CN107794080B - The method for modifying of F- T synthesis naphtha - Google Patents
The method for modifying of F- T synthesis naphtha Download PDFInfo
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- CN107794080B CN107794080B CN201610798360.XA CN201610798360A CN107794080B CN 107794080 B CN107794080 B CN 107794080B CN 201610798360 A CN201610798360 A CN 201610798360A CN 107794080 B CN107794080 B CN 107794080B
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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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
-
- 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
- C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
- C10G61/02—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen 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
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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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method for modifying of F- T synthesis naphtha, which includes: by F- T synthesis feed naphtha and C2‑C4Light hydrocarbon feedstocks mixing after successively pass through at least two concatenated fixed bed reaction areas, contact with the modifying catalyst in reaction zone carry out non-hydrogen modification react, obtain upgraded product from the last one reaction zone；Wherein, the fixed bed reaction area is single fixed bed reactors or single catalyst bed；According to the flow direction of the F- T synthesis feed naphtha and light hydrocarbon feedstocks, the at least two concatenated fixed bed reaction area is divided into the first reaction zone and remaining reaction area, and at least partly described F- T synthesis feed naphtha and light hydrocarbon feedstocks are sent into the remaining reaction area.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
Shortage and continuous improvement of the people to environmental requirement increasingly, produced through F-T synthetic technology without sulphur, nitrogen-free, low by coal, natural gas
The clean fuel liquid of aromatic hydrocarbons has become in the industry widely focus of attention.F-T synthetic naphtha fraction contains a large amount of alkene and contains
Oxygen compound cannot be needed directly as vehicle fuel by being further processed to obtain high-quality gasoline component or high added value
Chemical industry product.Currently, F-T synthetic naphtha production gasoline component Conventional processing methods be by hydrofinishing remove alkene and
Then oxygenatedchemicals improves octane number with the method reformed, such methods hydrogen consumption is very big, and big portion after alkene saturation
It is divided into linear paraffin, reforming effect is poor, and economy is bad.On the other hand, with China's " West-east Gas plan and civilian
The contradiction of the implementation of natural gas pipeline projects, domestic liquefied gas surplus is more prominent.Liquefied gas fraction can be made after desulfurization process
For civil liquefied gas sale, the Conventional processing methods of better economy are by gas fractionation unit by propylene therein, isobutyl
The high added values component such as alkene, iso-butane, which is separated, to be used, the remaining liquefied gas component for containing 50% or more C 4 olefin
Because olefin(e) centent height does not meet motor liquified gas standard, processing and utilization method that this part resource has lacked.
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 tower5/C6Using alkane hydroisomerization work
Skill processing increases isohydrocarbon；Tower bottom >=80 DEG C of fractions are increased using fixed-bed catalytic reforming process (cyclic reforming) processing
Add aromatic hydrocarbons；Enter stabilizer after isomerization and reformate mixing, tower bottom obtains motor petrol component that meet national standards.
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 by depickling, olefin(e) centent is relatively lower
Heavy distillat carry out low temperature aromatization reaction on moving bed reaction area top, the portion in the higher light fraction of olefin(e) centent and product
Point 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 top
Lower part is flowed to, reclaimable catalyst Returning reactor after steam stripping regeneration is recycled.This method is reacted using low temperature aromatization
Spent agent and light fraction afterwards carries out high temperature aromatization again.
Chinese patent CN 101747933A discloses a kind of naphtha and light-hydrocarbon aromatized method for modifying, this method comprises:
By naphtha and C3~C5Lighter hydrocarbons existing for the hydrogen-containing gas under the conditions of, in moving bed reaction-regenerating unit reactor with
Aromatized catalyst contact progress aromatization modification reaction, the catalyst inflow catalyst regenerator that activity reduces, by burning,
Dry, cooling regenerated catalyst reenters moving-burden bed reactor.This method can be by the naphtha and lower carbon number hydrocarbons of low octane rating
Be converted into high octane gasoline component and high-quality liquefied gas, because using hydrogen-containing gas as carrier gas, significantly reduce the product end point of distillation and
Catalyst carbon deposit rate, due to using moving bed reaction-continuous reproduction process, catalyst regeneration effect is good, long service life.
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: by F- T synthesis feed naphtha and C2-C4Light hydrocarbon feedstocks mixing after successively pass through at least two concatenated fixed bed reactions
Area contacts with the modifying catalyst in reaction zone and carries out non-hydrogen modification reaction, modification is obtained from the last one reaction zone and is produced
Object；Wherein, the fixed bed reaction area is single fixed bed reactors or single catalyst bed；
According to the flow direction of the F- T synthesis feed naphtha and light hydrocarbon feedstocks, at least two concatenated fixed bed is anti-
It answers area to be divided into the first reaction zone and remaining reaction area, at least partly described F- T synthesis feed naphtha and light hydrocarbon feedstocks is sent
Enter in the remaining reaction area.
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.
Light hydrocarbon feedstocks and F- T synthesis feed naphtha are carried out modification reaction by the present invention together, and liquid production both can be improved
Object yield can also dilute F- T synthesis feed naphtha and transmitting heat, reduce the generation of side reaction.
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 pipeline, 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 pipeline
36 pipeline, 37 pipeline, 38 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.
The method for modifying of F- T synthesis naphtha of the invention is by F- T synthesis feed naphtha and C2-C4Light hydrocarbon feedstocks
Parallel be sent at least two concatenated fixed bed reaction areas carries out non-hydrogen modification reaction, dry gas yied in gained upgraded product
Low, liquid product yield is high.
Since the modification reaction of F- T synthesis naphtha is exothermic reaction, it be easy to cause reaction temperature in fixed bed reaction area
Ascend to heaven, to reduce reaction efficiency.The method of the present invention can rationally control the reaction temperature in fixed bed reaction area, efficient balance
The reaction severity of each reaction zone.
A kind of specific embodiment: the F- T synthesis naphtha of 20-80 mass %, preferably 30-70 mass % is former
Material is sent into first reaction zone, by the F- T synthesis feed naphtha of 20-80 mass %, preferably 30-70 mass %
It is sent into the remaining reaction area；The light hydrocarbon feedstocks of 20-60 mass %, preferably 30-50 mass % are sent into described first
In reaction zone, the light hydrocarbon feedstocks of 40-80 mass %, preferably 50-70 mass % are sent into the remaining reaction area.
Preferably, the remaining reaction area mutually contacts, and forms the reactor or catalyst bed of multiple series windings, each anti-
Device or catalyst bed is answered to be sent into one F- T synthesis feed naphtha and one light hydrocarbon feedstocks.
According to the present invention, since light hydrocarbon feedstocks contain alkene, which occurs that more heat can be released when alkene oligomerization reaction
Amount has the temperature of catalyst bed and reaction product and increases significantly, in addition, fixed bed reaction area is exhausted
Heat, in order to rationally react resulting heat using each fixed bed reaction area, the method for modifying can also include: according to institute
The flow direction for stating F- T synthesis feed naphtha and light hydrocarbon feedstocks will be fed into each reactor or catalysis other than the first reaction zone
The F- T synthesis feed naphtha and light hydrocarbon feedstocks of agent bed react production with the upstream from the reactor or catalyst bed
The described reactor or catalyst bed are re-fed into after object mixing.The temperature of i.e. second and subsequent reactor or catalyst bed
It can be reacted by the F- T synthesis feed naphtha and light hydrocarbon feedstocks for entering the reactor or catalyst bed with previous reaction zone
The mixing of product controls.
Preferably, by the resulting upgraded product of the last one reaction zone and enter each reaction zone in front light hydrocarbon feedstocks and
F- T synthesis feed naphtha exchanges heat, to rationally utilize the heat of reaction product, reduces the heating load of method for modifying.
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, and unconverted light hydrocarbon feedstocks
It can be present in the gaseous product, the gaseous product of the part low value can be sent into fixed bed reaction area and be carried out further
Conversion, both can be improved liquid product yield, can also dilute raw material and transmitting heat, reduce the generation of side reaction.
A kind of specific embodiment: gained upgraded product is carried out gas-liquid separation (can first produce modification before gas-liquid separation
Object and F- T synthesis feed naphtha and light hydrocarbon feedstocks carry out heat exchange cooling), the gas-phase product that gas-liquid separation is obtained is at least
A part returns in first reaction zone.
Preferably, the gas-liquid separation is accounted for back to the gas-phase product for carrying out modification reaction in first reaction zone
The ratio of all gas-phase products of gained can 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: first reaction zone is a fixed bed reactors or the multiple catalyst beds of series winding
Fixed bed reactors in first catalyst bed.Catalyst bed in fixed bed reactors has individually charging system
System, can be separated between each other with support bar, porcelain ball etc..
A kind of specific embodiment: fixed bed reactors or catalyst in at least two concatenated fixed bed reaction area
The number of bed is 2-4.
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), F- T synthesis feed naphtha of the invention
It is preferred that directly from F- T synthesis device, and without the refinement treatment of removing alkene, oxygenatedchemicals or other impurity, such
F- T synthesis feed naphtha typically contains more alkene and oxygenatedchemicals.
The initial boiling point of the F- T synthesis feed naphtha can be 40-90 DEG C, and the end point of distillation can be 150-235 DEG C, alkene
Hydrocarbon content can be 50-90 mass %, and oxygenates level can be 5-50 mass %, preferably 5-30 mass %, C5-C12
The content of hydro carbons can be 50-95 mass %.
C of the present invention2-C4Light hydrocarbon feedstocks be mainly contain C2-C4Alkene and alkane hydrocarbon raw material, wherein C2-
C4The content of alkene is 40-90 mass %, preferably 50-90 mass %, C2-C4The content of alkane is 10-55 mass %, preferably
10-45 mass %, remaining can be the hydrocarbon of methane and light dydrocarbon.The light hydrocarbon feedstocks may include that the gas selected from F- T synthesis produces
At least one of object, the gaseous product of catalytic cracking, the gaseous product of thermal cracking and gaseous product of coking, it is preferably aforementioned
Liquefied gas fraction in gaseous product, or through separating the high values components such as propylene, isobutene and iso-butane in gaseous product
Remaining liquefied gas fraction afterwards.
In the present invention, the F- T synthesis feed naphtha and light hydrocarbon feedstocks of arbitrary proportion can be mixed carry out as needed
Non-hydrogen modification reaction.
A kind of specific embodiment: on the basis of the gross mass of the F- T synthesis feed naphtha and light hydrocarbon feedstocks, institute
The content for stating F- T synthesis feed naphtha can be 10-90 mass %, preferably 40-80 mass %, more preferably 50-70 matter
% is measured, the content of light hydrocarbon feedstocks can be 10-90 mass %, preferably 20-60 mass %, more preferably 30-50 mass %.
Another specific embodiment: the first reaction zone has a reactor or catalyst bed, and remaining reaction area has two
A reactor or catalyst bed mutually contacted；It is passed through F- T synthesis stone brain in the raw material of first reactor or catalyst bed
The content of oily raw material is 60-75 mass %, is passed through F- T synthesis stone brain in the raw material of second, third reactor or catalyst bed
The content of oily raw material is 50-60 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 includes carrier, V A race's element and rare earth element；It is calculated on the basis of carrier, the modifying catalyst can wrap
Include the rare earth element in terms of oxide of the VA race element and 0.01-5 mass % in terms of oxide of 0.01-20 mass %.
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 Gaoxin that F- T synthesis feed naphtha and light hydrocarbon feedstocks, which are converted to target product,
The reaction of alkane value gasoline component.The upgraded condition may include: temperature be 200-600 DEG C, preferably 220-500 DEG C, pressure
For 0.1-2.0MPa, preferably 0.3-1.0MPa, more preferably 0.3-0.6MPa, F- T synthesis feed naphtha and light hydrocarbon feedstocks
Combined feed mass space velocity can be 0.2-5.0 hours-1, preferably 0.4-1.5 hours-1。
In order to improve reaction efficiency, before modification reaction, preferably by the modifying catalyst in the fixed bed reaction area
It is contacted again with the F- T synthesis feed naphtha and light hydrocarbon feedstocks after carrying out in-situ activation；Wherein, the item of the in-situ activation
Part may include: temperature be 300-500 DEG C, preferably 400-450 DEG C, activation pressure 0.1-1.0MPa, preferably 0.3-
0.5MPa, activation time be 1-5 hour, activated media be nitrogen (purity is preferably greater than 99.8 mass %), activated media with urge
The volume ratio of agent is (100-1000): 1.
It can carry out regeneration by the modifying catalyst after to recycle, a kind of specific implementation of catalyst regeneration
Mode, the medium of catalyst regeneration are oxygen containing inert gas, and regenerating medium oxygen content is 0.5-5%, suitable regeneration temperature
It is 350-500 DEG C, pressure 0.1-1.0MPa, the volume ratio of regenerating medium and catalyst is (200-1000): 1.Regeneration
It can be reacted and be regenerated, switch over reaction and regeneration and use using double reaction systems using single reaction system interval
Multiple 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 sent out from the outlet of the reaction zone of the last one reaction zone is known as modifying and be produced by the present invention
The product sent out from the reaction zone outlet in addition to the last one reaction zone is known as reaction product by object.
A kind of specific embodiment of the invention is provided below in conjunction with attached drawing, but not thereby limiting the invention.
Fig. 1 includes three concatenated fixed bed reactors 6,7 and 8, respectively as three fixed bed reaction areas.
As shown in Figure 1, F- T synthesis feed naphtha enters modification reaction system by pipeline 1, the tube side of heat exchanger 3 is flowed through
It is divided into three tunnels after exchanging heat with the upgraded product for flowing through 3 shell side of heat exchanger from pipeline 29.Light hydrocarbon feedstocks enter modification instead by pipeline 2
System is answered, the tube side of heat exchanger 4 is flowed through and is divided into three tunnels after flowing through the upgraded product heat exchange of 4 shell side of heat exchanger from pipeline 30.
First via F- T synthesis feed naphtha is mixed through pipeline 16 with the first via light hydrocarbon feedstocks from pipeline 15,18
Afterwards, through pipeline 20, into heating furnace 5, to be heated to fixed bed anti-after pipeline 19 is mixed with the portion gas product from pipeline 21
Temperature needed for answering device 6 contacts with modifying catalyst into fixed bed reactors 6 through pipeline 22 and carries out non-hydrogen modification instead
It answers, reaction product is discharged by pipeline 23.
Second travelling expenses support synthetic naphtha raw material after pipeline 24 is mixed with the second road light hydrocarbon feedstocks from pipeline 17 again
Temperature needed for mixing with the reaction product of the fixed bed reactors 6 from pipeline 23 and be adjusted to fixed bed reactors 7, then
Contact and carry out non-hydrogen modification reaction with modifying catalyst into fixed bed reactors 7 through pipeline 25, reaction product is by pipeline
26 discharges.
Third travelling expenses support synthetic naphtha raw material after pipeline 27 is mixed with the third road light hydrocarbon feedstocks from pipeline 37 again
Temperature needed for mixing with the reaction product of the fixed bed reactors 7 from pipeline 26 and be adjusted to fixed bed reactors 8, then
It is contacted into fixed bed reactors 8 with modifying catalyst through pipeline 28 and carries out non-hydrogen modification reaction.
The resulting upgraded product of fixed bed reactors 8 is discharged by pipeline 29, is distinguished through heat exchanger 3, pipeline 30, heat exchanger 4
After F- T synthesis feed naphtha and light hydrocarbon feedstocks heat exchange, gas is entered by pipeline 32 after pipeline 31 is cooling by cooler 9
Liquid/gas 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 33, gas compressor 38, pipeline 21 mixed with first via F- T synthesis feed naphtha and first via light hydrocarbon feedstocks after together
Temperature needed for being heated to fixed bed reactors 6 into heating furnace 5 through pipeline 20, then enter fixed bed reactors 6 through pipeline 22
Carry out non-hydrogen modification reaction.
Remaining gas-phase product after pipeline 33, pipeline 35 are mixed with the liquid product from pipeline 34, through pipeline 36 into
Enter to be absorbed, parsed and stablized in product postprocessing unit 11 etc. processing steps, the dry gas in upgraded product is sent by pipeline 12
Product post-processing unit 11 out, liquefied gas group lease making pipeline 13 send out product postprocessing unit 11, and product liquid is as high-quality vapour
Oily blend component sends out product postprocessing unit 11 through pipeline 14.
The present invention is further illustrated below by example, but the present invention is not limited thereto.
The composition of F- T synthesis feed naphtha used in present example and comparative example is as shown in table 1, F- T synthesis stone
The initial boiling point of cerebrol raw material is 51.5 DEG C, and the end point of distillation is 230.5 DEG C, and the composition of light hydrocarbon feedstocks is as shown in table 2.
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.
Light hydrocarbon feedstocks conversion ratio=((product liquid quality-F- T synthesis feed naphtha inlet amount × product liquid is received
Rate)/light hydrocarbon feedstocks inlet amount) × 100%.
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
Catalyst packing: by three reactors (conveniently for statement, the fixed bed reactors 6, fixed bed of Fig. 1 shown device
Reactor 7 and fixed bed reactors 8 are referred to as first reactor, second reactor and third reactor) built-in tamp example 1
The modifying catalyst of preparation, the loadings of each reactor are 40 grams, and catalyst total filling amount is 120 grams.
In-situ activation processing: the in-situ activation processing before reacting in reaction unit modifying catalyst, activation are situated between
Matter is nitrogen, in-situ activation condition are as follows: pressure 0.3MPa, nitrogen and catalyst volume ratio 500:1, temperature of reactor 400
DEG C, activation time is 2 hours.
Non-hydrogen modification reaction:
1, reaction condition: reaction pressure 0.3MPa, each temperature of reactor are 250 DEG C, are with product liquid octane number RON
92 be target, improves temperature of reactor if catalyst activity reduction causes liquid product octane number to decline and makes up active damage
It loses, combined feed mass space velocity 0.8 hour of F- T synthesis feed naphtha and light hydrocarbon feedstocks-1(96.0 Grams Per Hour of total feed).
2, each reactor feed amount: the ratio of F- T synthesis feed naphtha is 60 matter in all modification reaction raw materials
%, 57.6 Grams Per Hour of inlet amount are measured, the ratio of light hydrocarbon feedstocks is 40 mass %, 38.4 Grams Per Hour of inlet amount；F- T synthesis stone
It is 55 mass % (31.68 Grams Per Hour) that the ratio that cerebrol raw material introduces three reactors parallel, which is respectively as follows: first reactor 6, the
Two reactors 7 are 25 mass % (14.4 Grams Per Hour), and third reactor 8 is 20 mass % (11.52 Grams Per Hour)；Light hydrocarbon feedstocks
It is 40 mass % (15.36 Grams Per Hour), second reactor that the ratio for introducing three reactors parallel, which is respectively as follows: first reactor 6,
7 be 32 mass % (12.29 Grams Per Hour), and third reactor 8 is 28 mass % (10.75 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 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
In reaction process second reactor and third reactor required temperature by mixed with the reaction product of previous reactor and with
The heat exchange of upgraded product controls.
It modifies the condition of reaction and the results are shown in Table 3.
Comparative example 1
By loading catalyst in three reactors of the method for example 2 device shown in Fig. 1, and carry out at in-situ activation
Reason.
Non-hydrogen modification reaction, is F- T synthesis naphtha using raw material.
1, reaction condition: reaction pressure 0.3MPa, temperature of reactor is 300 DEG C, with product liquid octane number RON for 92
For target, temperature of reactor is improved if catalyst activity reduction causes liquid product octane number to decline and makes up loss of activity,
The combined feed mass space velocity of F- T synthesis feed naphtha 0.8 hour-1(96.0 Grams Per Hour of total feed).
2, each reactor feed amount: first reactor F- T synthesis feed naphtha inlet amount is 55 matter of total feed
It measures % (52.8 Grams Per Hour), second reactor F- T synthesis feed naphtha inlet amount is 25 mass % (24.0 of total feed
Grams Per Hour), third reactor F- T synthesis feed naphtha inlet amount is the 20 mass % (19.2 Grams Per Hour) of total feed.
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
F- T synthesis feed naphtha is divided into three tunnels after exchanging heat with reaction product in reaction process, and the heating furnace by each reactor adds
Enter each reactor after heat to required reactor required temperature.
It modifies the condition of reaction and the results are shown in Table 3.
Comparative example 2
By loading catalyst in three reactors of the method for example 2 device shown in Fig. 1, and carry out at in-situ activation
Reason.
F- T synthesis feed naphtha and light hydrocarbon feedstocks are pressed into 60 mass % (57.6 Grams Per Hour of inlet amount), 40 mass %
The ratio of (38.4 Grams Per Hour of inlet amount) mixes, under the conditions of 0.3MPa, 250 DEG C by mixed modification raw material by connect into
The mode of material is passed through first reactor, then passes sequentially through second, third reactor, when mixing modification raw material is passed through first instead
After answering device, which sharply increases and is unable to control and is forced to stop, and fails to obtain effective experiment
As a result, situation is shown in Table 3.
As can be seen from Table 3, in example 2,50% or more light hydrocarbon feedstocks are converted into product liquid, product liquid
Relative productivity dramatically increases, and more individually increases by 30% or more by the modification of raw material of Fischer-Tropsch naphtha.By mixing refining in the feed
Light hydrocarbon feedstocks, using its modification reaction process in stronger exothermic effect, each reaction temperature is greatly lowered, reduce plus
Thermic load.The octane number of the method for the present invention product liquid is high, and it is that good gasoline reconciles that alkene, aromatic hydrocarbons, the content of benzene and sulphur are low
Component, liquefied gas product alkene and sulfur content are low, meet motor liquified gas standard.
Table 1
Note: other 23.83 mass % are all kinds of oxygenatedchemicals based on alcohol, ketone.
Table 2
| Hydro carbons | Content, quality % |
| CH4 | 0.93 |
| C2H4 | 2.76 |
| C2H6 | 1.82 |
| C3H6 | 32.64 |
| C3H8 | 18.65 |
| C4H8 | 26.62 |
| C4H10 | 12.82 |
| ≥C5 | 3.76 |
Table 3
| Instance number | Example 2 | Comparative example 1 | Comparative example 2 |
| Reaction temperature, DEG C | 250 | 300 | 250 |
| Reaction pressure, MPa | 0.3 | 0.3 | 0.3 |
| Combined feed mass space velocity, hour-1 | 0.8 | 0.8 | 0.8 |
| F- T synthesis feed naphtha inlet amount, Grams Per Hour | 57.6 | 96.0 | 57.6 |
| Light hydrocarbon feedstocks inlet amount, Grams Per Hour | 38.4 | 0 | 38.4 |
| Product liquid quality, Grams Per Hour | 65.26 | 71.69 | - |
| Liquid product yield, quality % | 67.98 | 74.68 | - |
| Yield of liquefied gas, quality % | 31.15 | 24.59 | - |
| Dry gas yield, quality % | 0.87 | 0.73 | - |
| Product liquid octane number, RON | 92.2 | 92.1 | - |
| Octane number yield, quality % | 62.7 | 68.8 | - |
| Product liquid olefin(e) centent, quality % | 4.67 | 3.85 | - |
| Product liquid arene content, quality % | 33.82 | 33.66 | - |
| Product liquid benzene content, quality % | 0.76 | 0.85 | - |
| Product liquid sulfur content, milligrams per gram | < 1 | < 1 | - |
| Product liquid nitrogen content, milligrams per gram | < 1 | < 1 | - |
| Liquefied gas product olefin(e) centent, quality % | 4.66 | 3.92 | - |
| Liquefied gas product sulfur content, milligrams per gram | < 1 | < 1 | - |
Claims (16)
1. a kind of method for modifying of F- T synthesis naphtha, which includes: by F- T synthesis feed naphtha and C2-C4
Light hydrocarbon feedstocks mixing after successively pass through at least two concatenated fixed bed reaction areas, contacted with the modifying catalyst in reaction zone
Non-hydrogen modification reaction is carried out, obtains upgraded product from the last one reaction zone；Wherein, the fixed bed reaction area is single
Fixed bed reactors or single catalyst bed；
According to the flow direction of the F- T synthesis feed naphtha and light hydrocarbon feedstocks, at least two concatenated fixed bed reaction area
It is divided into the first reaction zone and remaining reaction area, the F- T synthesis feed naphtha of 20-80 mass % is sent into described the
In one reaction zone, the F- T synthesis feed naphtha of 20-80 mass % is sent into the remaining reaction area；By 20-60
The light hydrocarbon feedstocks of quality % are sent into first reaction zone, described in the light hydrocarbon feedstocks feeding by 40-80 mass %
In remaining reaction area.
2. method for modifying according to claim 1, wherein the remaining reaction area mutually contacts, and forms multiple series windings
Reactor or catalyst bed, each reactor or catalyst bed are sent into one F- T synthesis feed naphtha and one is light
Hydrocarbon raw material.
3. method for modifying according to claim 2, the method for modifying further include: former according to the F- T synthesis naphtha
The flow direction of material and light hydrocarbon feedstocks will be fed into the F- T synthesis stone of each reactor or catalyst bed other than the first reaction zone
Cerebrol raw material and light hydrocarbon feedstocks are re-fed into described after mixing with the reaction product from the reactor or the upstream of catalyst bed
The reactor or catalyst bed.
4. method for modifying according to claim 1, the method for modifying further include: gained upgraded product is carried out gas-liquid point
From at least part for the gas-phase product for obtaining gas-liquid separation returns in first reaction zone.
5. method for modifying according to claim 4, wherein back to the institute for carrying out modification reaction in first reaction zone
Stating gas-phase product and accounting for the ratio of all gas-phase products obtained by the gas-liquid separation is 20-80 mass %.
6. method for modifying according to claim 1, wherein first reaction zone is a fixed bed reactors or series winding
First catalyst bed in the fixed bed reactors of multiple catalyst beds.
7. method for modifying according to claim 1, wherein fixed bed in at least two concatenated fixed bed reaction area
The number of reactor or catalyst bed is 2-4.
8. method for modifying according to claim 1, wherein the initial boiling point of the F- T synthesis naphtha is 40-90 DEG C, eventually
Evaporating a little is 150-235 DEG C, and olefin(e) centent is 50-90 mass %, and oxygenates level is 5-50 mass %, C5-C12Hydro carbons
Content is 50-95 mass %.
9. method for modifying according to claim 1, wherein the light hydrocarbon feedstocks include that the gas selected from F- T synthesis produces
At least one of object, the gaseous product of catalytic cracking, the gaseous product of thermal cracking and gaseous product of coking.
10. according to claim 1 or method for modifying described in 9, wherein C in the light hydrocarbon feedstocks2-C4The content of alkene is 40-
90 mass %, C2-C4The content of alkane is 10-55 mass %.
11. method for modifying according to claim 1, wherein with the F- T synthesis feed naphtha and light hydrocarbon feedstocks
On the basis of gross mass, the content of the F- T synthesis feed naphtha is 10-90 mass %, and the content of light hydrocarbon feedstocks is 10-90
Quality %.
12. method for modifying according to claim 1 or 2, wherein the first reaction zone has a reactor or catalyst bed
Layer, there are two the reactors or catalyst bed mutually contacted in remaining reaction area；It is passed through first reactor or catalyst bed
The content of F- T synthesis feed naphtha is 60-75 mass % in raw material, is passed through second, third reactor or catalyst bed
The content of F- T synthesis feed naphtha is 50-60 mass % in raw material.
13. 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 %.
14. method for modifying according to claim 13, 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 %.
15. method for modifying according to claim 13, 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 %.
16. method for modifying according to claim 1, wherein the upgraded condition includes: that reaction temperature is 200-600 DEG C,
Pressure is 0.1-2.0MPa, and the combined feed mass space velocity of F- T synthesis feed naphtha and light hydrocarbon feedstocks is 0.2-5.0 hours-1。
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| 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 |
| CN104711019A (en) * | 2015-03-05 | 2015-06-17 | 武汉凯迪工程技术研究总院有限公司 | System and method for producing diesel oil and jet fuel by utilizing Fischer-Tropsch synthetic oil |
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| EP0216972A1 (en) * | 1983-12-14 | 1987-04-08 | Exxon Research And Engineering Company | Fischer-Tropsch process with cobalt-promoted catalysts |
| WO2008055353A1 (en) * | 2006-11-08 | 2008-05-15 | Canada Chemical Corporation | Low pressure fixed bed fischer-tropsch process and apparatus |
| CN101747933A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Modifying method for naphtha and light hydrocarbon aromatization |
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