CN107267212A - A kind of separating technology of F- T synthesis crude product - Google Patents
A kind of separating technology of F- T synthesis crude product Download PDFInfo
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- CN107267212A CN107267212A CN201710658981.2A CN201710658981A CN107267212A CN 107267212 A CN107267212 A CN 107267212A CN 201710658981 A CN201710658981 A CN 201710658981A CN 107267212 A CN107267212 A CN 107267212A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
Abstract
The present invention relates to a kind of separating technology of F- T synthesis crude product, the technique includes oil product crude separation, oil hydrogenation, lighter hydrocarbons essence point, wax hydrogenation, cerotin and graded multiple processing steps, according to the difference of F- T synthesis crude product synthesis temperature, a variety of high value added products such as the serial wax of naphtha, pentane, n-hexane, normal heptane, normal octane, C50, C70, C80, H1 and the serial waxes of H105 of varying number can be obtained, the present invention has the added value for improving F- T synthesis crude product, technological process is simple, easily realizes the advantage of industrialized production.
Description
Technical field
The invention belongs to a kind of separating technology of F- T synthesis crude product, specifically a kind of F- T synthesis crude product production
LPG, a variety of alkane and wax separating technology.
Background technology
With increasingly exhausted and to environmental protection consciousness the continuous enhancing of the limited petroleum resources in the world, research is with finding ring
The substitute of the friendly petroleum-based energy in border turns into one of direction that world-technology is developed.Coal passes through F- T synthesis (Fischer-
Tropsch Synthesis) reaction, it is converted into oily or other chemical products, it is possible to resolve petroleum resources shortage, meets national economy
Rapid growth has obtained faster development to the demand of the energy.
Fischer-Tropsch synthetic can obtain the higher product of a variety of added values by secondary operation.CN 101230290 is disclosed
One kind is using Fischer Tropsch waxes as raw material, the method for production solvent naphtha, lube base oil and wax.This method satisfies hydrogenated olefin
Through being distillated into, light, weighing two cuts, (end point of distillation is less than 380 DEG C to 550 DEG C and initial boiling point with the Fischer Tropsch waxes after, deoxidation
More than 380 DEG C to 550 DEG C of two kinds of cuts), wherein, the secondary hydrofinishing of double distilled lease making is returned after decolourizing as the food wax of high-quality
Receive；Light fraction is in the presence of hydroisomerisation catalysts, hydrogenated isomerization conversion and further hydrofinishing and distillation point
From the solvent naphtha and lube base oil that can obtain high-quality.US 5882505 discloses a kind of using counter-current reactor conversion boiling point
Fischer Tropsch waxes production lube base oil method more than 370 DEG C, including：Exist and hygrogenating isomerization reaction in hydrogen-containing gas
Under the conditions of, raw material is contacted in fixed bed reactors with hydroisomerisation catalysts；Under Hydrodewaxing reaction condition, it will add
Product after hydrogen isomerization reaction is contacted at least one fixed bed reactors with catalyst for hydrogenation de-waxing, wherein, it is described to add
Hydrogen isomerization reaction product and hydrogen-containing gas reverse flow.CN 1364188A disclose a kind of preparation side of lube base oil
Method, this method includes to be obtained by fischer tropsch process and the synthetic wax without progress hydroisomerization processing is with least containing hydrogenation group
Point, the catalysis of the aluminosilicate zeolites crystallite of dealuminzation and the basic low in acidity refractory oxide combination agent material without aluminum oxide
Agent is contacted.
But US 5882505 and CN 1364188A is main for the purpose of producing lube base oil, because heavy wax exists
It is easier to occur cracking reaction and change into small molecule on zeolite, using the method for similar above two patent, can not only obtains
To high-quality wax, while also little to the yield contribution for improving lube base oil；Although and patent CN 101230290 is by Fischer-Tropsch
Synthetic wax separated before hygrogenating isomerization reaction is carried out goes out heavy distillat therein, obtains the heavy wax component of high-quality simultaneously
Substantially reduce because heavy wax is easier excessively lighting caused by cracking, improve the added value of Fischer Tropsch waxes, but should
Method is separated using the method for vacuum distillation to wax, and vacuum rectification tower bottom temperature is up to 350~400 DEG C, and material exists
The tower reactor high temperature lower residence time is longer, and thermal cracking easily occurs for hydrocarbon component and coking, causes to remove the high-melting-point obtained after light component
The quality of wax is not high.
The F- T synthesis waxy stone of Erdos coal liquifaction branch company of Shenhua and the production of Shanxi Lu An coal liquifactions company mainly leads to
Hydrogenation is crossed to produce the products such as gasoline, diesel oil.However, when F- T synthesis waxy stone is cracked into gasoline, diesel product, process
Condition is harsher；And according to investigations, the price of in the market diesel oil per ton is between 8600~8700 yuan, and F- T synthesis per ton is thick
The price of wax so not only reduces the value of the product of wax between 8000~9000 yuan by process, and adds
Processing cost, does not calculate economically.The yield of another aspect China paraffin primary product is high, the special wax of high economic value and
Special wax product is few, relies primarily on import.And Fischer-Tropsch wax is mainly by relative molecular mass in 500-1000 straight chain, the height of saturation
Carbon alkane is constituted, and this just imparts the fine crystal structure of this chemicals, high-melting-point, narrow melting range, low oil content, low pin
In-degree, low mobility, low melting viscosity, hard, wear-resisting and stability are high, the lower carbon number hydrocarbons component in Fischer Tropsch waxes are separated de-
Except the fusing point of wax can be improved, fusing point is produced up to more than 100 DEG C of high melting-point wax, this high melting-point wax is in thermosol, plastics, oil
There is the purposes of uniqueness in the fields such as ink, coating, and economic value is very high.Therefore exploitation carries out the new work of deep processing to F- T synthesis waxy stone
Skill is imperative.
Chinese patent CN 104673383 discloses a kind of method that high melting-point wax is produced by Fischer-Tropsch synthetic, raw material thing
Stream initially enters the first distillation unit, is evaporated under certain temperature and pressure, and feed stream is divided into wax oil cut logistics and again
Cut logistics；Heavy distillat logistics enters after-fractionating unit, is evaporated under certain temperature and pressure, by heavy distillat logistics point
Into middle wax logistics and high melting-point wax logistics；The height that high melting-point wax logistics enters with hydrogen gas stream after hydrofinishing unit, hydrogenation
Fusing point wax is divided into two strands of the first logistics and hydrogenation high melting-point wax logistics；It is hydrogenated with high melting-point wax logistics and enters the 3rd distillation unit,
Evaporated under certain temperature and pressure, hydrogenation high melting-point wax logistics is divided into the first high melting-point wax logistics and the second high melting-point wax
Logistics, but the patent directly using obtained wax oil as product, not to wax oil carry out essence point so that the wax oil product add
Value is little.The B of patent CN 104178219 disclose a kind of method that F- T synthesis waxy stone produces microwax, first to F- T synthesis
Waxy stone carries out demetalization processing, obtains demetalization waxy stone；Hydrofinishing processing is carried out to demetalization waxy stone again, hydrofinishing is obtained
Product；Then separating treatment is carried out to hydrotreated product, obtains microwax.It is miscellaneous that this method needs not move through sulphur removal, nitrogen, aromatic hydrocarbons etc.
The step of matter, it is directly over removing the metallic catalyst carried secretly in F- T synthesis waxy stone, then carries out after hydrofinishing processing, will
Light wax component in obtained hydrotreated product is separated, you can it is low to obtain oil content, sulphur, nitrogen, oxygen, metal impurities into
Point few microwax, the patent remain unchanged using vacuum distillation by the way of, be easily caused the product of the wax obtained after removing light component
Matter is not high.
Above-mentioned Patents or the product for obtaining lubricating oil, base oil and blended wax, do not carry out essence point to wax；Or
The high melting-point wax product and mixed gatch of three kinds of different models are obtained, essence point is not carried out to wax oil；It is not a kind of at present right
Oil from Fischer-Tropsch synthesis " eating dry squeeze only " obtains the technique of a variety of high value added products, therefore under current market situation, needs badly
Develop a kind of technique of F- T synthesis crude oil product essence separation production multiple product.
The content of the invention
The technical problem to be solved in the present invention is to be given birth in view of the shortcomings of the prior art there is provided one kind by F- T synthesis crude product
Produce the separating technology of LPG, a variety of alkane and wax.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of separating technology of F- T synthesis crude product, the process uses following steps：
(1) raw material crude separation
F- T synthesis crude product initially enters gas removal tower, and gas removal column overhead distillates CO, H2、CO2、N2、H2O、
CH4, C2 and a small amount of C3, C4 on-condensible gas, gas removal tower bottom of towe distillates more than C2 heavy constituent, and the heavy constituent delivers to LPG
Knockout tower is separated, and LPG separation column overhead distillates LPG products, and more than the C4 heavy constituents that LPG product tower bottom of towe is distillated deliver to wax
Knockout tower is separated, and wax knockout tower isolates C5~C19 oil distillates and more than C19 wax fractions, and wax separation column overhead is distillated
C5~C19 oil distillates are separated after oily hydrogenation plant hydrogenation into naphtha splitter, and naphtha splitter tower top evaporates
C5~C8 the light components gone out deliver to the essence point that light component knockout tower carries out lighter hydrocarbons, and naphtha splitter bottom C9~C19 heavy constituents are done
Tank field storage is delivered to for cetane improver product；
(2) essence of lighter hydrocarbons point
C5~C6 light components that light component separation column overhead is distillated are separated into C5 knockout towers, and C5 light components are from C5 points
Distillated from column overhead, C6 heavy constituents are separated from C5 knockout tower bottom of towe, C5 light components are purified into pentane purifying column, are obtained
Purity is more than 99.9wt% pentane product, and C6 heavy constituents enter n-hexane purifying column, obtains purity and is more than 99.9wt%'s
Normal hexane product, accessory substance isopentane and isohexane after purification enter blending tank；
Light component knockout tower bottom of towe C7~C8 heavy constituents are separated into C7 knockout towers, separate what column overhead came out from C7
C7 components are purified into normal heptane purifying column, the normal heptane product that purity is more than 99.9wt% are obtained, from C7 knockout towers 12
The heavy constituent that bottom of towe comes out is separated into C8 knockout towers, and the C8 components come out from C8 separation column overhead are purified into normal octane
Tower is purified, and obtains the normal octane product that purity is more than 99.9wt%, the purification of normal octane purifying column and normal heptane purifying column
Accessory substance isoheptane and isooctane deliver to blending tank, and more than the C8 components that C8 knockout tower bottom of towe is distillated equally are improved as hexadecane
Agent product delivers to tank field storage；
(3) essence of wax point
The waxy stone cut that wax knockout tower bottom of towe is distillated enters No. 1 molecular distillation apparatus after wax hydrogenation plant hydrogenation to be carried out
Essence point, the component below 80 DEG C of fusing point distillated at the top of No. 1 molecular distillation apparatus is divided into No. 4 molecular distillation apparatus
From, from No. 4 molecular distillation apparatus at the top of distillate liquid wax product, the heavy constituent distillated from No. 4 molecular distillation apparatus bottoms enters 5
Number molecular distillation apparatus is separated, and the serial wax products of C50 are distillated at the top of No. 5 molecular distillation apparatus, from No. 5 molecular distillations dresses
Bottom set portion distillates the serial wax products of C70, and more than the 80 DEG C heavy constituents of fusing point distillated from No. 1 molecular distillation apparatus bottom enter No. 2
Molecular distillation apparatus is separated, and the serial wax products of C80 is distillated at the top of No. 2 molecular distillation apparatus, from No. 2 molecular distillation apparatus
The heavy constituent that bottom is distillated is separated into No. 3 molecular distillation apparatus, and the serial waxes of H1 are distillated at the top of No. 3 molecular distillation apparatus
Product, the serial wax products of H105 are distillated from No. 3 molecular distillation apparatus bottoms.
Without impurity such as sulphur, nitrogen in the crude product that F- T synthesis crude product as described above synthesizes for co-based fischer-tropsch, crude product.
The temperature of gas removal tower as described above is 350-360 DEG C, and pressure is 1.9-2.1MPa；
The outflow of gas removal column overhead CO, H as described above2、CO2、N2、H2O、CH4, C2 and a small amount of C3, C4 fixed gas
Body can deliver to full factory's fuel gas pipe network as fuel gas；
The temperature of LPG knockout towers as described above is 320-330 DEG C, and pressure is 1.7-1.9MPa；
The temperature of wax knockout tower as described above is 350-360 DEG C, and pressure is 0.02-0.03MPa；
The catalyst of oil hydrogenation plant filling as described above is developed for Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences, should
Catalyst is that, using aluminium oxide-silicon oxide as carrier, one or both of fluorine, boron or phosphorus are one kind in auxiliary agent, nickel, tungsten or cerium
Or two kinds are active metal, the wherein mass fraction of alumina support is 60%-80%, and the mass fraction of silica support is
10%-28%, the mass fraction that auxiliary agent is counted using element quality is 5%-10%, and mass fraction of the active metal in terms of oxide is
1%-5%；
The reaction pressure of oil hydrogenation plant as described above is 2-20MPa, and reaction temperature is 260-380 DEG C, volume space velocity
0.5-10LHSV-1；
The temperature of naphtha splitter as described above is 175-185 DEG C, and pressure is 0.10-0.20MPa；
The temperature of light component knockout tower as described above is 245-255 DEG C, and pressure is 0.25-0.30MPa；
The temperature of C5 knockout towers as described above is 120-130 DEG C, and pressure is 0.35-0.45MPa；
The temperature of pentane purifying column as described above is 60-70 DEG C, and pressure is 0.20-0.30MPa；
The temperature of n-hexane purifying column as described above is 100-110 DEG C, and pressure is 0.25-0.30MPa；
The temperature of C7 knockout towers as described above is 120-130 DEG C, and pressure is 0.09-0.10MPa；
The temperature of normal heptane purifying column as described above is 110-120 DEG C, and pressure is 0.08-0.12MPa；
The temperature of C8 knockout towers as described above is 230-240 DEG C, and pressure is 0.07-0.08MPa；
The temperature of normal octane purifying column as described above is 120-130 DEG C, and pressure is 0.06-0.07MPa；
Pentane purifying column as described above, n-hexane purifying column, normal heptane purifying column and each tower top of normal octane purifying column evaporate
Go out thing isopentane, isohexane, isoheptane and isooctane deliver to tank field storage after mixing in-tank mixing as mixed solvent.
Wax hydrogenation plant hydroconversion condition is as described above：Pressure is 2.0~10.0MPa, and temperature is 240~360 DEG C, empty
1~4LHSV of speed-1, hydrofinishing processing is carried out under the conditions of the temperature and pressure, more fully oxygenatedchemicals can be entered
Row hydrogenation；
The catalyst used in wax hydrogenation plant as described above is developed for Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences,
The catalyst is using aluminium oxide-silicon oxide as carrier, and one or both of fluorine, boron or phosphorus are one kind in auxiliary agent, nickel, tungsten or molybdenum
Or two kinds are active metal, the wherein mass fraction of alumina support is 50%-60%, and the mass fraction of silica support is
20%-25%, the mass fraction that auxiliary agent is counted using element quality is 1-6%, and mass fraction of the active metal in terms of oxide is
10%-25%；
1-5 cerotin fractionated molecule distilling apparatus as described above is the shaping equipment of a combination, and 5 sets of shaping equipments are total to
With a set of heat-conducting oil system and constant temperature water system；
The operating condition of No. 1 molecular distillation apparatus as described above is：1~20Pa of pressure, 160~200 DEG C of temperature；No. 4
The operating condition of molecular distillation apparatus is：1~20Pa of pressure, 120~160 DEG C of temperature；The operating condition of No. 5 molecular distillation apparatus
For：1~20Pa of pressure, temperature is 150~190 DEG C；The operating condition of No. 2 molecular distillation apparatus is：1~20Pa of pressure, temperature
For 200~260 DEG C；The operating condition of No. 3 molecular distillation apparatus is：1~20Pa of pressure, temperature is 260~320 DEG C；
The fusing point for the liquid wax that the present invention is obtained is 30~50 DEG C, and the fusing point of C50 series waxes is 50~65 DEG C, C70 series
The fusing point of wax is 70~80 DEG C, 80~95 DEG C of the fusing point of C80 series waxes, 96~102 DEG C of the fusing point of H1 series waxes, H105 series waxes
102~108 DEG C of fusing point.
Compared with prior art, the present invention develops crude separation, lighter hydrocarbons essence point, wax using F- T synthesis crude oil product as raw material
Smart division technique flow, can produce a variety of different models and normal alkane and wax product, meet the different market demands, and this hair
It is bright in technological process be provided with oil hydrogenation and wax be hydrogenated with two kinds of refined units, can by alkene, oxygenatedchemicals in material with
And the impurity of the influence product colourity of heated coking generation effectively removes and avoids heavy wax in conventional technique and is easier cracking
Caused excessive lighting, improves value-added content of product, and technological process is simple, easily realizes industrialized production.
Brief description of the drawings
Fig. 1 is the process chart of the present invention.
As illustrated, 1 is gas removal tower, 2 be LPG knockout towers, and 3 be wax knockout tower, and 4 be oily hydrogenation plant, and 5 be that wax adds
Hydrogen production device, 6 be No. 1 molecular distillation apparatus, and 7 be naphtha splitter.8 be light component knockout tower, and 9 be C5 knockout towers, and 10 be just
Pentane purifying column, 11 be n-hexane purifying column, and 12 be C7 knockout towers, and 13 be normal heptane purifying column, and 14 be blending tank, and 15 be C8 points
From tower, 16 be normal octane purifying column, and 17 be No. 4 molecular distillation apparatus, and 18 be No. 5 molecular distillation apparatus, and 19 be No. 2 molecular distillations
Device, 20 be No. 3 molecular distillation apparatus.
Embodiment
Embodiment 1
A kind of separating technology of F- T synthesis crude product, technological process are as shown in figure 1, raw material is high temperature (130 DEG C) cobalt-based
F- T synthesis crude oil product, crude oil product each several part mass fraction is：On-condensible gas 22.06%, n-alkane 75.71%, isomeric alkane
Without impurity such as sulphur, nitrogen in hydrocarbon 1.69%, alkene 0.52%, alcohols 0.02%, crude oil product, using following separating step and condition：
(1) raw material crude separation
Raw material crude oil product initially enter gas removal tower 1, and the tower top of gas removal tower 1 distillates CO, H2、CO2、N2、H2O、CH4、
C2 and a small amount of C3, C4 on-condensible gas, gas removal tower bottom of towe distillate more than C2 heavy constituent, and the heavy constituent delivers to LPG separation
Tower 2 is separated, and the tower top of LPG knockout towers 2 distillates LPG products, and more than the C4 heavy constituents that the bottom of towe of LPG products tower 2 is distillated deliver to wax
Knockout tower 3 is separated, and wax knockout tower 3 isolates C5-C19 oil distillates and more than C19 wax fractions, and the top of wax knockout tower tower 3 is distillated
C5-C19 oil distillates by oily hydrogenation plant 4 hydrogenation after separated into naphtha splitter 7, the tower of naphtha splitter 7
Push up the C5-C8 light components distillated and deliver to the essence point that light component knockout tower 8 carries out lighter hydrocarbons, naphtha separates 7 bottom of towe C9-C19 restructuring
Divide and deliver to tank field storage as cetane improver product；
(2) essence of lighter hydrocarbons point
The C5-C6 light components that the tower top of light component knockout tower 8 is distillated are separated into C5 knockout towers 9, and C5 light components are from C5
The tower top of knockout tower 9 is distillated, and C6 heavy constituents are separated from the bottom of towe of C5 knockout towers 9, and C5 light components are carried into pentane purifying column 10
It is pure, the pentane product that purity is more than 99.9wt% is obtained, C6 heavy constituents enter n-hexane purifying column 11, obtain purity and be more than
99.9wt% normal hexane product, accessory substance isopentane and isohexane after purification enter blending tank 14；
The bottom of towe C7-C8 heavy constituents of light component knockout tower 8 are separated into C7 knockout towers 12, are gone out from the tower top of C7 knockout towers 12
The C7 components come are purified into normal heptane purifying column 13, obtain the normal heptane product that purity is more than 99.9wt%, from C7 points
Separated from the heavy constituent that the bottom of towe of tower 12 comes out into C8 knockout towers 15, the C8 components come out from the tower top of C8 knockout towers 15 enter
Normal octane purifying column 16 is purified, and obtains the normal octane product that purity is more than 99.9wt%, normal octane purifying column 16 and positive heptan
The purification accessory substance isoheptane and isooctane of alkane purifying column 13 deliver to blending tank 14, more than the C8 groups that the bottom of towe of C8 knockout towers 15 is distillated
Divide same as cetane improver product and deliver to tank field storage；
(3) essence of wax point
The waxy stone cut that the bottom of towe of wax knockout tower 3 is distillated enters No. 1 molecular distillation apparatus 6 after the hydrogenation of wax hydrogenation plant 5
Essence point is carried out, enters No. 4 molecular distillation apparatus 17 from the component below 80 DEG C of the fusing point that No. 1 top of molecular distillation apparatus 6 is distillated
Separated, distillate liquid wax product from No. 4 tops of molecular distillation apparatus 17, distillated from No. 4 bottoms of molecular distillation apparatus 17
Heavy constituent is separated into No. 5 molecular distillation apparatus 18, and the serial wax products of C50 are distillated from No. 5 tops of molecular distillation apparatus 18,
The serial wax products of C70,80 DEG C of the fusing point distillated from No. 1 bottom of molecular distillation apparatus 6 are distillated from No. 5 bottoms of molecular distillation apparatus 18
Above heavy constituent is separated into No. 2 molecular distillation apparatus 19, and the serial waxes of C80 are distillated from No. 2 tops of molecular distillation apparatus 19
Product, the heavy constituent distillated from No. 2 bottoms of molecular distillation apparatus 19 is separated into No. 3 molecular distillation apparatus 20, from No. 3 points
The sub- top of distilling apparatus 20 distillates the serial wax products of H1, and the serial wax products of H105 are distillated from No. 3 bottoms of molecular distillation apparatus 20.
The temperature of described gas removal tower 1 is 360 DEG C, and pressure is 2.0MPa；
The described outflow of the tower top of gas removal tower 1 CO, H2、CO2、N2、H2O、CH4、C2And a small amount of C3、C4On-condensible gas can
Full factory's fuel gas pipe network is delivered to as fuel gas；
The temperature of described LPG knockout towers 2 is 320 DEG C, and pressure is 1.8MPa；
The temperature of described wax knockout tower 3 is 350 DEG C, and pressure is 0.02MPa；
The catalyst that described oily hydrogenation plant 4 is loaded is Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's exploitation, should
Catalyst is using aluminium oxide-silicon oxide as carrier, and the mass fraction of auxiliary agent fluorine is 10%, and the mass fraction of active component nickel oxide is
2%, aluminum oxide is 60%, and remaining is silica；
The reaction pressure of described oily hydrogenation plant 4 is 2-4MPa, and reaction temperature is 370-380 DEG C, volume space velocity
5LHSV-1；
The temperature of described naphtha splitter 7 is 175 DEG C, and pressure is 0.20MPa；
The temperature of described light component knockout tower 8 is 245 DEG C, and pressure is 0.25MPa；
The temperature of described C5 knockout towers 9 is 125 DEG C, and pressure is 0.38MPa；
The temperature of described pentane purifying column 10 is 65 DEG C, and pressure is 0.25MPa；
The temperature of described n-hexane purifying column 11 is 110 DEG C, and pressure is 0.30MPa；
The temperature of described C7 knockout towers 12 is 120 DEG C, and pressure is 0.10MPa；
The temperature of described normal heptane purifying column 13 is 120 DEG C, and pressure is 0.12MPa；
The temperature of described C8 knockout towers 15 is 235 DEG C, and pressure is 0.075MPa；
The temperature of described normal octane purifying column 16 is 125 DEG C, and pressure is 0.06MPa；
Described pentane purifying column 10, n-hexane purifying column 11, normal heptane purifying column 13 and each tower of normal octane purifying column 16
Distillate isopentane is pushed up, isohexane, isoheptane and isooctane deliver to tank field storage after mixing in blending tank 14 as mixed solvent.
The described hydroconversion condition of wax hydrogenation plant 5 is：Pressure is 5.0-6.0MPa, and temperature is 280-285 DEG C, air speed 2LHSV-1, hydrofinishing processing is carried out under the conditions of the temperature and pressure, more fully oxygenatedchemicals can be hydrogenated with；
The catalyst used in described wax hydrogenation plant 5 is Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's exploitation, should
Catalyst is that, using aluminium oxide-silicon oxide as carrier, fluorine is auxiliary agent, and tungsten-molybdenum is active metal, wherein the composition in terms of mass fraction
For：Aluminum oxide is 50%, and fluorine is 6%, and tungsten oxide is 10%, and nickel oxide is 14%, and remaining is silica；
1-5 cerotin fractionated molecule distilling apparatus is the shaping equipment of a combination, and 5 sets of shaping equipments share a set of heat conduction
Oil system and constant temperature water system；
For cerotin subregion, the operating condition of No. 1 device of molecular distillation 6 is：Pressure 20Pa, 200 DEG C of temperature；No. 4 points
The operating condition of sub- distilling apparatus 17 is：Pressure 20Pa, 160 DEG C of temperature；The operating condition of No. 5 molecular distillation apparatus 18 is：Pressure
Power 20Pa, temperature is 190 DEG C；The operating condition of No. 2 molecular distillation apparatus 19 is：Pressure 20Pa, temperature is 260 DEG C；No. 3 molecules
The operating condition of distilling apparatus 20 is：Pressure 20Pa, temperature is 320 DEG C；
Products obtained therefrom quantity is as shown in table 1 after being separated through the technique：
The embodiment 1 of table 1 obtains each product yield
The fusing point of the wax series of products of gained is：The fusing point of liquid wax is 30 DEG C, and the fusing point of C50 series waxes is 55 DEG C, C70
The fusing point of serial wax is 75 DEG C, 85 DEG C of the fusing point of C80 series waxes, 100 DEG C of the fusing point of H1 series waxes, the fusing point of H105 series waxes
108℃。
Embodiment 2
Raw material is low temperature (60 DEG C) co-based fischer-tropsch synthetic crude oil, and the crude oil product each several part mass fraction is：On-condensible gas
92.53%, n-alkane 7.08%, isoparaffin 0.20%, alkene 0.17%, alcohols 0.02%, separating technology parameter is：
The temperature of described gas removal tower 1 is 355 DEG C, and pressure is 1.9MPa；
The temperature of described LPG knockout towers 2 is 325 DEG C, and pressure is 1.7MPa；
The temperature of described wax knockout tower 3 is 360 DEG C, and pressure is 0.03MPa；
The catalyst that described oily hydrogenation plant 4 is loaded is using aluminium oxide-silicon oxide as carrier, and the mass fraction of auxiliary agent phosphorus is
5%, the mass fraction of active component tungsten oxide and cerium oxide is 5%, and aluminum oxide is 70%, and remaining is silica；
The reaction pressure of described oily hydrogenation plant is 11-12MPa, and reaction temperature is 320-330 DEG C, volume space velocity
0.5LHSV-1；
The temperature of described naphtha splitter 7 is 185 DEG C, and pressure is 0.15MPa；
The temperature of described light component knockout tower 8 is 255 DEG C, and pressure is 0.27MPa；
The temperature of described C5 knockout towers 9 is 120 DEG C, and pressure is 0.45MPa；
The temperature of described pentane purifying column 10 is 70 DEG C, and pressure is 0.20MPa；
The temperature of described n-hexane purifying column 11 is 100 DEG C, and pressure is 0.28MPa；
The temperature of described C7 knockout towers 12 is 125 DEG C, and pressure is 0.09MPa；
The temperature of described normal heptane purifying column 13 is 115 DEG C, and pressure is 0.10MPa；
The temperature of described C8 knockout towers 15 is 230 DEG C, and pressure is 0.08MPa；
The temperature of described normal octane purifying column 16 is 120 DEG C, and pressure is 0.07MPa；
The described hydroconversion condition of wax hydrogenation plant 5 is：Pressure is 2-3MPa, and temperature is 355-360 DEG C, air speed 1LHSV-1；
The catalyst of described wax hydrogenation plant 5 is that, using aluminium oxide-silicon oxide as carrier, boron is auxiliary agent, and tungsten-nickel is activity
Metal, wherein the composition in terms of mass fraction is：Aluminum oxide is 60%, and boron is 5%, and tungsten oxide is 2%, and nickel oxide is 8%, its
Remaining is silica；
For cerotin subregion, the operating condition of No. 1 device of molecular distillation 6 is：Pressure 10Pa, 160 DEG C of temperature；No. 4 points
The operating condition of sub- distilling apparatus 17 is：Pressure 10Pa, 120 DEG C of temperature；The operating condition of No. 5 molecular distillation apparatus 18 is：Pressure
Power 10Pa, temperature is 150 DEG C；The operating condition of No. 2 molecular distillation apparatus 19 is：Pressure 10Pa, temperature is 200 DEG C；No. 3 molecules
The operating condition of distilling apparatus 20 is：Pressure 10Pa, temperature is 260 DEG C；
Remaining operating condition be the same as Example 1, products obtained therefrom quantity is as shown in table 2 after being separated through the technique：
The embodiment 2 of table 2 obtains each product yield
Embodiment 3
Raw material is normal temperature (40 DEG C) synthetic crude oil, and the crude oil product each several part mass fraction is：On-condensible gas 49.73%,
N-alkane 47.03%, isoparaffin 1.32%, alkene 1.81%, alcohols 0.11%, separating technology parameter is：
The temperature of described gas removal tower 1 is 350 DEG C, and pressure is 2.1MPa；
The temperature of described LPG knockout towers 2 is 330 DEG C, and pressure is 1.9MPa；
The temperature of described wax knockout tower 3 is 355 DEG C, and pressure is 0.025MPa；
The catalyst that described oily hydrogenation plant 4 is loaded is using aluminium oxide-silicon oxide as carrier, the quality point of auxiliary agent fluorine and boron
Number is 3%, active component tungsten oxide 1%, and the mass fraction of cerium oxide is 3%, and aluminum oxide is 80%, and remaining is oxidation
Silicon；
The reaction pressure of described oily hydrogenation plant is 19-20MPa, and reaction temperature is 260-270 DEG C, volume space velocity
10LHSV-1；
The temperature of described naphtha splitter 7 is 180 DEG C, and pressure is 0.10MPa；
The temperature of described light component knockout tower 8 is 250 DEG C, and pressure is 0.30MPa；
The temperature of described C5 knockout towers 9 is 130 DEG C, and pressure is 0.35MPa；
The temperature of described pentane purifying column 10 is 60 DEG C, and pressure is 0.30MPa；
The temperature of described n-hexane purifying column 11 is 105 DEG C, and pressure is 0.25MPa；
The temperature of described C7 knockout towers 12 is 130 DEG C, and pressure is 0.10MPa；
The temperature of described normal heptane purifying column 13 is 110 DEG C, and pressure is 0.08MPa；
The temperature of described C8 knockout towers 15 is 240 DEG C, and pressure is 0.07MPa；
The temperature of described normal octane purifying column 16 is 130 DEG C, and pressure is 0.07MPa；
The described hydroconversion condition of wax hydrogenation plant 5 is：Pressure is 9-10MPa, and temperature is 240-245 DEG C, air speed 4LHSV-1；
The catalyst of described wax hydrogenation plant 5 is that, using aluminium oxide-silicon oxide as carrier, fluorine, phosphorus are auxiliary agent, and nickel is activity
Metal, wherein the composition in terms of mass fraction is：Aluminum oxide is 50%, and fluorine, phosphorus are 2.5%, and nickel oxide is 25%, and remaining is
SiO2；
For cerotin subregion, the operating condition of No. 1 device of molecular distillation 6 is：Pressure 15Pa, 180 DEG C of temperature；No. 4 points
The operating condition of sub- distilling apparatus 17 is：Pressure 15Pa, 140 DEG C of temperature；The operating condition of No. 5 molecular distillation apparatus 18 is：Pressure
Power 5Pa, temperature is 170 DEG C；The operating condition of No. 2 molecular distillation apparatus 19 is：Pressure 5Pa, temperature is 220 DEG C；No. 3 molecules steam
The operating condition of distillation unit 20 is：Pressure 5Pa, temperature is 280 DEG C；
Remaining operating condition be the same as Example 1, products obtained therefrom quantity is as shown in table 3 after being separated through the technique：
The embodiment 3 of table 3 obtains each product yield
Embodiment 4
For cerotin subregion, the operating condition of No. 1 device of molecular distillation 6 is：Pressure 1Pa, 180 DEG C of temperature；No. 4 molecules
The operating condition of distilling apparatus 17 is：Pressure 1Pa, 130 DEG C of temperature；The operating condition of No. 5 molecular distillation apparatus 18 is：Pressure
1Pa, temperature is 170 DEG C；The operating condition of No. 2 molecular distillation apparatus 19 is：Pressure 1Pa, temperature is 240 DEG C；No. 3 molecular distillations
The operating condition of device 20 is：Pressure 1Pa, temperature is 300 DEG C, remaining operating condition be the same as Example 1, institute after being separated through the technique
Obtain product quantity as shown in table 4：
The embodiment 4 of table 4 obtains each product yield
The fusing point of the wax series of products of gained is：The fusing point of liquid wax is 40 DEG C, and the fusing point of C50 series waxes is 60 DEG C, C70
The fusing point of serial wax is 80 DEG C, 90 DEG C of the fusing point of C80 series waxes, 101 DEG C of the fusing point of H1 series waxes, the fusing point of H105 series waxes
108℃。
Claims (20)
1. a kind of separating technology of F- T synthesis crude product, it is characterised in that comprise the following steps：
(1) raw material crude separation
F- T synthesis crude product initially enters gas removal tower, and gas removal column overhead distillates CO, H2、CO2、N2、H2O、CH4、C2
And a small amount of C3, C4 on-condensible gas, gas removal tower bottom of towe distillates more than C2 heavy constituent, and the heavy constituent delivers to LPG knockout towers
Separated, LPG separation column overhead distillates LPG products, and more than the C4 heavy constituents that LPG product tower bottom of towe is distillated deliver to wax knockout tower
Separated, wax knockout tower isolates C5~C19 oil distillates and more than C19 wax fractions, C5~C19 that wax separation column overhead is distillated
Oil distillate is separated after oily hydrogenation plant hydrogenation into naphtha splitter, and the C5 that naphtha splitter tower top is distillated~
C8 light components deliver to the essence point that light component knockout tower carries out lighter hydrocarbons, and naphtha splitter bottom C9~C19 heavy constituents are as hexadecane
Modifier product delivers to tank field storage；
(2) essence of lighter hydrocarbons point
C5~C6 light components for distillating of light component separation column overhead are separated into C5 knockout towers, and C5 light components are from C5 knockout towers
Tower top is distillated, and C6 heavy constituents are separated from C5 knockout tower bottom of towe, and C5 light components are purified into pentane purifying column, obtain purity
Pentane product more than 99.9wt%, C6 heavy constituents enter n-hexane purifying column, obtain purity more than 99.9wt% just oneself
Alkane product, accessory substance isopentane and isohexane after purification enter blending tank；
Light component knockout tower bottom of towe C7~C8 heavy constituents are separated into C7 knockout towers, and the C7 groups that column overhead comes out are separated from C7
Divide and purified into normal heptane purifying column, the normal heptane product that purity is more than 99.9wt% is obtained, from the bottom of towe of C7 knockout towers 12
Heavy constituent out is separated into C8 knockout towers, and the C8 components come out from C8 separation column overhead are entered into normal octane purifying column
Row purification, obtains the purification by-product of the normal octane product that purity is more than 99.9wt%, normal octane purifying column and normal heptane purifying column
Thing isoheptane and isooctane deliver to blending tank, and more than the C8 components that C8 knockout tower bottom of towe is distillated equally are produced as cetane improver
Product deliver to tank field storage；
(3) essence of wax point
The waxy stone cut that wax knockout tower bottom of towe is distillated enters No. 1 molecular distillation apparatus after wax hydrogenation plant hydrogenation and carries out essence
Point, the component below 80 DEG C of fusing point distillated at the top of No. 1 molecular distillation apparatus is separated into No. 4 molecular distillation apparatus,
Liquid wax product is distillated at the top of No. 4 molecular distillation apparatus, the heavy constituent distillated from No. 4 molecular distillation apparatus bottoms enters No. 5
Molecular distillation apparatus is separated, and the serial wax products of C50 is distillated at the top of No. 5 molecular distillation apparatus, from No. 5 molecular distillation apparatus
Bottom distillates the serial wax products of C70, and more than the 80 DEG C heavy constituents of fusing point distillated from No. 1 molecular distillation apparatus bottom enter No. 2 points
Sub- distilling apparatus is separated, and the serial wax products of C80 is distillated at the top of No. 2 molecular distillation apparatus, from No. 2 molecular distillation apparatus bottoms
The heavy constituent that portion is distillated is separated into No. 3 molecular distillation apparatus, and the serial wax productions of H1 are distillated at the top of No. 3 molecular distillation apparatus
Product, the serial wax products of H105 are distillated from No. 3 molecular distillation apparatus bottoms.
2. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that described F- T synthesis
Without sulphur, nitrogen impurity in the crude product that crude product synthesizes for co-based fischer-tropsch, crude product.
3. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that described gas removal
The temperature of tower is 350-360 DEG C, and pressure is 1.9-2.1MPa.
4. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that described LPG knockout towers
Temperature be 320-330 DEG C, pressure is 1.7-1.9MPa.
5. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that described wax knockout tower
Temperature be 350-360 DEG C, pressure is 0.02-0.03MPa.
6. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that described oil hydrogenation dress
Put the catalyst of filling be Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences exploitation, the catalyst be using aluminium oxide-silicon oxide as
Carrier, one or both of fluorine, boron or phosphorus are auxiliary agent, and one or both of nickel, tungsten or cerium are active metal, wherein aoxidizing
The mass fraction of alumina supporter is 60%-80%, and the mass fraction of silica support is 10%-28%, and auxiliary agent is in terms of element quality
Mass fraction be 5%-10%, the mass fraction that active metal is counted using oxide is 1%-5%.
7. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that described oil hydrogenation dress
The reaction pressure put is 2-20MPa, and reaction temperature is 260-380 DEG C, volume space velocity 0.5-10LHSV-1。
8. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that described naphtha point
Temperature from tower is 175-185 DEG C, and pressure is 0.10-0.20MPa.
9. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that described light component point
Temperature from tower is 245-255 DEG C, and pressure is 0.25-0.30MPa.
10. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that described C5 knockout towers
Temperature be 120-130 DEG C, pressure is 0.35-0.45MPa.
11. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that described pentane is carried
The temperature of pure tower is 60-70 DEG C, and pressure is 0.20-0.30MPa.
12. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that described n-hexane is carried
The temperature of pure tower is 100-110 DEG C, and pressure is 0.25-0.30MPa.
13. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that described C7 knockout towers
Temperature be 120-130 DEG C, pressure is 0.09-0.10MPa.
14. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that described normal heptane is carried
The temperature of pure tower is 110-120 DEG C, and pressure is 0.08-0.12MPa.
15. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that described C8 knockout towers
Temperature be 230-240 DEG C, pressure is 0.07-0.08MPa.
16. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that described normal octane is carried
The temperature of pure tower is 120-130 DEG C, and pressure is 0.06-0.07MPa.
17. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that described wax hydrogenation dress
Putting hydroconversion condition is：Pressure is 2.0~10.0MPa, and temperature is 240~360 DEG C, 1~4LHSV of air speed-1。
18. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that described wax hydrogenation dress
Put the middle catalyst used be using aluminium oxide-silicon oxide as carrier, one or both of fluorine, boron or phosphorus be auxiliary agent, nickel, tungsten or
One or both of molybdenum is active metal, and wherein the mass fraction of alumina support is 50%-60%, the matter of silica support
Amount fraction is 20%-25%, and the mass fraction that auxiliary agent is counted using element quality is 1-6%, quality of the active metal in terms of oxide
Fraction is 10%-25%.
19. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that No. 1 described molecule
The operating condition of distilling apparatus is：1~20Pa of pressure, 160~200 DEG C of temperature；The operating condition of No. 4 molecular distillation apparatus is：
1~20Pa of pressure, 120~160 DEG C of temperature；The operating condition of No. 5 molecular distillation apparatus is：1~20Pa of pressure, temperature is 150
~190 DEG C；The operating condition of No. 2 molecular distillation apparatus is：1~20Pa of pressure, temperature is 200~260 DEG C；No. 3 molecular distillations
The operating condition of device is：1~20Pa of pressure, temperature is 260~320 DEG C.
20. a kind of separating technology of F- T synthesis crude product as claimed in claim 1, it is characterised in that what separating technology was obtained
The fusing point of liquid wax is 30~50 DEG C, and the fusing point of C50 series waxes is 50~65 DEG C, and the fusing point of C70 series waxes is 70~80 DEG C,
80~95 DEG C of the fusing point of C80 series waxes, 96~102 DEG C of the fusing point of H1 series waxes, 102~108 DEG C of the fusing point of H105 series waxes.
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