CN114805005B - Method and device for separating 1-octene from Fischer-Tropsch synthesis oil-washed naphtha - Google Patents
Method and device for separating 1-octene from Fischer-Tropsch synthesis oil-washed naphtha Download PDFInfo
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- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 title claims abstract description 133
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 27
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 126
- 238000000605 extraction Methods 0.000 claims abstract description 48
- 238000006266 etherification reaction Methods 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 14
- 238000000638 solvent extraction Methods 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 229960004063 propylene glycol Drugs 0.000 claims description 5
- 235000013772 propylene glycol Nutrition 0.000 claims description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 229940102253 isopropanolamine Drugs 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000005215 recombination Methods 0.000 claims description 2
- 230000006798 recombination Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 5
- 239000005977 Ethylene Substances 0.000 abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 21
- 238000006392 deoxygenation reaction Methods 0.000 description 13
- 239000003921 oil Substances 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- RCBGGJURENJHKV-UHFFFAOYSA-N 2-methylhept-1-ene Chemical compound CCCCCC(C)=C RCBGGJURENJHKV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/14875—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with organic compounds
- C07C7/14891—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with organic compounds alcohols
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method and a device for separating 1-octene from Fischer-Tropsch synthesis oil washing naphtha. The method comprises the following steps: (1) Rectifying Fischer-Tropsch synthesis oil-washed naphtha to obtain C8 narrow fraction; (2) Carrying out primary extraction and deoxidation on the C8 narrow fraction to obtain a deoxidized product with the oxide content of 0.7-0.9 wt%; then carrying out secondary extraction deoxidation on the deoxidized product to obtain deoxidized C8 narrow fraction with oxide content not more than 0.01 wt%; (3) Carrying out methanol etherification reaction on the deoxidized C8 narrow fraction to obtain an etherified C8 narrow fraction; (4) And (3) carrying out light component removal and rectification on the etherified C8 narrow fraction, and then carrying out precise rectification on heavy components in a tower kettle obtained by the light component removal and rectification to obtain 1-octene. The method has the advantages of simple operation, high separation efficiency, low cost and the like, and the purity of the 1-octene product obtained by separation and purification is higher, so that the ethylene copolymerization requirement can be met.
Description
Technical Field
The invention relates to the technical field of high-purity olefin production from coal-based raw materials, in particular to a method and a device for separating 1-octene from Fischer-Tropsch synthesis oil-washed naphtha.
Background
The Fischer-Tropsch synthetic oil-washed naphtha is a coal chemical product rich in alpha-olefin, and particularly, the Fischer-Tropsch synthetic oil-washed naphtha is rich in 1-octene, can be widely used in the production of ethylene comonomer, bromoalkane, higher alcohol, synthetic lubricating oil and the like, and has higher economic value. However, when Fischer-Tropsch olefins are developed from Fischer-Tropsch naphtha, the production of downstream products, particularly the processing and production of industries such as high-end polyethylene, is seriously affected by the presence of oxygenates such as alcohols, aldehydes, acids, esters, and the like in addition to alkanes and olefins.
The combined process route of 'alkali wash-etherification-rectification-extractive rectification' developed by the SASOL company in south Africa is reported to realize the preparation of the polymer grade 1-hexene and 1-octene, but the process has the defects of high complexity, high energy consumption and high operation cost.
The 1-octene separation technology provided by CN103360195A adopts a method of pre-separation, azeotropic rectification and deoxidation, fine separation, heavy removal and refining treatment, has the defects of larger solvent consumption, complex operation, high energy consumption and the like in an azeotropic deoxidation link, and is difficult to remove partial impurities of the 1-octene crude product subjected to heavy removal.
Disclosure of Invention
The invention aims to solve the problems of complex process, high cost, low product purity and the like of an oxygenate removal process in the prior art, and provides a method and a device for separating 1-octene from Fischer-Tropsch synthesis oil-washed naphtha.
To achieve the above object, in one aspect the present invention provides a process for separating 1-octene from fischer-tropsch gasoil naphtha, said process comprising the steps of:
(1) Rectifying Fischer-Tropsch synthesis oil-washed naphtha to obtain C8 narrow fraction;
(2) Carrying out primary extraction and deoxidation on the C8 narrow fraction to obtain a deoxidized product with the oxide content of 0.7-0.9 wt%; then carrying out secondary extraction deoxidation on the deoxidized product to obtain deoxidized C8 narrow fraction with oxide content not more than 0.01 wt%;
(3) Carrying out methanol etherification reaction on the deoxidized C8 narrow fraction to obtain an etherified C8 narrow fraction;
(4) And (3) carrying out light component removal and rectification on the etherified C8 narrow fraction, and then carrying out precise rectification on heavy components in a tower kettle obtained by the light component removal and rectification to obtain 1-octene.
In a second aspect, the invention provides a device for separating 1-octene from Fischer-Tropsch synthesis oil-washed naphtha, which comprises a first rectifying tower, a second rectifying tower, a first countercurrent liquid-liquid extraction deoxidizing tower, a second countercurrent liquid-liquid extraction deoxidizing tower, methanol etherification reaction equipment, a light component removal rectifying tower and a precise rectifying tower which are sequentially communicated.
Through the technical scheme, the beneficial technical effects obtained by the invention are as follows:
the invention needs to pretreat Fischer-Tropsch synthetic oil wash naphtha before separating and purifying 1-octene, remove oxygen-containing compounds through operations such as extraction, rectification, chemical reaction and the like, then pre-cut single carbon components, precisely rectify and separate a crude product of 1-octene, and finally refine the crude product to obtain a high-quality 1-octene product. The method has the advantages of simple operation, high separation efficiency, low cost and the like, and the purity of the 1-octene product obtained by separation and purification is higher, so that the ethylene copolymerization requirement can be met.
The invention adopts the liquid-liquid extraction deoxidation technology, can effectively remove the oxide in the raw material, and the deacidification and the deoxidation are synchronously carried out, so that the olefin loss rate is lower; partial isomerism olefin of the 1-octene is removed through methanol etherification, and separation of the 1-octene, the n-octane and octene isomers can be completed through precise rectification, and no solvent is needed to be added. The invention can separate the 1-octene product with high added value from the Fischer-Tropsch synthesis oil washing naphtha in a simple and efficient way, and is beneficial to the development of the 1-octene production process.
Drawings
FIG. 1 is a schematic illustration of a process scheme for separating 1-octene from Fischer-Tropsch synthesis gas wash naphtha, according to one embodiment of the invention.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
In a first aspect the present invention provides a process for the separation of 1-octene from Fischer-Tropsch synthesis oil washed naphtha, said process comprising the steps of:
(1) Rectifying Fischer-Tropsch synthesis oil-washed naphtha to obtain C8 narrow fraction;
(2) Carrying out primary extraction and deoxidation on the C8 narrow fraction obtained in the step (1) to obtain a deoxidized product with the oxide content of 0.7-0.9 wt%; then carrying out secondary extraction deoxidation on the deoxidized product to obtain deoxidized C8 narrow fraction with oxide content not more than 0.01 wt%;
(3) Carrying out methanol etherification reaction on the deoxidized C8 narrow fraction obtained in the step (2) to obtain an etherified C8 narrow fraction;
(4) And (3) carrying out light component removal and rectification on the etherified C8 narrow fraction obtained in the step (3), and then carrying out precise rectification on the heavy component in the tower bottom obtained by the light component removal and rectification to obtain 1-octene.
The invention needs to pretreat Fischer-Tropsch synthetic oil wash naphtha before separating and purifying 1-octene, remove oxygen-containing compounds through operations such as extraction, rectification, chemical reaction and the like, then pre-cut single carbon components, precisely rectify and separate a crude product of 1-octene, and finally refine the crude product to obtain a high-quality 1-octene product. The method has the advantages of simple operation, high separation efficiency, low cost and the like, and the purity of the 1-octene product obtained by separation and purification is higher, so that the ethylene copolymerization requirement can be met.
In some embodiments, the Fischer-Tropsch synthesis oil wash naphtha comprises C5-C12 paraffins and C5-C12 olefins, wherein the alpha olefins comprise 55-60wt%, the normal paraffins comprise 25-30wt%, the beta olefins comprise 5-10wt%, the oxygenates comprise 2-3wt%, and small amounts of isoolefins.
In some embodiments, in step (1), the rectification comprises a first rectification and a second rectification, C7 and lower light components in the fischer-tropsch synthesis oil wash naphtha are removed by the first rectification to obtain C8 and higher heavy components; and removing the heavy components of C8 and above in the recombination to obtain a C8 narrow fraction.
Specifically, the first rectification is performed in a first rectification tower, the theoretical plate number of the first rectification tower is 40, the plate number of the rectification section is 18, the plate number of the stripping section is 22, the reflux ratio is 5, and the operation pressure is normal pressure; the Fischer-Tropsch synthesis oil washing naphtha enters the first rectifying tower from a 19 th tower plate, light components C7 and below are obtained from the tower top, the extraction distillation rate is 0.38-0.44, the content of C8 in the light components is less than 1wt%, heavy components C8 and above are obtained from the tower bottom, and the content of C7 and below in the heavy components is less than 1wt%.
The second rectification is carried out in a second rectification tower, the theoretical plate number of the second rectification tower is 40, the plate number of the rectification section is 23, the plate number of the stripping section is 17, the reflux ratio is 5, and the operation pressure is normal pressure; adding the heavy components in the tower bottom obtained from the first rectifying tower into the second rectifying tower from a 24 th tower plate, obtaining C8 narrow fraction from the tower top, and obtaining the distillation rate of 0.5-0.57, wherein the content of C7 and the following components is less than 3wt%; obtaining a component with more than C8 as a heavy component from a tower kettle, wherein the content of the C8 component is less than 2wt%.
In some preferred embodiments, the C8 narrow cut has a C8 component content of greater than 97wt% and an oxide content of 2.2 to 2.8wt%.
In some embodiments, in step (2), the primary extractive deoxygenation is counter-current liquid-liquid extractive deoxygenation at a temperature of 15-40 ℃ for a time of 10-15min.
In some preferred embodiments, the primary extraction and deoxygenation employs a first extractant which is a complex solvent of an alcohol organic solvent and an amine organic solvent in a volume ratio of 1:1-2:1.
In some preferred embodiments, the alcoholic organic solvent is at least one of 1, 4-butanediol, 1, 2-propanediol, ethylene glycol, and methanol.
In some preferred embodiments, preferably, the amine-based organic solvent is at least one of N, N-dimethylformamide, ethanolamine, diethanolamine, and isopropanolamine.
In some preferred embodiments, the volumetric flow ratio of the first extractant to the C8 narrow cut is from 2:1 to 4:1.
The density of the C8 narrow fraction was 0.72g/cm 3 In order to ensure that the extraction is carried out, the density of the first extractant is larger than that of the C8 narrow fraction, and in order to improve the extraction efficiency, the density of the first extractant is larger than 1g/cm 3 。
In some preferred embodiments, the first extractant has a density of 1.07 to 1.13g/cm 3 ；
In step (2) of the present invention, the oxide content in the C8 narrow cut after the primary extraction deoxygenation is 0.7 to 0.9wt%.
In some embodiments, in step (2), the secondary extractive deoxygenation is counter-current liquid-liquid extractive deoxygenation at a temperature of 15-40 ℃ for a time of 10-15min.
In some preferred embodiments, the secondary extraction deoxygenation employs a second extractant that is a complex solvent of an alcoholic organic solvent and an amine organic solvent in a volume ratio of 1:1-2:1.
In some preferred embodiments, the alcoholic organic solvent is at least one of 1, 4-butanediol, 1, 2-propanediol, ethylene glycol, and methanol.
In some preferred embodiments, preferably, the amine-based organic solvent is at least one of N, N-dimethylformamide, ethanolamine, diethanolamine, and isopropanolamine.
In some preferred embodiments, the volumetric flow ratio of the second extractant to the C8 narrow cut is from 2:1 to 4:1.
The density of the C8 narrow fraction was 0.72g/cm 3 In order to ensure that the extraction is carried out, the density of the second extractant is greater than that of the C8 narrow fraction, so as to improve the extraction efficiencyThe density of the second extractant is more than 1g/cm 3 。
In some preferred embodiments, the second extractant has a density of 1.07 to 1.13g/cm 3 。
In the invention, there is no necessary connection between the primary extraction deoxidation and the secondary extraction, and the same extractant or different extractants can be used. In order to simplify the preparation process of the extractant, the same extractant is preferably adopted for the primary extraction deoxidation and the secondary extraction deoxidation, and the extractant after the secondary extraction deoxidation can be reused for the primary extraction deoxidation in order to save the use amount of the extractant.
In some preferred embodiments, the second extractant is used as the extractant for the primary extractive deoxygenation when the oxide content is less than 0.01% after the secondary extractive deoxygenation.
In the step (2) of the present invention, the oxide content in the C8 narrow fraction after the secondary extraction deoxidation is 0.01% by weight or less.
In some embodiments, in step (3), the methanol etherification reaction is carried out at a reaction temperature of 80 to 90 ℃ for a reaction time of 1.5 to 2.0 hours.
In some preferred embodiments, the mass ratio of methanol to the deoxygenated C8 narrow fraction in the methanol etherification reaction is in the range of 0.2:1 to 0.3:1.
In some preferred embodiments, the catalyst for the etherification reaction of methanol is a large particle acid resin catalyst, and any catalyst can be used as the catalyst of the present invention as long as the acid resin can provide a protonic acid. For example, macroporous strongly acidic cationic resins.
In the process of methanol etherification, in order to ensure that the solution in the reactor flows and can fully contact with the catalyst, a stirring paddle is additionally arranged at the bottom of the reactor for continuous stirring, and the rotating speed is 50-100r/min. And because the solvent property of the methanol and the C8 narrow fraction is poor, a condensing reflux device is additionally arranged at the top of the reactor to recycle the methanol, and corresponding methanol is additionally arranged at the bottom of the reactor to maintain the reaction.
In the step (3) of the invention, partial methyl heptene, especially 2-methyl-1-heptene affecting the purity of the 1-octene product, in the C8 narrow fraction is mainly removed by the methanol etherification reaction, and corresponding methyl ether substances are generated, and the boiling point is correspondingly increased by 20-30 ℃.
In some embodiments, in step (4), the light ends distillation is performed in a light ends distillation column having a theoretical plate number of 135, a distillation stage plate number of 55, a stripping stage plate number of 80, a reflux ratio of 40, and an operating pressure of normal pressure; the etherified C8 narrow fraction obtained in the step (3) is added into the light component removing rectifying tower from a 56 th tower plate, the light component obtained from the tower top is a substance with the boiling point of 1-octene, such as methyl heptene, methyl heptane, methanol and the like, the tower top extraction rate is 0.08-0.1, the 1-octene content in the light component is less than 65wt%, and the 1-octene content in the heavy component obtained from the tower bottom is more than 58wt%.
In some embodiments, in step (4), the precision rectification is performed in a precision rectification column having a theoretical plate number of 140, a rectification stage plate number of 76, a stripping stage plate number of 64, a reflux ratio of 40, and an operating pressure of normal pressure; adding the heavy component in the tower bottom of the light component removing rectifying tower into the precise rectifying tower from a 77 th tower plate, wherein the purity of 1-octene in the light component obtained from the tower top is more than 97wt%, the tower top extraction rate is 0.57-0.60, and the content of 1-octene in the heavy component obtained from the tower bottom is less than 1wt%.
In the present invention, the purity of the finally obtained 1-octene product is more than 97wt%, and the yield of 1-octene is more than 87wt%.
The invention adopts the liquid-liquid extraction deoxidation technology, can effectively remove the oxide in the raw material, and the deacidification and the deoxidation are synchronously carried out, so that the olefin loss rate is lower; partial isomerism olefin of the 1-octene is removed through methanol etherification, and separation of the 1-octene, the n-octane and octene isomers can be completed through precise rectification, and no solvent is needed to be added. The invention can separate the 1-octene product with high added value from the Fischer-Tropsch synthesis oil washing naphtha in a simple and efficient way, and is beneficial to the development of the 1-octene production process.
In a second aspect the present invention provides an apparatus for separating 1-octene from Fischer-Tropsch synthesis oil washed naphtha, as shown in figure 1, said apparatus comprising a first rectifying column A, a second rectifying column B, a first countercurrent liquid-liquid extraction deoxygenation column C, a second countercurrent liquid-liquid extraction deoxygenation column D, methanol etherification reaction equipment E, a light ends rectifying column F and a precision rectifying column G, which are in sequential communication.
In some embodiments, the first rectification column a has a theoretical plate number of 40, a rectification stage plate number of 18, a stripping stage plate number of 22, and a feed plate number of 19.
In some embodiments, the second rectification column B has a theoretical plate number of 40, a rectification stage plate number of 23, a stripping stage plate number of 17, and a feed plate number of 24.
In some embodiments, the first counter-current liquid-liquid extraction deoxygenation column C and the second counter-current liquid-liquid extraction deoxygenation column D employ a sieve tray column or a packed column for sufficient contact between the two phases.
In some embodiments, the methanol etherification reaction equipment E is a fixed bed catalytic reactor, a catalyst bed layer is arranged in the methanol etherification reaction equipment E, a stirring paddle is arranged at the bottom of the methanol etherification reaction equipment E, and a condensation reflux component is arranged at the top of the methanol etherification reaction equipment E.
In some embodiments, the light ends removal rectification column F has a theoretical plate number of 135, a rectification stage plate number of 55, a stripping stage plate number of 80, and a feed plate number of 56.
In some embodiments, the precision rectification column G has a theoretical plate number of 140, a rectification stage plate number of 76, a stripping stage plate number of 64, and a feed plate number of 77.
The separation of 1-octene from Fischer-Tropsch synthesis gas wash naphtha using the method of the first aspect and the apparatus of the second aspect described above, is described in connection with FIG. 1 and comprises the steps of:
(1) Pretreatment: feeding Fischer-Tropsch synthesis oil-washed naphtha (stream 1) into a first rectifying tower A with a theoretical plate number of 40, carrying out first rectification, obtaining components (stream 2) with C7 and below from the top of the tower, and obtaining components (stream 3) with C8 and above from the bottom of the tower; then, C8 and above components (stream 3) are sent into a second rectifying tower B with the theoretical plate number of 40, the second rectification is carried out, the content of the C8 components (stream 5) obtained at the top of the tower is 98wt percent, and the residual liquid at the bottom of the tower is C9 and above components (stream 4);
(2) Countercurrent extraction: feeding the C8 component (stream 5) obtained in the step (1) into a first countercurrent liquid-liquid extraction deoxidization tower C for primary extraction deoxidization, and then feeding the stream (stream 7) after primary extraction deoxidization into a second countercurrent liquid-liquid extraction deoxidization tower D for secondary extraction deoxidization; wherein the extractant is a compound solvent (stream 6) of an alcohol and an amine organic solvent according to a ratio of 1:1, wherein the alcohol reagent is composed of at least one solvent of 1, 4-butanediol, 1, 2-propanediol, ethylene glycol and methanol, and the amine reagent is composed of at least one solvent of N, N-dimethylformamide, ethanolamine, diethanolamine and isopropanolamine; the ratio of extractant flow rate to C8 component (stream 5) flow rate is 1:1; collecting and regenerating the extract (stream 8) for recycling;
(3) Etherification of methanol: after two-stage countercurrent contact, the deacidification and oxidation C8 component (stream 9) and methanol (stream 10) are sent into a methanol etherification reaction device E according to the mass ratio of 1:2, and methanol etherification reaction is carried out under the condition that the solution temperature is 90 ℃ and the mechanical stirring is carried out for 30r/min, so that part of impurities are removed;
(4) And (3) light weight removal: after the etherification reaction of methanol for 30min, feeding the mixed solution (stream 11) of methanol and deacidification and deoxidation C8 into a light component removal tower F with the theoretical plate number of 135, carrying out light component removal treatment on the mixed solution (stream 11), obtaining a heavy component C8 mixed solution (stream 13) at the tower bottom, and recycling and reutilizing the unreacted methanol solution (stream 12) obtained at the tower top;
(5) And (3) precision rectification: the heavy component C8 mixed solution (stream 13) obtained in the tower kettle is sent into a precise rectifying tower G with the theoretical plate number of 140, the C8 mixed solution (stream 13) is precisely rectified, wherein the reflux ratio is 5, the mixed solution is fed from a 40 th tower plate, the purity of a 1-octene product (stream 14) obtained in the tower top is 98.3wt%, and the residual liquid in the tower kettle is a small amount of mixed solution (stream 15) such as 1-octene, n-octane, isomeric octene, internal olefin, C8 etherate and the like.
In order to further understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless otherwise specified, all reagents involved in the examples of the present invention are commercially available products and are commercially available. The present invention will be described in detail by examples.
In the following examples, fischer-Tropsch synthesis gas wash naphtha was produced from Ningxia coal industry company at 400 kilotons per year coal to oil project, the composition comprising: C5-C12 alkane and alkene components, wherein the alpha-alkene accounts for 55-60%, the normal alkane accounts for 25-30%, the beta-alkene accounts for 5-10%, the oxygen-containing compound accounts for 2-3%, and a small amount of isoolefin.
Examples
A process for separating 1-octene from fischer-tropsch synthesis oil washed naphtha, as described in connection with figure 1, comprising the steps of:
(1) Feeding Fischer-Tropsch synthesis oil-washed naphtha (stream 1) from a 19 th column plate into a first rectifying column A, wherein the theoretical column plate number is 40, the column plate number of a rectifying section is 18, the column plate number of a stripping section is 22, the reflux ratio is 5, the operating pressure is normal pressure, carrying out first rectification, obtaining light components (stream 2) with C7 and below from the top of the column, the recovery rate is 0.44, and the C8 content in the light components at the top of the column is less than 1wt%; obtaining heavy components (stream 3) with C8 and above from a tower kettle, wherein the content of C7 and below components in the heavy components in the tower kettle is less than 1wt%;
(2) Feeding the C8 and above heavy components (stream 3) obtained in the step (1) into a second rectifying tower B from 24 th tower plates, wherein the theoretical plate number is 40, the rectifying section tower plate number is 23, the stripping section tower plate number is 17, the reflux ratio is 5, the operating pressure is normal pressure, carrying out second rectification, obtaining C8 narrow fraction (stream 5) from the tower top, the recovery rate is 0.57, and the content of the C8 components is more than 97wt%; obtaining heavy components (stream 4) with the content of C9 and above from the tower kettle, wherein the content of C8 components is less than 2wt%;
(3) Feeding the C8 narrow fraction (stream 5) obtained in the step (2) into a first countercurrent liquid-liquid extraction deoxidizing tower C, wherein the oxide content in the C8 narrow fraction is about 2.5wt%, a mixture of propylene glycol and ethanolamine with the volume ratio of 1:1 is adopted as an extractant (stream 6), the volume flow ratio of the extractant (stream 6) to the C8 narrow fraction (stream 5) is 2:1, the extractant is slowly added from a tower top distributor, primary extraction deoxidization is carried out, the extraction temperature is 30 ℃, and two phases can be separated after the extractant passes through the C8 narrow fraction for about 3min, so that the complete separation balance time of the two phases is prolonged to 15min; collecting and regenerating the extract (stream 8) for recycling;
(4) Transferring the C8 narrow fraction (stream 7) obtained in the step (3) after the primary extraction and deoxidation into a second countercurrent liquid-liquid extraction and deoxidation tower D, wherein the oxide content in the C8 narrow fraction (stream 7) after the primary deoxidation is about 0.8 weight percent, and performing secondary extraction and deoxidation according to the flow of the step (3); collecting and regenerating the extract (stream 8) for recycling; the primary deoxidation adopts a fresh extractant, and the content of oxide after deoxidation is less than 0.01 weight percent, so that the primary deoxidation can be used as the extractant for primary extraction deoxidation;
(5) Feeding the deoxidized C8 narrow fraction (stream 9) obtained in the step (4) into a methanol etherification reaction device E, adding a methanol solvent from the bottom of the reaction device, carrying out methanol etherification reaction under the mechanical stirring condition that the reaction temperature is 80 ℃ and 80r/min, wherein the reaction time is 2.0h, mainly removing part of methyl heptene, especially 2-methyl-1-heptene, affecting the purity of a 1-octene product in the C8 narrow fraction, generating corresponding methyl ether substances, and correspondingly improving the boiling point by 20-30 ℃;
(6) Delivering the etherified C8 narrow fraction (stream 11) obtained in the step (5) into a light component removal tower F from a 56 th column plate, wherein the theoretical column plate number is 135, the column plate number of a rectifying section is 55, the column plate number of a stripping section is 80, the reflux ratio is 40, the operating pressure is normal pressure, the etherified C8 narrow fraction (stream 11) is subjected to light component removal treatment, a heavy component C8 mixed solution (stream 13) is obtained in a tower kettle, and the content of 1-octene components in the heavy component in the tower kettle is more than 58wt%; the unreacted methanol solution (stream 12) obtained from the tower top is recycled, the distillation rate at the tower top is 0.1, the light components at the tower top are methyl heptene, methyl heptane, methanol and other substances with the boiling point lower than 1-octene, and the content of 1-octene in the light components is less than 65wt%;
(7) Feeding the heavy component (stream 13) in the tower kettle obtained in the step (6) into a precise rectifying tower G from a 77 th column plate, wherein the number of theoretical column plates is 140, the number of column plates in a rectifying section is 76, the number of column plates in a stripping section is 64, the reflux ratio is 40, the operating pressure is normal pressure, precise rectifying is carried out on the heavy component (stream 13) in the tower kettle, a 1-octene product (stream 14) is obtained at the top of the tower, and the extraction rate at the top of the tower is 0.60; the residual liquid in the tower kettle is a mixed solution (stream 15) of a small amount of 1-octene, n-octane, isooctane, internal olefin, C8 etherate and the like, and the content of the 1-octene component in the heavy component in the tower kettle is less than 1wt%.
Through detection, the purity of the 1-octene product finally obtained in the embodiment is 97.66wt percent, the yield is 87.5wt percent, and the obtained 1-octene product meets the ethylene copolymerization requirement and reaches the foreign 1-octene high-grade specification.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (9)
1. A process for separating 1-octene from fischer-tropsch synthesis oil washed naphtha, said process comprising the steps of:
(1) Rectifying Fischer-Tropsch synthesis oil-washed naphtha to obtain C8 narrow fraction;
(2) Carrying out primary extraction and deoxidation on the C8 narrow fraction to obtain a deoxidized product with the oxide content of 0.7-0.9 wt%; then carrying out secondary extraction deoxidation on the deoxidized product to obtain deoxidized C8 narrow fraction with oxide content not more than 0.01 wt%;
(3) Carrying out methanol etherification reaction on the deoxidized C8 narrow fraction to obtain an etherified C8 narrow fraction;
(4) Carrying out light component removal and rectification on the etherified C8 narrow fraction, and then carrying out precise rectification on heavy components in a tower kettle obtained by the light component removal and rectification to obtain 1-octene;
in the step (2), the primary extraction and deoxidation is countercurrent liquid-liquid extraction and deoxidation, wherein the temperature of the primary extraction and deoxidation is 15-40 ℃ and the time is 10-15min;
the primary extraction and deoxidation adopts a first extractant, wherein the first extractant is a compound solvent of an alcohol organic solvent and an amine organic solvent in a volume ratio of 1:1-2:1;
in the step (2), the secondary extraction deoxidation is countercurrent liquid-liquid extraction deoxidation, wherein the temperature of the secondary extraction deoxidation is 15-40 ℃ and the time is 10-15min;
the secondary extraction and deoxidation adopts a second extractant, and the second extractant is a compound solvent of an alcohol organic solvent and an amine organic solvent with the volume ratio of 1:1-2:1.
2. The process of claim 1 wherein the fischer-tropsch synthesis oil wash naphtha comprises C5-C12 paraffins and C5-C12 olefins, wherein alpha olefins comprise 55-60wt%, normal paraffins comprise 25-30wt%, beta olefins comprise 5-10wt% and oxygenates comprise 2-3wt%.
3. The process of claim 1 or 2, wherein in step (1), the rectification comprises a first rectification and a second rectification, C7 and lower light components in the fischer-tropsch synthesis oil washed naphtha being removed by the first rectification to obtain C8 and higher heavy components; and removing the heavy components of C8 and above in the recombination to obtain a C8 narrow fraction.
4. A process according to claim 3, wherein the first rectification is carried out in a first rectification column having a theoretical plate number of 40, a rectification stage plate number of 18, a stripping stage plate number of 22, a reflux ratio of 5, and an operating pressure of normal pressure; the Fischer-Tropsch synthesis oil washing naphtha enters the first rectifying tower from a 19 th tower plate, light components C7 and below are obtained from the tower top, the extraction rate is 0.38-0.44, the content of C8 in the light components is less than 1wt%, heavy components C8 and above are obtained from the tower bottom, and the content of C7 and below in the heavy components is less than 1wt%;
and/or the second rectification is carried out in a second rectification tower, the theoretical plate number of the second rectification tower is 40, the plate number of the rectification section is 23, the plate number of the stripping section is 17, the reflux ratio is 5, and the operation pressure is normal pressure; adding heavy components in the tower bottom obtained by the first rectifying tower into the second rectifying tower from a 24 th tower plate, obtaining C8 narrow fraction from the tower top, and obtaining the distillation rate of 0.5-0.57, wherein the content of C7 and the following components is less than 3wt%; obtaining a component with more than C8 as a heavy component from a tower kettle, wherein the content of the C8 component is less than 2wt%;
and/or, in the C8 narrow fraction, the content of the C8 component is more than 97wt%, and the content of the oxide is 2.2-2.8wt%.
5. The method of claim 1, wherein the alcoholic organic solvent is at least one of 1, 4-butanediol, 1, 2-propanediol, ethylene glycol, and methanol;
and/or the amine organic solvent is at least one of N, N-dimethylformamide, ethanolamine, diethanolamine and isopropanolamine;
and/or the volume flow ratio of the first extractant to the C8 narrow fraction is from 2:1 to 4:1;
and/or the density of the first extractant is 1.07-1.13g/cm 3 。
6. The process of claim 1, wherein the volumetric flow ratio of the second extractant to the C8 narrow fraction is from 2:1 to 4:1;
and/or the density of the second extractant is 1.07-1.13g/cm 3 ；
And/or, the second extractant is used as the extractant for the primary extraction deoxidation when the oxide content is below 0.01% after the secondary extraction deoxidation.
7. The process according to claim 1, wherein in step (3), the methanol etherification reaction is carried out at a reaction temperature of 80 to 90 ℃ for a reaction time of 1.5 to 2.0 hours;
and/or, in the methanol etherification reaction, the mass ratio of the methanol to the deoxidized C8 narrow fraction is 0.2:1-0.3:1;
and/or the catalyst for the etherification reaction of the methanol is a large-particle acidic resin catalyst.
8. The process according to claim 1, wherein in the step (4), the light ends distillation is carried out in a light ends distillation column having a theoretical plate number of 135, a distillation stage plate number of 55, a stripping stage plate number of 80, a reflux ratio of 40, and an operation pressure of normal pressure; adding the reacted C8 narrow fraction obtained in the step (3) into the light component removing rectifying tower from a 56 th tower plate, wherein the light component obtained from the tower top is a substance with the boiling point of 1-octene, the tower top extraction rate is 0.08-0.1, the content of 1-octene in the light component is less than 65wt%, and the content of 1-octene in the heavy component obtained from the tower bottom is more than 58wt%.
9. The method according to claim 1, wherein in the step (4), the precision rectification is performed in a precision rectification column having a theoretical plate number of 140, a rectification stage plate number of 76, a stripping stage plate number of 64, a reflux ratio of 40, and an operation pressure of normal pressure; adding the heavy component in the tower bottom of the light component removing rectifying tower into the precise rectifying tower from a 77 th tower plate, wherein the purity of 1-octene in the light component obtained from the tower top is more than 97wt%, the tower top extraction rate is 0.57-0.60, and the content of 1-octene in the heavy component obtained from the tower bottom is less than 1wt%.
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