described protective material is to load on VIB on unformed aluminum oxide or the silica-alumina supports or/and VIII family non-precious metal catalyst, and the volume ratio of protective material and Hydrobon catalyst is 0-30: 100.
6, according to the method for claim 1, it is characterized in that noble metal catalyst or non-precious metal catalyst that described isomery hydrocracking catalyst is the amorphous aluminum silicide load, the metal component of non-precious metal catalyst is that VIB is or/and VIII family base metal, wherein the group vib metal is Mo or/and W, and VIII family metal is that Co is or/and Ni; The metal component of noble metal catalyst is that Pt is or/and Pd.
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| US5378348A (en) * | 1993-07-22 | 1995-01-03 | Exxon Research And Engineering Company | Distillate fuel production from Fischer-Tropsch wax |
| US6296757B1 (en) * | 1995-10-17 | 2001-10-02 | Exxon Research And Engineering Company | Synthetic diesel fuel and process for its production |
| US5766274A (en) * | 1997-02-07 | 1998-06-16 | Exxon Research And Engineering Company | Synthetic jet fuel and process for its production |
| US6656342B2 (en) * | 2001-04-04 | 2003-12-02 | Chevron U.S.A. Inc. | Graded catalyst bed for split-feed hydrocracking/hydrotreating |
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