CN107794085A - A kind of method for modifying of Fischer-Tropsch naphtha - Google Patents
A kind of method for modifying of Fischer-Tropsch naphtha Download PDFInfo
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- CN107794085A CN107794085A CN201610797824.5A CN201610797824A CN107794085A CN 107794085 A CN107794085 A CN 107794085A CN 201610797824 A CN201610797824 A CN 201610797824A CN 107794085 A CN107794085 A CN 107794085A
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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
-
- 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
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Abstract
The invention discloses a kind of method for modifying of F- T synthesis naphtha, the method for modifying includes：By F- T synthesis feed naphtha successively by the cryogenic reaction zone and high temperature reaction zone of series connection, contacted with the modifying catalyst in reaction zone and carry out non-hydrogen modification reaction；The F- T synthesis feed naphtha includes 10 90 mass % high olefin content naphtha and 10 90 mass % high Determination of Alkane Content naphtha；Olefin(e) centent is 50 90 mass % in the high olefin content naphtha, and Determination of Alkane Content is more than 80 mass % in the high Determination of Alkane Content naphtha；The high olefin content naphtha is sent into the cryogenic reaction zone, the high Determination of Alkane Content naphtha is sent into the high temperature reaction zone, while cryogenic reaction zone reaction product enters in high temperature reaction zone.The method for modifying of the present invention can produce high-octane rating product liquid.
Description
Technical field
The present invention relates to a kind of inferior naphtha method for modifying, is a kind of modification of F- T synthesis naphtha specifically
Method.
Background technology
Counted according to World Energy Conference, worldwide coal proven reserve and can recovery time exceed well over oil, in recent years, day
The recoverable reserves that right gas is verified continues to increase.The characteristics of China's energy resource structure is total is " rich coal, oil starvation ".With world petroleum resource
Increasingly shortage and continuous improvement of the people to environmental requirement, by coal, natural gas through Fischer-Tropsch (F-T) synthetic technology produce without sulphur,
Nitrogen-free, the clean fuel liquid of low aromatic hydrocarbons turn into the industry widely focus of attention.F-T synthetic naphtha cuts contain a large amount of alkene
Hydrocarbon and oxygenatedchemicals, it is impossible to directly as vehicle fuel, it is necessary to by further handling to obtain high-quality gasoline component or height
Added value chemical industry product.At present, the Conventional processing methods of F-T synthetic naphthas production gasoline component are removed by hydrofinishing
Alkene and oxygenatedchemicals, octane number then is improved with the method reformed, this kind of method hydrogen consumption is very big, and alkene saturation
Most of afterwards is linear paraffin, and reforming effect is poor, and economy is bad.
United States Patent (USP) US7033552 discloses a kind of F- T synthesis naphtha and distillate modification production gasoline component, evaporated
Divide the method for fuel or lubricant base stock.This method includes：Hydrocarbon source is separated into gaseous hydrocarbon, condensate and viscous crude；Gaseous state
Hydrocarbon produces synthesis gas and obtains naphtha and distillate through F- T synthesis；Reformed after Fischer-Tropsch naphtha and the hydrogenated processing of condensate
Obtain containing aromatic hydrocarbons more than 10%, the gasoline component of octane number more than 80 and by-product hydrogen；The hydrogen of by-product is used for distillate and thick
The hydro-upgrading production distillate fuel or lubricant base stock of oil, the hydrogen of the by-product are also used for F- T synthesis naphtha and coagulated
Hydrofinishing before condensate oil reformation.
United States Patent (USP) US6875339 discloses a kind of method of F- T synthesis naphtha octane improvement, and this method includes：
By the C from F- T synthesis4-C8Straight-chain hydrocarbons contacts under hydro condition with phosphorous shape-selective molecular sieve catalyst carries out isomerization
Reaction, isomerization product carry out aromatization with shape-selective catalyst under hydro condition and produce hydrogen supply isomerization list
Member, aromatization products are fractionated, and unconverted straight-chain hydrocarbons are sent back to isomerization or aromatization unit, containing aromatic hydrocarbons and isomery
The product liquid octane of hydrocarbon is worth to improvement.
United States Patent (USP) US4013737 discloses a kind of low octane rating synthetic gasoline method for modifying, and this method includes：It will contain
The C of oxide5-C14Linear alkene low octane rating synthetic gasoline and solid phosphoric acid catalyst haptoreaction, improve octane number
Olefin-containing product is separated into gasoline product and higher boiling product, and higher boiling product returns to reaction member；In synthetic gasoline raw material
Mix C3、C4Alkene participates in modification reaction, while adds propane and butane absorption reaction heat in the feed.
Chinese patent CN 103396833A disclose a kind of method of synthetic naphtha production motor petrol, this method bag
Include：ICL for Indirect Coal Liquefaction synthetic naphtha Jing Guo hydrofinishing is fractionated, the C of the line of fractionation column one5/C6It is different using paraffin hydro
Structure PROCESS FOR TREATMENT increases isohydrocarbon；Bottom of towe >=80 DEG C of cuts use fixed-bed catalytic reforming process (cyclic reforming)
Processing increase aromatic hydrocarbons；Enter stabilizer after isomerization and reformate mixing, bottom of towe obtains the motor petrol for meeting national standard
Component.
Chinese patent CN 104140847A disclose a kind of side of F- T synthesis naphtha modification production high-knock rating gasoline
Method, this method include：By the F- T synthesis naphtha of high olefin content by depickling dehydration aftercut, olefin(e) centent relatively low one
A little heavy distillat carries out low temperature aromatization reaction on moving bed reaction area top, in olefin(e) centent higher light fraction and product
Part rich gas carries out high temperature aromatization in moving bed reaction area bottom, and global molecular sieve catalyst is from moving bed reaction area
Portion flows to bottom, and reclaimable catalyst Returning reactor after steam stripping regeneration recycles.This method is anti-using low temperature aromatization
Spent agent and light fraction after answering carry out high temperature aromatization again.
The content of the invention
It is an object of the invention to provide a kind of method for modifying of F- T synthesis naphtha, method for modifying of the invention can give birth to
Produce high-octane rating product liquid.
To achieve these goals, the present invention provides a kind of method for modifying of F- T synthesis naphtha, the method for modifying bag
Include：By the modification in F- T synthesis the feed naphtha successively cryogenic reaction zone and high temperature reaction zone, with reaction zone by series connection
Catalyst contact carries out non-hydrogen modification reaction；The high alkene that the F- T synthesis feed naphtha includes 10-90 mass % contains
Measure naphtha and 10-90 mass % high Determination of Alkane Content naphtha；Olefin(e) centent is 50-90 in the high olefin content naphtha
Quality %, Determination of Alkane Content is more than 80 mass % in the high Determination of Alkane Content naphtha；The high olefin content naphtha is sent into
The cryogenic reaction zone, the high Determination of Alkane Content naphtha is sent into the high temperature reaction zone, while cryogenic reaction zone reaction production
Thing enters in high temperature reaction zone.
The method for modifying dry gas yield of the F- T synthesis naphtha of the present invention is low, and liquid product yield is high, the liquid of production
Product can be used as premium blend component, and the octane number of product liquid is high, and octane number high income, arene content is low, and benzene contains
Measure low, sulfur content and nitrogen content are respectively less than 1 micro- gram gram.
In addition, the method for the present invention is easy, investment operation expense is low, can be significantly improved and changed by the way of parallel feeding
The selectivity of qualitative response, the relative stability of catalyst is improved, extend the catalyst runs cycle, F- T synthesis stone can be effectively improved
The added value of cerebrol raw material.
F- T synthesis feed naphtha of different nature is used different modification temperature by the present invention in differential responses area
Carry out modification reaction, it is possible to increase liquid product yield and octane number yield.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is a kind of schematic flow sheet of embodiment of F- T synthesis naphtha method for modifying of the present invention.
Description of reference numerals
The heat exchanger of 1 pipeline, 2 pipeline, 3 heat exchanger 4
The fixed bed reactors of 5 heating furnace, 6 fixed bed reactors, 7 fixed bed reactors 8
The product postprocessing unit of 9 cooler, 10 gas-liquid separator 11
The pipeline of 12 pipeline, 13 pipeline, 14 pipeline 15
The pipeline of 16 pipeline, 17 heating furnace, 18 pipeline 19
The pipeline of 20 pipeline, 21 pipeline, 22 pipeline 23
The pipeline of 24 pipeline, 25 pipeline, 26 pipeline 27
The pipeline of 28 pipeline, 29 pipeline, 30 pipeline 31
The gas compressor of 32 pipeline, 33 pipeline, 34 pipeline 35
Embodiment
The embodiment of the present invention is described in detail below in conjunction with accompanying drawing.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
High olefin content naphtha carries out modification reaction, cryogenic reaction zone reaction production in cryogenic reaction zone in the inventive method
Thing enters after being mixed with high Determination of Alkane Content naphtha to be connected in the high temperature reaction zone in cryogenic reaction zone downstream and carries out modification reaction, is shown
Writing improves the modification effect of high Determination of Alkane Content naphtha；Using in high olefin content naphtha course of reaction due to alkene oligomerization
It stronger exothermic effect caused by reaction, can reduce the material temperature into cryogenic reaction zone, and at a lower temperature
Reacted, while reduce the heating load into high temperature reaction zone raw material, make the energy resource consumption of upgrading processes significantly reduce.
A kind of preferred embodiment：The high alkene that the F- T synthesis feed naphtha includes 40-70 mass % contains
Measure naphtha and 30-60 mass % high Determination of Alkane Content naphtha.
The reaction mechanism of non-hydrogen modification reaction is to be cracked into F- T synthesis feed naphtha after the hydro carbons of small molecule again
Overlapped and structural rearrangement, therefore contain a certain amount of gaseous product in upgraded product, can be by the gas of the part low value
Body product is sent into insulation fix bed reaction zone and further converted, and can both improve liquid product yield, can also dilute
Raw material and transmission heat, reduce the generation of side reaction.
A kind of embodiment：Upgraded product obtained by high temperature reaction zone is carried out into gas-liquid separation (can be with before gas-liquid separation
Upgraded product and F- T synthesis feed naphtha are first subjected to heat exchange cooling), the gas-phase product that gas-liquid separation is obtained is at least
A part returns to cryogenic reaction zone.
Preferably, the gas-phase product returned in cryogenic reaction zone accounts for all gas-phase products obtained by the gas-liquid separation
Ratio be 20-80 mass %, preferably 30-70 mass %.
It should be noted that the gas-phase product that the gas-liquid separation obtains refers under normal temperature, normal pressure for gaseous state
Product, liquefied gas and dry gas can be included, dry gas is mainly hydrogen and C1-C2Hydro carbons, liquefied gas are mainly C3-C4Hydro carbons.Liquid
Phase product and remaining gas-phase product can be sent into product absorbing-stabilizing system and carry out Vapor recovery unit, obtain liquefied gas and liquid production
Thing.
A kind of embodiment：The cryogenic reaction zone and high temperature reaction zone each include consolidating for single or multiple series windings
Fixed bed reactor or beds.Beds in fixed bed reactors have independent feed system, between each other may be used
To be separated with support bar, porcelain ball etc..
A kind of embodiment：Fixed bed reactors or beds in the cryogenic reaction zone and high temperature reaction zone
Number be respectively 1-4.The sum of the fixed bed reactors or beds of cryogenic reaction zone and high temperature reaction zone series winding
It is preferred that 2-4.
Because the modification reaction of F- T synthesis naphtha is exothermic reaction, flying for reaction temperature in reaction zone is easily caused
Rise, so as to reduce reaction efficiency and contain potential safety hazard, in order to rationally control the reaction temperature in reaction zone, efficient balance is each anti-
Answer the reaction severity in area.
A kind of embodiment：There are the fixed bed reactors or beds of multiple series windings in cryogenic reaction zone, by height
Olefin(e) centent naphtha is divided into multiply and is sent into cryogenic reaction zone the fixed bed reactors or beds each contacted.
Preferably, it is sent into the high olefin content naphtha of the fixed bed reactors of cryogenic reaction zone first or beds
The 50-70 mass % of high olefin content naphtha total amount are accounted for, are sent into the high alkene of second fixed bed reactors or beds
Hydrocarbon content naphtha accounts for the 30-50 mass % of high olefin content naphtha total amount.
F- T synthesis feed naphtha is well-known to those skilled in the art, refers to pass through as raw material using coal, natural gas
Cross the F- T synthesis gasoline fraction product of indirect liquefaction high―temperature nuclei technique (HTFT).
The initial boiling point of the F- T synthesis naphtha can be 50-90 DEG C, and the end point of distillation can be 110-230 DEG C, C5-C12Hydrocarbon
The content of class can be 50-95 mass %.
The present invention high olefin content naphtha preferably directly from F- T synthesis device, and without removing alkene, contain
The refinement treatment of oxygen compound or other impurity, such high olefin content naphtha contain more alkene and oxygenatedchemicals,
The preferred 60-85 mass % of olefin(e) centent in the high olefin content naphtha, oxygenates level are 5-30 mass %.High alkane
Hydrocarbon content naphtha can be selected from F- T synthesis naphtha, reforming raffinate oil, the secondary operation stone of hydrofinishing of hydrofinishing
At least one of cerebrol and light naphthar, its olefin(e) centent is relatively low, and olefin(e) centent is less than 5 in the high Determination of Alkane Content naphtha
Quality %, more preferably less than 3 mass %.
According to the present invention, modifying catalyst is used to F- T synthesis feed naphtha carrying out non-hydrogen modification reaction.It is described
Modifying catalyst can include carrier, V A race's elements and rare earth element；Calculated on the basis of carrier, the modifying catalyst can
By the member of the rare earth in terms of oxide of the VA races element including 0.01-20 mass % in terms of oxide and 0.01-5 mass %
Element.
Preferably, the carrier includes 40-75 mass % ZSM-5 zeolite, 3-25 mass % aluminum oxide and 8-35 matter
% amorphous aluminum silicate is measured, the silica alumina ratio of the ZSM-5 zeolite can be 10-300.
VA races element can be included selected from least one of phosphorus, antimony and bismuth；The rare earth element can include 20-
40 mass % lanthanum, 40-60 mass % cerium, 0-10 mass % praseodymium and 0-10 mass % neodymium.
Preferred embodiment, under given conditions, modifying catalyst is carried out at aging with 100% vapor
Reason, make modifying catalyst that there is good stability and regenerability, catalyst shape can be stripe shape, microspheric form, piece type,
Grain type or microspheric.Preferred 500-600 DEG C of steam treatment temperature, steam treatment time are 0.5-8 hours, and preferably 2-6 is small
When.The α values of carrier are 10-100, are preferably 20-60 after steam treatment.(assay method of α values is write with reference to Yang Cuiding etc.
《Petrochemical Engineering Analysis method (RIPP experimental methods)》, Science Press publishes, and " constant temperature method determines the α of acidic catalyst to P255
Value ").
Non-hydrogen modification reaction refers to that it is high-knock rating gasoline group that F- T synthesis feed naphtha is changed into target product
The reaction divided.The upgraded condition can include：The temperature of the cryogenic reaction zone is 200-300 DEG C, preferably 250-280
DEG C, the temperature of the high temperature reaction zone is 350-500 DEG C, preferably 360-460 DEG C, pressure 0.1-2.0MPa, is preferably
0.3-1.0MPa, more preferably 0.3-0.6MPa, the combined feed mass space velocity of F- T synthesis feed naphtha are small for 0.2-5.0
When-1, preferably 0.4-1.5 hours-1。
Because reaction zone is adiabatic, in order to rationally utilize the heat of reaction product obtained by each reaction zone, the modification
Method can also include：To all reaction zones, according to the flow direction of the F- T synthesis feed naphtha, except first fixed bed
Outside reactor or beds, will be fed into the F- T synthesis feed naphthas of each fixed bed reactors or beds with
The described fixed bed reactors are re-fed into after reaction product mixing from the upstream of the fixed bed reactors or beds
Or the non-hydrogen modification reaction is carried out in beds.Furthermore it is possible to by last fixed bed reactors or catalyst
F- T synthesis feed naphtha of the upgraded product with entering above each fixed bed reactors or beds obtained by bed
Exchanged heat, so as to rationally utilize the heat of upgraded product, reduce the heating load of method for modifying of the present invention.
In order to improve reaction efficiency, the method for modifying can also include：By the modifying catalyst in the fixed bed
Contacted again with the F- T synthesis feed naphtha after carrying out in-situ activation in reaction zone；Wherein, the condition of the in-situ activation
It can include：Temperature is 300-500 DEG C, preferably 350-450 DEG C, preferably pressure 0.1-1.0MPa, 0.3-0.5MPa, living
The change time is 1-5 hours, and activated media is nitrogen (purity is preferably greater than 99.8 mass %), the volume of activated media and catalyst
Than for (100-1000)：1.
Regeneration can be carried out by the modifying catalyst after to recycle, a kind of specific implementation of catalyst regeneration
Mode, catalyst regenerating medium are oxygen containing inert gas, and regenerating medium oxygen content is 0.5-5%, and suitable regeneration temperature is
350-500 DEG C, pressure 0.1-1.0MPa, the volume ratio of regenerating medium and catalyst is (200-1000):1.Regeneration can
React and regenerate and use more to be reacted and regenerated using single reaction system interval, switched over using double reaction systems
Reactor switches the regeneration mode for carrying out a variety of fixed bed reactors such as circular regeneration in turn.
In order to express easily, the present invention will export the product sent out from last fixed bed reactors or beds
Referred to as upgraded product, it will export the product sent out from except last fixed bed reactors or beds and be referred to as reacting production
Thing.
A kind of embodiment of the present invention is provided below in conjunction with the accompanying drawings, but the present invention is not therefore and by any
Limitation.
Fig. 1 includes the fixed bed reactors 6,7 and 8 of three series connection, respectively as three fixed bed reaction areas.
As shown in figure 1, high olefin content naphtha enters modification reaction system by pipeline 1, flow through the tube side of heat exchanger 3 with
It is divided into two-way after the upgraded product heat exchange of the shell side of heat exchanger 3 is flowed through from pipeline 26, high Determination of Alkane Content naphtha is entered by pipeline 2
Enter modification by pipeline 15 after the tube side of heat exchanger 4 and the upgraded product heat exchange for flowing through the shell side of heat exchanger 4 from pipeline 27 to react
System.
First via high olefin content naphtha is after pipeline 16 mixes with the portion gas product from pipeline 19 through pipeline
18 are heated to the temperature of cryogenic reaction zone into heating furnace 5, are contacted through pipeline 20 into fixed bed reactors 6 with modifying catalyst
And non-hydrogen modification reaction is carried out, reaction product is discharged by pipeline 21.
Second reaction product of the tunnel high olefin content naphtha through pipeline 22 and the fixed bed reactors 6 from pipeline 21 is mixed
Merge the temperature that regulation reaches cryogenic reaction zone, then connect through pipeline 23 into fixed bed reactors 7 with modifying catalyst
Touch and carry out non-hydrogen modification reaction, reaction product is discharged by pipeline 24.
Reaction product of the high Determination of Alkane Content naphtha through pipeline 34 and the fixed bed reactors 7 from pipeline 24 is mixed into
Heating furnace 17 is heated to the temperature of high temperature reaction zone, is then contacted through pipeline 25 into fixed bed reactors 8 with modifying catalyst
And carry out non-hydrogen modification reaction.
The gained upgraded product of fixed bed reactors 8 is discharged by pipeline 26, through heat exchanger 3, pipeline 27, heat exchanger 4 respectively with
After high olefin content naphtha and the heat exchange of high Determination of Alkane Content naphtha, entered after pipeline 28 is cooled down by cooler 9 by pipeline 29
Enter gas-liquid separator 10.
In gas-liquid separator 10, upgraded product is separated into gas-phase product and liquid product, and partial gas phase product is through pipe
Line 30, gas compressor 35, pipeline 19 enter heating furnace 5 together with after the mixing of first via high olefin content naphtha through pipeline 18
The temperature of cryogenic reaction zone needed is heated to, then modification reaction is continued to participate in into fixed bed reactors 6 through pipeline 20.
Remaining gas-phase product enters through pipeline 33 and changed after pipeline 30,32 mixes with the liquid product from pipeline 31
The processing step such as absorbed, parse, stablize in the product postprocessing unit 11 of qualitative response system, the dry gas in upgraded product by
Pipeline 12 sends out product postprocessing unit 11, and liquefied gas component sends out product postprocessing unit 11 through pipeline 13, and product liquid is made
For premium blend component product postprocessing unit 11 is sent out through pipeline 14.
The present invention is further illustrated below by example, but the present invention is not limited thereto.
The composition of high olefin content naphtha used in present example and comparative example is as shown in table 1, high Determination of Alkane Content stone
The composition of cerebrol is as shown in table 2, and the initial boiling point of high olefin content naphtha is 53.6 DEG C, and the end point of distillation is 226.5 DEG C, and high alkane contains
The initial boiling point for measuring naphtha is 56.2 DEG C, and the end point of distillation is 219.3 DEG C.
Octane number yield=liquid product yield × product liquid octane number in present example and comparative example.
Upgraded product obtained by present example and comparative example is drawn from reactor and gas is obtained after refrigerated separation
Phase product and liquid product, and detected as follows：
The composition of gas-phase product uses Agilent 7890A chromatographics, and concrete analysis condition is：Carrier gas N2, hair
Tubule quartz column, fid detector；35 DEG C of initial temperature, 8 DEG C/min of programming rate, 190 DEG C of final temperature, vaporizer and detector temperature
150 DEG C of degree, determines each component position according to the residence time, each component content is determined using normalizing sizing technique；Gas-phase product includes
Dry gas and liquefied gas two parts, the main component of wherein dry gas is C1、C2Hydro carbons and a small amount of hydrogen, the composition of liquefied gas is C3、
C4Hydro carbons.
The composition of liquid product is analyzed using Shimadzu GC-2010AF chromatographs, and concrete analysis condition is：Carrier gas N2, capillary
Pipe quartz column, fid detector；180 DEG C of sample introduction current divider temperature, 36 DEG C of initial temperature, 200 DEG C of final temperature, vaporizer and detector
180 DEG C of temperature, each component position is determined according to the residence time, and each component content is determined using normalizing sizing technique.
The octane number of product liquid detects machine testing using the CFR-1 octane numbers of Waukesha companies.
Example 1
Prepare present example and the modifying catalyst used in comparative example.
(1) preparation of carrier：By silica/alumina molar ratio be 56 130 grams of HZSM-5 zeolite powders (feldspar is built in Hunan
Change the production of limited company molecular sieve factory), 35 grams of boehmite powder (alumina content is 75 mass %) and Ludox
(SiO2Content is 30 mass %) after 35 grams of mixing, add the aqueous solution of nitric acid that 100 grams of concentration are 1.0 mass % and stir, stand
Making peptization, then mediate and be extruded into the bar of 2 millimeters of diameter, the strip particles of length 2-3 millimeters is cut into 110 DEG C of dryings 4 hours, and 550
DEG C roasting 4 hours, be made carrier, aluminum oxide therein is γ-Al2O3。
(2) steam treatment：The carrier prepared in step (1) is loaded in tubular reactor, under normal pressure in the air stream
550 DEG C are warming up to, keeps the temperature to change logical 100% steam treatment 4 hours.
(3) impregnate：100 grams of carrier after the steam treatment prepared in step (2) is taken, with 50 milliliters of phosphoric acid solution (matter
Amount concentration is 100 mg/mls) dipping 1 hour, take solid after dipping, 120 DEG C of dryings 2 hours, then it is dilute with 100 milliliters of mixing
Soil (containing the mass % of lanthana 40, the mass % of cerium oxide 60) aqueous solution (and in terms of mixed rare-earth oxide, mass concentration be 10 milli
Grams per milliliter) impregnated 2 hours at 80 DEG C, take solid after dipping, 120 DEG C of drying 8 hours, 550 DEG C of roastings 4 hours, obtain modification and urge
Agent.
The constituent content calculated in modifying catalyst on the basis of carrier is following (being analyzed using x-ray fluorescence method)：0.53
The phosphorus pentoxide of quality % mixed rare earth oxide, 5.29 mass %, HZSM-5 of the carrier including 69.8 mass %,
12.2 mass % γ-Al2O3With 18 mass % amorphous aluminum silicate, alumina content is 36.2 matter in amorphous aluminum silicate
Measure %.
Example 2
Reaction unit used by the present embodiment is as shown in figure 1, each reactor is provided with independent feedstock oil charging
System.
Catalyst packing：In three reactors (for statement conveniently, fixed bed reactors 6, the fixed bed reaction shown in Fig. 1
Device 7 and fixed bed reactors 8, be referred to as first reactor, second reactor and the 3rd reactor) in filling example 1 prepare
Modifying catalyst, the loadings of each reactor are 40 grams, 120 grams of catalyst total filling amount.
In-situ activation processing：Activation process before being reacted in reaction unit modifying catalyst, activated media are
Nitrogen, in-situ activation condition are：Pressure is 0.3MPa, and nitrogen is 500 with catalyst volume ratio:1, reaction temperature is 400 DEG C, living
It is 2 hours to change the time.
Non-hydrogen modification reaction：
1st, reaction condition：Reaction pressure 0.3MPa, combined feed mass space velocity 0.6 hour-1(72.0 grams of total feed/small
When), the temperature of cryogenic reaction zone is 280 DEG C, and the temperature of high temperature reaction zone is 398 DEG C, with total product liquid octane number RON
92 be target, causes fluid product octane number to decline if catalyst activity reduces, and improves reaction temperature and makes up loss of activity.
2nd, each reactor feed amount：The ratio of high olefin content naphtha is 60 mass % in raw material is modified, inlet amount
43.2 Grams Per Hours, ratio of the high Determination of Alkane Content naphtha in raw material is modified are 40 mass %, into the 3rd reactor 8, charging
Measure 28.8 Grams Per Hours；Wherein high olefin content naphtha introduces the ratio of the reactor of two series windings of cryogenic reaction zone parallel
Respectively：First reactor 6 is 60 mass % (25.9 Grams Per Hour), and second reactor 7 is 40 mass % (17.3 Grams Per Hour)；
Modification course of reaction in second reactor temperature by mixed with the reaction product of previous reactor and with upgraded product
Exchange heat to control, the temperature of the 3rd reactor is mixed also by the heat exchange with upgraded product and with the reaction product of previous reactor
Close to raise, insufficient section is supplemented by heating furnace.
3rd, upgraded product is handled：Upgraded product obtains gas-phase product and liquid phase production after being exchanged heat with raw material, cool down, separate
Thing, 30 mass % of gas-phase product are returned into first reactor and continue to participate in modification reaction, remaining gas-phase product produces with liquid phase
Thing is sent into product Vapor recovery unit unit below together, isolates dry gas component, liquefied gas component and product liquid component.
Modify the condition of reaction and the results are shown in Table 3.
Comparative example 1
Reaction unit, loaded catalyst, in-situ activation processing method are the same as example 2 used by this comparative example.
Non-hydrogen modification reaction：
1st, reaction condition：Reaction pressure 0.3MPa, combined feed mass space velocity are 0.6 hour-1(72.0 grams of total feed/small
When), each temperature of reactor is 426 DEG C, is target with product liquid octane number RON 92, if catalyst activity, which reduces, causes liquid
Body product octane number declines then raising reaction temperature and makes up loss of activity.
2nd, each reactor feed：Using high Determination of Alkane Content naphtha as raw material, it is introduced to the three of series connection from first reactor
Individual reactor and modifying catalyst haptoreaction.
3rd, upgraded product is handled：Upgraded product obtains gas-phase product and liquid phase production after being exchanged heat with raw material, cool down, separate
Thing, 30 mass % of gas-phase product are returned into first reactor and continue to participate in modification reaction, remaining gas-phase product produces with liquid phase
Thing is sent into product Vapor recovery unit unit below together, isolates dry gas component, liquefied gas component and product liquid component.Modification
High Determination of Alkane Content naphtha and the temperature after upgraded product heat exchange, reacted as needed for the Heating Furnace Control of each reactor in course of reaction
Degree.
Modify the condition of reaction and the results are shown in Table 3.
Comparative example 2
Reaction unit, loaded catalyst, in-situ activation processing method are the same as example 2 used by this comparative example.
Non-hydrogen modification reaction：
1st, reaction condition：In reaction pressure 0.3MPa, combined feed mass space velocity 0.6 hour-1(72.0 grams of total feed/small
When), each temperature of reactor is 372 DEG C, is target with product liquid octane number RON 92, if catalyst activity, which reduces, causes liquid
Body product octane number declines then raising reaction temperature and makes up loss of activity.
2nd, each reactor parallel feeding amount (the parallel feeding condition that mixing naphtha optimizes)：High olefin content naphtha
(in 60 mass % ratio) uniformly mixes with high Determination of Alkane Content naphtha (in 40 mass % ratio), first reactor mixing
Feedstock amount is the 50 mass % (36.0 Grams Per Hour) of total feed, and second reactor mixed material inlet amount is combined feed
The 30 mass % (21.6 Grams Per Hour) of amount, the 3rd reactor mixed material inlet amount are 20 mass % (14.4 of total feed
Grams Per Hour).
3rd, upgraded product is handled：Upgraded product obtains gas-phase product and liquid phase production after being exchanged heat with raw material, cool down, separate
Thing, 30% return first reactor of gas-phase product is continued to participate in into modification reaction, remaining gas-phase product and liquid product one
The product Vapor recovery unit unit being sent into below is acted, isolates dry gas component, liquefied gas component and product liquid component.Modification reaction
During mix F- T synthesis feed naphtha pass through with upgraded product heat exchange after be divided into three tunnels, by the Heating Furnace Control of each reactor
The temperature of required reaction.
Modify the condition of reaction and the results are shown in Table 3.
As can be seen from Table 3, to F- T synthesis feed naphtha of different nature, distinguished using the subregion of the present invention
Method for modifying, significantly improve the modification effect of high Determination of Alkane Content naphtha, the product liquid as premium blend component
Yield dramatically increase, meanwhile, the energy resource consumption of upgrading processes substantially reduces, and can effectively improve F- T synthesis feed naphtha
Added value.
Table 1
Note：Other 13.71% are all kinds of oxygenatedchemicals based on alcohol, ketone.
Table 2
| Hydro carbons | Content, quality % |
| The alkane of carbon 5 | 4.83 |
| The alkane of carbon 6 | 12.60 |
| The alkane of carbon 7 | 15.33 |
| The alkane of carbon 8 | 16.72 |
| The alkane of carbon 9 | 15.85 |
| The alkane of carbon 10 | 14.65 |
| The alkane of carbon 11 | 13.06 |
| The alkane of carbon 12 | 4.56 |
| Alkene | 0.32 |
| Cycloalkane | 0.52 |
| Aromatic hydrocarbons | 1.56 |
Table 3
Claims (16)
1. a kind of method for modifying of F- T synthesis naphtha, the method for modifying include：F- T synthesis feed naphtha is passed through successively
The cryogenic reaction zone and high temperature reaction zone of series connection are crossed, is contacted with the modifying catalyst in reaction zone and carries out non-hydrogen modification reaction；
The F- T synthesis feed naphtha includes 10-90 mass % high olefin content naphtha and 10-90 mass % height
Determination of Alkane Content naphtha；Olefin(e) centent is 50-90 mass % in the high olefin content naphtha, the high Determination of Alkane Content stone brain
Determination of Alkane Content is more than 80 mass % in oil；
The high olefin content naphtha is sent into the cryogenic reaction zone, the high Determination of Alkane Content naphtha is sent into the height
Warm reaction zone, while cryogenic reaction zone reaction product enters in high temperature reaction zone.
2. method for modifying according to claim 1, wherein, the F- T synthesis feed naphtha includes 40-70 mass %
High olefin content naphtha and 30-60 mass % high Determination of Alkane Content naphtha.
3. method for modifying according to claim 1, the method for modifying also includes：By upgraded product obtained by high temperature reaction zone
Gas-liquid separation is carried out, at least a portion for the gas-phase product that gas-liquid separation is obtained returns to cryogenic reaction zone.
4. method for modifying according to claim 3, wherein, the gas-phase product returned in cryogenic reaction zone accounts for described
The ratio of all gas-phase products is 20-80 mass % obtained by gas-liquid separation.
5. method for modifying according to claim 1, wherein, the cryogenic reaction zone and high temperature reaction zone each include single
Or the fixed bed reactors or beds of multiple series windings.
6. method for modifying according to claim 5, wherein, fixed bed reaction in the cryogenic reaction zone and high temperature reaction zone
The number of device or beds is respectively 1-4.
7. method for modifying according to claim 5, wherein, there are the fixed bed reactors of multiple series windings the cryogenic reaction zone
Or beds, high olefin content naphtha is divided into the fixed bed reactors each contacted in multiply feeding cryogenic reaction zone
Or beds.
8. method for modifying according to claim 7, wherein, it is sent into the fixed bed reactors of cryogenic reaction zone first or catalysis
The high olefin content naphtha of agent bed accounts for the 50-70 mass % of high olefin content naphtha total amount, is sent into second fixed bed
The high olefin content naphtha of reactor or beds accounts for the 30-50 mass % of high olefin content naphtha total amount.
9. method for modifying according to claim 1, wherein, the initial boiling point of the F- T synthesis naphtha is 50-90 DEG C, eventually
It is a little 110-230 DEG C to evaporate, C5-C12The content of hydro carbons is 50-95 mass %.
10. method for modifying according to claim 1, wherein, the high olefin content Oxygenates Contents Detection in Naphtha
For 5-30 mass %, olefin(e) centent is less than 5 mass % in the high Determination of Alkane Content naphtha.
11. method for modifying according to claim 1, wherein, the high Determination of Alkane Content naphtha is selected from taking for hydrofinishing
Hold in the palm at least one of synthetic naphtha, reforming raffinate oil, the secondary operation naphtha of hydrofinishing and light naphthar.
12. method for modifying according to claim 1, wherein, the modifying catalyst includes carrier, V A race's elements and dilute
Earth elements；Calculated on the basis of carrier, the modifying catalyst includes the 0.01-20 mass % VA races element in terms of oxide
With the 0.01-5 mass % rare earth element in terms of oxide.
13. method for modifying according to claim 12, wherein, ZSM-5 zeolite of the carrier including 40-75 mass %,
3-25 mass % aluminum oxide and 8-35 mass % amorphous aluminum silicate.
14. method for modifying according to claim 12, wherein, VA races element is included in phosphorus, antimony and bismuth extremely
Few one kind；The rare earth element includes 20-40 mass % lanthanum, 40-60 mass % cerium, 0-10 mass % praseodymium and 0-10 matter
Measure % neodymium.
15. method for modifying according to claim 1, wherein, the upgraded condition includes：The temperature of the cryogenic reaction zone
For 200-300 DEG C, the temperature of the high temperature reaction zone is 350-500 DEG C.
16. the method for modifying according to claim 1 or 15, wherein, the upgraded condition includes：Pressure is 0.1-
2.0MPa, the combined feed mass space velocity of F- T synthesis feed naphtha is 0.2-5.0 hours-1。
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| CN111073695A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis naphtha modification method |
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|---|---|---|---|---|
| US4044064A (en) * | 1976-03-29 | 1977-08-23 | Mobil Oil Corporation | Conversion of Fischer-Tropsch heavy product to high quality jet fuel |
| US4071574A (en) * | 1976-03-29 | 1978-01-31 | Mobil Oil Corporation | Conversion of Fischer-Tropsch heavy product to high quality jet fuel |
| US4111792A (en) * | 1976-10-14 | 1978-09-05 | Mobil Oil Corporation | Combination process for upgrading synthol naphtha fractions |
| US20030141222A1 (en) * | 2002-01-31 | 2003-07-31 | O'rear Dennis J. | Upgrading Fischer-Tropsch and petroleum-derived naphthas and distillates |
| CN104140847A (en) * | 2013-05-10 | 2014-11-12 | 中石化洛阳工程有限公司 | Method for production of high-octane gasoline by modification of Fischer-Tropsch synthetic naphtha |
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2016
- 2016-08-31 CN CN201610797824.5A patent/CN107794085B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4044064A (en) * | 1976-03-29 | 1977-08-23 | Mobil Oil Corporation | Conversion of Fischer-Tropsch heavy product to high quality jet fuel |
| US4071574A (en) * | 1976-03-29 | 1978-01-31 | Mobil Oil Corporation | Conversion of Fischer-Tropsch heavy product to high quality jet fuel |
| US4111792A (en) * | 1976-10-14 | 1978-09-05 | Mobil Oil Corporation | Combination process for upgrading synthol naphtha fractions |
| US20030141222A1 (en) * | 2002-01-31 | 2003-07-31 | O'rear Dennis J. | Upgrading Fischer-Tropsch and petroleum-derived naphthas and distillates |
| CN104140847A (en) * | 2013-05-10 | 2014-11-12 | 中石化洛阳工程有限公司 | Method for production of high-octane gasoline by modification of Fischer-Tropsch synthetic naphtha |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111073695A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis naphtha modification method |
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