CN107794085B - 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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- CN107794085B CN107794085B CN201610797824.5A CN201610797824A CN107794085B CN 107794085 B CN107794085 B CN 107794085B CN 201610797824 A CN201610797824 A CN 201610797824A CN 107794085 B CN107794085 B CN 107794085B
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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
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of method for modifying of F- T synthesis naphtha, which includes: that F- T synthesis feed naphtha is successively passed through concatenated cryogenic reaction zone and high temperature reaction zone, contacts with the modifying catalyst in reaction zone and carries out non-hydrogen modification reaction；The F- T synthesis feed naphtha includes the high olefin content naphtha of 10-90 mass % and the high Determination of Alkane Content naphtha of 10-90 mass %；Olefin(e) centent is 50-90 mass % in the high olefin content naphtha, and Determination of Alkane Content is greater 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.Method for modifying of the invention is able to produce high-octane rating product liquid.
Description
Technical field
The present invention relates to a kind of inferior naphtha method for modifying, specifically, being a kind of modification of F- T synthesis naphtha
Method.
Background technique
Counted according to World Energy Conference, worldwide coal proven reserve and can mining time far more than petroleum, in recent years, day
The recoverable reserves that right gas is verified continues to increase.Energy resource structure total feature in China's 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, low aromatic hydrocarbons clean fuel liquid have become in the industry widely focus of attention.F-T synthetic naphtha fraction contains a large amount of alkene
Hydrocarbon and oxygenatedchemicals cannot be needed directly as vehicle fuel by being further processed to obtain high-quality gasoline component or height
Added value chemical industry product.Currently, the Conventional processing methods of F-T synthetic naphtha production gasoline component are removed by hydrofinishing
Then alkene and oxygenatedchemicals improve octane number with the method reformed, such methods hydrogen consumption is very big, and alkene is saturated
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, evaporates
Divide the method for fuel or lubricant base stock.This method comprises: hydrocarbon source is separated into gaseous hydrocarbon, condensate and viscous crude；Gaseous state
Hydrocarbon generates synthesis gas and obtains naphtha and distillate through F- T synthesis；Fischer-Tropsch naphtha and condensate are reformed afterwards through hydrogenated processing
It obtains containing 10% or more aromatic hydrocarbons, the gasoline component of 80 or more octane number and by-product hydrogen；The hydrogen of by-product is 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 coagulate
Hydrofinishing before condensate oil reformation.
United States Patent (USP) US6875339 discloses a kind of method of F- T synthesis naphtha octane improvement, this method comprises:
By the C from F- T synthesis4-C8Straight-chain hydrocarbons, which 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 generate hydrogen supply isomerization list
Member, aromatization products are fractionated, and send unconverted straight-chain hydrocarbons back to isomerization or aromatization unit, contain aromatic hydrocarbons and isomery
The product liquid octane number of hydrocarbon is improved.
United States Patent (USP) US4013737 discloses a kind of low octane rating synthetic gasoline method for modifying, this method comprises: 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 high boiling point product, and high boiling point product returns to reaction member；In synthetic gasoline raw material
Mix C3、C4Alkene participates in modification reaction, while adding propane and butane absorption reaction heat in the feed.
Chinese patent CN 103396833A discloses a kind of method of synthetic naphtha production motor petrol, this method packet
It includes: the ICL for Indirect Coal Liquefaction synthetic naphtha Jing Guo hydrofinishing being fractionated, the C of one line of fractionation column5/C6It is different using paraffin hydro
Structure process increases isohydrocarbon；Tower bottom >=80 DEG C of fractions use fixed-bed catalytic reforming process (cyclic reforming)
Processing increases aromatic hydrocarbons；Enter stabilizer after isomerization and reformate mixing, tower bottom obtains motor petrol that meet national standards
Component.
Chinese patent CN 104140847A discloses a kind of side of F- T synthesis naphtha modification production high-knock rating gasoline
Method, this method comprises: the F- T synthesis naphtha of high olefin content is dehydrated aftercut, olefin(e) centent relatively low one by depickling
A little heavy distillat is in moving bed reaction area top progress low temperature aromatization reaction, the higher light fraction of olefin(e) centent and product
Part rich gas carries out high temperature aromatization in moving bed reaction area lower part, and global molecular sieve catalyst is from moving bed reaction area
Portion flows to lower part, and reclaimable catalyst Returning reactor after steam stripping regeneration is recycled.This method is anti-using low temperature aromatization
Spent agent and light fraction after answering carry out high temperature aromatization again.
Summary of the invention
The object of the present invention is to provide a kind of method for modifying of F- T synthesis naphtha, method for modifying of the invention can be given birth to
Produce high-octane rating product liquid.
To achieve the goals above, the present invention provides a kind of method for modifying of F- T synthesis naphtha, the method for modifying packet
It includes: F- T synthesis feed naphtha is successively passed through into the modification in concatenated cryogenic reaction zone and high temperature reaction zone, with reaction zone
Catalyst contact carries out non-hydrogen modification reaction；The F- T synthesis feed naphtha includes that the high alkene of 10-90 mass % contains
Measure the high Determination of Alkane Content naphtha of naphtha and 10-90 mass %；Olefin(e) centent is 50-90 in the high olefin content naphtha
Quality %, Determination of Alkane Content is greater than 80 mass % in the high Determination of Alkane Content naphtha；The high olefin content naphtha is sent into
The high Determination of Alkane Content naphtha is sent into the high temperature reaction zone by the cryogenic reaction zone, while cryogenic reaction zone reaction produces
Object enters in high temperature reaction zone.
The method for modifying dry gas yield of F- T synthesis naphtha of the 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, method of the invention is easy, investment operation expense is low, can significantly improve and changes by the way of parallel feeding
The selectivity of qualitative response improves the relative stability of catalyst, extends the catalyst runs period, can effectively improve F- T synthesis stone
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
Modification reaction is carried out, can be improved liquid product yield and octane number yield.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, 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 flow diagram of specific embodiment of F- T synthesis naphtha method for modifying of the present invention.
Description of symbols
1 pipeline, 2 pipeline, 3 heat exchanger, 4 heat exchanger
5 heating furnace, 6 fixed bed reactors, 7 fixed bed reactors, 8 fixed bed reactors
9 cooler, 10 gas-liquid separator, 11 product postprocessing unit
12 pipeline, 13 pipeline, 14 pipeline, 15 pipeline
16 pipeline, 17 heating furnace, 18 pipeline, 19 pipeline
20 pipeline, 21 pipeline, 22 pipeline, 23 pipeline
24 pipeline, 25 pipeline, 26 pipeline, 27 pipeline
28 pipeline, 29 pipeline, 30 pipeline, 31 pipeline
32 pipeline, 33 pipeline, 34 pipeline, 35 gas compressor
Specific embodiment
Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
High olefin content naphtha carries out modification reaction in cryogenic reaction zone in the method for the present invention, and cryogenic reaction zone reaction produces
Object carries out modification into the high temperature reaction zone for being connected in cryogenic reaction zone downstream after mixing with high Determination of Alkane Content naphtha and reacts, and shows
Write the modification effect for improving high Determination of Alkane Content naphtha；Using in high olefin content naphtha reaction process due to alkene oligomerization
The stronger exothermic effect generated is reacted, the material temperature into cryogenic reaction zone can be made to reduce, and at a lower temperature
It is reacted, while reducing the heating load into high temperature reaction zone raw material, significantly reduce the energy consumption of upgrading processes.
A kind of preferred embodiment: the F- T synthesis feed naphtha includes that the high alkene of 40-70 mass % contains
Measure the high Determination of Alkane Content naphtha of naphtha and 30-60 mass %.
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
Overlapping and structural rearrangement are carried out, therefore contains a certain amount of gaseous product in upgraded product, it can be by the gas of the part low value
Body product is sent into insulation fix bed reaction zone and is further converted, and liquid product yield both can be improved, can also dilute
Raw material and transmitting heat, reduce the generation of side reaction.
A kind of specific embodiment: upgraded product obtained by high temperature reaction zone is carried out 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, all gas-phase products obtained by the gas-liquid separation are accounted for back to the gas-phase product in cryogenic reaction zone
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 room temperature, normal pressure for gaseous state
Product, may include liquefied gas and dry gas, and 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 produces
Object.
A kind of specific embodiment: the cryogenic reaction zone and high temperature reaction zone respectively include consolidating for single or multiple series windings
Fixed bed reactor or catalyst bed.Catalyst bed in fixed bed reactors has independent feed system, between each other may be used
To be separated with support bar, porcelain ball etc..
A kind of specific embodiment: fixed bed reactors or catalyst bed in the cryogenic reaction zone and high temperature reaction zone
Number be respectively 1-4.The sum of the fixed bed reactors or catalyst bed of cryogenic reaction zone and high temperature reaction zone series winding
It is preferred that 2-4.
Since the modification reaction of F- T synthesis naphtha is exothermic reaction, it be easy to cause flying for reaction temperature in reaction zone
It rises, to reduce reaction efficiency and contain security risk, 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 specific embodiment: there are the fixed bed reactors or catalyst bed of multiple series windings in cryogenic reaction zone, will be high
Olefin(e) centent naphtha is divided into the fixed bed reactors or catalyst bed that multiply is sent into each series winding in cryogenic reaction zone.
Preferably, it is sent into the high olefin content naphtha of the fixed bed reactors of cryogenic reaction zone first or catalyst bed
The 50-70 mass % for accounting for high olefin content naphtha total amount, is sent into the high alkene of second fixed bed reactors or catalyst bed
Hydrocarbon content naphtha accounts for the 30-50 mass % of high olefin content naphtha total amount.
F- T synthesis feed naphtha be it is well-known to those skilled in the art, refer to using coal, natural gas as raw material pass through
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 %.
High olefin content naphtha of the invention 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 selected from the F- T synthesis naphtha of hydrofinishing, reforming raffinate oil, hydrofinishing secondary operation stone
At least one of cerebrol and light naphthar, olefin(e) centent is lower, 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 carrying out F- T synthesis feed naphtha into non-hydrogen modification reaction.It is described
Modifying catalyst may include carrier, V A race's element and rare earth element；It is calculated on the basis of carrier, the modifying catalyst can
To include the VA race element in terms of oxide of 0.01-20 mass % and the rare earth member in terms of oxide of 0.01-5 mass %
Element.
Preferably, the carrier includes the ZSM-5 zeolite of 40-75 mass %, the aluminium oxide of 3-25 mass % and 8-35 matter
The amorphous aluminum silicate of % is measured, the silica alumina ratio of the ZSM-5 zeolite can be 10-300.
VA race element may include selected from least one of phosphorus, antimony and bismuth；The rare earth element may include 20-
The lanthanum of 40 mass %, the cerium of 40-60 mass %, the praseodymium of 0-10 mass % and 0-10 mass % neodymium.
Preferred embodiment under given conditions carries out at aging modifying catalyst with 100% vapor
Reason, keep modifying catalyst with good stability and regenerability, catalyst shape can for stripe shape, microspheric form, piece type,
Grain shape or microspheric.Preferred 500-600 DEG C of steam treatment temperature, the steam treatment time is 0.5-8 hours, and preferably 2-6 is small
When.The α value of carrier is 10-100, preferably 20-60 after steam treatment.(measuring method of α value is write referring to Yang Cuiding etc.
" petrochemical analysis method (RIPP experimental method) ", Science Press publish, the P255 " α of constant temperature method measurement acidic catalyst
Value ").
Non-hydrogen modification reaction refers to that it is high-knock rating gasoline group that F- T synthesis feed naphtha, which is converted to target product,
The reaction divided.The upgraded condition may include: that 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, preferably
0.3-1.0MPa, more preferably 0.3-0.6MPa, the combined feed mass space velocity of F- T synthesis feed naphtha are that 0.2-5.0 is small
When-1, preferably 0.4-1.5 hours-1。
Since reaction zone is insulation, 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, in addition to first fixed bed
Outside reactor or catalyst bed, will be fed into the F- T synthesis feed naphtha of each fixed bed reactors or catalyst bed with
The described fixed bed reactors are re-fed into after the reaction product mixing of upstream from the fixed bed reactors or catalyst bed
Or the non-hydrogen modification reaction is carried out in catalyst bed.Furthermore it is possible to by the last one fixed bed reactors or catalyst
The resulting upgraded product of bed and the F- T synthesis feed naphtha for entering each fixed bed reactors in front or catalyst bed
It exchanges heat, to rationally utilize the heat of upgraded product, reduces 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
It is 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 may include: temperature is 300-500 DEG C, it is preferably 350-450 DEG C, pressure 0.1-1.0MPa, preferably 0.3-0.5MPa, living
Changing the 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.
It can carry out regeneration by the modifying catalyst after to recycle, a kind of specific implementation of catalyst regeneration
Mode, catalyst regeneration 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
To be reacted and be regenerated using single reaction system interval, switch over reaction and regeneration using double reaction systems and using more
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 product that the present invention will be sent out from the last one fixed bed reactors or catalyst bed outlet
Referred to as upgraded product is produced being known as reacting from the product in addition to the last one fixed bed reactors or catalyst bed outlet submitting
Object.
A kind of specific embodiment of the invention is provided with reference to the accompanying drawing, but the present invention is not therefore and by any
Limitation.
Fig. 1 includes three concatenated fixed bed reactors 6,7 and 8, 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 flowing through the upgraded product heat exchange of 3 shell side of heat exchanger from pipeline 26, high Determination of Alkane Content naphtha is entered by pipeline 2
The tube side of heat exchanger 4 is reacted by pipeline 15 into modification after exchanging heat with the upgraded product for flowing through 4 shell side of heat exchanger from pipeline 27
System.
First via high olefin content naphtha is after pipeline 16 is mixed with the portion gas product from pipeline 19 through pipeline
18 are heated to the temperature of cryogenic reaction zone into heating furnace 5, contact into fixed bed reactors 6 with modifying catalyst through pipeline 20
And non-hydrogen modification reaction is carried out, reaction product is discharged by pipeline 21.
Reaction product of the second tunnel high olefin content naphtha through pipeline 22 and the fixed bed reactors 6 from pipeline 21 is mixed
Merge the temperature for adjusting and reaching cryogenic reaction zone, then enters fixed bed reactors 7 through pipeline 23 and connect with modifying catalyst
It touches and carries out non-hydrogen modification reaction, reaction product is discharged by pipeline 24.
High Determination of Alkane Content naphtha is mixed into through pipeline 34 and the reaction product of the fixed bed reactors 7 from pipeline 24
Heating furnace 17 is heated to the temperature of high temperature reaction zone, then contacts into fixed bed reactors 8 with modifying catalyst through pipeline 25
And carry out non-hydrogen modification reaction.
8 gained upgraded product of fixed bed reactors 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, after pipeline 28 is cooling by cooler 9 by pipeline 29 into
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 through pipeline 18 together after mixing with first via high olefin content naphtha
It is heated to the temperature of the cryogenic reaction zone needed, then continues to participate in modification reaction into fixed bed reactors 6 through pipeline 20.
Remaining gas-phase product enters through pipeline 33 and changes after pipeline 30,32 is mixed with the liquid product from pipeline 31
The processing steps 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 group lease making pipeline 13 sends out product postprocessing unit 11, and product liquid is made
Product postprocessing unit 11 is sent out through pipeline 14 for premium blend component.
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.
Present example and the obtained upgraded product of comparative example obtain gas from extraction in reactor and after refrigerated separation
Phase product and liquid product, and detected as follows:
The composition of gas-phase product uses Agilent 7890A chromatographic, makes a concrete analysis of condition are as follows: carrier gas N2, hair
Tubule quartz column, fid detector；35 DEG C of initial temperature, 8 DEG C/min of heating 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, determines each component content using normalizing sizing technique；Gas-phase product includes
Dry gas and liquefied gas two parts, wherein the main component of dry gas is C1、C2Hydro carbons and a small amount of hydrogen, the ingredient of liquefied gas are C3、
C4Hydro carbons.
The composition of liquid product is analyzed using Shimadzu GC-2010AF chromatograph, makes a concrete analysis of condition are as follows: 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, each component content is determined using normalizing sizing technique.
The octane number of product liquid detects machine testing using the CFR-1 octane number of Waukesha company.
Example 1
Prepare modifying catalyst used in present example and comparative example.
(1) preparation of carrier: (feldspar is built in Hunan to 130 grams of HZSM-5 zeolite powder for being 56 by silica/alumina molar ratio
Change the production of limited liability company's molecular sieve factory), 35 grams of boehmite powder (alumina content be 75 mass %) and silica solution
(SiO2After content is 30 mass %), 35 grams of mixing, the aqueous solution of nitric acid that 100 grams of concentration are 1.0 mass % is added and stirs, stands
Make peptization, then mediate and be extruded into 2 millimeters of diameter of item, 110 DEG C drying 4 hours, be cut into 2-3 millimeters of length of strip particle, 550
DEG C roasting 4 hours, be made carrier, aluminium oxide therein be γ-Al2O3。
(2) steam treatment: the carrier prepared in step (1) is packed into tubular reactor, under normal pressure in the air stream
550 DEG C are warming up to, the temperature is kept to change logical 100% steam treatment 4 hours.
(3) it impregnates: 100 grams of carrier after taking the steam treatment prepared in step (2), with 50 milliliters of phosphoric acid solution (matter
Amount concentration is 100 mg/mls) dipping 1 hour, take solid after dipping, 120 DEG C drying 2 hours, then it is dilute with 100 milliliters of mixing
Soil (containing 40 mass % of lanthana, 60 mass % of cerium oxide) aqueous solution (and in terms of mixed rare-earth oxide, mass concentration be 10 milli
Grams per milliliter) 80 DEG C impregnate 2 hours, take dipping after solid, 120 DEG C drying 8 hours, 550 DEG C roast 4 hours, obtain modify urge
Agent.
The constituent content calculated on the basis of carrier in modifying catalyst is following (being analyzed using x-ray fluorescence method): 0.53
The phosphorus pentoxide of the mixed rare earth oxide of quality %, 5.29 mass %, the carrier include 69.8 mass % HZSM-5,
γ-the Al of 12.2 mass %2O3With the amorphous aluminum silicate of 18 mass %, 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: three reactors (, fixed bed reactors 6, fixed bed reaction convenient for statement shown in Fig. 1
Device 7 and fixed bed reactors 8 are referred to as first reactor, second reactor and third 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: the activation processing before reacting in reaction unit modifying catalyst, activated media are
Nitrogen, in-situ activation condition are as follows: pressure 0.3MPa, nitrogen and catalyst volume ratio are 500:1, and reaction temperature is 400 DEG C, living
Changing the time is 2 hours.
Non-hydrogen modification reaction:
1, 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, if catalyst activity reduction causes liquid product octane number to decline, improves reaction temperature and makes up loss of activity.
2, each reactor feed amount: the ratio of high olefin content naphtha is 60 mass %, inlet amount in modification raw material
43.2 Grams Per Hours, ratio of the high Determination of Alkane Content naphtha in modification raw material is 40 mass %, into third 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
Being respectively as follows: first reactor 6 is 60 mass % (25.9 Grams Per Hour), and second reactor 7 is 40 mass % (17.3 Grams Per Hour)；
Modification reaction process in second reactor temperature by mixed with the reaction product of previous reactor and with upgraded product
To control, the temperature of third reactor is mixed also by the heat exchange with upgraded product and with the reaction product of previous reactor for heat exchange
It closes to increase, insufficient section is supplemented by heating furnace.
3, upgraded product is handled: upgraded product obtains gas-phase product after exchanging heat, cooling down with raw material, separate and liquid phase produces
30 mass % of gas-phase product are returned to first reactor and continue to participate in modification reaction by object, remaining gas-phase product and liquid phase produce
Object is sent into subsequent product Vapor recovery unit unit together, isolates dry gas component, liquefied gas component and product liquid component.
It modifies the condition of reaction and the results are shown in Table 3.
Comparative example 1
Reaction unit, loaded catalyst used by this comparative example, in-situ activation processing method are the same as example 2.
Non-hydrogen modification reaction:
1, reaction condition: reaction pressure 0.3MPa, combined feed mass space velocity are 0.6 hour-1(72.0 grams of total feed/small
When), it is target with product liquid octane number RON 92 that each temperature of reactor, which is 426 DEG C, if catalyst activity reduction causes liquid
The decline of body product octane number then improves reaction temperature and makes up loss of activity.
2, using high Determination of Alkane Content naphtha as raw material, it each reactor feed: is introduced concatenated three from first reactor
A reactor and modifying catalyst haptoreaction.
3, upgraded product is handled: upgraded product obtains gas-phase product after exchanging heat, cooling down with raw material, separate and liquid phase produces
30 mass % of gas-phase product are returned to first reactor and continue to participate in modification reaction by object, remaining gas-phase product and liquid phase produce
Object is sent into subsequent product Vapor recovery unit unit together, isolates dry gas component, liquefied gas component and product liquid component.Modification
After high Determination of Alkane Content naphtha and upgraded product exchange heat in reaction process, the temperature of the reaction as needed for the Heating Furnace Control of each reactor
Degree.
It modifies the condition of reaction and the results are shown in Table 3.
Comparative example 2
Reaction unit, loaded catalyst used by this comparative example, in-situ activation processing method are the same as example 2.
Non-hydrogen modification reaction:
1, reaction condition: in reaction pressure 0.3MPa, combined feed mass space velocity 0.6 hour-1(72.0 grams of total feed/small
When), it is target with product liquid octane number RON 92 that each temperature of reactor, which is 372 DEG C, if catalyst activity reduction causes liquid
The decline of body product octane number then improves reaction temperature and makes up loss of activity.
2, each reactor parallel feeding amount (the parallel feeding condition that mixing naphtha optimizes): high olefin content naphtha
(in the ratio of 60 mass %) is uniformly mixed with high Determination of Alkane Content naphtha (in the ratio of 40 mass %), first reactor mixing
Feedstock amount is the 50 mass % (36.0 Grams Per Hour) of total feed, and second reactor mixed raw material inlet amount is combined feed
The 30 mass % (21.6 Grams Per Hour) of amount, third reactor mixed raw material inlet amount are 20 mass % (14.4 of total feed
Grams Per Hour).
3, upgraded product is handled: upgraded product obtains gas-phase product after exchanging heat, cooling down with raw material, separate and liquid phase produces
30% return first reactor of gas-phase product is continued to participate in modification reaction, remaining gas-phase product and liquid product one by object
It rises and is sent into subsequent product Vapor recovery unit unit, isolate dry gas component, liquefied gas component and product liquid component.Modification reaction
Mixing F- T synthesis feed naphtha is divided into three tunnels after exchanging heat with upgraded product in the process, by the Heating Furnace Control of each reactor
The temperature of required reaction.
It modifies 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 subregion of the invention
Method for modifying significantly improves the modification effect of high Determination of Alkane Content naphtha, the product liquid as premium blend component
Yield dramatically increase, meanwhile, the energy consumption of upgrading processes is substantially reduced, 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 % |
| 5 alkane of carbon | 4.83 |
| 6 alkane of carbon | 12.60 |
| 7 alkane of carbon | 15.33 |
| 8 alkane of carbon | 16.72 |
| 9 alkane of carbon | 15.85 |
| 10 alkane of carbon | 14.65 |
| 11 alkane of carbon | 13.06 |
| 12 alkane of carbon | 4.56 |
| Alkene | 0.32 |
| Cycloalkane | 0.52 |
| Aromatic hydrocarbons | 1.56 |
Table 3
Claims (15)
1. a kind of method for modifying of F- T synthesis naphtha, the method for modifying include: successively to pass through F- T synthesis feed naphtha
Concatenated cryogenic reaction zone and high temperature reaction zone 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 the high olefin content naphtha of 10-90 mass % and the height of 10-90 mass %
Determination of Alkane Content naphtha；Olefin(e) centent is 50-90 mass %, the high Determination of Alkane Content stone brain in the high olefin content naphtha
Determination of Alkane Content is greater 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.
The temperature of the cryogenic reaction zone is 200-300 DEG C, and the temperature of the high temperature reaction zone is 350-500 DEG C.
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 further include: by upgraded product obtained by high temperature reaction zone
Gas-liquid separation is carried out, at least part 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 accounted for back to the gas-phase product in cryogenic reaction zone described
The ratio of all gas-phase products obtained by gas-liquid separation is 20-80 mass %.
5. method for modifying according to claim 1, wherein the cryogenic reaction zone and high temperature reaction zone respectively include single
Or the fixed bed reactors or catalyst bed 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 catalyst bed is respectively 1-4.
7. method for modifying according to claim 5, wherein there are the fixed bed reactors of multiple series windings in the cryogenic reaction zone
Or catalyst bed, high olefin content naphtha is divided into the fixed bed reactors that multiply is sent into each series winding in cryogenic reaction zone
Or catalyst bed.
8. method for modifying according to claim 7, wherein be 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 catalyst bed 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
Evaporating a little is 110-230 DEG C, 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 element and dilute
Earth elements；It is calculated on the basis of carrier, the modifying catalyst includes the VA race element in terms of oxide of 0.01-20 mass %
With the rare earth element in terms of oxide of 0.01-5 mass %.
13. method for modifying according to claim 12, wherein the carrier include 40-75 mass % ZSM-5 zeolite,
The aluminium oxide of 3-25 mass % and the amorphous aluminum silicate of 8-35 mass %.
14. method for modifying according to claim 12, wherein VA race element include in phosphorus, antimony and bismuth extremely
Few one kind；The rare earth element includes the lanthanum of 20-40 mass %, the cerium of 40-60 mass %, the praseodymium of 0-10 mass % and 0-10 matter
Measure the neodymium of %.
15. method for modifying according to claim 1, wherein the upgraded condition includes: that pressure is 0.1-2.0MPa, is taken
The combined feed mass space velocity for holding in the palm synthetic naphtha raw material is 0.2-5.0 hours-1。
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Citations (4)
| 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 |
| 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 |
|---|---|---|---|---|
| US6863802B2 (en) * | 2002-01-31 | 2005-03-08 | Chevron U.S.A. | Upgrading fischer-Tropsch and petroleum-derived naphthas and distillates |
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Patent Citations (4)
| 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 |
| 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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