CN101177627A - Hydrogenation processing method for f-t synthetic oil - Google Patents
Hydrogenation processing method for f-t synthetic oil Download PDFInfo
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- CN101177627A CN101177627A CNA2007100653116A CN200710065311A CN101177627A CN 101177627 A CN101177627 A CN 101177627A CN A2007100653116 A CNA2007100653116 A CN A2007100653116A CN 200710065311 A CN200710065311 A CN 200710065311A CN 101177627 A CN101177627 A CN 101177627A
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Abstract
The invention discloses a hydrogenation processing method of Fischer-Tropsch synthetic oil and the method is that the Fischer-Tropsch synthetic oil is divided into lightweight cut and heavyweight cut which are mixed with synthetic wax after prerefining and then are subjected to hydrogenation processing; the products of the hydrogenation processing enter a first high-pressure separator and the liquid products separated enter a fractionating system through a low-pressure separator; the separated hydrogen-rich gas is mixed with heavy component separated from the fractionating system and then is subjected to hydrogen cracking; cracking products enter a second high-pressure separator and the separated liquid products enter the same low-pressure separator and fractionating system with the hydrogenation processing; the separated hydrogen-rich gas is pressurized by a circulating hydrogen compressor and is mixed with new supplementary hydrogen and then enters a hydrogen preprocessing reactor. Cetane value of diesel oil acquired is higher than 70, solidifying point is below 0 DEG C and the content of sulfur and nitrogen is extremely low, meanwhile, naphtha acquired is high-quality raw material used for producing ethylene by steam cracking.
Description
Technical field
The present invention relates to a kind of hydroprocessing process of Fisher-Tropsch synthesis fuels, particularly relate to light ends oil and heavy distillate, and synthetic cured part is processed as the hydroprocessing process of high-quality automotive fuel and high-quality industrial chemicals Fisher-Tropsch synthesis fuels.
Background technology
Fossil oil mainly comprises coal and oil, and from world wide, the reserves of coal far surpass reserves.Therefore, how substituting oil with coal is the important topic of energy field.The important course of processing that coal substitutes oil is the liquidation of coal process, and the further processing treatment process of gelatin liquefaction product.
According to the different routes of chiral process, coal liquefaction can be divided into direct liquefaction and indirect liquefaction two big classes.DCL/Direct coal liquefaction is that coal is directly changed into liquid product.Its technology mainly contains Exxon (Exxon) Exxon donor solvent process (being called for short the EDS method), H-coal process etc.The EDS method is the effect by hydrogen supply dissolvent, under certain temperature and pressure coal hydrogenation is liquefied as liquid fuel; H-coal process is to adopt the pressurized catalysis fluidized-bed reactor, by the effect of high temperature and catalyzer, makes coal be cracked into micromolecular liquid hydrocarbon fuel under hydrogen pressure.The diesel yield of Hydrogenation liquefaction process is about 70%, LPG and gasoline account for 20%, and all the other also contain heteroatomss such as a considerable amount of oxygen, nitrogen, sulphur for the intermediates based on polycyclic aromatic hydrocarbons, aromaticity content is also higher, further is processed as products such as high-quality gasoline, diesel oil than difficulty.
CN1382772A has introduced a kind of method from coal direct liquefaction oil greatly preparing hihg-quality diesel oil or rocket engine fuel, liquefied coal coil stable hydrogenation after the filtration, then diesel oil distillate, the tail oil cut that obtains carried out the deep hydrogenation upgrading, separate the hydro-upgrading reactor effluent and obtain gas, naphtha fraction, diesel oil distillate and tail oil cut or gas, naphtha fraction, rocket engine fuel, diesel oil distillate and tail oil cut, hydrogen rich stream recycles, and part tail oil cut loops back coal liquefaction system as hydrogen supply agent.
CN1493663A has introduced a kind of combined technical method of being produced fine-quality diesel oil by coal direct liquefaction oil, liquefied coal coil stable hydrogenation after the filtration, to obtain diesel oil distillate then and carry out hydro-upgrading, and separate the hydro-upgrading reactor effluent and obtain naphtha fraction, diesel oil distillate.Because the coal direct liquefaction oil aromaticity content is higher, the cetane value of the diesel oil distillate that above-mentioned two kinds of methods obtain only can reach about 45, can not satisfy Europe II diesel oil standard.
ICL for Indirect Coal Liquefaction be coal at high temperature with oxygen and water vapour reaction decomposes, make coal all be gasificated into unstripped gas (CO+H
2Mixture), under the effect of catalyzer, further synthesize liquid oil or petroleum chemicals again.At present, indirect liquefaction has been realized industrial production in many countries, mainly divides two kinds of production technique, the one, and fischer-tropsch (Fischer-Tropsch) synthesis technique is with the direct synthetic oil of unstripped gas; The 2nd, the Bill that rubs (Mobil) technology by the unstripped gas synthesizing methanol, becomes gasoline by methanol conversion again.Wherein fischer-tropsch is synthetic is the processing method with better prospect.The wider distribution of Fisher-Tropsch synthesis fuels, the product that different synthesis conditions obtains distributes different, is distributed as the product under a kind of representative condition: C
4 -Following product accounts for about 40% of total synthetic product, C
5 +Above product accounts for about 60% of total synthetic product, wherein C
5～C
9Cut about 30%, C
10～C
13Cut about 15%, C
14～C
18Cut about 9%, C
19 +Cut about 6% etc.C
4 -Following gaseous hydrocarbons product obtains end products such as LPG, polymerization-grade propylene, polymer grade ethylene through separation and olefin metathesis conversion.C
5 +Above liquid product can further be processed as various products.
CN1594509A etc. adopt the catalyst based hydrocracking that carries out of Fe with the heavy hydrocarbon and/or the kettle bottom wax of Fisher-Tropsch synthesis fuels in suspension bed, produce petroleum naphtha and diesel product.Concrete grammar is that catalyst based and Fischer-Tropsch synthesis of heavy hydrocarbon of Fe and/or kettle bottom wax raw material are mixed at storage tank, is mixed and heated to 300～400 ℃ with hydrogen then and enters suspended-bed reactor, carries out hydrocracking; The reaction conditions of hydrocracking is 3.0～20.0MPa, and temperature of reaction is 350～500 ℃, and hydrogen to oil volume ratio is 300～1800, and the liquid air speed is 0.1～3.0h
-1The hydrogenation performance of suspension bed technology a little less than, severe reaction conditions, product property needs further to improve.
CN1125960A etc. adopt extraordinary amorphous aluminum silicide carried noble metal, are lubricant base with Fisher-Tropsch synthesis fuels production.Wherein catalyzer is by precious metal and the specific surface 100～500m of 0.05～10wt%
2The silica/alumina carrier of/g constitutes.The relevant patent documentation that with the Fischer-Tropsch synthesis oil is raw material system lubricant base is more, but straight chain hydrocarbon content is more in the Fisher-Tropsch synthesis fuels, is not the desirable feedstock of lubricant base.
USP6,475,375, USP6,656,343 grades have been introduced and a kind of Fisher-Tropsch synthesis fuels have been converted into the method for compression ignition type (CI) engine with naphtha fuel or its blending component.Concrete grammar is, the naphtha fraction of Fisher-Tropsch synthesis fuels is carried out hydrotreatment, hydrocracking is carried out in the last running of Fisher-Tropsch synthesis fuels, the petroleum naphtha that petroleum naphtha after the hydrotreatment and hydrocracking obtain is as fuel or its blending component of compression ignition engine, the controlling index of these petroleum naphthas is: final boiling point is lower than 160 ℃, cloud point is below-30 ℃, and cetane value is more than 30.But naphtha fraction is not the ideal fuels of compression ignition engine, and with its concocted diesel oil, though can reduce its condensation point, other index such as flash-point etc. will be affected.
USP5,689,031 to have introduced Fisher-Tropsch synthesis fuels production be the method for diesel oil.Propose to keep a small amount of oxygenatedchemicals (thinking the alcohols that C12 is above) in the Fisher-Tropsch synthesis fuels, can improve the lubricity of combined diesel oil, needn't add expensive additive during use, simultaneously in order to reduce condensation point, all components need be carried out hydroisomerization.Concrete grammar is, Fisher-Tropsch synthesis fuels is separated into heavier cut and lighter cut, further this lighter cut is separated, and heavier cut and be lower than about 500 lighter cut and carry out hydroisomerization is the product of this isomery and the not part of hydrotreatment (being generally 500～700 cuts) blending.This patent provides a kind of method of improving the combined diesel oil lubricity, but operation is comparatively complicated.
USP5,378,348 propose a kind of Fisher-Tropsch synthesis fuels mainly to be produced method into rocket engine fuel.At first be light naphtha fraction, kerosene(oil)fraction (320～500) and 500 with the Fisher-Tropsch synthesis fuels fractionation
+With kerosene(oil)fraction hydrotreatment hydroisomerizing then, produce and be the high quality synjet.With 500 °F
+Cut fraction hydrogenation isomery (having the cracking function), kerosene(oil)fraction that obtains and virgin kerosene cut carry out hydrotreatment and hydroisomerizing jointly, and the diesel oil distillate that obtains is as product, 700 °F
+The cut circulation.Lock out operation in this flow process is more, and long flow path, energy consumption are big.In addition, though the kerosene(oil)fraction foreign matter content that Fisher-Tropsch synthesis fuels obtains is lower, its smoke point is difficult to be improved, and the cost that is processed as the high quality rocket engine fuel is higher.
USP6,589,415, USP6,583,186 have introduced the method for Fisher-Tropsch synthesis fuels being carried out hydrocracking, and its principal feature is that hydrocracking is carried out in the last running of synthetic oil, with the lighting end of the synthetic oil cooling logistics as the hydrocracking reaction bed.Its main deficiency is as can be seen, and the synthetic oil raw material that enters hydrocracking does not pass through hydrotreatment, wherein contains a certain amount of impurity (as oxygen), and these impurity generally are the objectionable impuritiess of hydrocracking catalyst, can cause the permanent deactivation of catalyzer.In addition, the lighting end of synthetic oil also enters hydrocracking reactor, and consequently liquid product yield can reduce.
USP4,080,397, USP4, it is the method for stop bracket gasoline that 059,648 grade has been introduced Fisher-Tropsch synthesis fuels production.Detailed process is for to carry out hydrotreatment with Fisher-Tropsch synthesis fuels, and the last running after the hydrotreatment adopts the selective splitting catalyzer that contains ZSM system molecular sieve to handle, and the gasoline fraction that obtains has higher octane value.But with the Fisher-Tropsch synthesis fuels is that the raw material production stop bracket gasoline does not have reasonableness economically, show that mainly liquid product yield is low, gasoline octane rating improves limited (generally only being about 85), and the diesel oil distillate that this process obtains is second-rate, should not directly use.
USP4,684,756 have introduced a kind of method of producing premium-type gasoline with f-t synthetic wax.Principal feature is to adopt the fluidized-bed process process, adopts the hydrocracking catalyst or the catalyst for hydrogenation de-waxing of catalytic cracking catalyst or low hydrogenation performance, f-t synthetic wax is cracked into the split product that is rich in alkene.The split product that will be rich in alkene then carries out oligomerisation reaction, obtains high quality (high-octane rating) gasoline.This method is a purpose to produce gasoline, and reaction process is comparatively complicated.
Summary of the invention
The working method that the purpose of this invention is to provide a kind of Fisher-Tropsch synthesis fuels, this method has overcome the defective that prior art exists, be a kind of technology method simple, with low cost, light ends oil, heavy distillate and the synthetic cured part of Fisher-Tropsch synthesis fuels can be processed as high-quality oil fuel and industrial chemicals with this method.
The hydroprocessing process that the purpose of this invention is to provide a kind of Fisher-Tropsch synthesis fuels, this method comprises the steps:
(1) light ends of Fisher-Tropsch synthesis fuels oil and heavy distillate carry out hydrotreatment under the hydrogenation catalyst effect, generate refined products I;
(2) the refined products I that obtains of step (1) mixes with synthetic wax, carries out hydrotreatment under the hydrogenation catalyst effect, generates refined products II;
(3) the refined products II that obtains of step (2) enters first high-pressure separator after heat exchange, isolates hydrogen-rich gas I and product liquid I;
(4) the product liquid I that obtains of step (3) enters light pressure separator and fractionating system successively, obtains petroleum naphtha, diesel oil and tail oil I;
(5) the hydrogen-rich gas I that obtains of the tail oil I that obtains of step (4) and step (3) mixes the back and carries out hydrocracking generate crackate under the hydrocracking catalyst effect;
(6) isocrackate that obtains of step (5) enters second high-pressure separator after heat exchange, isolates hydrogen-rich gas II and product liquid II; With
(7) the product liquid II that obtains of step (6) enters light pressure separator and fractionating system successively, obtains petroleum naphtha, diesel oil and tail oil II.
In the inventive method, the final boiling point of the light ends oil of the Fisher-Tropsch synthesis fuels described in the step (1) is 280～420 ℃; The final boiling point of heavy distillate is 350～520 ℃; The described Fisher-Tropsch synthesis fuels synthetic wax of step (2) is the waxy stone after Fisher-Tropsch synthesis fuels separates the weight component.
In the method for the invention, the hydrogen-rich gas that step (3) and step (6) obtain is through the recycle compressor supercharging, and mixes with the new hydrogen that replenishes, and is recycled to then in each hydrotreatment or the hydrocracking operation.
In the inventive method, step (1) also can be described as the hydrogenation pre-treatment step, and wherein said hydroprocessing condition is: the hydrogen dividing potential drop is 3～20MPa, and temperature is 100～300 ℃, and volume space velocity is 0.1～20h during liquid
-1, hydrogen to oil volume ratio is 100～2000; Preferred hydroprocessing condition is: the hydrogen dividing potential drop is 5～15MPa, and temperature is 120～220 ℃, and volume space velocity is 0.2～10h during liquid
-1, hydrogen to oil volume ratio is 200～1000.
In the inventive method, the described hydroprocessing condition of step (2) is: the hydrogen dividing potential drop is 3～20MPa, and temperature is 200～430 ℃, and volume space velocity is 0.1～20h during liquid
-1, hydrogen to oil volume ratio is 300～2000; Preferred hydroprocessing condition is: the hydrogen dividing potential drop is 5～15MPa, and temperature is 250～400 ℃, and volume space velocity is 0.2～10h during liquid
-1, hydrogen to oil volume ratio is 300～1500.
In the inventive method, the described hydrotreatment temperature of reaction of step (2) should be higher than the described hydrogenation pretreatment reaction of step (1) temperature, and the described hydrotreatment temperature of reaction of step (2) is higher 10～300 ℃ than the described hydrotreatment temperature of reaction of step (1) usually; The described hydrotreatment temperature of reaction of preferred steps (2) is higher 30～200 ℃ than the described hydrotreatment temperature of reaction of step (1).
In the inventive method, the operational condition of the described hydrocracking of step (5) is as follows: the hydrogen dividing potential drop is 3～20MPa, and temperature is 300～450 ℃, and volume space velocity is 0.1～20h during liquid
-1, hydrogen to oil volume ratio is 300～3000; Preferably, the operational condition of the described hydrocracking of step (5) is: the hydrogen dividing potential drop is 5～15MPa, and temperature is 320～430 ℃, and volume space velocity is 0.2～10h during liquid
-1, hydrogen to oil volume ratio is 400～2000.
In the inventive method, in step (4) and the described low pressure separation system of step (7), the cut point of petroleum naphtha and diesel oil is 120～260 ℃, and the cut point of diesel oil and tail oil is 330～385 ℃.
In the inventive method, the employed tail oil I of step (5) all is recycled to cracking case with the resulting tail oil I of step (4), or partly be recycled to cracking case, discharge raw material, as the preparing ethylene by steam cracking raw material as other process of a part.
Further, if desired, separate the tail oil II that obtains by step (7) and can also be circulated back to the upper level cracking case whole or in part, make it carry out cracking and separate.The number of times that those skilled in the art can determine recycle easily according to the composition and the overall cost keeping of products at different levels.
Temperature of reaction mentioned herein is meant average reaction temperature.
In the inventive method, first high-pressure separator can be a high pressure hot separator described in the step (3), also can be cold high pressure separator.When first high-pressure separator was cold high pressure separator described in the step (3), the hydrogen-rich gas of separating can directly enter cracking case; When first high-pressure separator was high pressure hot separator described in the step (3), the gaseous product that high pressure hot separator is separated needed advanced cold high pressure separator, and the hydrogen-rich gas of being separated by cold high pressure separator enters cracking case again.
In the inventive method, second high-pressure separator can be a high pressure hot separator described in the step (6), also can be cold high pressure separator.When second high-pressure separator was cold high pressure separator described in the step (6), the hydrogen-rich gas of separating can directly enter circulating hydrogen compressor; When second high-pressure separator was high pressure hot separator described in the step (6), the gaseous product of being separated needed advanced cold high pressure separator, and the hydrogen-rich gas of being separated by cold high pressure separator enters circulating hydrogen compressor again.
In the inventive method, light pressure separator can be same described in step (4) and the step (7), also can be separately independently, and is preferably same; The low pressure fractionating system can be same described in step (4) and the step (7), also can be separately independently, and is preferably same.
In the method for the invention, step (1) and (2) employed hydrotreating catalyst can be identical or different.Set out with regard to easy handling and the angle of being convenient to handle, preferably use identical catalyzer.
In the inventive method, step (1) and (2) employed hydrotreating catalyst, or be referred to as hydrofining (processing) catalyzer that hydrorefined catalyzer can be a routine, for example can be VIB and/or the VIII family non-precious metal catalyst that loads on aluminum oxide or the siliceous alumina supporter.
In the methods of the invention, described hydrotreating catalyst is a carrier with aluminum oxide or siliceous aluminum oxide usually, with VIB (as Mo, W etc.) and/or VIII (as Ni, Fe, Co etc.) family's base metal is active ingredient, gross weight with catalyzer is a benchmark, described base metal as: the weight contents in catalyzer such as Mo, W, Ni, Fe, Co count 1%～50% with oxidation state, are preferably 10%～40%.
Can contain an amount of auxiliary agent in the described hydrotreating catalyst, as be selected from phosphorus, fluorine, titanium, zirconium and the boron etc. one or more.
The hydrotreating catalyst that the inventive method is used can be according to method preparation well known to those skilled in the art, also can select existing commercial Hydrobon catalyst, the for example various hydrofinings of Fushun Petrochemical Research Institute development, hydrotreating catalyst etc. are comprising 3936 catalyzer, 3996 catalyzer, FF-16 catalyzer, FF-26 catalyzer, 481-3 catalyzer, FDS-4A catalyzer, FDS-4 catalyzer, FH-5 catalyzer, FH-5A catalyzer or FH-98 catalyzer etc.Certainly, also can select to have with these catalyzer on the market similar catalyst of similar functions.
The hydrocracking catalyst that the inventive method is used is the dual-functional hydrogenation cracking catalyst of routine, and this type of catalyzer is being cracked into macromolecule hydrocarbon the micromolecular while, straight-chain paraffin can be tautomerized to have branched structure, and then reduce the condensation point of diesel oil distillate.
The hydrocracking catalyst that uses in the inventive method contains acid sites and hydrogenation sites simultaneously.Generally being to be carrier to have certain tart catalytic material, as among molecular sieve, amorphous aluminum silicide or the clay etc. one or more, is hydrogenation sites with VIB (as Mo, W etc.) and/or VIII (as Ni, Fe, Co, Pt, Pd etc.) family's metal.The acid sites of described hydrocracking catalyst has cracking and two kinds of functions of isomery simultaneously.As the molecular sieve of acidic components one or more in Y molecular sieve, beta-molecular sieve, SAPO molecular sieve, ZSM molecular sieve or the NU-10 molecular sieve etc. preferably, also can contain acidic components such as amorphous aluminum silicide simultaneously.When described catalyzer is the active centre with above-mentioned base metal, be benchmark with the gross weight of catalyzer, count 1%～50% as the weight content of base metal in catalyzer in active centre with oxidation state, be preferably 10%～40%; When described catalyzer is the active centre with above-mentioned precious metal (as Pt, Pd etc.), be benchmark with the gross weight of catalyzer, count 0.1%～3% as the weight content of precious metal in catalyzer in active centre with element simple substance.
The hydrocracking catalyst that the present invention uses can be according to method preparation well known to those skilled in the art, also can select existing commercial Hydrobon catalyst, the various hydrocracking catalysts of Fushun Petrochemical Research Institute development for example, comprising 3901 catalyzer, 3974 catalyzer, 3976 catalyzer, 3955 catalyzer, FC-12 catalyzer, FC-14 catalyzer, FC-16 catalyzer, FC-20 catalyzer, FC-22 catalyzer, FC-24 catalyzer, FC-26 catalyzer, FC-28 catalyzer, ZHC-02 catalyzer or 3911 catalyzer etc.Certainly, also can select to have with these catalyzer on the market similar catalyst of similar functions.
In actually operating, can before Primary Catalysts (hydrotreating catalyst and hydrocracking catalyst) bed, load an amount of protective material, with the interception impurities in raw materials, prolong the work-ing life of Primary Catalysts.Protective material can be selected the protective material of this area routine.
The inventive method has taken into full account the characteristics of each cut of Fisher-Tropsch synthesis fuels, has determined suitable flow process.At the higher characteristics of the oil diene content of the light ends in the synthetic oil, at first under the mitigation condition with the synthetic oil hydrotreatment, diolefine is the chemical substance that is easy to polymerization and then coking takes place, hydrotreatment under the mitigation condition, when effectively diene hydrogenation being monoolefine or alkane, avoided diene polymerization, greatly the running period of extension fixture; Acidity is higher in the lighting end simultaneously, and hydrotreatment under the mitigation condition can reduce the corrosion of peracid reactant flow to device.After mild hydrogenation was handled, diolefine all was converted into monoolefine or alkane in the reaction product, and acidity is reduced to 3～5mgKOH/100mL by being higher than 1000mgKOH/100mL, carried out conventional hydrotreatment then, carried out reactions such as the saturated and hydrogenation deoxidation of alkene.
Adopt the inventive method, the raw material that enters hydrocracking has been carried out effective hydrotreatment, heteroatoms wherein such as oxygen etc. remove fully substantially, and is less to the hydrocracking catalyst influence that contains acid sitess such as molecular sieve, can guarantee the hydrocracking catalyst long-term operation.The inventive method adopts two high pressure separation systems, hydrogenation pre-treatment, hydrotreatment products are carried out gas-liquid separation in the first high pressure separation system, contain hydrogen-rich gas directly as the hydrogen make-up of cracking case, crackate carries out gas-liquid separation in the second high pressure separation system, contain hydrogen-rich gas through the circulating hydrogen compressor supercharging, as the quenching hydrogen of recycle hydrogen, quenching hydrogen and the cracking case of hydrogenation pre-treatment, hydrotreating reactor.Because present method has effectively reused circulating hydrogen, therefore, can significantly reduce the design capacity of recycle compressor.
The diesel cetane-number of the inventive method gained is higher than 70, and condensation point is below 0 ℃, and the sulphur nitrogen content is extremely low, is high-quality clean fuel, also can be used as the high-quality blend component that improves diesel cetane-number.The inventive method gained naphtha fraction is a high quality steam cracking ethylene preparation raw material, and yield of ethene can reach 37%～39%, and the yield of ethene of common petroleum naphtha only is about 27%～28%.
Description of drawings
Fig. 1 is the inventive method process flow diagram.
Embodiment
Below in conjunction with accompanying drawing the inventive method is described in detail, this description of drawings be to be same light pressure separator with step (4) and the employed light pressure separator of step (7), and the example that employed low pressure fractionating system is same low pressure fractionating system in step (4) and the step (7).
The mixing oil 1 of light ends in Fisher-Tropsch synthesis fuels oil and heavy distillate mixes with hydrogen-rich gas 2, enters hydrogenation pretreatment reaction device 3, through wherein hydrogenation protecting catalyst bed and hydrofining reaction bed, obtains refined products I (4) successively.Synthetic wax 22 and hydrogen-rich gas 2 in refined products I (4) and the Fisher-Tropsch synthesis fuels are mixed into hydrotreating reactor 5, through hydrofining reaction bed wherein, obtain refined products II (6).Refined products II (6) enters first high-pressure separator 7, the gas stream of gained (8) is mainly hydrogen, comprise part light hydrocarbon (this gas is hydrogen-rich gas I) simultaneously, this gas stream (8) is mixed into cracking case 11 with 16 turning oils that come out 20 (being tail oil I or tail oil II) at the bottom of separation column, carries out hydrocracking reaction; The product liquid (9) that first high-pressure separator 7 is come out (being product liquid I) enters separation column 16 through the light pressure separator (not shown), isolates gas 17, petroleum naphtha 18, diesel oil 19 and tail oil 20 (being tail oil I or II); The crackate 12 that is come out by cracking case 11 enters second high-pressure separator 13, obtains gaseous product (8 ') (being hydrogen-rich gas II) and product liquid 14 (being product liquid II); The gaseous product (8 ') of second high-pressure separator 13 is after circulating hydrogen compressor 15 compressions, mix with the new hydrogen 10 that replenishes and to obtain hydrogen-rich gas 2, capable of circulation to hydrogenation pretreatment reaction device 3 and hydrotreating reactor 5, as the recycle hydrogen 2 and the quenching hydrogen of hydrogenation pretreatment reaction device 3 and hydrotreating reactor 5, simultaneously also as the quenching hydrogen of hydrocracking reactor 11; The product liquid 14 of second high-pressure separator 13 mixes with the product liquid 9 that first high-pressure separator 7 is come out, and enters knockout tower 16 after handling through light pressure separator.
Below in conjunction with embodiment the present invention is further detailed, but is not limited to following embodiment.The percentage composition that wherein relates to is a weight percentage." hydrotreatment " and " hydrofining " same meaning among the present invention.
Embodiment 1,2,3,4
Embodiment 1,2,3 and 4 adopts the flow process of Fig. 1, and raw materials used character sees Table 1.The operational condition of embodiment 1,2 each reactor and the character of products obtained therefrom see Table 2, and the operational condition of embodiment 3,42 each reactor and the character of products obtained therefrom see Table 3.
Table 1 stock oil character
| Stock oil | Light constituent | Heavy constituent |
| Density/gm -3 | 0.7519 | 0.8303 |
| Boiling range/℃ | 40～180 | 181～650 |
| Bromine valency/gBr (100mL) -1 | 45.12 | |
| Acid number/mgKOHg -1 | 0.85 | |
| Acidity/mgKOH (100mL) -1 | 1200 | |
| Oxygen level, % | 5.3 | 0.6 |
| Diolefine, % | 22.24 |
The operational condition of table 2 embodiment 1,2 each reactor and the character of products obtained therefrom
The operational condition of table 3 embodiment 3,4 each reactor and the character of products obtained therefrom
Annotate: the temperature of reaction among the embodiment refers to average reaction temperature.
Be illustrated more clearly in the advantage of the inventive method by above embodiment, and the inventive method products therefrom the level that can reach.According to method of the present invention, each component of Fisher-Tropsch synthesis fuels can be fully used, can be with the light ends oil and the heavy distillate of Fisher-Tropsch synthesis fuels, and synthetic cured part is processed as high-quality automotive fuel and high-quality industrial chemicals.
Below described embodiment of the present invention in detail, can do a lot of improvement and variation obviously for a person skilled in the art and can not deviate from essence spirit of the present invention.All these changes and improvements are all within protection scope of the present invention.
Claims (10)
1. the hydroprocessing process of a Fisher-Tropsch synthesis fuels, this method comprises the steps:
(1) light ends of Fisher-Tropsch synthesis fuels oil and heavy distillate carry out hydrotreatment under the hydrogenation catalyst effect, generate refined products I;
(2) the refined products I that obtains of step (1) mixes with synthetic wax, carries out hydrotreatment under the hydrogenation catalyst effect, generates refined products II;
(3) the refined products II that obtains of step (2) enters first high-pressure separator after heat exchange, isolates hydrogen-rich gas I and product liquid I;
(4) the product liquid I that obtains of step (3) enters light pressure separator and fractionating system, obtains petroleum naphtha, diesel oil and tail oil I;
(5) the hydrogen-rich gas I that obtains of the tail oil I that obtains of step (4) and step (3) mixes the back and carries out hydrocracking generate crackate under the hydrocracking catalyst effect;
(6) isocrackate that obtains of step (5) enters second high-pressure separator after heat exchange, isolates hydrogen-rich gas II and product liquid II; With
(7) the product liquid II that obtains of step (6) enters light pressure separator and fractionating system, obtains petroleum naphtha, diesel oil and tail oil II.
2. the hydroprocessing process of Fisher-Tropsch synthesis fuels as claimed in claim 1 is characterized in that the final boiling point of the described Fisher-Tropsch synthesis fuels light ends of step (1) oil is 280～420 ℃, and the final boiling point of heavy distillate is 350～520 ℃; The described Fisher-Tropsch synthesis fuels synthetic wax of step (2) is the waxy stone after Fisher-Tropsch synthesis fuels separates the weight component; And wherein the hydrogen-rich gas that obtains of step (3) and step (6) and mixes with the new hydrogen that replenishes through the recycle compressor supercharging, is recycled to then in each hydrotreatment or the hydrocracking operation.
3. the hydroprocessing process of Fisher-Tropsch synthesis fuels as claimed in claim 1, wherein in step (4) and the described fractionating system of step (7), the cut point of petroleum naphtha and diesel oil is 120～260 ℃, the cut point of diesel oil and tail oil is 330～385 ℃; Wherein the resulting tail oil I of step (4) all is recycled to cracking case, or is partly recirculated to cracking case.
4. as the hydroprocessing process of any described Fisher-Tropsch synthesis fuels of claim 1-3, wherein the hydroprocessing condition described in the step (1) is: the hydrogen dividing potential drop is 3～20MPa, and temperature is 100～300 ℃, and volume space velocity is 0.1～20h during liquid
-1, hydrogen to oil volume ratio is 100～2000; Be preferably: the hydrogen dividing potential drop is 5～15MPa, and temperature is 120～220 ℃, and volume space velocity is 0.2～10h during liquid
-1, hydrogen to oil volume ratio is 200～1000; Wherein the described hydroprocessing condition of step (2) is: the hydrogen dividing potential drop is 3～20MPa, and temperature is 200～430 ℃, and volume space velocity is 0.1～20h during liquid
-1, hydrogen to oil volume ratio is 300～2000; Be preferably: the hydrogen dividing potential drop is 5～15MPa, and temperature is 250～400 ℃, and volume space velocity is 0.2～10h during liquid
-1, hydrogen to oil volume ratio is 300～1500.
5. as the hydroprocessing process of any described Fisher-Tropsch synthesis fuels of claim 1-3, wherein the described hydrotreatment temperature of reaction of step (2) is higher 10～300 ℃ than the described hydrotreatment temperature of reaction of step (1); Preferably wherein the described hydrotreatment temperature of reaction of step (2) is higher 30～200 ℃ than the described hydrotreatment temperature of reaction of step (1).
6. as the hydroprocessing process of any described Fisher-Tropsch synthesis fuels of claim 1-3, wherein the operational condition of the described hydrocracking of step (5) is as follows: the hydrogen dividing potential drop is 3～20MPa, and temperature is 300～450 ℃, and volume space velocity is 0.1～20h during liquid
-1, hydrogen to oil volume ratio is 300～3000; Be preferably: the hydrogen dividing potential drop is 5～15MPa, and temperature is 320～430 ℃, and volume space velocity is 0.2～10h during liquid
-1, hydrogen to oil volume ratio is 400～2000.
7. as the hydroprocessing process of any described Fisher-Tropsch synthesis fuels of claim 1-3, wherein second high-pressure separator is high pressure hot separator and/or cold high pressure separator described in first high-pressure separator described in the step (3) and the step (6); When employed first high-pressure separator of step (3) was cold high pressure separator, the hydrogen-rich gas of separating can directly enter cracking case; When employed first high-pressure separator was high pressure hot separator in the step (3), the gaseous product of being separated by high pressure hot separator needed advanced cold high pressure separator, and the hydrogen-rich gas of being separated by cold high pressure separator enters cracking case again; When employed second high-pressure separator was cold high pressure separator in the step (6), the hydrogen-rich gas of separating can directly enter circulating hydrogen compressor; When employed second high-pressure separator was high pressure hot separator in the step (6), the gaseous product of being separated by high pressure hot separator needed advanced cold high pressure separator, and the hydrogen-rich gas of being separated by cold high pressure separator enters circulating hydrogen compressor again.
8. as the hydroprocessing process of any described Fisher-Tropsch synthesis fuels of claim 1-3, wherein the light pressure separator described in step (4) and the step (7) is same or separately independently; And the low pressure fractionating system described in step (4) and the step (7) is same or separately independently.
9. as the hydroprocessing process of Fisher-Tropsch synthesis fuels as described in any one of the claim 1-3, wherein step (1) and the employed hydrotreating catalyst of step (2) are identical or different, preferably identical; Preferred, described hydrotreating catalyst is to be carrier with aluminum oxide or siliceous aluminum oxide, with VIB and/or VIII base metal is active ingredient, in oxide weight, in total catalyst weight, the weight content of described base metal in the catalyzer gross weight is about 1%～50%, preferably approximately 10%～40%; Also contain one or more elements in phosphorus, fluorine, titanium, zirconium, the boron in this catalyzer as auxiliary agent; Described catalyzer for example is that described hydrotreating catalyst is 3936 catalyzer, 3996 catalyzer, FF-16 catalyzer, FF-26 catalyzer, 481-3 catalyzer, FDS-4A catalyzer, FDS-4 catalyzer, FH-5 catalyzer, FH-5A catalyzer or the FH-98 catalyzer that Fushun Petrochemical Research Institute produces.
10. as the hydroprocessing process of Fisher-Tropsch synthesis fuels as described in any one of the claim 1-3, wherein said hydrocracking catalyst is the hydrocracking catalyst that contains acid sites and hydrogenation sites simultaneously; Being to be carrier with in molecular sieve, amorphous aluminum silicide, the clay one or more, is hydrogenation sites with VIB and/or VIII metal; When being the active centre, be 1%～50% in the non-noble metal weight content of oxide compound with the base metal; Preferred 10%～40%, wherein said molecular sieve is Y molecular sieve, beta-molecular sieve, SAPO molecular sieve, ZSM molecular sieve or NU-10 molecular sieve; Described catalyzer for example is 3901 catalyzer, 3974 catalyzer, 3976 catalyzer, 3955 catalyzer that Fushun Petrochemical Research Institute produces, FC-12 catalyzer, FC-14 catalyzer, FC-16 catalyzer, FC-20 catalyzer, FC-22 catalyzer, FC-24 catalyzer, FC-26 catalyzer, FC-28 catalyzer, ZHC-02 catalyzer or 3911 catalyzer.
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| CNA2007100653116A CN101177627A (en) | 2007-04-11 | 2007-04-11 | Hydrogenation processing method for f-t synthetic oil |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205274A (en) * | 2013-03-20 | 2013-07-17 | 中科合成油工程有限公司 | Method for converting fischer-tropsch synthesis products into naphtha, diesel and liquefied petroleum gas |
| CN105733673A (en) * | 2016-02-26 | 2016-07-06 | 武汉凯迪工程技术研究总院有限公司 | Device and method for producing environment-friendly type solvent oil from Fischer-Tropsch synthesis oil |
| CN113337317A (en) * | 2021-06-29 | 2021-09-03 | 海南盈科生物科技有限公司 | Method for preparing biodiesel by indirect liquefaction of biomass |
-
2007
- 2007-04-11 CN CNA2007100653116A patent/CN101177627A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205274A (en) * | 2013-03-20 | 2013-07-17 | 中科合成油工程有限公司 | Method for converting fischer-tropsch synthesis products into naphtha, diesel and liquefied petroleum gas |
| CN105733673A (en) * | 2016-02-26 | 2016-07-06 | 武汉凯迪工程技术研究总院有限公司 | Device and method for producing environment-friendly type solvent oil from Fischer-Tropsch synthesis oil |
| CN105733673B (en) * | 2016-02-26 | 2018-01-23 | 武汉凯迪工程技术研究总院有限公司 | Utilize the device and method of Fischer-Tropsch synthesis oil production environment-friendlysolvent solvent oil |
| CN113337317A (en) * | 2021-06-29 | 2021-09-03 | 海南盈科生物科技有限公司 | Method for preparing biodiesel by indirect liquefaction of biomass |
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