CN103146426B - Method of converting fischer-tropsch synthesis products into naphtha, diesel and liquefied petroleum gas - Google Patents
Method of converting fischer-tropsch synthesis products into naphtha, diesel and liquefied petroleum gas Download PDFInfo
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Abstract
The invention discloses a method of converting fischer-tropsch synthesis products into naphtha, diesel and liquefied petroleum gas. The method comprises the following steps: (1) mixing fischer-tropsch oil, fischer-tropsch wax and hydrogen, and performing refining reaction in a refining reactor; (2) carrying out gas-liquid separation on products of the refining reaction in a thermal high-pressure separator I; enabling liquid phase separated by the thermal high-pressure separator I to enter a thermal low-pressure separator I, and enabling gas phase separated by the thermal high-pressure separator I to enter a cold high-pressure separator I; (3) separating in a fractionating tower to obtain diesel oil, heavy diesel oil and refined tail oil; and enabling the heavy diesel oil to enter a pour-point reaction apparatus for pour-point reaction; and circulating refined tail oil to a cracking reactor for cracking reaction; (4) enabling the reaction product of pour-point reaction and the reaction product of the cracking reaction to enter a thermal high-pressure separator II for gas-liquid separation; enabling the liquid phase separated by the thermal high-pressure separator II to enter a thermal low-pressure separator II, and the gas phase separated by the thermal high-pressure separator II to enter a cold high-pressure separator II; and (5) separating by a fractionating tower to obtain diesel oil.
Description
Technical field
The present invention relates to a kind of method Fischer-Tropsch synthetic being converted into petroleum naphtha, diesel oil and liquefied petroleum gas (LPG).
Background technology
China is the country of coal oil starvation more than, if coal can be converted into liquid fuel on a large scale with the processing method of high effect cleaning, effectively will alleviate the pressure of oil supply, promotes that sustain economic stably develops.The product (i.e. Fischer-Tropsch synthetic) that ICL for Indirect Coal Liquefaction generates comprises the thick product such as hydrocarbon gas, liquid hydrocarbon, synthetic wax.The hydrocarbon composition of Fischer-Tropsch synthetic and main character and petroleum products differ greatly, and form, and sulphur, nitrogen content are extremely low primarily of alkane and alkene, but containing a certain amount of oxygen.Each cut that Fischer-Tropsch synthetic obtains needs, through corresponding hydrogenation upgrading, just can obtain qualified liquid fuel and chemical.Usually, liquid hydrocarbon and synthetic wax can produce the products such as diesel oil, gasoline, petroleum naphtha and refining wax after hydrotreatment.
US6309432 discloses a kind of method of processing upgrading Fischer-Tropsch synthesis oil, this method first by Fischer-Tropsch synthesis oil with 371 DEG C for dividing point cuts into weight two cuts, the lighting end of less than 371 DEG C is successively separated to be separated with cold point through overheated point and obtains 246-371 DEG C of cut and C5-246 DEG C of cut, the last running of 246-371 DEG C of cut and more than 371 DEG C is through hydroisomerizing cracking case, at olefin saturated, while oxygenatedchemicals hydrogenation, normal paraffin generation hydroisomerizing and hydrocracking reaction, isomerized products is mainly mono methyl branching hydro carbons, C5-246 DEG C of cut is without hydrotreatment, but remove separation column after mixing with hydrocracking reactor product out, cutting obtains the cuts such as corresponding rocket engine fuel.Due to the alkene containing high level in Fischer-Tropsch oil and oxygen level, direct and isocracking catalyst exposure, can affect stability and the running period of catalyzer, and quality product is poor.
CN200510068181.2 provides the method for a kind of integrated form hydrogenation of Fischer-Tropsch synthesis oil upgrading, and complete for Fischer-Tropsch synthesis oil cut, hydrogen are first entered hydrofining reactor by this method, and the reaction such as hydrogenation deoxidation, olefin saturated occurs under Hydrobon catalyst effect.Synthetic oil after hydrofining is successively after high and low pressure is separated, enter separation column cutting, after cutting out light, heavy naphtha and kerosene, diesel oil distillate, the tail oil that Fractionator Bottom obtains enters hydrocracking reactor, under the effect of hydroisomerizing cracking catalyst, heavy ends is converted into intermediate oil product to greatest extent.Product and the hydrofining reaction product of hydrocracking reactor mix and successively after high and low pressure is separated, and enter separation column and carry out cutting and obtain object product.Its weak point is to adopt integrated form flow process, and flexibility of operation is less, and when producing low-coagulation diesel oil, diesel yield is on the low side.
CN200510068183.1 provides the processing method of a kind of Fischer-Tropsch synthetic hydrogenation upgrading, it is three components such as high temperature condensation product, low temperature cold condensate and synthetic wax hydrogenation respectively that Fischer-Tropsch synthesis natural separation is obtained, wherein high temperature condensation product and low temperature cold condensate are mixed into hydrotreating reactor, under hydrogen atmosphere (hydrogen dividing potential drop 2.0-15.0MPa) and Hydrobon catalyst effect, in 250-420 DEG C, the reaction such as hydrogenation deoxidation, olefin saturated occurs, the product after hydrofining enters separation column and is cut into petroleum naphtha, diesel oil and heavy oil fraction; Isomery hydrocracking reactor is entered after heavy oil fraction mixes with synthetic wax, isocracking reaction is there is in 300-450 DEG C under hydrogen atmosphere (2.0-15.0MPa) and catalyst action, isocracking reaction product obtains petroleum naphtha, diesel oil and tail oil fraction through fractionation cutting, tail oil fraction loops back isocracking reactor and continues cracking reaction, or as Lube basic oil material feedstocks.This method diesel product yield reaches more than 85wt%, and its cetane value is more than 80.Its weak point is that Fischer Tropsch condensate removes hydrofining reactor separately, and the easy coking of catalyzer, causes deactivation rate to be accelerated, and shortens the purification operations cycle; Synthetic wax does not enter hydrofining and directly enters hydrocracking, and causing hydrocracking to be invested increases; Meanwhile, heavy gas oil isomerization-visbreaking reactor is not set in the method, the low-coagulation diesel oil product of high yield cannot be obtained.
Summary of the invention
The object of this invention is to provide a kind of method Fischer-Tropsch synthetic being converted into petroleum naphtha, diesel oil and liquefied petroleum gas (LPG), be specially a kind of hydrocarbon that synthesized by indirect coal liquefaction and be converted into the method with economic benefit product.
A kind of method Fischer-Tropsch synthetic being converted into petroleum naphtha, diesel oil and liquefied petroleum gas (LPG) provided by the present invention, comprises the steps:
(1) Fischer-Tropsch oil, Fischer-Tropsch wax are mixed with hydrogen, enter in refining reaction device and carry out refining reaction;
(2) reaction product of described refining reaction enters to high pressure hot separator I and carries out gas-liquid separation; Liquid phase after described high pressure hot separator I is separated enters to thermal low-pressure separators I, and the gas phase after described high pressure hot separator I is separated enters to cold high pressure separator I;
Liquid phase after described thermal low-pressure separators I is separated enters to separation column I, and the gas phase after described thermal low-pressure separators I is separated enters to cold low separator I; Liquid phase after described cold high pressure separator I is separated enters to described cold low separator I; Liquid phase after described cold low separator I is separated enters to described separation column I;
(3) after described separation column I is separated, diesel oil, heavy gas oil and refining tail oil is obtained;
The gas that obtains is separated and raw naphtha enters stripper-reabsorber through described separation column I; Product at the bottom of described stripper-reabsorber tower enters petroleum naphtha stabilizer tower, and the tower top of described petroleum naphtha stabilizer tower obtains liquefied petroleum gas (LPG), obtains petroleum naphtha at the bottom of the tower of described petroleum naphtha stabilizer tower;
Described heavy gas oil enters pour point depression reactor and carries out pour point depression reaction;
Described refining tail oil enters cracking case and carries out cracking reaction;
(4) reaction product of described pour point depression reaction and the reaction product of described cracking reaction enter high pressure hot separator II and carry out gas-liquid separation; Liquid phase after described high-pressure separator II is separated enters thermal low-pressure separators II, and the gas phase after described high-pressure separator II is separated enters cold high pressure separator II;
Liquid phase after described thermal low-pressure separators II is separated enters separation column II, and the gas phase after described thermal low-pressure separators II is separated enters cold low separator II; Liquid phase after described cold high pressure separator II is separated enters described cold low separator II; Liquid phase after described cold low separator II is separated enters described separation column II;
(5) after described separation column II is separated, diesel oil is obtained;
The gas that obtains is separated and raw naphtha enters described stripper-reabsorber through described separation column II; Product at the bottom of described stripper-reabsorber tower enters described petroleum naphtha stabilizer tower, and the tower top of described petroleum naphtha stabilizer tower obtains liquefied petroleum gas (LPG), obtains petroleum naphtha at the bottom of the tower of described petroleum naphtha stabilizer tower.
In above-mentioned method, gas phase after described cold high pressure separator I is separated is divided into two strands of gases after circulating hydrogen compressor I boosts, wherein one gas enters in described refining reaction device, enters to described refining reaction device again after another strand of gas mixes with the hydrogen that new hydrogen gas compressor produces.
In above-mentioned method, gas phase after described cold high pressure separator II is separated is divided into three strands of gases after circulating hydrogen compressor II boosts, wherein two strands of gases enter in described cracking case and described pour point depression reactor respectively, enter respectively in described cracking case and described pour point depression reactor after the hydrogen that one gas and described new hydrogen gas compressor produce in addition mixes again.
In above-mentioned method, the gas phase of gas phase after being separated through described cold low separator II after described cold low separator I is separated enters in hydrogen gas recovering device,
The tail gas of described hydrogen gas recovering device enters in described stripper-reabsorber,
The hydrogen recovery rate of described hydrogen gas recovering device can reach 50 ~ 99%, and hydrogen purity can reach 70 ~ 99.99%.
In above-mentioned method, described separation column I and separation column II be all selected from following any one:
1) combination of stripping tower, atmospheric tower and vacuum distillation tower;
2) combination of stripping tower and atmospheric tower;
3) combination of atmospheric tower and vacuum distillation tower;
4) atmospheric tower;
Described atmospheric tower and/or vacuum distillation tower arrange one or more side-cut stripper.
In above-mentioned method, described hydrogen gas recovering device adopts membrane sepn mode and/or pressure-variable adsorption mode purifying hydrogen of hydrogen.
In above-mentioned method, in step (1), the temperature of described refining reaction can be 140 ~ 450 DEG C, and pressure can be 2.0 ~ 17.0MPa, and cumulative volume air speed can be 0.5 ~ 6h
-1, the entrance hydrogen to oil volume ratio of described refining reaction device can be 200 ~ 1000, and in preferred described step (1), refining reaction temperature is 300 ~ 400 DEG C, and pressure is 4.5 ~ 9.5MPa, and cumulative volume air speed is 1.0 ~ 4.0h
-1, reactor inlet hydrogen to oil volume ratio is 300 ~ 700, wherein " hydrogen to oil volume ratio " volume ratio that is the hydrogen that passes into and the described Fischer-Tropsch oil added and described Fischer-Tropsch wax summation.
In above-mentioned method, in step (2), the service temperature of described high pressure hot separator I can be 150 ~ 350 DEG C, and working pressure can be 2.0 ~ 17.0MPa; In preferred described step (2), the service temperature of high pressure hot separator I is 200 ~ 300 DEG C, and working pressure is 3.5 ~ 9.0MPa; And/or,
The service temperature of described cold high pressure separator I can be 20 ~ 100 DEG C, and working pressure can be 2.0 ~ 17.0MPa; The service temperature of preferred described cold high pressure separator I is 40 ~ 80 DEG C, and working pressure is 3.5 ~ 9.0MPa; And/or,
The service temperature of described thermal low-pressure separators I can be 150 ~ 350 DEG C, and working pressure can be 0.5 ~ 4.0MPa; The service temperature of preferred described thermal low-pressure separators I is 200 ~ 300 DEG C, and working pressure is 1.0 ~ 3.0MPa; And/or,
The service temperature of described cold low separator I can be 20 ~ 100 DEG C, and working pressure can be 0.5 ~ 4.0MPa, and the service temperature of preferred described cold low separator I is 40 ~ 80 DEG C, and working pressure is 1.0 ~ 3.0MPa.
In above-mentioned method, described in step (3) and (5), the number of theoretical plate of stripping tower can be 4 ~ 40, tower top temperature can be 60 ~ 180 DEG C, column bottom temperature can be 150 ~ 400 DEG C, working pressure can be 0.05 ~ 2.0MPa, and preferred described step (3) and (5) middle stripping tower number of theoretical plate are 8 ~ 15, and tower top temperature is 80 ~ 150 DEG C, column bottom temperature is 160 ~ 300 DEG C, and working pressure is 0.5 ~ 0.8MPa; Described atmospheric tower number of theoretical plate can be 10 ~ 60, tower top temperature is 60 ~ 200 DEG C, column bottom temperature can be 250 ~ 500 DEG C, working pressure can be 0.05 ~ 2.0MPa, preferred described atmospheric tower number of theoretical plate is 20 ~ 40, tower top temperature is 100 ~ 150 DEG C, and column bottom temperature is 270 ~ 370 DEG C, and working pressure is 0.1 ~ 0.5MPa; Described vacuum distillation tower number of theoretical plate can be 10 ~ 60, tower top temperature can be 30 ~ 150 DEG C, column bottom temperature can be 200 ~ 400 DEG C, working pressure can be 0 ~ 0.1MPa, preferred described vacuum distillation tower number of theoretical plate is 20 ~ 40, tower top temperature is 50 ~ 100 DEG C, and column bottom temperature is 250 ~ 350 DEG C, and working pressure is 0 ~ 0.05Mpa.
In above-mentioned method, in step (3), the temperature of described cracking reaction can be 200 ~ 500 DEG C, and pressure can be 2.0 ~ 18.0MPa, and cumulative volume air speed can be 0.5 ~ 4h
-1, the entrance hydrogen to oil volume ratio of described cracking case can be 300 ~ 1000, and in preferred described step (3), cracking reaction temperature is 280 ~ 450 DEG C, and pressure is 6.0 ~ 13.0MPa, cumulative volume air speed 1.0 ~ 3.5h
-1, cracking case entrance hydrogen to oil volume ratio 400 ~ 800; And/or,
The temperature of described pour point depression reaction can be 250 ~ 500 DEG C, and pressure can be 2.0 ~ 18.0MPa, and cumulative volume air speed can be 0.5 ~ 6h
-1, the entrance hydrogen to oil volume ratio of described pour point depression reactor can be 200 ~ 3000, and preferred described pour point depression temperature of reaction is 280 ~ 450 DEG C, and pressure is 6.0 ~ 13.0MPa, cumulative volume air speed 1.0 ~ 4.0h
-1, reactor inlet hydrogen to oil volume ratio 400 ~ 800; And/or,
In above-mentioned method, in step (4), the service temperature of described high pressure hot separator II is 200 ~ 350 DEG C, and working pressure is 2.0 ~ 18.0MPa, in preferred described step (4), the service temperature of high pressure hot separator II is 230 ~ 300 DEG C, and working pressure is 6.5 ~ 13.0MPa; And/or,
The service temperature of described cold high pressure separator II can be 20 ~ 100 DEG C, and working pressure can be 2.0 ~ 18.0MPa, and the service temperature of preferred described cold high pressure separator II is 40 ~ 80 DEG C, and working pressure is 6.0 ~ 13.0MPa; And/or,
The service temperature of described thermal low-pressure separators II can be 180 ~ 350 DEG C, and working pressure can be 0.5 ~ 4.0MPa, and the service temperature of preferred described thermal low-pressure separators II is 200 ~ 300 DEG C, and working pressure is 1.0 ~ 3.0MPa; And/or,
The service temperature of described cold low separator II can be 20 ~ 100 DEG C, and working pressure can be 0.5 ~ 4.0MPa, and the service temperature of preferred described cold low separator II is 40 ~ 80 DEG C, and working pressure is 1.0 ~ 3.0MPa.
The number of theoretical plate of step (3) and (5) described stripper-reabsorber can be 5 ~ 40, and tower top temperature can be-40 ~ 120 DEG C, and column bottom temperature can be-40 ~ 250 DEG C, and working pressure can be 0.5 ~ 6.0MPa; Preferred described step (3) and (5) middle stripper-reabsorber number of theoretical plate are 9 ~ 25, and tower top temperature is 30 ~ 60 DEG C, and column bottom temperature is 60 ~ 150 DEG C, and working pressure is 0.5 ~ 2.0MPa; The number of theoretical plate of described petroleum naphtha stabilizer tower can be 10 ~ 60, and tower top temperature can be 30 ~ 150 DEG C, and column bottom temperature can be 150 ~ 300 DEG C, and working pressure can be 0.3 ~ 2.0MPa; Preferred described petroleum naphtha stabilizer tower number of theoretical plate is 25 ~ 35, and tower top temperature is 40 ~ 80 DEG C, and column bottom temperature is 160 ~ 250 DEG C, and working pressure is 0.5 ~ 1.5MPa.
In above-mentioned method, make-up hydrogen compressor top hole pressure can be 2.5 ~ 20.0MPa, and preferred described make-up hydrogen compressor top hole pressure is 5.0 ~ 15.0MPa.
Tool of the present invention has the following advantages:
(1) refining reaction adopts hydrofining once by hydrogen addition technology, and cracking reaction adopts For Extinction Hydrocracking technology, and pour point depression reaction is once by hydrodewaxing technology;
(2) refining reaction product, cracked reaction product and pour point depression reaction product are separated the separate mode adopting hot high score, low point of heat, cold high score and cold low point;
(3) cracking reaction and pour point depression reaction share a set of product separation system, product fractionation system and recycle hydrogen compression system;
(4) refining reaction and cracking reaction are provided with product separation system and product fractionation system respectively;
(5) absorbing-stabilizing system is provided with, the liquefied petroleum gas (LPG) in gas recovery and petroleum naphtha;
(6) refining low point of gas and cracking low point of gas are provided with hydrogen recovery scheme.
Accompanying drawing explanation
Fig. 1 is that F-T synthesis hydrocarbon is converted into the schematic flow sheet of petroleum naphtha, diesel oil and liquefied petroleum gas (LPG) by the present invention;
Fig. 2 is the schematic flow sheet of embodiment 1; Wherein,
1-refining reaction device; 2-high pressure hot separator I; 3-cold high pressure separator I; 4-thermal low-pressure separators I; 5-cold low separator I; 6-separation column I; 6-1-refining separation column; 6-2-refining normal line diesel oil stripping tower; 6-3-refining normal two wires diesel oil stripping tower; 6-4-refining vacuum distillation tower; 6-5-refining Top of Vacuum Tower pumped vacuum systems; 7-make-up hydrogen compressor; 8-circulating hydrogen compressor I; 9-cracking case; 10-high pressure hot separator II; 11-cold high pressure separator II; 12-thermal low-pressure separators II; 13-cold low separator II; 14-separation column II; 14-1-cracking separation column; The normal line diesel oil stripping tower of 14-2-cracking; 14-3-cracking normal two wires diesel oil stripping tower; 14-4-cracked vacuum tower; 14-5-cracked vacuum tower top pumped vacuum systems; 15-circulating hydrogen compressor II; 16-pour point depression reactor; 17-hydrogen gas recovering device; 18-stripper-reabsorber; 19-petroleum naphtha stabilizer tower; 20-rich gas compressor; 21-heavy gas oil digester; 101-Fischer-Tropsch oil; 102-Fischer-Tropsch wax; 103-hydrogen make-up; 104-refining heavy gas oil; 105-refining tail oil; 106(106 ?1,106 ?2,106 ?3,106 ?4), 107(107 ?1,107 ?2,107 ?3,107 ?4)-stripped vapor; 111,112-Top of Vacuum Tower vacuumizes steam; 121-diesel oil; 122-liquefied petroleum gas (LPG); 123-petroleum naphtha; 124-go back crude oil; 125-recover hydrogen; 126-dry gas; 127-subtract top gas; 131,132,133-sulfur-bearing oily(waste)water; 141,142-oily(waste)water.
Embodiment
The experimental technique used in following embodiment if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
Method of the present invention is explained further below in conjunction with Fig. 1.
(1) refining reaction and product separation part
From Fischer-Tropsch oil 101 oil and the Fischer-Tropsch wax 102 of F-T synthesis device, be mixed into refining reaction device 1 with hydrogen, olefin saturated and oxygenatedchemicals occur under hydrogen, Hydrobon catalyst and certain temperature, pressure and the hydrofining reaction such as to remove.Refining reaction product first carries out gas-liquid separation through high pressure hot separator I 2, reduce phlegm and internal heat after the step-down of hot high score oil light pressure separator I 4, cold high pressure separator 3 is gone to carry out gas, liquid, water three phase separation after the heat exchange of hot high score gas and cooling, cold high pressure separator 3 top gas is divided into two strands after circulating hydrogen compressor I 8 boosts, one removes refining reaction device 1 as quenching hydrogen, and one is mixed into mixed hydrogen oil again and removes refining reaction device 1 with refining reaction raw material after mixing with the new hydrogen of part from make-up hydrogen compressor 7.Separation column I 6 is removed after liquid step-down in thermal low-pressure separators 4; Remove cold low separator 5 after the gas cooling of thermal low-pressure separators 4, the water in cold high pressure separator 3, oil enter cold low separator 5 after step-down, and cold low separator 5 gas dehydrogenation gas recovering device 17, cold low point of oil removes separation column I 6.
(2) refining fractionating section
Refining heat low point of oil and refining cold low point of oil enter separation column I 6, separation column I 6 is separated the gas that obtains and refining petroleum naphtha goes in stripper-reabsorber 18, the diesel oil generated is product diesel oil, and the heavy gas oil of generation removes pour point depression reactor 16, and the refining tail oil of generation removes cracking case 9.
(3) cracking reaction, pour point depression reaction and product separation part
Refining tail oil 105, cracking unconverted oil and mix and be heated to certain temperature through heat exchange and process furnace after hydrogen mixes and go, in cracking case 9, in cracking case 9, hydrocracking reaction to occur.Refining heavy gas oil 104 removes pour point depression reactor 16 with mix to be heated to after certain temperature through heat exchange and process furnace after hydrogen mixes, and in pour point depression reactor 16, generation hydrodewaxing reacts.Cracked reaction product and pour point depression reaction product are mixed into high pressure hot separator II 10 after heat exchange respectively and carry out gas-liquid separation, the oily light pressure separator II 12 that reduces phlegm and internal heat after reducing pressure of hot high score, hot high score gas goes cold anticyclone to be separated II device 11 to carry out gas after cooling, liquid is separated, the top gas of cold high pressure separator II 11 goes circulating hydrogen compressor II 15 to boost, cracking recycle hydrogen after boosting is divided into three strands, wherein two strands are removed cracking case 9 and pour point depression reactor 16 as quenching hydrogen, two portions are further divided in addition after one and the new hydrogen mixing after boosting, wherein a part mixes cracking case 9 with cracking reaction charging, another part mixes pour point depression reactor 16 with pour point depression raw material.Go after liquid step-down in thermal low-pressure separators II 12 in separation column II 14; Cold low separator II 13 is removed after the gas cooling of thermal low-pressure separators II 12, oil in cold high pressure separator II 11 enters cold low separator II 13 after step-down, the gas dehydrogenation gas recovering device 17 of cold low separator II 13, the cold low point of oil of cracking removes separation column II 14.
(4) cracking fractionating section
The heat of cracking low point of oil and the cold low point of oil of cracking enter separation column II 14, the gas that separation column II 14 produces and pressure naphtha go in stripper-reabsorber 18, the diesel oil generated is product diesel oil, and the heavy gas oil of generation removes fischer-tropsch catalysts reducing apparatus through desulfurization, and unconverted oil returns in cracking case 9.
(5) compression section
Hydrogen make-up divides two strands after make-up hydrogen compressor 7 boosts, and one goes in refining reaction device 1, and another stock goes in cracking case 9 with in pour point depression reactor 16.
(6) hydrogen recovery part
Refine in low point of gas and cracking low point of gas mixing dehydrogenation gas recovering device 17, the recover hydrogen obtained through hydrogen gas recovering device goes out device, and tail gas goes stripper-reabsorber to reclaim liquefied gas.
(7) Vapor recovery unit part
The overhead gas of separation column I 6 and separation column II 14 removes stripper-reabsorber 18 through boosting, the tail gas that hydrogen gas recovering device 17 produces, refining petroleum naphtha and pressure naphtha also remove stripper-reabsorber 18, stripper-reabsorber 18 overhead gas goes out device as dry gas, deethanizing oil de-stone cerebrol stabilizer tower 19 at the bottom of tower, obtain liquefied gas product from petroleum naphtha stabilizer tower 19 tower top, at the bottom of tower, obtain naphtha product and cyclic absorption agent.
Explain the present invention further by way of example below, but the present invention is not limited to these embodiments.
Fischer-Tropsch oil used in this embodiment and the main character of Fischer-Tropsch wax are in table 1;
The main character of table 1 Fischer-Tropsch oil and Fischer-Tropsch wax
According to the flow process shown in Fig. 2, from Fischer-Tropsch oil stream stock 101 and the Fischer-Tropsch wax stream stock 102 of F-T synthesis device, refining reaction device 1 is mixed into hydrogen, olefin saturated oxygenatedchemicals occurs under hydrogen, Hydrobon catalyst and temperature 305 DEG C, pressure 8.0MPaG and the hydrofining reaction such as to remove, cumulative volume air speed is 2.0h
-1, reactor inlet hydrogen to oil volume ratio is 350.Refining reaction product first carries out gas-liquid separation through high pressure hot separator I 2 under 254 DEG C and 7.45MPaG pressure, refining hot high score oil to reduce phlegm and internal heat light pressure separator I 4 through being depressurized to 2.4MPaG, refining hot high score gas goes cold high pressure separator 3 to carry out gas, liquid, water three phase separation through being cooled to 50 DEG C, the top gas of cold high pressure separator 3 is after circulating hydrogen compressor I 8 boosts to 8.85MPaG and boost to the new hydrogen mixing of the part of 9.3MPaG from make-up hydrogen compressor 7 and remove refining reaction device 1, removes separation column I 6 after the liquid step-down in thermal low-pressure separators I 4; The gas cooling to 50 DEG C of thermal low-pressure separators I 4 removes cold low separator I 5, water in cold high pressure separator I 3, oil enter in cold low separator I 5 through being depressurized to 2.3MPaG, the gas dehydrogenation gas recovering device 17 that cold low separator I 5 produces, refining cold low point of oil removes separation column I 6.
Refining heat low point of oil and refining cold low point of oil are mixed into refining separation column charging flash tank after heat exchange, flash distillation is carried out under 283 DEG C and 0.37MPaG condition, flash gas directly removes refining separation column 6-1, flashed liquid is heated to 355 DEG C through process furnace and removes refining separation column 6-1, refining separation column 6 ?1 number of theoretical plate be 26, tower top temperature is 120 DEG C, column bottom temperature is 341 DEG C, working pressure is 0.15MPaG, refining separation column 6-1 overhead gas and refining petroleum naphtha remove stripper-reabsorber 18, a normal line diesel oil obtains product diesel oil through a refining normal line diesel oil stripping tower 6-2, normal two wires diesel oil also obtains product diesel oil through refining normal two wires diesel oil stripping tower 6-3, at the bottom of refining separation column 6-1 tower, oil removes refining vacuum distillation tower 6-4 after process furnace is heated to 333 DEG C.Refining vacuum distillation tower number of theoretical plate is 26, and tower top temperature is 65 DEG C, and column bottom temperature is 309 DEG C, working pressure is 80mmHG, refining subtract top gas and removes process furnace, and refining vacuum 1st side cut diesel oil is product diesel oil, refining second line of distillation diesel oil removes pour point depression reactor 16, and refining tail oil removes cracking case 9.
Refining tail oil, cracking unconverted oil and mix and be heated to 350 DEG C through process furnace after hydrogen mixes and remove cracking case 9, in the reactor hydrocracking reaction occurs, temperature of reaction is 354 DEG C, and pressure is 8.0MPaG, and cumulative volume air speed is 2.0h
-1, reactor inlet hydrogen to oil volume ratio is 500.Refining second line of distillation diesel oil removes pour point depression reactor 16 with mix after hydrogen mixes after process furnace is heated to 349 DEG C, and in pour point depression reactor 16, generation hydrodewaxing reacts, and temperature of reaction is 353 DEG C, and pressure is 7.55MPaG, and cumulative volume air speed is 2.0h
-1, reactor inlet hydrogen to oil volume ratio is 500.Cracked reaction product and pour point depression reaction product mix laggard high pressure hot separator II 10 at 261 DEG C, gas-liquid separation is carried out under 7.25MPaG pressure, heat of cracking high score oil is depressurized to 2.4MPaG and reduces phlegm and internal heat light pressure separator II 12, heat of cracking high score gas goes cold high pressure separator II 11 to carry out gas through being cooled to 50 DEG C, liquid is separated, cold high pressure separator II 11 top gas boosts to 9.0MPaG through circulating hydrogen compressor II 15 and cracking reaction part and pour point depression reactive moieties are gone in the new hydrogen mixing after make-up hydrogen compressor 7 boosts, cracking separation column 14-1 is removed after liquid step-down in thermal low-pressure separators II 12, the gas cooling to 50 DEG C of thermal low-pressure separators II 12 removes cold low separator II 13, oil in cold high pressure separator II 11 is depressurized to 2.3MPaG and removes cold low separator II 13, the gas dehydrogenation gas recovering device 17 of cold low separator II 13, the cold low point of oil of cracking removes cracking fractionating section.
The heat of cracking low point of oil and the cold low point of oil of cracking are mixed into cracking separation column charging flash tank after heat exchange, flash distillation is carried out under 264 DEG C and 0.18MPaG condition, flash gas directly removes cracking separation column 14-1, flashed liquid is heated to 355 DEG C through process furnace and removes cracking separation column 14-1, cracking separation column number of theoretical plate is 26, tower top temperature is 165 DEG C, column bottom temperature is 304 DEG C, working pressure is 0.1MPaG, cracking fractionation overhead gas and pressure naphtha go Vapor recovery unit part, a normal line diesel oil and normal two wires diesel oil obtain diesel product through a cracking normal line diesel oil stripping tower 14-2 and cracking normal two wires diesel oil stripping tower 14-3 respectively, at the bottom of the tower of cracking separation column 14-1, oil removes cracked vacuum tower 14-4 through decompression.Cracked vacuum tower number of theoretical plate is 26, and tower top temperature is 65 DEG C, and column bottom temperature is 309 DEG C, and working pressure is 80mmHG.Cracking subtracts top gas and refining subtract top gas mixed flow stock 127 and remove process furnace, cracking vacuum 1st side cut diesel oil is that the normal line diesel oil of product diesel oil and cracking, cracking normal two wires diesel oil, a refining normal line diesel oil, refining normal two wires diesel oil, refining vacuum 1st side cut diesel oil mixed flow stock 121 are as finished diesel fuel, cracking second line of distillation diesel oil removes fischer-tropsch catalysts reducing apparatus (not shown) through desulfurization as going back crude stream stock 124, and at the bottom of cracked vacuum tower, oil returns cracking reaction part as turning oil.
Refining low point of gas and cracking low point of gas mixing dehydrogenation gas recovering device 17, the recover hydrogen stream stock 125 obtained through hydrogen gas recovering device 17 goes out device, and tail gas removes stripper-reabsorber 18 Ethylene recov liquefied oil gas.
Refining separation column top gas, cracking separation column top gas, hydrogen recovery partial tail gas, refining petroleum naphtha and pressure naphtha remove stripper-reabsorber, stripper-reabsorber number of theoretical plate is 17, tower top temperature is 43 DEG C, column bottom temperature is 123 DEG C, working pressure is 0.73MPaG, obtain dry gas stream stock 126 from stripper-reabsorber top and go out device, deethanizing oil de-stone cerebrol stabilizer tower 19 at the bottom of tower, petroleum naphtha stabilizer tower number of theoretical plate is 25, tower top temperature is 63 DEG C, column bottom temperature is 193 DEG C, working pressure is 0.99MPaG, liquefied gas product flow stock 122 is obtained from petroleum naphtha stabilizer tower tower top, the petroleum naphtha part obtained at the bottom of tower returns stripper-reabsorber as cyclic absorption agent, all the other are as naphtha product stream stock 123.
In above-described embodiment, the mass rate of each raw material and product is as shown in table 2.
Table 2 embodiment 1 Raw and product data (unit: kg/h)
In above-described embodiment, the main physical parameter of the liquefied petroleum gas (LPG) obtained, petroleum naphtha and diesel oil is as shown in table 3, table 4 and table 5, and can be learnt by data in table, the liquefied petroleum gas (LPG) that the present invention obtains, petroleum naphtha and diesel oil are qualified product.
The main physical parameter of table 3 liquefied petroleum gas product
The main physical parameter of table 4 diesel product
The main physical parameter of table 5 naphtha product
Claims (10)
1. Fischer-Tropsch synthetic is converted into a method for petroleum naphtha, diesel oil and liquefied petroleum gas (LPG), comprises the steps:
(1) Fischer-Tropsch oil, Fischer-Tropsch wax are mixed with hydrogen, enter in refining reaction device and carry out refining reaction;
(2) reaction product of described refining reaction enters to high pressure hot separator I and carries out gas-liquid separation; Liquid phase after described high pressure hot separator I is separated enters to thermal low-pressure separators I, and the gas phase after described high pressure hot separator I is separated enters to cold high pressure separator I;
Liquid phase after described thermal low-pressure separators I is separated enters to separation column I, and the gas phase after described thermal low-pressure separators I is separated enters to cold low separator I; Liquid phase after described cold high pressure separator I is separated enters to described cold low separator I; Liquid phase after described cold low separator I is separated enters to described separation column I;
(3) after described separation column I is separated, diesel oil, heavy gas oil and refining tail oil is obtained;
The gas that obtains is separated and raw naphtha enters stripper-reabsorber through described separation column I; Product at the bottom of described stripper-reabsorber tower enters petroleum naphtha stabilizer tower, and the tower top of described petroleum naphtha stabilizer tower obtains liquefied petroleum gas (LPG), obtains petroleum naphtha at the bottom of the tower of described petroleum naphtha stabilizer tower;
Described heavy gas oil enters pour point depression reactor and carries out pour point depression reaction;
Described refining tail oil is circulated to cracking case and carries out cracking reaction;
(4) reaction product of described pour point depression reaction and the reaction product of described cracking reaction enter high pressure hot separator II and carry out gas-liquid separation; Liquid phase after described high pressure hot separator II is separated enters thermal low-pressure separators II, and the gas phase after described high-pressure separator II is separated enters cold high pressure separator II;
Liquid phase after described thermal low-pressure separators II is separated enters separation column II, and the gas phase after described thermal low-pressure separators II is separated enters cold low separator II; Liquid phase after described cold high pressure separator II is separated enters described cold low separator II; Liquid phase after described cold low separator II is separated enters described separation column II;
(5) after described separation column II is separated, diesel oil is obtained;
The gas that obtains is separated and raw naphtha enters described stripper-reabsorber through described separation column II; Product at the bottom of described stripper-reabsorber tower enters described petroleum naphtha stabilizer tower, and the tower top of described petroleum naphtha stabilizer tower obtains liquefied petroleum gas (LPG), obtains petroleum naphtha at the bottom of the tower of described petroleum naphtha stabilizer tower.
2. method according to claim 1, it is characterized in that: the gas phase after described cold high pressure separator I is separated is divided into two strands of gases after circulating hydrogen compressor I boosts, wherein one gas enters in described refining reaction device, enters to described refining reaction device again after another strand of gas mixes with the hydrogen that new hydrogen gas compressor produces.
3. method according to claim 1 and 2, it is characterized in that: the gas phase after described cold high pressure separator II is separated is divided into three strands of gases after circulating hydrogen compressor II boosts, wherein two strands of gases enter in described cracking case and described pour point depression reactor respectively, enter respectively in described cracking case and described pour point depression reactor after the hydrogen that one gas and described new hydrogen gas compressor produce in addition mixes again.
4. method according to claim 1 and 2, is characterized in that: the gas phase of gas phase after being separated through described cold low separator II after described cold low separator I is separated enters in hydrogen gas recovering device,
The tail gas of described hydrogen gas recovering device enters in described stripper-reabsorber.
5. method according to claim 1 and 2, is characterized in that: described separation column I and separation column II be all selected from following any one:
1) combination of stripping tower, atmospheric tower and vacuum distillation tower;
2) combination of stripping tower and atmospheric tower;
3) combination of atmospheric tower and vacuum distillation tower;
4) atmospheric tower;
Described atmospheric tower and/or vacuum distillation tower arrange one or more side-cut stripper.
6. method according to claim 1 and 2, is characterized in that: in step (1), and the temperature of described refining reaction is 140 ~ 450 DEG C, and pressure is 2.0 ~ 17.0MPa, and cumulative volume air speed is 0.5 ~ 6h
-1, the entrance hydrogen to oil volume ratio of described refining reaction device is 200 ~ 1000.
7. method according to claim 1 and 2, is characterized in that: in step (2), and the service temperature of described high pressure hot separator I is 150 ~ 350 DEG C, and working pressure is 2.0 ~ 17.0MPa; And/or,
The service temperature of described cold high pressure separator I is 20 ~ 100 DEG C, and working pressure is 2.0 ~ 17.0MPa; And/or,
The service temperature of described thermal low-pressure separators I is 150 ~ 350 DEG C, and working pressure is 0.5 ~ 4.0MPa; And/or,
The service temperature of described cold low separator I is 20 ~ 100 DEG C, and working pressure is 0.5 ~ 4.0MPa.
8. method according to claim 5, is characterized in that: in step (3) and (5), the number of theoretical plate of described stripping tower is 4 ~ 40, and tower top temperature is 60 ~ 180 DEG C, and column bottom temperature is 150 ~ 400 DEG C, and working pressure is 0.05 ~ 2.0MPa;
Described atmospheric tower number of theoretical plate is 10 ~ 60, and tower top temperature is 60 ~ 200 DEG C, and column bottom temperature is 250 ~ 500 DEG C, and working pressure is 0.05 ~ 2.0MPa;
Described vacuum distillation tower number of theoretical plate is 10 ~ 60, and tower top temperature is 30 ~ 150 DEG C, and column bottom temperature is 200 ~ 400 DEG C, and working pressure can be 0 ~ 0.1MPa.
9. method according to claim 1 and 2, is characterized in that: in step (3), and the temperature of described cracking reaction is 200 ~ 500 DEG C, and pressure is 2.0 ~ 18.0MPa, and cumulative volume air speed is 0.5 ~ 4h
-1, the entrance hydrogen to oil volume ratio of described cracking case is 300 ~ 1000; And/or,
The temperature of described pour point depression reaction is 250 ~ 500 DEG C, and pressure is 2.0 ~ 18.0MPa, and cumulative volume air speed is 0.5 ~ 6h
-1, the entrance hydrogen to oil volume ratio of described pour point depression reactor is 200 ~ 3000; And/or,
In step (4), the service temperature of described high pressure hot separator II is 200 ~ 350 DEG C, and working pressure is 2.0 ~ 18.0MPa; And/or,
The service temperature of described cold high pressure separator II is 20 ~ 100 DEG C, and working pressure is 2.0 ~ 18.0MPa; And/or,
The service temperature of described thermal low-pressure separators II is 180 ~ 350 DEG C, and working pressure is 0.5 ~ 4.0MPa; And/or,
The service temperature of described cold low separator II is 20 ~ 100 DEG C, and working pressure is 0.5 ~ 4.0MPa.
10. method according to claim 1 and 2, is characterized in that: in step (3) and (5), the number of theoretical plate of described stripper-reabsorber is 5 ~ 40, and tower top temperature is-40 ~ 120 DEG C, and column bottom temperature is-40 ~ 250 DEG C, and working pressure is 0.5 ~ 6.0MPa;
The number of theoretical plate of described petroleum naphtha stabilizer tower is 10 ~ 60, and tower top temperature is 30 ~ 150 DEG C, and column bottom temperature is 150 ~ 300 DEG C, and working pressure is 0.3 ~ 2.0MPa.
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| CN105778995B (en) * | 2016-04-18 | 2018-03-20 | 武汉凯迪工程技术研究总院有限公司 | The method and its equipment of Low Temperature Fischer Tropsch artificial oil and inferior feedstock oil Unionfining production fine-quality diesel oil |
| CN108203598A (en) * | 2017-12-15 | 2018-06-26 | 赛鼎工程有限公司 | A kind of technique of F- T synthesis light hydrocarbon hydrofinishing |
| CN108003935B (en) * | 2017-12-15 | 2020-06-16 | 神华集团有限责任公司 | Method for producing clean diesel oil by Fischer-Tropsch synthesis of light and heavy product combination |
| CN108165307A (en) * | 2017-12-15 | 2018-06-15 | 赛鼎工程有限公司 | A kind of technique of Fischer-Tropsch synthesis of heavy hydrocarbon hydrofinishing |
| CN111378491B (en) * | 2018-12-28 | 2021-08-31 | 中国石油化工股份有限公司 | Inferior heavy oil hydrotreating process |
| CN113046126B (en) * | 2021-02-24 | 2022-11-15 | 中科合成油工程有限公司 | Method for improving diesel oil yield of process for producing diesel oil by Fischer-Tropsch synthesis oil |
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