CN109096036B - Method and device for separating 1-decene from Fischer-Tropsch synthetic oil by using reaction separation coupling process - Google Patents

Method and device for separating 1-decene from Fischer-Tropsch synthetic oil by using reaction separation coupling process Download PDF

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CN109096036B
CN109096036B CN201810900859.6A CN201810900859A CN109096036B CN 109096036 B CN109096036 B CN 109096036B CN 201810900859 A CN201810900859 A CN 201810900859A CN 109096036 B CN109096036 B CN 109096036B
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CN109096036A (en
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李洪
赵悦
李鑫钢
高鑫
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Tianjin University
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Abstract

The invention relates to a method and a device for separating 1-decene from a Fischer-Tropsch synthesis oil light oil C10 narrow fraction, comprising the following steps: removing oxygen-containing compounds by extractive distillation or azeotropic distillation; adding a reactant to convert one of the substances into a derivative thereof, and obtaining C10 normal hydrocarbon by a reaction separation coupling method; the 1-decene conversion olefin derivative is separated from alkane by a reactive distillation method, and then the olefin derivative is subjected to reverse reaction to obtain a 1-decene product again. The method is characterized in that the separation problem of the mixture with extremely similar boiling points or azeotropic points is converted into the separation problem of the mixture with larger boiling point difference by a reversible reaction auxiliary separation method, and the high-purity 1-decene product with high added value is separated from the narrow fraction of the Fischer-Tropsch synthetic oil C10 by the method of extraction/azeotropic distillation and reaction separation coupling, and meanwhile, the production energy consumption and the equipment investment cost are lower, and higher economic benefit can be created.

Description

Method and device for separating 1-decene from Fischer-Tropsch synthetic oil by using reaction separation coupling process
Technical Field
The invention relates to a method for separating and purifying 1-decene from a narrow fraction section of Fischer-Tropsch synthetic oil C10, which is particularly suitable for a process for producing high-purity 1-decene from a coal-based raw material.
Background
Fischer-Tropsch synthesis, i.e. an indirect coal liquefaction process, in the presence of a catalyst, gasifying the synthesis gas (CO, H)2) Converting into gasoline, diesel oil and other hydrocarbon products. The crude reaction products mainly comprise light oil, heavy oil and heavy wax. The main substances in the light oil are normal alkane and normal olefin, and the olefin component is mostly alpha-olefin. When conventional naphtha and diesel oil are used as main products, the olefin needs to be hydrotreated.If the desired alpha-olefin component can be separated from the product by any suitable means to further produce high value products, the process economics will be greatly enhanced. At present, the capacity of separating and purifying alpha-olefin from F-T synthetic oil is not available at home, and only Sasol company in south Africa has the technology globally, so that if the technology for separating and purifying the alpha-olefin can be developed, the purpose of value-added utilization of Fischer-Tropsch synthetic light oil can be achieved, and the capacity and the market of the global alpha-olefin are also influenced greatly.
The C10 alpha-olefin (1-decene) has high added value, can be used as a solvent, can be used as a raw material for preparing essence, spice, medicine, dye, grease, resin and the like, and can also be used for preparing nontoxic plasticizers of diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP), and the dosage of the alpha-olefin (1-decene) in the wire and cable materials is increased rapidly. Currently, there is no single 1-decene production facility in the world, and all the facilities are produced along with the production of 1-hexene, 1-octene and other alpha-olefins. With the increase in the market demand of 1-decene, the industrialization of its production process is a necessary trend.
The SHOP process from Shell produces linear alpha-olefins and internal olefins, the resulting product having catalyst properties and oligomerization conditions determined by oligomerizing ethylene in the presence of a non-Ziegler-Ni catalyst to form C4-C20+The olefin mixture (C) of (1) wherein the majority is alpha-olefin and the mass content is about 94-97%, and wherein the mass content of 1-decene is about 8-12% (SYED NAQVI N].Caledonia:SRI CONSULTING,2002:4-19.)。
Chevron Phillips chemical company adopts a traditional Ziegler process, takes triethylaluminum as a catalyst, ethylene reacts with a chain growth product of the triethylaluminum to replace alpha-olefin with even carbon number, and the carbon number range of the product produced by the process is C4-C30+Wherein the mass content of the 1-decene product is about 13% (ELVIRAO, CAMARA G, RALFG, et al chemical environmental Handbook: Linear alpha olefins [ M)].Caliofrnia:SRI CONSULTING,2004:10-11)。
The Amoco process of BP company is an improvement on Chevron ethylene oligomerization process, and is mainly characterized in that a chain extension reaction and a chain replacement reaction are carried out in two steps, and an ethylene chain extension product can be further processed into linear alpha-olefin. The method is mainly used for producing low-carbon olefin, and the content of the produced 1-decene is about 22 percent (Li Junliang, Wu Yarong. 1-decene production technology and application thereof [ J ] petrochemical technology, 2008,15(1): 66-69.).
French Petroleum Institute (IFP) developed AlphaSelect for the production of alpha-olefinsTMThe process mainly comprises selectively producing alpha-olefin C4-C8, wherein the mass content of 1-decene is 9-14% (SYED NAQVI N. linear alpha olefins process environmental impact program report [ R ]].US:Nexant Chem Systems,200l:5；7；18.)。
The production process developed by Saudi Arabia Basic Industrial Corp (SABIC) comprises the steps of preparing a catalyst, and preparing the catalyst. The mass content of the 1-decene in the product is 13 percent, and the purity of the 1-decene product can reach 96.9 percent. And the conversion rate can be improved by controlling the conditions such as temperature and the like, and related products with high purity can be selectively obtained (the production application and the market prospect of Liyufang, Wuming. 1-decene [ J ]. acetaldehyde acetic acid chemical industry, 2008(7): 38-40.).
The invention provides a novel process method and a device for efficiently separating and purifying 1-decene from Fischer-Tropsch oil C10 narrow fraction.
Disclosure of Invention
The invention aims to overcome the defects of the existing 1-decene production technology and provides a high-efficiency and energy-saving method and device for separating and purifying 1-decene from a Fischer-Tropsch synthetic oil C10 narrow fraction step by step to obtain a 1-decene product.
The technical scheme for realizing the purpose of the invention is as follows:
a method for separating 1-decene from a Fischer-Tropsch synthetic oil C10 narrow fraction comprises the steps of removing oxygen-containing compounds, separating normal hydrocarbons and isomeric hydrocarbons by a reversible reaction auxiliary separation method, and separating normal paraffins and normal olefins by a reactive distillation method, and specifically comprises the following steps:
carrying out azeotropic distillation or extractive distillation treatment on a narrow fraction section of Fischer-Tropsch synthetic oil C10, and adding a third reagent to remove oxygen-containing compounds in the narrow fraction;
secondly, the narrow fraction section of C10 obtained in the last step and from which the oxygen-containing compounds are removed enters a reaction separation coupling unit, a complex reactant is added, and the heterogeneous hydrocarbon has a plurality of branched chains and is relatively active, but the steric hindrance of the normal hydrocarbon is small, so that the normal hydrocarbon and the heterogeneous hydrocarbon have reaction kinetic difference in different reactions, and the normal hydrocarbon and the heterogeneous hydrocarbon are separated by utilizing the characteristic in a reaction separation coupling mode;
and thirdly, the normal hydrocarbon obtained in the last step enters another reaction separation coupling unit, a reactant is added, the olefin is separated in a reaction separation coupling mode by utilizing the characteristics that the olefin contains unsaturated double bonds and is easy to generate chemical reaction and the alkane property is stable, and the 1-decene is obtained again through reverse reaction.
In the step, a third method is added for extraction and rectification to obtain at least one of succinonitrile and glycerol; or in the step, azeotropic distillation is adopted, and a third party experiment is added to obtain at least one of dimethyl ether and diethyl ether, so that the removal efficiency of the oxygen-containing compound can be improved by the azeotropic agent.
Furthermore, in the step two, the complexing reactant can be a substance which is easy to react with isoparaffin to form solid or a substance which is easy to react with normal paraffin to form solid.
In addition, in the step II, the complexing reagent is thiourea or urea modified by brominated-N-ethylpyridine [ EPy ] [ Br ] ionic liquid, and the urea (or the thiourea) is mixed with [ EPy ] [ Br ] in equal molar amount at normal temperature and stirred to obtain { CO (NH2)2- [ EPy ] [ Br ] } (or { S (NH2)2- [ EPy ] [ Br ] }), and the urea and the ionic liquid are added in equal molar amount. The ionic liquid modified reactant can improve the reaction activity and the recovery rate of the product.
And the reaction in the reaction separation coupling unit in the step three is a complex reaction, a hydrosilation reaction or a hydrosulfide reaction.
In the step three, the reactant is a nickel dithio diene complex, NiL2Where L is a dithiino-metallocene, e.g. mnt (S)2C2(CN)2) Or tfd (S)2C2(CF3)2) Binuclear molybdenum complex (R-CpMo- (. mu. -S)2S2CHX, wherein R ═ H, CH3,CO2Na,X＝H,CN,CMe3(ii) a Diphenylsilane, H2Si(C6H5)2)、HSiR3(R＝CH2CH3,C6H5) Or hydrogen sulfide.
A device for separating 1-decene from a narrow fraction of Fischer-Tropsch synthetic oil C10 comprises an extractive distillation or azeotropic distillation tower (T11), a third-party reagent recovery tower (T12), a reactor (R21), a separator (T22), a normal olefin reaction distillation tower (T31), a reverse reaction distillation tower (T32), a condenser, a reboiler, a pump, related feeding pipelines and pipelines for connecting the devices, wherein the pipelines are connected as follows
The raw material (S01) is added from a feed inlet of an azeotropic distillation tower (T11), the feed inlet is arranged at the middle upper part of the azeotropic distillation tower (T11), one part of the tower bottom material flow of the azeotropic distillation tower (T11) returns to the azeotropic distillation tower (T11) through a reboiler, and the other part is extracted; the overhead material flow enters a phase separator through a condenser, one part of the overhead material flow returns to an azeotropic distillation tower (T11), and the other part of the overhead material flow enters a feed inlet at the middle upper part of an entrainer recovery tower (T12);
the overhead stream of the entrainer recovery tower (T12) and the overhead stream of the azeotropic distillation tower (T11) enter a phase separator through the same condenser; part of the tower bottom material flow returns to the entrainer recovery tower (T12) through a reboiler, and part of the tower bottom material flow enters a feed inlet of the normal hydrocarbon reactor (R21);
the stream taken out of the bottom outlet of the normal hydrocarbon reactor (R21) enters a normal hydrocarbon separator (T23) through a filter (F22) and a peristaltic pump. The normal hydrocarbon separator (T23) is provided with two discharge ports, the lower discharge port is connected with the feed port of the normal hydrocarbon reactor (R21), and the upper discharge port is connected with the feed port of the normal olefin reaction rectifying tower (T31);
the normal olefin reaction rectifying tower (T31) is provided with two feeding holes with different heights in the reaction section, the tower top material flows through a condenser and enters a reflux buffer tank, one part of the tower top material is used as reflux, and the other part of the tower top material is extracted; returning a part of the tower bottom material flow to the normal olefin reaction rectifying tower (T31) through a reboiler, and feeding a part of the tower bottom material flow into a feed inlet of a reverse reaction rectifying tower (T32);
the feed inlet of the reverse reaction rectifying tower (T32) is arranged at the reaction section, and the outlet of the top material flow is connected with the feed inlet of the normal olefin reaction rectifying tower (T31); part of the tower bottom material flow returns to the reverse reaction rectifying tower (T32) through a reboiler, and part of the tower bottom material flow is extracted as a product.
Further, the operation is as follows
The method comprises the steps of feeding narrow C10 distillate (S01) as raw material into an azeotropic distillation tower (T11), adding an entrainer (S04), removing oxygen-containing compounds (S02) in the narrow C10 distillate, feeding an entrainer and C10 hydrocarbon mixture (S03) into an entrainer recovery tower (T12), recovering the entrainer (S04-a), and obtaining C10 hydrocarbon (S05) with the removed oxygen-containing compounds;
secondly, the C10 hydrocarbon (S05) enters a reversible reaction auxiliary separation unit (R21, T22), firstly enters a normal hydrocarbon reactor (R21), and a reactant (S06) is added, the normal hydrocarbon is converted into a derivative by utilizing the kinetic difference of the normal hydrocarbon and the isomeric hydrocarbon in the reaction, the isomeric hydrocarbon (S08) is removed through a filter (F22), the rest product (S09) enters a normal hydrocarbon separator (T23) to be separated, the C10 normal hydrocarbon (S11) is obtained, and the reactant (S06-a) is recovered;
the C10 normal hydrocarbon (S11) enters a next reaction rectification separation coupling unit (T31, T32), firstly enters a normal olefin reaction rectification tower (T31), and is added with a normal olefin reactant (S12), 1-decene is converted into a normal olefin derivative (S14) by utilizing the chemical stability difference of alkane and olefin, the normal olefin derivative (S14) is separated from n-decane (S13), the normal olefin derivative (S14) enters a reverse reaction rectification tower (T32), 1-decene (S15) is obtained again through reverse reaction, and the reactant (S12-a) is recycled.
The theoretical plate number of the azeotropic distillation tower (T11) is 10-100, the operating pressure is 0.05-5 atm, and the reflux ratio is 0.1-20; the number of theoretical plates of an entrainer recovery tower (T12) is 10-100, the feeding position is 1-100, the reflux ratio is 0.1-20, and the operating pressure is 0.05-5 atm.
The normal hydrocarbon reactor (R21) has an operating pressure of 0.05 to 10atm, a reaction temperature of-5 to 60 ℃, a normal hydrocarbon separator (T23) having an operating pressure of 0.05 to 10atm, a temperature of 25 to 150 ℃ and a mass ratio of the reactant to the normal hydrocarbon of 1 to 10.
The theoretical plate numbers of the reaction section, the rectification section and the stripping section of the olefin reaction rectification tower (T31) are respectively 10-100, 10-100 and 10-100, the operating pressure is 0.05-10 atm, and the reflux ratio is 0.1-20;
the theoretical plate numbers of the reaction section, the rectification section and the stripping section of the reverse reaction rectification tower (T32) are respectively 10-100, 10-100 and 10-100, the operating pressure is 0.05-10 atm, and the reflux ratio is 0.1-20.
Moreover, the azeotropic distillation tower (T11) is replaced by an extraction distillation tower (T13), C10 hydrocarbon (S05) without oxygen-containing compounds is extracted from the tower top, a mixture of an extracting agent and the oxygen-containing compounds (S18) is extracted from the tower bottom, the theoretical plate number of the extraction distillation tower (T21) is 10-100, the operating pressure is 0.05-5 atm, and the reflux ratio is 0.1-20; the entrainer recovery tower (T12) is replaced by an extractant recovery tower (T14), the number of theoretical plates is 10-100, the feeding position is 1-100, the reflux ratio is 0.1-20, and the operating pressure is 0.05-5 atm;
the normal hydrocarbon reactor (R21) is replaced by an isomeric hydrocarbon reactor (R22), the operating pressure is 0.05-10 atm, the reaction temperature is-5-60 ℃, the operating pressure is 0.05-10 atm, the temperature is 25-150 ℃, and the mass ratio of the reactant to the isomeric hydrocarbon is 1-10; the normal hydrocarbon separator (T23) is replaced by a normal hydrocarbon separation tower (T24), the theoretical plate number is 10-100, the operation pressure is 0.05-5 atm, and the reflux ratio is 0.1-20;
the normal olefin reaction rectifying tower (T31) is replaced by a structure of a reactor and a separation tower, a normal olefin reactor (R31) and a normal alkane separation tower (T33). The normal olefin reactor (R31) has the operation pressure of 0.05-10 atm, the reaction temperature of 25-350 ℃, the theoretical plate number of the normal alkane separating tower (T33) of 10-100, the operation pressure of 0.05-10 atm and the reflux ratio of 0.1-20.
The reverse reaction rectifying tower (T32) is replaced by a structure of a reactor and a separation tower, the reverse reactor (R32) and the normal olefin separation tower (T34), the operating pressure of the reverse reactor (R32) is 0.05-10 atm, the reaction temperature is 25-350 ℃, the theoretical plate number of the normal olefin separation tower (T34) is 10-100, the operating pressure is 0.05-10 atm, and the reflux ratio is 0.1-20.
The invention has the advantages and positive effects as follows
The method and the device for separating 1-decene from Fischer-Tropsch synthetic oil have the advantages that 1-decene products with high added values can be separated from Fischer-Tropsch synthetic oil, the development of a 1-decene production process is facilitated, meanwhile, the energy consumption and equipment cost are low, higher economic benefits can be created, and further, the market competitiveness of industries and enterprises is improved.
After separation and purification by the process, the mass content of the 1-decene product can reach more than 99 percent, and the recovery rate can reach more than 95 percent. The method is characterized in that the separation problem of the mixture with extremely similar boiling points or azeotropic points is converted into the separation problem of the mixture with larger boiling point difference by a reversible reaction auxiliary separation method, and the high-purity 1-decene product with high added value is separated from the narrow fraction of the Fischer-Tropsch synthetic oil C10 by the method of extraction/azeotropic distillation and reaction separation coupling, and meanwhile, the production energy consumption and the equipment investment cost are lower, and higher economic benefit can be created.
Drawings
FIG. 1 is a schematic view of the process flow of an azeotropic distillation column, a normal hydrocarbon reactor and a separator, and a reactive distillation column.
FIG. 2 is a schematic view of the process flow of the extractive distillation column, the normal hydrocarbon reactor and the separator, and the normal olefin reactor and the separator.
FIG. 3 is a schematic diagram of a process flow of an azeotropic distillation column, an isomeric hydrocarbon reactor and a separation column, and a normal olefin reactor and a separator.
T11-azeotropic rectifying tower, T12-entrainer recovery tower, T13-extractive rectifying tower, T14-extractant recovery tower, R21-normal hydrocarbon reactor, R22-isomeric hydrocarbon reactor, F22-suction filter, T23-normal hydrocarbon separator, T-24 normal hydrocarbon separation tower, T31-normal olefin reaction rectifying tower, T32-reverse reaction rectifying tower, R31-normal olefin reactor, R32-reverse reactor, T33-normal paraffin separation tower and T34-normal olefin separation tower.
S01-C10 narrow cut, S02-oxygenate, mixture of S03-C10 hydrocarbon and entrainer, S04-third party reagent, S04-a-recovered third party reagent, S04-b-supplemented third party reagent, S05-C10 hydrocarbon with oxygenate removed, S06-reactant, S06-a-recovered reactant, S06-b-supplemented reactant, S07-reaction product, S08-isohydrocarbon, S09-normal hydrocarbon derivative, S10-water, S11-normal hydrocarbon, S12-normal olefin reactant, S12-a-recovered normal olefin reactant, S12-b-supplemented normal olefin reactant, S13-normal decane, S14-olefin derivative, S15-1-decene, S16-normal olefin reactor product, s17-reverse reactor product, S18-mixture of oxygenate and extractant.
Detailed Description
The method and apparatus provided by the present invention will be further described with reference to the accompanying drawings, but the scope of the present invention is not limited to the embodiments.
The narrow cut (S01) of the C10 feedstock contains normal paraffins and alpha olefins, and also includes some isoparaffins, internal olefins, branched olefins, minor amounts of naphthenes, aromatics, cycloolefins, and one or more oxygenates including alcohols, aldehydes, ketones, acids, esters, and the like.
The device mainly comprises an extraction rectifying tower or an azeotropic rectifying tower for removing an oxygen-containing compound part, an extracting agent or an azeotropic agent recovery tower, a reaction separation coupling device (the reaction rectifying tower or a reactor and a separator) for separating normal hydrocarbon and an isomeric hydrocarbon part, and a reaction separation coupling device (the reaction rectifying tower or the reactor and the separator) for separating normal alkane and normal alkene parts.
The technological process includes extraction or azeotropic rectification, two-step reaction and separation coupling and other sequential technological processes. The method specifically comprises the following steps:
(1) carrying out azeotropic distillation or extractive distillation treatment on the narrow fraction section of the Fischer-Tropsch synthesis oil C10, and adding a third party reagent to remove oxygen-containing compounds in the narrow fraction;
(2) the narrow C10 fraction obtained in the last step and from which the oxygen-containing compound is removed enters a reaction separation coupling unit, a complex reactant is added, the isomeric hydrocarbon has more branched chains and is more active, but the steric hindrance of the normal hydrocarbon is small, so the normal hydrocarbon and the isomeric hydrocarbon have reaction kinetic difference in different reactions, and the normal hydrocarbon and the isomeric hydrocarbon are separated by utilizing the characteristic in a reaction separation coupling mode;
(3) and (3) enabling the normal hydrocarbon obtained in the last step to enter another reaction separation coupling unit, adding a reactant, separating the normal hydrocarbon by a reaction separation coupling mode by utilizing the characteristics that the olefin contains unsaturated double bonds and is easy to generate chemical reaction and the alkane has stable property, and obtaining the 1-decene again by reverse reaction.
The raw material in the step (1) is Fischer-Tropsch synthesis oil C10 narrow fraction, and comprises normal alkane and alpha-olefin, and also comprises some isoparaffin, internal olefin, branched olefin, a small amount of cycloparaffin, aromatic hydrocarbon, cycloolefine, and one or more of oxygen-containing compounds such as alcohol, aldehyde, ketone, acid, ester and the like. The extractant may be one or more of Succinonitrile (SN) and Glycerol (GI). The entrainer can be one or more aqueous solutions of low carbon ethers such as dimethyl ether (DME) and diethyl ether (DEE). The theoretical plate number of the extraction rectifying tower or the azeotropic rectifying tower is 10-100, the feeding position is 1-100, the reflux ratio is 0.1-20, and the operating pressure is 0.05-5 atm. The theoretical plate number of the entrainer recovery tower is 10-100, the feeding position is 1-100, the reflux ratio is 0.1-20, and the operating pressure is 0.05-5 atm.
The narrow cut into the reactor in step (2) is the oxygenate-depleted C10 hydrocarbon. The added reactants are divided into two types, one is a substance which reacts with the isomeric hydrocarbon, such as thiourea; another class is substances that react with normal hydrocarbons, such as urea. The reactants are modified by bromide-N-ethyl pyridine [ EPy ] [ Br ] ionic liquid. The reaction rectifying tower or the structure of reactor and separator may be adopted, and the separator includes rectifying tower, absorbing tower, etc. The mass ratio of the reactant to the normal hydrocarbon is 1 to 10. The operating pressure of the reactor is 0.05-10 atm, and the temperature is-5-60 ℃. The operating pressure of the separator is 0.05-10 atm, and the temperature is 25-150 ℃.
The reaction in the step (3) is a complex reaction, a hydrosilation reaction or a hydrosulfide reaction, and the added reactants are respectively a nickel dithiodiene complex (NiL)2Where L is a dithiino-metallocene, e.g. mnt (S)2C2(CN)2) Or tfd (S)2C2(CF3)2) Binuclear molybdenum complex (R-CpMo- (. mu. -S)2S2CHX, wherein R ═ H, CH3,CO2Na,X＝H,CN,CMe3) And the like; diphenylsilane (H)2Si(C6H5)2)、HSiR3(R＝CH2CH3,C6H5) IsosilanesA derivative; hydrogen sulfide (H)2S). The alpha-olefins can react with the reactants described above to form the corresponding olefin derivatives, while the alkanes do not react. The reaction rectifying tower or the structure of reactor and separator may be adopted, and the separator includes rectifying tower, absorbing tower, etc. The molar ratio of the reactant to the normal olefin is 1-10. The theoretical plate numbers of the reaction section, the rectification section and the stripping section of the olefin reaction rectification tower are respectively 10-100, 10-100 and 10-100, the feeding position is 1-300, the reflux ratio is 0.1-20, the operating pressure is 0.05-10 atm, and the operating temperature is 25-350 ℃. The operating pressure of the first reactor is 0.05-10 atm, the operating temperature is 25-350 ℃, the theoretical plate number of the first separation tower is 10-100, the feeding position is 1-100, the reflux ratio is 0.1-20, and the operating pressure is 0.05-10 atm. The theoretical plate number of the reaction section, the rectification section and the stripping section of the reverse reaction rectification tower is 10-100, the feeding position is 1-300, the reflux ratio is 0.1-20, and the operating pressure is 0.05-10 atm. The operating pressure of the second reactor is 0.05-10 atm, the operating temperature is 25-350 ℃, the theoretical plate number of the second separation tower is 10-100, the feeding position is 1-100, the reflux ratio is 0.1-20, and the operating pressure is 0.05-10 atm.
Example 1
The method is used for the separation and purification process of 1-decene, and comprises an azeotropic rectifying tower (T11), an entrainer recovery tower (T12), a normal hydrocarbon reactor (R21), a normal hydrocarbon separator (T22), a normal olefin reaction rectifying tower (T31), a reverse reaction rectifying tower (T32), a condenser, a reboiler, a pump, related feeding pipelines and pipelines for connecting the devices as shown in figure 1. The raw material is Fischer-Tropsch synthesis oil C10 narrow fraction, which comprises normal alkane and alpha-olefin, and also comprises some isoparaffin, internal olefin, branched olefin, a small amount of naphthene, aromatic hydrocarbon, cycloolefin, and one or more of oxygen-containing compounds such as alcohol, aldehyde, ketone, acid, ester, etc. Wherein the mass content of the 1-decene is about 60 percent, and the mass content of the n-decane is about 20 percent. The number of the tower plates of the azeotropic distillation tower (T11) is 10 theoretical plates, the reflux ratio is 20, the operating pressure is 5atm, and the entrainer is dimethyl ether aqueous solution. The narrow fraction of C10 is fed from the 10 th theoretical plate of azeotropic rectifying tower (T11), the C10 hydrocarbon and dimethyl ether water solution form the lowest azeotrope and is extracted from the top of the tower, and the oxygen-containing compound is extracted from the bottom of the tower. The number of the trays of an entrainer recovery tower (T12) is 100 theoretical plates, the reflux ratio is 0.1, the operating pressure is 0.05atm, the entrainer is extracted from the top of the tower for recycling, and C10 hydrocarbon which is removed with oxygen-containing compounds is extracted from the bottom of the tower. Adding C10 hydrocarbon into a normal hydrocarbon reactor (R21), adding urea modified by brominated-N-ethylpyridine [ EPy ] [ Br ] ionic liquid, namely { CO (NH2)2- [ EPy ] [ Br ] } as a reactant, and adding tetrahydrofuran-water solution as an activating agent, wherein the ratio of urea: tetrahydrofuran: 12g of water, 10ml of water, 5ml of water, reaction temperature of-5 ℃, pressure of 0.1atm and reaction time of 1h, wherein the normal C10 hydrocarbon reacts with { CO (NH2)2- [ EPy ] [ Br ] } to generate complex crystals and the complex crystals are precipitated in a solid form. The normal C10 hydrocarbon- { CO (NH2)2- [ EPy ] [ Br ] } complex enters a normal hydrocarbon separator (T23), water is added for decomplexation, and normal hydrocarbon is separated again, wherein the reaction temperature is 150 ℃, and the reaction time is 20 min. The number of the trays of the normal olefin reaction rectifying tower (T31) is 300 theoretical plates, wherein 1-100 theoretical plates are used as a rectifying section, 101-200 theoretical plates are used as a reaction section, 201-300 theoretical plates are used as a stripping section, the reflux ratio is 0.1, and the operating pressure is 0.05 atm. Adding normal hydrocarbon into a normal olefin reaction rectifying tower (T31) from a 200 th theoretical plate, simultaneously adding diphenylsilane from a 101 th theoretical plate, reacting 1-decene with diphenylsilane to generate n-decyl diphenylsilane, extracting unreacted alkane from the top of the tower, and extracting generated n-decyl diphenylsilane from the bottom of the tower. The number of the trays of the reverse reaction rectifying tower (T32) is 30 theoretical plates, wherein 1-10 theoretical plates are rectifying sections, 11-20 theoretical plates are reaction sections, and 21-30 theoretical plates are stripping sections. n-decyl diphenyl silane is added into a reverse reaction rectifying tower (T32) from a 10 th theoretical plate to carry out reverse reaction, diphenyl silane and 1-decene are regenerated, diphenyl silane is extracted from the top of the tower and recycled, and 1-decene is extracted from the bottom of the tower as a product. The final 1-decene product mass content was 99.1%, and the yield was 95.3%.
The reactant is urea, and under the same conditions, the mass content of the 1-decene product is 99.0 percent, and the yield is 92.9 percent.
Example 2
The method is used for the separation and purification process of 1-decene, and comprises a azeotropic distillation tower (T11), an entrainer recovery tower (T12), a normal hydrocarbon reactor (R21), a normal hydrocarbon separator (T22), a normal olefin reaction distillation tower (T31), a reverse reaction distillation tower (T32), a condenser, a reboiler, a pump, related feeding pipelines and pipelines for connecting the devices as shown in figure 1. The raw material is Fischer-Tropsch synthesis oil C10 narrow fraction, which comprises normal alkane and alpha-olefin, and also comprises some isoparaffin, internal olefin, branched olefin, a small amount of naphthene, aromatic hydrocarbon, cycloolefin, and one or more of oxygen-containing compounds such as alcohol, aldehyde, ketone, acid, ester, etc. Wherein the mass content of the 1-decene is about 60 percent, and the mass content of the n-decane is about 20 percent. The number of the tower plates of the azeotropic distillation tower (T11) is 100 theoretical plates, the reflux ratio is 0.1, the operating pressure is 0.05atm, and the entrainer is aether water solution. The narrow fraction of C10 was fed from the 2 nd theoretical plate of azeotropic distillation column (T11), the C10 hydrocarbon formed the lowest azeotrope with the aqueous ether solution, which was withdrawn from the top of the column, and the oxygenate was withdrawn from the bottom of the column. The number of plates of an entrainer recovery tower (T12) is 10 theoretical plates, the reflux ratio is 20, the operating pressure is 5atm, the entrainer extracted from the top of the tower is recycled, and C10 hydrocarbon without oxygen-containing compounds is extracted from the bottom of the tower. Adding C10 hydrocarbon into a normal hydrocarbon reactor (R21), adding urea modified by brominated-N-ethylpyridine [ EPy ] [ Br ] ionic liquid, namely { CO (NH2)2- [ EPy ] [ Br ] } as a reactant, and adding tetrahydrofuran-water solution as an activating agent, wherein the ratio of urea: tetrahydrofuran: 12g of water, 12ml of water and 5ml of water, wherein the initial reaction temperature is 60 ℃, then the reaction temperature is reduced to 25 ℃ at the speed of 0.5 ℃/min, the pressure is 1atm, the reaction time is 1h, and the normal C10 hydrocarbon reacts with { CO (NH2)2- [ EPy ] [ Br ] } to generate complex crystals and the complex crystals are precipitated in a solid form. The normal C10 hydrocarbon- { CO (NH2)2- [ EPy ] [ Br ] } complex enters a normal hydrocarbon separator (T23), water is added for decomplexation, and normal hydrocarbon is separated again, wherein the reaction temperature is 150 ℃, and the reaction time is 20 min. The number of the trays of the normal olefin reaction rectifying tower (T31) is 30 theoretical plates, wherein 1-10 theoretical plates are used as a rectifying section, 11-20 theoretical plates are used as a reaction section, 21-30 theoretical plates are used as a stripping section, the reflux ratio is 20, and the operating pressure is 10 atm. Adding normal hydrocarbon into a normal olefin reaction rectifying tower (T31) from a 10 th theoretical plate, simultaneously adding hydrogen sulfide from a 20 th theoretical plate, reacting 1-decene with the hydrogen sulfide to generate 2-decanethiol, extracting unreacted alkane from the tower top, and extracting the generated 2-decanethiol from the tower bottom. The number of the trays of the reverse reaction rectifying tower (T32) is 300 theoretical plates, wherein 1-100 theoretical plates are a rectifying section, 101-200 theoretical plates are a reaction section, and 201-300 theoretical plates are a stripping section. And 2-decylthiol is added into a reverse reaction rectifying tower (T32) from the 200 th theoretical plate to perform reverse reaction, hydrogen sulfide and 1-decylene are regenerated, the hydrogen sulfide is extracted from the top of the tower and recycled, and the 1-decylene is taken as a product and extracted from the bottom of the tower. The final 1-decene product mass content was 99.3%, and the yield was 96.7%.
Example 3
The method is used for the separation and purification process of 1-decene, and comprises an extractive distillation tower (T13), an extractant recovery tower (T14), a normal hydrocarbon reactor (R21), a normal hydrocarbon separator (T23), a normal olefin reactor (R31), a normal alkane separation tower (T33), a reverse reactor (R32), a normal olefin separation tower (T34), a condenser, a reboiler, a pump, related feed lines and lines for connecting the devices as shown in figure 2. The raw material is Fischer-Tropsch synthesis oil C10 narrow fraction, which comprises normal alkane and alpha-olefin, and also comprises some isoparaffin, internal olefin, branched olefin, a small amount of naphthene, aromatic hydrocarbon, cycloolefin, and one or more of oxygen-containing compounds such as alcohol, aldehyde, ketone, acid, ester, etc. Wherein the mass content of the 1-decene is about 60 percent, and the mass content of the n-decane is about 20 percent. The number of the trays of the extractive distillation column (T13) is 10 theoretical plates, the reflux ratio is 20, the operating pressure is 0.05atm, the feeding position is the 5 th theoretical plate, and the added extractant is succinonitrile. The extractant recovery column (T14) had 10 theoretical plates, a reflux ratio of 20, an operating pressure of 0.05atm and a feed position of 5 th theoretical plate. Adding urea modified by brominated-N-ethylpyridine [ EPy ] [ Br ] ionic liquid into a normal hydrocarbon reactor (R21), namely { CO (NH2)2- [ EPy ] [ Br ] } is used as a reactant, and adding tetrahydrofuran-water solution is used as an activating agent, wherein the ratio of urea: tetrahydrofuran: 12g of water, 12ml of water and 7ml of water, wherein the reaction temperature is-5 ℃ and the reaction time is 20 min. The hydrolysis complex is added into a normal hydrocarbon separator (T23), the reaction temperature is 25 ℃, the pressure is 0.05atm, and the reaction time is 1 h. The reactant added into the normal olefin reactor (R31) is nickel-dithiodiene complex, NiL2, wherein L is (S2C2(CN)2), the reaction temperature is 25 ℃, the pressure is 10atm, and the reaction time is 1 h. The normal paraffin separation column (T33) is a rectifying column, the theoretical plate number is 10 theoretical plates, the reflux ratio is 20, and the operating pressure is 10 atm. The reverse reaction of the normal olefin reactor (R31) took place in the reverse reactor (R32) at a reaction temperature of 25 ℃ and a pressure of 0.05atm for a reaction time of 1 hour. The normal olefin separation column (T34) was a rectification column having 10 theoretical plates as the number of theoretical plates, a reflux ratio of 20 and an operating pressure of 0.05 atm. The final 1-decene product has a mass content of 99.0% and a yield of 95.0%.
Example 4
The method is used for the separation and purification process of 1-decene, and comprises an extractive distillation tower (T13), an extractant recovery tower (T14), an isomeric hydrocarbon reactor (R22), a normal hydrocarbon separator (T24), a normal olefin reactor (R31), a normal paraffin separation tower (T33), a reverse reactor (R32), a normal olefin separation tower (T34), a condenser, a reboiler, a pump, related feeding pipelines and pipelines for connecting the devices, as shown in figure 3. The raw material is Fischer-Tropsch synthesis oil C10 narrow fraction, which comprises normal alkane and alpha-olefin, and also comprises some isoparaffin, internal olefin, branched olefin, a small amount of naphthene, aromatic hydrocarbon, cycloolefin, and one or more of oxygen-containing compounds such as alcohol, aldehyde, ketone, acid, ester, etc. Wherein the mass content of the 1-decene is about 60 percent, and the mass content of the n-decane is about 20 percent. The number of the trays of the extractive distillation column (T13) is 100 theoretical plates, the reflux ratio is 0.1, the operating pressure is 5atm, the feeding position is the 5 th theoretical plate, and the added extractant is glycerol. The number of trays in the extractant recovery column (T14) was 100 theoretical plates, the reflux ratio was 0.1, the operating pressure was 5atm, and the feed position was the 5 th theoretical plate. Adding thiourea modified by brominated-N-ethylpyridine [ EPy ] [ Br ] ionic liquid into an isomeric hydrocarbon reactor (R22), namely { S (NH2)2- [ EPy ] [ Br ] } as a reactant, and adding tetrahydrofuran-water solution as an activating agent, wherein the ratio of thiourea: tetrahydrofuran: 12g of water, 12ml of water and 7ml of water, wherein the reaction temperature is 60 ℃ and the reaction time is 1 h. The normal hydrocarbon separation column (T24) had a theoretical plate number of 30, a reflux ratio of 1.5 and an operating pressure of 1 atm. The reactant added into the normal olefin reactor (R31) is phenylsilane, the reaction temperature is 50 ℃, the pressure is 0.05atm, and the reaction time is 1 h. The normal paraffin separation column (T33) is a rectifying column, the theoretical plate number is 100 theoretical plates, the reflux ratio is 0.1, and the operating pressure is 0.05 atm. The reverse reaction of the normal olefin reactor (R31) occurred in the reverse reactor (R32), the reaction temperature was 50 ℃, the pressure was 10atm, and the reaction time was 1 h. The normal separation column (T34) was a rectifying column, the number of theoretical plates was 100 theoretical plates, the reflux ratio was 0.1, and the operating pressure was 10 atm. The final 1-decene product mass content was 99.5%, and the yield was 96.1%.
The reactant is thiourea, and under the same conditions, the mass content of the 1-decene product is 99.1 percent, and the yield is 93.3 percent.

Claims (3)

1. A process for the separation of 1-decene from a narrow fraction of Fischer-Tropsch synthesis oil C10, characterized in that: the method comprises the steps of removing oxygen-containing compounds, separating normal hydrocarbons and isomeric hydrocarbons by a reversible reaction-assisted separation method, and separating normal alkanes and normal olefins by a reactive distillation method, and specifically comprises the following steps:
carrying out azeotropic distillation or extractive distillation treatment on a narrow fraction section of Fischer-Tropsch synthetic oil C10, and adding a third reagent to remove oxygen-containing compounds in the narrow fraction;
secondly, the narrow fraction section of C10 obtained in the last step and from which the oxygen-containing compounds are removed enters a reaction separation coupling unit, a complex reactant is added, and the heterogeneous hydrocarbon has a plurality of branched chains and is relatively active, but the steric hindrance of the normal hydrocarbon is small, so that the normal hydrocarbon and the heterogeneous hydrocarbon have reaction kinetic difference in different reactions, and the normal hydrocarbon and the heterogeneous hydrocarbon are separated by utilizing the characteristic in a reaction separation coupling mode; the complexing reagent is thiourea or urea modified by ionic liquid; the ionic liquid is brominated-N-ethyl pyridine;
and thirdly, the normal hydrocarbon obtained in the last step enters another reaction separation coupling unit, a reactant is added, the olefin is separated in a reaction separation coupling mode by utilizing the characteristics that the olefin contains unsaturated double bonds and is easy to generate chemical reaction and the alkane property is stable, and the 1-decene is obtained again through reverse reaction.
2. The process according to claim 1 for the separation of 1-decene from a fischer-tropsch synthesis oil C10 narrow fraction, characterized in that: in the step, a third-party reagent is added into the extraction and rectification to be at least one of succinonitrile and glycerol; or in the step, azeotropic distillation is adopted to add a third-party reagent which is at least one of dimethyl ether and diethyl ether.
3. The process according to claim 1 for the separation of 1-decene from a fischer-tropsch synthesis oil C10 narrow fraction, characterized in that: and step three, the reaction in the reaction separation coupling unit is a complex reaction, a hydrosilation reaction or a hydrosulfide reaction.
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