CN111718746B - Method for deoxidizing and refining Fischer-Tropsch synthetic oil - Google Patents
Method for deoxidizing and refining Fischer-Tropsch synthetic oil Download PDFInfo
- Publication number
- CN111718746B CN111718746B CN201910214756.9A CN201910214756A CN111718746B CN 111718746 B CN111718746 B CN 111718746B CN 201910214756 A CN201910214756 A CN 201910214756A CN 111718746 B CN111718746 B CN 111718746B
- Authority
- CN
- China
- Prior art keywords
- extraction
- stage
- aqueous solution
- content
- phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 93
- 238000007670 refining Methods 0.000 title claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 207
- 238000000605 extraction Methods 0.000 claims abstract description 205
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 177
- 239000007864 aqueous solution Substances 0.000 claims abstract description 108
- 150000001875 compounds Chemical class 0.000 claims abstract description 77
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 68
- 239000001301 oxygen Substances 0.000 claims abstract description 68
- 238000005406 washing Methods 0.000 claims abstract description 56
- 239000000284 extract Substances 0.000 claims abstract description 41
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000005194 fractionation Methods 0.000 claims abstract description 14
- 238000004821 distillation Methods 0.000 claims description 52
- 150000002148 esters Chemical class 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 39
- 150000001299 aldehydes Chemical class 0.000 claims description 39
- 150000002576 ketones Chemical class 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 31
- -1 glycol ethers Chemical class 0.000 claims description 24
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 22
- 238000003786 synthesis reaction Methods 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 9
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 9
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 9
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 3
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 3
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 abstract description 51
- 238000011084 recovery Methods 0.000 abstract description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 5
- 239000012071 phase Substances 0.000 description 197
- 229930195733 hydrocarbon Natural products 0.000 description 118
- 239000004215 Carbon black (E152) Substances 0.000 description 117
- 150000002430 hydrocarbons Chemical class 0.000 description 117
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 85
- 239000003921 oil Substances 0.000 description 62
- 239000000047 product Substances 0.000 description 59
- 238000004064 recycling Methods 0.000 description 31
- 150000001336 alkenes Chemical class 0.000 description 26
- 150000001335 aliphatic alkanes Chemical class 0.000 description 25
- 239000012074 organic phase Substances 0.000 description 23
- 238000004817 gas chromatography Methods 0.000 description 19
- 239000012188 paraffin wax Substances 0.000 description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 16
- 239000003125 aqueous solvent Substances 0.000 description 15
- 238000001514 detection method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- UGDAWAQEKLURQI-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;hydrate Chemical compound O.OCCOCCO UGDAWAQEKLURQI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003635 deoxygenating effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
Abstract
The invention relates to the field of Fischer-Tropsch synthetic oil refining, and discloses a method for deoxidizing and refining Fischer-Tropsch synthetic oil, which comprises the steps of carrying out atmospheric and vacuum fractionation on Fischer-Tropsch synthetic oil to obtain a first-stage fraction, a second-stage fraction and a third-stage fraction; (2) carrying out first extraction on the first-stage fraction by using a methanol aqueous solution to obtain an extract phase 1 and a raffinate phase 1; performing second extraction on the second-stage fraction by using an ethanol aqueous solution to obtain an extract phase 2 and a raffinate phase 2; performing third extraction on the third-stage fraction by using an ethylene glycol ether aqueous solution to obtain an extract phase 3 and a raffinate phase 3; (3) and respectively washing the raffinate phase 1, the raffinate phase 2 and the raffinate phase 3 to obtain the deoxidized and refined Fischer-Tropsch synthetic oil. The method not only keeps the content of alpha-olefin in the process of removing the oxygen-containing compound, but also reduces the content of the oxygen-containing compound in the deoxidized and refined Fischer-Tropsch synthetic oil to be less than 100ppm, and has high oil recovery rate.
Description
Technical Field
The invention relates to the field of Fischer-Tropsch synthetic oil refining, in particular to a method for deoxidizing and refining Fischer-Tropsch synthetic oil.
Background
The alpha-olefin is an important organic raw material and an intermediate product, and has extremely wide application. The use of 1-butene, 1-hexene and 1-octene as comonomers in Polyethylene (PE) resins may improve PE properties. C 6 -C 10 The alpha-olefin is used for producing the plasticizing alcohol, and PE products added with the plasticizing alcohol have better low-temperature flexibility, processability and outdoor weather resistance, and are particularly suitable for manufacturing cables, wires, automobile accessories or decorative parts. C 8 -C 10 The alpha-olefin(s) of (a) can be synthesized into a poly-alpha-olefin (PAO) lubricating oil, and the PAO is a high-quality synthetic lubricating oil. C 11 -C 14 By hydroxylation of alpha-olefins to give C 12 -C 15 The detergent alcohol can produce detergent with excellent biodegradability. The alpha-olefin can also be used for producing alkylbenzene or alkylphenol so as to prepare lubricating oil and additive.
The fischer-tropsch synthesis reaction is a reaction in which synthesis gas is formed into a series of compounds containing alkanes, alkenes and oxygen at a certain temperature and pressure and using an iron or cobalt catalyst. The carbon chain length of the product is from 1 to more than 100, the oxygen-containing compound is mainly fatty alcohol, and a small amount of acid, ester, ketone, aldehyde and the like are also contained, the olefin is mainly linear alpha-olefin, and the content of the alpha-olefin in the Fischer-Tropsch light oil can reach more than 50%.
The alpha-olefin in the Fischer-Tropsch synthesis product can be used for producing PAO (polycyclic aromatic hydrocarbons), alkyl benzene and the like. However, the oxygenates must first be removed because the oxygenates have a negative effect on both of these reactions. However, currently, the removal of oxygenates in industry mainly employs a method of hydrogenating compounds containing olefins, alkanes and oxygenates. Hydrogenation processes also accompany olefin hydrosaturation during the hydrogenation removal of oxygenates, which is not a desirable result.
Other methods for separating and extracting fatty alcohol and removing oxygen-containing compounds also comprise adsorption, extraction and the like.
US3485879 discloses a process for separating alcohols from olefins and alkanes by selective adsorption on alumina, but this process has a problem of difficult industrial scale-up.
US2746984 discloses the separation of aliphatic alcohols from alcohol-hydrocarbon mixtures by reacting boric acid with the alcohol in the alcohol-hydrocarbon mixture to form an ester, followed by extraction with solvents such as methanol, ethanol, water, etc., followed by hydrolysis of the borate ester to obtain the aliphatic alcohol. However, the method is complicated in operation because of two chemical reactions, namely esterification and hydrolysis, and the content of the oxygen-containing compounds in the separated hydrocarbon is not mentioned.
US2610977 discloses the separation of alcohols from hydrocarbons and in particular discloses a process for extraction with an aqueous solution of a lower alcohol, the lower alcohol being aqueous methanol, but using an extraction phase with an oil ratio of 8-9: 1, the dosage of the extractant is large, and the recovery solvent adopts a low-carbon hydrocarbon extraction mode.
GB716131 discloses extraction with aqueous solutions of lower alcohols, but because of the wide distillation range of the feed oil, the extraction of small molecular oxygen-containing compounds and large molecular oxygen-containing compounds with the same extractant results in high hydrocarbon content in the extract, and the azeotropic distillation method is used to remove residual hydrocarbons in the alcohol, but because of the large number of components of the system, there is often multi-azeotropic and the separation effect is not good.
CN101891589B discloses a method for extracting fatty alcohol, which comprises rectifying to divide fischer-tropsch product into four-stage fractions; and respectively extracting the four fractions by using water and ethanol aqueous solutions with different concentrations. In order to reduce the hydrocarbon content in the fatty alcohol, the method also comprises the step of back-extracting the alcohol phase obtained by the extraction by using alkanes with different carbon numbers respectively. However, the recovery rate of the aliphatic alcohol was only about 95%, and it was found that the amount of the oxygen-containing compound remaining in the hydrocarbon phase was relatively large.
Both CN100575320C and CN100383096C disclose methods of extracting oxygenates from a hydrocarbon stream using a mixture of methanol and water as solvent, but the methods are directed only to C 10 -C 13 The oxygenate is removed from the stream of (a).
WO9958625 discloses a process for removing oxygenate impurities from a hydrocarbon stream using a light polar solvent formed from an acetonitrile/water solvent. But the method is only for C 8 -C 10 The oxygenate is removed from the stream of (a).
US4686317 discloses a process for removing light hydrocarbons (C) 2 To C 9 ) A process for the extraction of oxygenates from a hydrocarbon stream comprising extracting the oxygenates with a heavy oil polar solvent such as propylene carbonate and 2-ethanolamine, washing the extracted hydrocarbon stream with water to recover dissolved solvent and combining the extracted solvent phase with an aqueous phase in a scrubber for the recovery of the solvent by distillation. But the method is only for C 2 -C 9 To remove oxygenates.
The alpha-olefin content in the Fischer-Tropsch synthesis product light oil and the heavy oil is higher, and the alpha-olefins with different distillation ranges have different purposes, so that the deoxidation technology of the whole fractions of the Fischer-Tropsch light oil and the heavy oil needs to be developed, but in the prior art, the alpha-olefin content is difficult to maintain by adopting a hydrodeoxygenation method; in the methods of adsorption and extraction, some methods only perform separation of oxygen-containing compounds on a hydrocarbon stream with a narrow distillation range, and have poor separation effect on the hydrocarbon stream with a wide distillation range, even if deoxygenation refining is performed on the hydrocarbon stream with the wide distillation range, the residual amount of the oxygen-containing compounds in the hydrocarbon phase is often large, the subsequent utilization of olefin cannot be ensured, and the oil yield needs to be improved. Moreover, the prior art mostly only performs separation and extraction on alcohol in the hydrocarbon stream, but does not perform separation on ketone, aldehyde, acid and ester in the hydrocarbon stream.
Disclosure of Invention
The invention aims to overcome the problems that the content of alpha-olefin is difficult to maintain, the separation effect of oxygen-containing compounds is poor, the separation of ketone, aldehyde, acid and ester in hydrocarbon material flow is not performed, and the oil yield is required to be improved in the prior art, and provides a method for deoxidizing and refining Fischer-Tropsch synthetic oil.
In order to achieve the above object, the first aspect of the present invention provides a method for deoxygenating and refining fischer-tropsch synthetic oil, wherein the method comprises the following steps:
(1) carrying out atmospheric and vacuum fractionation on Fischer-Tropsch synthetic oil to obtain a first-stage fraction, a second-stage fraction and a third-stage fraction, wherein,
the distillation range of the first-stage fraction is IBP-T a The temperature is less than or equal to 140 ℃ and T is less than or equal to a ≤170℃；
The distillation range of the second-stage fraction is more than T a And is not more than T b The temperature is less than or equal to 240 ℃ and T is less than or equal to b ≤300℃；
The distillation range of the third-stage fraction is more than T b ℃；
(2) Carrying out first extraction on the first-stage fraction by using a methanol aqueous solution to obtain an extract phase 1 and a raffinate phase 1; performing second extraction on the second-stage fraction by using an ethanol aqueous solution to obtain an extract phase 2 and a raffinate phase 2; performing third extraction on the third-stage fraction by using an ethylene glycol ether aqueous solution to obtain an extract phase 3 and a raffinate phase 3;
(3) washing the raffinate phase 1, the raffinate phase 2 and the raffinate phase 3 respectively to obtain deoxidized and refined Fischer-Tropsch synthetic oil;
the Fischer-Tropsch synthetic oil comprises 0.1-10 wt% of oxygen-containing compounds by total weight of the Fischer-Tropsch synthetic oil, wherein the oxygen-containing compounds comprise alcohols, ketones, aldehydes, acids and esters.
Preferably, in step (1), the distillation range of the first-stage fraction is IBP-T a Fraction at 150 ℃ or lower, wherein T is not more than 150 ℃ a Less than or equal to 160 ℃; the distillation range of the second-stage fraction is more than T a And is not more than T b The temperature is less than or equal to 260 ℃ and T is more than or equal to b Less than or equal to 280 ℃; the distillation range of the third-stage fraction is more than T b ℃。
Preferably, in the step (2), the concentration of the methanol aqueous solution is not more than 85 wt%, preferably 60 to 75 wt%; the amount of the methanol aqueous solution is 0.5-4 times of the weight of the first-stage distillate, and preferably 0.8-2 times.
Preferably, in the step (2), the concentration of the ethanol water solution is not more than 80 wt%, preferably 60-75 wt%; the dosage of the ethanol water solution is 0.5-4 times of the weight of the second-stage distillate, and preferably 0.8-2 times.
Preferably, in the step (2), the concentration of the glycol ether aqueous solution is not more than 80 wt%, preferably 60-70 wt%; the dosage of the glycol ether aqueous solution is 0.5 to 4 times of the weight of the third section fraction, and preferably 0.8 to 2 times.
Preferably, the glycol ethers are selected from one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether and diethylene glycol monobutyl ether.
Preferably, the distillation range of the Fischer-Tropsch synthetic oil is IBP-380 ℃, and preferably IBP-350 ℃.
The invention carries out atmospheric and vacuum fractionation on Fischer-Tropsch synthetic oil to obtain three-section fractions, and then extracts the three-section fractions respectively, wherein the distillation range is IBP-T a Fraction at 140 deg.C or less, T a 170 ℃ or less, preferably 150 ℃ or less T a At the temperature of less than or equal to 160 ℃, adoptExtracting with methanol water solution; for distillation range greater than T a And is not more than T b Fraction at 240 ℃ or lower, T b Less than or equal to 300 ℃, preferably less than or equal to 260 ℃ and less than or equal to T b Extracting with ethanol water solution at temperature of less than or equal to 280 deg.C; for distillation range greater than T b The DEG C fraction is extracted by adopting an ethylene glycol ether aqueous solution, the method not only keeps the content of alpha-olefin in the Fischer-Tropsch synthetic oil, but also can effectively remove alcohol, ketone, aldehyde, acid and ester in the Fischer-Tropsch synthetic oil, the content of oxygen-containing compounds in the Fischer-Tropsch synthetic oil after deoxygenation refining is reduced to be below 100ppm, and the oil recovery rate is high.
Drawings
FIG. 1 is a schematic diagram of a Fischer-Tropsch synthesis oil deoxygenation refining process of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for deoxidizing and refining Fischer-Tropsch synthetic oil in a first aspect, wherein the method comprises the following steps:
(1) carrying out atmospheric and vacuum fractionation on Fischer-Tropsch synthetic oil to obtain a first-stage fraction, a second-stage fraction and a third-stage fraction, wherein,
the distillation range of the first-stage fraction is IBP-T a The temperature is less than or equal to 140 ℃ and T is less than or equal to a ≤170℃；
The distillation range of the second-stage fraction is more than T a And is not more than T b The temperature is less than or equal to 240 ℃ and T is less than or equal to b ≤300℃；
The distillation range of the third-stage fraction is more than T b ℃；
(2) Carrying out first extraction on the first-stage fraction by using a methanol aqueous solution to obtain an extract phase 1 and a raffinate phase 1; performing second extraction on the second-stage fraction by using an ethanol aqueous solution to obtain an extract phase 2 and a raffinate phase 2; performing third extraction on the third-stage fraction by using an ethylene glycol ether aqueous solution to obtain an extract phase 3 and a raffinate phase 3;
(3) washing the raffinate phase 1, the raffinate phase 2 and the raffinate phase 3 respectively to obtain deoxidized and refined Fischer-Tropsch synthetic oil;
the Fischer-Tropsch synthetic oil comprises 0.1-10 wt% of oxygen-containing compounds by total weight of the Fischer-Tropsch synthetic oil, wherein the oxygen-containing compounds comprise alcohols, ketones, aldehydes, acids and esters.
In the present invention, T a It means the final distillation point of the first stage fraction, and can be 140-170 deg.C, T b The final distillation point of the second stage fraction can be 240-300 ℃, and corresponding fractionation can be carried out according to different Fischer-Tropsch synthetic oils because the components of different Fischer-Tropsch synthetic oils are different, so that the final distillation temperature is T a For example, T a The temperature may be any value within a range of 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃ or any two of these values.
In the invention, the Fischer-Tropsch synthetic oil comes from light oil and heavy oil fractions in the Fischer-Tropsch synthetic reaction process, and the composition of the Fischer-Tropsch synthetic oil can contain alkane, olefin and oxygen-containing compounds.
In the present invention, the term "IBP" refers to the initial boiling point, i.e. the temperature recorded at the instant when the first drop of condensate falls from the end of the condenser when the distillation range of the oil is measured.
In the present invention, the raffinate phase 1, the raffinate phase 2, and the raffinate phase 3 are each washed with water to obtain a hydrocarbon phase 1, a hydrocarbon phase 2, and a hydrocarbon phase 3, and the hydrocarbon phase 1, the hydrocarbon phase 2, and the hydrocarbon phase 3 are collectively referred to as a deoxygenated and purified fischer-tropsch synthetic oil. That is, the deoxygenated refined Fischer-Tropsch oil comprises a hydrocarbon phase 1, a hydrocarbon phase 2, and a hydrocarbon phase 3.
In the present invention, the atmospheric and vacuum fractionation may be a means conventionally used in the art, and the pressure and temperature of the atmospheric and vacuum fractionation are not particularly limited, and the purpose is to obtain a fraction having a distillation range required in the present invention.
According to a preferred process of the invention, in step (1)The distillation range of the first-stage fraction is IBP-T a The temperature is less than or equal to 150 ℃ and T is more than or equal to a Less than or equal to 160 ℃; the distillation range of the second-stage fraction is more than T a And is not more than T b The temperature is less than or equal to 260 ℃ and T is more than or equal to b Less than or equal to 280 ℃; the distillation range of the third-stage fraction is more than T b ℃。T a It means the final distillation point of the first stage fraction, and can be 150-160 deg.C, T b The final distillation point of the second stage fraction can be 260-280 ℃, and corresponding fractionation can be carried out according to different Fischer-Tropsch synthetic oils because the components of different Fischer-Tropsch synthetic oils are different, so that the final distillation temperature is T a For example, T a The temperature may be 150 ℃, 151 ℃, 152 ℃, 153 ℃, 154 ℃, 155 ℃, 156 ℃, 157 ℃, 158 ℃, 159 ℃, 160 ℃ or any value in the range of any two of these values.
According to the method of the present invention, in the step (2), the concentration of the aqueous methanol solution may be not more than 85% by weight, and specifically, the content of methanol in the aqueous methanol solution may be not more than 85% by weight based on the total weight of the aqueous methanol solution. Preferably, the concentration of the aqueous methanol solution is 60 to 75 wt%, for example, 60 wt%, 65 wt%, 70 wt%, 75 wt%, and any value in the range of any two of these values.
According to the method of the present invention, in the step (2), the amount of the aqueous methanol solution may be 0.5 to 4 times, preferably 0.8 to 2 times, for example, 0.8 times, 0.9 times, 1 time, 1.1 times, 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, 1.8 times, 1.9 times, 2 times, and any value in the range of any two of these values, based on the weight of the first stage fraction.
According to the method of the present invention, in the step (2), the concentration of the aqueous ethanol solution may be not more than 80% by weight, and specifically, the content of ethanol in the aqueous ethanol solution may be not more than 80% by weight, based on the total weight of the aqueous ethanol solution. Preferably, the concentration of the ethanol aqueous solution is 60 to 75 wt%, for example, 60 wt%, 65 wt%, 70 wt%, 75 wt%, and any value in the range of any two of these values.
According to the method of the present invention, the amount of the aqueous ethanol solution may be 0.5 to 4 times, preferably 0.8 to 2 times, for example, 0.8 times, 0.9 times, 1 time, 1.1 times, 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, 1.8 times, 1.9 times, 2 times, and any value in the range of any two of these values, based on the weight of the second-stage fraction.
According to the method of the present invention, in the step (2), the concentration of the aqueous solution of glycol ethers may be not more than 80% by weight, and specifically, the content of ethanol in the aqueous solution of glycol ethers may be not more than 80% by weight based on the total weight of the aqueous solution of glycol ethers. Preferably, the concentration of the aqueous glycol ether solution is 60 to 70 wt%, for example, 60 wt%, 65 wt%, 70 wt%, or any value in the range of any two of these values.
According to the method of the invention, the glycol ethers may be selected from, but not limited to: one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether and diethylene glycol monobutyl ether.
According to the method of the present invention, the aqueous solution of glycol ethers may be used in an amount of 0.5 to 4 times, preferably 0.8 to 2 times, for example, 0.8 times, 0.9 times, 1 time, 1.1 times, 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, 1.8 times, 1.9 times, 2 times, and any value in the range of any two of these values, based on the weight of the third fraction.
According to the method, the temperature of the first extraction can be 15-50 ℃, and preferably 20-50 ℃; the first extraction method can be a multi-stage countercurrent extraction method; the theoretical stage number of the first extraction can be 3-10 stages, and preferably 5-7 stages.
According to the method, the temperature of the second extraction can be 15-50 ℃, and preferably 20-50 ℃; the second extraction method can be a multi-stage countercurrent extraction method; the theoretical stage number of the second extraction can be 3-10 stages, and preferably 5-7 stages.
According to the method, the temperature of the third extraction can be 15-50 ℃, and preferably 20-50 ℃; the third extraction method can be a multi-stage countercurrent extraction method; the theoretical stage number of the third extraction can be 3-10 stages, and preferably 5-7 stages.
According to the method, the fraction distribution of the Fischer-Tropsch synthetic oil is wide, the heavier the fraction in the Fischer-Tropsch synthetic oil is, the lower the olefin content in an oil product is, the higher the alkane content is, the lower the content of the oxygen-containing compound is, and the olefin content of the fraction at the temperature of more than 380 ℃ is lower, so that the Fischer-Tropsch synthetic oil is fractionated before extraction to obtain the Fischer-Tropsch synthetic oil with the distillation range of IBP-380 ℃, and preferably IBP-350 ℃.
According to the method, the method further comprises the step of carrying out solvent separation on the extraction phase 1, the extraction phase 2 and the extraction phase 3 respectively to obtain an oxygen-containing compound and a circulating solvent, wherein the oxygen-containing compound refers to the organic phase 1, the organic phase 2 and the organic phase 3 in the figure 1, and the circulating solvent refers to a recyclable solvent. Specifically, taking the extraction phase 1 as an example, introducing the extraction phase 1 into a first rectification tower, obtaining methanol at the tower top of the first rectification tower, introducing a kettle bottom product of the first rectification tower into a first decanter, recovering an aqueous solvent at the bottom of the first decanter, and preparing the aqueous solution with the methanol obtained at the tower top of the first rectification tower to obtain a methanol aqueous solution with a required concentration, returning the aqueous solution to the first extraction tower for recycling as a circulating solvent, and obtaining an organic phase 1 at the top of the first decanter, wherein the organic phase 1 contains an oxygen-containing compound, olefin and paraffin stream.
According to the process of the present invention, the raffinate 1, raffinate 2 and raffinate 3 comprise a small amount of solvent alcohol (raffinate 1 comprises methanol, raffinate 2 comprises ethanol and raffinate 3 comprises glycol ethers), and thus the raffinate 1, raffinate 2 and raffinate 3 are introduced into separate water wash columns. Taking raffinate phase 1 as an example, introducing raffinate phase 1 into a first water washing tower, washing off the solvent by a water washing method, taking a hydrocarbon phase as a tower top product, and leading out the hydrocarbon phase to obtain the hydrocarbon phase 1, wherein the tower bottom product returns to the first extraction tower for recycling.
According to the method of the invention, the content of the oxygen-containing compound in the deoxidized refined Fischer-Tropsch synthetic oil can reach less than 100ppm (0.01 wt%), preferably less than 50ppm (0.005 wt%); the recovery of olefins and paraffins is higher than 95% by weight, and preferably may be higher than 98% by weight.
According to an embodiment of the invention, as shown in FIG. 1, the method for deoxidizing and refining Fischer-Tropsch synthetic oil comprises the following steps:
(1) carrying out atmospheric and vacuum fractionation on Fischer-Tropsch synthetic oil to obtain a first-stage fraction, a second-stage fraction and a third-stage fraction, wherein the distillation range of the first-stage fraction is IBP-T a The temperature is less than or equal to 140 ℃ and T is less than or equal to a Less than or equal to 170 ℃; the distillation range of the second-stage fraction is more than T a And is not more than T b The temperature is less than or equal to 240 ℃ and T is less than or equal to b Less than or equal to 300 ℃; the distillation range of the third-stage fraction is more than T b ℃；
(2) And carrying out first extraction on the first section of fraction by using a methanol aqueous solution to obtain an extract phase 1 and a raffinate phase 1. The first fraction is fed into the first extraction column at or near the bottom of the column, and an extractant 1 comprising an aqueous methanol solution having a concentration of not more than 85% by weight, preferably 60 to 75% by weight, is fed into the first extraction column at or near the top of the column. And introducing a raffinate phase 1 at the top of the first extraction tower into a first water washing tower, wherein the raffinate phase 1 contains olefin, paraffin and a small amount of methanol. The methanol is washed away by a water washing method, a hydrocarbon phase 1 is taken out as a first water washing tower top product, a first water washing tower bottom product (methanol water solution) is returned to the first extraction tower for recycling, and the hydrocarbon phase 1 comprises more than 99 weight percent of olefin and paraffin (the content of alpha-olefin is more than 60 weight percent, and the content of n-paraffin is more than 20 weight percent) and less than 100ppm (0.01 weight percent) of oxygenated compounds, preferably less than 50ppm (0.005 weight percent) of oxygenated compounds. Extract phase 1 from the bottom of the first extraction column is introduced into a first rectification column, the overhead product from which contains more than 90 wt% methanol and small amounts of olefins and paraffins. More than 80 wt% of the olefins and paraffins in extract phase 1 are recovered in the first rectifier overhead. The method comprises the following steps of (1) obtaining methanol from the top of a first rectifying tower, introducing a kettle bottom product of the first rectifying tower into a first decanter, recovering a water solvent from the bottom of the first decanter, preparing the water solvent with the methanol obtained from the top of the first rectifying tower to obtain a methanol water solution with required concentration, returning the methanol water solution to a first extraction tower for recycling, and obtaining an organic phase 1 from the top of the first decanter, wherein the organic phase 1 contains an oxygen-containing compound, olefin and paraffin flow;
and carrying out second extraction on the second-stage fraction by using an ethanol aqueous solution to obtain an extract phase 2 and a raffinate phase 2. The second-stage fraction is conveyed into the second extraction tower at the bottom or close to the bottom of the second extraction tower, and the extracting agent 2 containing the ethanol aqueous solution is conveyed into the second extraction tower at the top or close to the top of the second extraction tower, wherein the concentration of the ethanol aqueous solution is not more than 80 wt%, and preferably 60-75 wt%. And introducing a raffinate phase 2 at the top of the second extraction tower into a second water washing tower, wherein the raffinate phase 2 contains olefin, paraffin and a small amount of ethanol. The ethanol is washed away by a water washing method, and a hydrocarbon phase 2 is taken out as a second water washing tower top product, a second water washing tower bottom product (ethanol water solution) is returned to a second extraction tower for recycling, wherein the hydrocarbon phase 2 comprises more than 99 weight percent of olefin and paraffin (the content of alpha-olefin is more than 50 weight percent, and the content of n-paraffin is more than 30 weight percent) and less than 100ppm (0.01 weight percent) of oxygenated compounds, preferably less than 50ppm (0.005 weight percent) of oxygenated compounds. The extract phase 2 from the bottom of the second extraction column is introduced into a second rectification column, the overhead product from which contains more than 90% by weight ethanol and small amounts of olefins and paraffins. More than 80 wt% of the olefins and paraffins in extract phase 2 are recovered in the second rectification column overhead product. The method comprises the following steps of obtaining ethanol or an azeotrope of ethanol and water from the top of a second rectifying tower, introducing a bottom product of the second rectifying tower into a second decanter, recovering a water solvent from the bottom of the second decanter, preparing the water solvent with the ethanol or the azeotrope of ethanol and water obtained from the top of the second rectifying tower to obtain an ethanol aqueous solution with a required concentration, returning the ethanol aqueous solution to a second extraction tower for recycling, and obtaining an organic phase 2 from the top of the second decanter, wherein the organic phase 2 contains oxygen-containing compounds, olefin and paraffin hydrocarbon streams;
and carrying out third extraction on the third-stage fraction by using an ethylene glycol ether aqueous solution to obtain an extract phase 3 and a raffinate phase 3. The third fraction is fed into the third extraction column at or near the bottom of the column, and an extractant 3 comprising an aqueous solution of glycol ethers is fed into the third extraction column at or near the top of the column, the concentration of the aqueous solution of glycol ethers being not more than 80% by weight, preferably 60-70% by weight. And introducing a raffinate phase 3 at the top of the third extraction tower into a third water washing tower, wherein the raffinate phase 3 contains olefin, paraffin and a small amount of glycol ethers. The glycol ethers are washed away by a water washing method, and a hydrocarbon phase 3 is led out as the top product of a third water washing tower, the bottom product (the water solution of the glycol ethers) of the third water washing tower returns to a third extraction tower for recycling, wherein the hydrocarbon phase 3 comprises more than 99 weight percent of olefin and paraffin (the content of alpha-olefin is more than 40 weight percent, and the content of n-paraffin is more than 40 weight percent) and less than 100ppm (0.01 weight percent) of oxygenated compounds, preferably less than 50ppm (0.005 weight percent) of oxygenated compounds. The extract phase 3 at the bottom of the third extraction column is introduced into a third rectification column, from which the overhead product contains more than 90 wt.% glycol ethers and small amounts of olefins and paraffins. More than 80 wt% of the olefins and paraffins in extract phase 3 are recovered in the third rectification column overhead product. Glycol ethers or an azeotrope of the glycol ethers and water are obtained at the top of the third rectifying tower, a kettle bottom product of the third rectifying tower is introduced into a third decanter, the water solvent is recovered at the bottom of the third decanter, and is prepared with the glycol ethers or the azeotrope of the glycol ethers and the water obtained at the top of the third rectifying tower to obtain a glycol ether aqueous solution with the required concentration, the glycol ether aqueous solution is returned to the third extraction tower for recycling, and an organic phase 3 is obtained at the top of the third decanter, wherein the organic phase 3 contains an oxygen-containing compound, olefin and paraffin stream.
The present invention will be described in detail below by way of examples.
The composition and content of the Fischer-Tropsch synthetic oil are shown in Table 1.
TABLE 1
| Composition (I) | Alpha-olefins | N-alkanes | Alcohol(s) | Aldehydes and ketones | Acids and esters |
| Content by weight% | 60.26 | 31.69 | 3.16 | 0.64 | 0.12 |
Example 1
(1) The Fischer-Tropsch synthesis oil shown in the table 1 is subjected to atmospheric and vacuum fractionation to obtain a first stage fraction, a second stage fraction and a third stage fraction, wherein,
the distillation range of the first stage fraction is 59-160 ℃, wherein the content of alpha-olefin is 71.29 wt%, the content of normal alkane is 22.02 wt%, the content of alcohol in the oxygen-containing compound is 2.60 wt%, the content of aldehyde and ketone is 0.62 wt%, and the content of acid and ester is 0.14 wt%;
the second stage fraction had a distillation range of more than 160 ℃ and not more than 280 ℃, and contained 67.21 wt% of α -olefin, 25.32 wt% of n-alkane, 3.56 wt% of alcohol in the oxygen-containing compound, 0.74 wt% of aldehyde and ketone, and 0.11 wt% of acid and ester;
the distillation range of the third stage fraction is a fraction of more than 280 ℃ and not more than 350 ℃, wherein the content of alpha-olefin is 45.32 wt%, the content of normal alkane is 45.54 wt%, the content of alcohol in the oxygen-containing compound is 3.35 wt%, the content of aldehyde and ketone is 0.52 wt%, and the content of acid and ester is 0.10 wt%;
(2) taking 1000g of the first-stage fraction, and carrying out multi-stage countercurrent extraction in a first extraction tower by using a 65 wt% methanol aqueous solution, wherein the extraction temperature is 20 ℃, the dosage of the methanol aqueous solution is 1000g, and the extraction theoretical stage number is 7, so as to obtain an extract phase 1 and a raffinate phase 1. Introducing raffinate phase 1 at the top of the first extraction tower into a first water washing tower, washing methanol off by a water washing method, taking out hydrocarbon phase 1 as a tower top product, returning a tower bottom product (methanol aqueous solution) to the first extraction tower for recycling, and obtaining 947.1g of hydrocarbon phase 1, wherein the recovery rate of the hydrocarbon phase 1 is 98.0%, the alpha-olefin content in the hydrocarbon phase 1 is 72.30 wt%, the normal alkane content is 23.21 wt%, and the oxygen-containing compound content is 70ppm (the alcohol content is 0ppm, the aldehyde and ketone content is 52ppm, and the acid and ester content is 18ppm) through gas chromatography detection. Introducing an extract phase 1 at the bottom of a first extraction tower into a first rectifying tower, obtaining methanol at the top of the first rectifying tower, introducing a kettle bottom product of the first rectifying tower into a first decanter, recovering an aqueous solvent at the bottom of the first decanter, preparing the aqueous solvent and the methanol obtained at the top of the first rectifying tower to obtain a 65 wt% methanol aqueous solution, returning the aqueous solution to the first extraction tower for recycling, and obtaining an organic phase 1 at the top of the first decanter;
and taking 1000g of the second-stage fraction, and carrying out multi-stage countercurrent extraction in a second extraction tower by using 69 wt% ethanol aqueous solution at the extraction temperature of 20 ℃, wherein the dosage of the ethanol aqueous solution is 1000g, and the extraction theoretical stage number is 7, so as to obtain an extract phase 2 and a raffinate phase 2. Introducing a raffinate phase 2 at the top of the second extraction tower into a second water washing tower, washing off ethanol by a water washing method, taking the hydrocarbon phase 2 out as a tower top product, returning a tower bottom product (an ethanol aqueous solution) to the second extraction tower for recycling to obtain 941.6g of the hydrocarbon phase 2, wherein the recovery rate of the hydrocarbon phase 2 is 98.5%, and the alpha-olefin content, the normal alkane content and the oxygen-containing compound content in the hydrocarbon phase 2 are respectively 68.13 wt%, 26.43 wt% and 68ppm (the alcohol content is 0ppm, the aldehyde content and the ketone content is 54ppm and the acid content and the ester content are 14ppm) respectively according to gas chromatography detection. Introducing an extraction phase 2 at the bottom of a second extraction tower into a second rectifying tower, obtaining an azeotrope of ethanol and water at the top of the second rectifying tower, introducing a kettle bottom product of the second rectifying tower into a second decanter, recovering an aqueous solvent at the bottom of the second decanter, preparing the aqueous solvent with the azeotrope of ethanol and water obtained at the top of the second rectifying tower to obtain an ethanol aqueous solution with the concentration of 69 weight percent, returning the aqueous solution to the second extraction tower for recycling, and obtaining an organic phase 2 at the top of the second decanter;
and taking 1000g of the third-stage fraction, and carrying out multistage countercurrent extraction in a third extraction tower by using 65 wt% of aqueous solution of ethylene glycol monomethyl ether at the extraction temperature of 20 ℃, using 1000g of an extracting agent and having 7 extraction theoretical stages to obtain an extract phase 3 and a raffinate phase 3. Introducing a raffinate phase 3 at the top of the third extraction tower into a third water washing tower, washing off ethylene glycol monomethyl ether by a water washing method, taking out the hydrocarbon phase 3 as a tower top product, returning a tower bottom product (an aqueous solution of the ethylene glycol monomethyl ether) to the third extraction tower for recycling to obtain 939.2g of the hydrocarbon phase 3, wherein the recovery rate of the hydrocarbon phase 3 is 97.8%, and the alpha-olefin content, the normal alkane content and the oxygen-containing compound content in the hydrocarbon phase 3 are respectively 46.21 wt%, 46.32 wt% and 68ppm (the alcohol content is 0ppm, and the aldehyde and ketone content is 52ppm, namely the acid content and the ester content is 16ppm) through gas chromatography detection. Introducing an extraction phase 3 at the bottom of a third extraction tower into a third rectifying tower, obtaining an azeotrope of ethylene glycol monomethyl ether and water at the top of the third rectifying tower, introducing a kettle bottom product of the third rectifying tower into a third decanter, recovering a water solvent at the bottom of the third decanter, preparing the water solvent with the azeotrope of the ethylene glycol monomethyl ether and the water obtained at the top of the third rectifying tower to obtain an aqueous solution of the ethylene glycol monomethyl ether with the concentration of 65 weight percent, returning the aqueous solution to the third extraction tower for recycling, and obtaining an organic phase 3 at the top of the third decanter;
in summary, the content of the oxygen-containing compounds in the hydrocarbon phase 1, the hydrocarbon phase 2 and the hydrocarbon phase 3 is 70ppm, 68ppm and 68ppm, that is, the content of the oxygen-containing compounds in the deoxygenated refined Fischer-Tropsch synthesis oil is less than 100 ppm.
Example 2
(1) The Fischer-Tropsch synthesis oil shown in the table 1 is subjected to atmospheric and vacuum fractionation to obtain a first stage fraction, a second stage fraction and a third stage fraction, wherein,
the distillation range of the first-stage fraction is 59-150 ℃, wherein the content of alpha-olefin is 72.12 wt%, the content of normal alkane is 21.32 wt%, the content of alcohol in the oxygen-containing compound is 2.54 wt%, the content of aldehyde and ketone is 0.60 wt%, and the content of acid and ester is 0.14 wt%;
the second stage fraction had a distillation range of greater than 150 ℃ and not greater than 260 ℃ and contained 68.01 wt% of α -olefin, 24.52 wt% of n-alkane, 3.57 wt% of alcohol in the oxygen-containing compound, 0.75 wt% of aldehydes and ketones, and 0.12 wt% of acids and esters;
the distillation range of the third stage fraction is a fraction of more than 260 ℃ and not more than 350 ℃, wherein the content of alpha-olefin is 46.18 wt%, the content of normal alkane is 44.12 wt%, the content of alcohol in the oxygen-containing compound is 3.41 wt%, the content of aldehyde and ketone is 0.59 wt%, and the content of acid and ester is 0.10 wt%;
(2) and taking 1000g of the first-stage fraction, and carrying out multi-stage countercurrent extraction in a first extraction tower by using 75 wt% of methanol aqueous solution at the extraction temperature of 15 ℃, wherein the dosage of the methanol aqueous solution is 2000g, and the extraction theoretical stage number is 5, so as to obtain an extract phase 1 and a raffinate phase 1. Introducing a raffinate phase 1 at the top of the first extraction tower into a first water washing tower, washing methanol off by a water washing method, taking out a hydrocarbon phase 1 as a tower top product, returning a tower bottom product (a methanol aqueous solution) to the first extraction tower for recycling to obtain 941.1g of the hydrocarbon phase 1, wherein the recovery rate of the hydrocarbon phase 1 is 97.3%, and the alpha-olefin content in the hydrocarbon phase 1 is 72.98% by weight, the normal alkane content is 22.13% by weight and the oxygen-containing compound content is 45ppm (the alcohol content is 0ppm, the aldehyde and ketone content is 37ppm, and the acid and ester content is 8ppm) through gas chromatography detection. Introducing an extraction phase 1 at the bottom of a first extraction tower into a first rectifying tower, obtaining methanol at the top of the first rectifying tower, introducing a kettle bottom product of the first rectifying tower into a first decanter, recovering an aqueous solvent at the bottom of the first decanter, preparing the aqueous solvent and the methanol obtained at the top of the first rectifying tower to obtain a 75 wt% methanol aqueous solution, returning the aqueous solution to the first extraction tower for recycling, and obtaining an organic phase 1 at the top of the first decanter;
and taking 1000g of the second-stage fraction, and carrying out multi-stage countercurrent extraction in a second extraction tower by using 75 wt% ethanol aqueous solution at the extraction temperature of 15 ℃, wherein the dosage of the ethanol aqueous solution is 2000g, and the extraction theoretical stage is 5 stages, so as to obtain an extract phase 2 and a raffinate phase 2. Introducing the raffinate phase 2 at the top of the second extraction tower into a second water washing tower, washing off ethanol by a water washing method, taking out the hydrocarbon phase 2 as a tower top product, returning a tower bottom product (ethanol aqueous solution) to the second extraction tower for recycling to obtain 936.5g of the hydrocarbon phase 2, wherein the recovery rate of the hydrocarbon phase 2 is 98.0%, and the alpha-olefin content in the hydrocarbon phase 2 is 68.91% by weight, the normal alkane content is 25.36% by weight, and the oxygen-containing compound content is 43ppm (the alcohol content is 0ppm, the aldehyde and ketone content is 32ppm, and the acid and ester content is 11ppm) through gas chromatography detection. Introducing an extraction phase 2 at the bottom of a second extraction tower into a second rectifying tower, obtaining an azeotrope of ethanol and water at the top of the second rectifying tower, introducing a kettle bottom product of the second rectifying tower into a second decanter, recovering an aqueous solvent at the bottom of the second decanter, preparing the aqueous solvent with the azeotrope of ethanol and water obtained at the top of the second rectifying tower to obtain an ethanol aqueous solution with the concentration of 75 weight percent, returning the ethanol aqueous solution to the second extraction tower for cyclic utilization, and obtaining an organic phase 2 at the top of the second decanter;
and taking 1000g of the third-stage fraction, and performing multi-stage countercurrent extraction in a third extraction tower by using a 70 wt% aqueous solution of ethylene glycol monoethyl ether at the extraction temperature of 15 ℃, the dosage of an extracting agent of 2000g and the extraction theoretical stage number of 5 to obtain an extract phase 3 and a raffinate phase 3. Introducing the raffinate phase 3 at the top of the third extraction tower into a third water washing tower, washing off ethylene glycol monoethyl ether by a water washing method, taking out the hydrocarbon phase 3 as a tower top product, returning a tower bottom product (an aqueous solution of the ethylene glycol monoethyl ether) to the third extraction tower for recycling to obtain 929.3g of the hydrocarbon phase 3, wherein the recovery rate of the hydrocarbon phase 3 is 96.9%, and the alpha-olefin content in the hydrocarbon phase 3 is 47.21 wt%, the normal alkane content is 44.96 wt%, and the oxygen-containing compound content is 35ppm (the alcohol content is 0ppm, the aldehyde and ketone content is 26ppm, and the acid and ester content is 9ppm) through gas chromatography detection. Introducing an extract phase 3 at the bottom of a third extraction tower into a third rectifying tower, obtaining an azeotrope of ethylene glycol monoethyl ether and water at the top of the third rectifying tower, introducing a kettle bottom product of the third rectifying tower into a third decanter, recovering a water solvent at the bottom of the third decanter, preparing the water solvent with the azeotrope of the ethylene glycol monoethyl ether and the water obtained at the top of the third rectifying tower to obtain an aqueous solution of the ethylene glycol monoethyl ether with the concentration of 70 weight percent, returning the aqueous solution to the third extraction tower for recycling, and obtaining an organic phase 3 at the top of the third decanter;
in summary, the content of the oxygen-containing compounds in the hydrocarbon phase 1, the hydrocarbon phase 2 and the hydrocarbon phase 3 is divided into 45ppm, 43ppm and 35ppm, that is, the content of the oxygen-containing compounds in the deoxygenated refined Fischer-Tropsch synthesis oil is less than 100 ppm.
Example 3
(1) The Fischer-Tropsch synthesis oil shown in the table 1 is subjected to atmospheric and vacuum fractionation to obtain a first stage fraction, a second stage fraction and a third stage fraction, wherein,
the distillation range of the first-stage fraction is 59-170 ℃, wherein the content of alpha-olefin is 70.97 wt%, the content of normal alkane is 23.02 wt%, the content of alcohol in the oxygen-containing compound is 2.61 wt%, the content of aldehyde and ketone is 0.64 wt%, and the content of acid and ester is 0.14 wt%;
the second stage fraction had a distillation range of more than 170 ℃ and not more than 300 ℃, and contained 62.69 wt% of α -olefin, 29.24 wt% of n-alkane, 3.54 wt% of alcohol in the oxygen-containing compound, 0.71 wt% of aldehyde and ketone, and 0.11 wt% of acid and ester;
the distillation range of the third stage fraction is a fraction of more than 300 ℃ and not more than 380 ℃, wherein the content of alpha-olefin is 40.46 wt%, the content of normal alkane is 48.91 wt%, the content of alcohol in the oxygen-containing compound is 3.21 wt%, the content of aldehyde and ketone is 0.51 wt%, and the content of acid and ester is 0.08 wt%;
(2) and taking 1000g of the first-stage fraction, and carrying out multistage countercurrent extraction in a first extraction tower by using 60 wt% methanol aqueous solution at the extraction temperature of 50 ℃, wherein the dosage of the methanol aqueous solution is 500g, and the extraction theoretical stage number is 10, so as to obtain an extract phase 1 and a raffinate phase 1. Introducing raffinate phase 1 at the top of the first extraction tower into a first water washing tower, washing methanol off by a water washing method, taking out hydrocarbon phase 1 as a tower top product, returning a tower bottom product (methanol aqueous solution) to the first extraction tower for recycling, and obtaining 947.7g of hydrocarbon phase 1, wherein the recovery rate of the hydrocarbon phase 1 is 98.1%, the alpha-olefin content in the hydrocarbon phase 1 is 72.1 wt%, the normal alkane content is 23.6 wt%, and the oxygen-containing compound content is 80ppm (the alcohol content is 0ppm, the aldehyde and ketone content is 62ppm, and the acid and ester content is 18ppm) through gas chromatography detection. Introducing an extract phase 1 at the bottom of a first extraction tower into a first rectifying tower, obtaining methanol at the top of the first rectifying tower, introducing a kettle bottom product of the first rectifying tower into a first decanter, recovering an aqueous solvent at the bottom of the first decanter, preparing the aqueous solvent and the methanol obtained at the top of the first rectifying tower to obtain a 60 wt% methanol aqueous solution, returning the aqueous solution to the first extraction tower for recycling, and obtaining an organic phase 1 at the top of the first decanter;
and taking 1000g of the second-stage fraction, and carrying out multi-stage countercurrent extraction in a second extraction tower by using 60 wt% ethanol aqueous solution at the extraction temperature of 50 ℃, wherein the dosage of the ethanol aqueous solution is 500g, and the extraction theoretical stage number is 10, so as to obtain an extract phase 2 and a raffinate phase 2. Introducing a raffinate phase 2 at the top of the second extraction tower into a second water washing tower, washing off ethanol by a water washing method, leading out a hydrocarbon phase 2 as a tower top product, returning a tower bottom product (an ethanol aqueous solution) to the second extraction tower for recycling to obtain 941.1g of the hydrocarbon phase 2, wherein the recovery rate of the hydrocarbon phase 2 is 98.4%, and the alpha-olefin content, the normal alkane content and the oxygen-containing compound content in the hydrocarbon phase 2 are respectively 65.1 wt%, 31.1 wt% and 85ppm (the alcohol content is 0ppm, the aldehyde content and the ketone content are 65ppm and the acid content and the ester content are 20ppm) respectively according to gas chromatography detection. Introducing an extraction phase 2 at the bottom of a second extraction tower into a second rectification tower, obtaining an azeotrope of ethanol and water at the top of the second rectification tower, introducing a kettle bottom product of the second rectification tower into a second decanter, recovering a water solvent at the bottom of the second decanter, preparing the azeotrope of ethanol and water obtained at the top of the second rectification tower with the water solvent to obtain an ethanol aqueous solution with the concentration of 60 weight percent, returning the ethanol aqueous solution to the second extraction tower for recycling, and obtaining an organic phase 2 at the top of the second decanter;
and taking 1000g of the third-stage fraction, and carrying out multi-stage countercurrent extraction in a third extraction tower by using 60 wt% of aqueous solution of diethylene glycol monomethyl ether, wherein the extraction temperature is 50 ℃, the dosage of an extracting agent is 500g, and the theoretical stage of extraction is 10 stages, so as to obtain an extract phase 3 and a raffinate phase 3. Introducing the raffinate phase 3 at the top of the third extraction tower into a third water washing tower, washing off diethylene glycol monomethyl ether by a water washing method, taking out the hydrocarbon phase 3 as a tower top product, returning a tower bottom product (a water solution of diethylene glycol monomethyl ether) to the third extraction tower for recycling to obtain 949.5g of the hydrocarbon phase 3, wherein the recovery rate of the hydrocarbon phase 3 is 98.7%, and the alpha-olefin content, the n-alkane content and the oxygen-containing compound content in the hydrocarbon phase 3 are respectively 41.23 wt%, 49.65 wt% and 78ppm (the alcohol content is 0ppm, the aldehyde content and the ketone content is 63ppm, and the acid content and the ester content are 15ppm) through gas chromatography detection. Introducing an extraction phase 3 at the bottom of a third extraction tower into a third rectifying tower, obtaining an azeotrope of diethylene glycol monomethyl ether and water at the top of the third rectifying tower, introducing a kettle bottom product of the third rectifying tower into a third decanter, recovering a water solvent at the bottom of the third decanter, preparing the water solvent with the azeotrope of diethylene glycol monomethyl ether and water obtained at the top of the third rectifying tower to obtain a 60 wt% aqueous solution of diethylene glycol monomethyl ether, returning the aqueous solution to the third extraction tower for recycling, and obtaining an organic phase 3 at the top of the third decanter;
in summary, the content of the oxygen-containing compounds in the hydrocarbon phase 1, the hydrocarbon phase 2 and the hydrocarbon phase 3 is respectively 80ppm, 85ppm and 78ppm, that is, the content of the oxygen-containing compounds in the deoxidized and refined Fischer-Tropsch synthesis oil is less than 100 ppm.
Example 4
(1) The Fischer-Tropsch synthesis oil shown in the table 1 is subjected to atmospheric and vacuum fractionation to obtain a first stage fraction, a second stage fraction and a third stage fraction, wherein,
the distillation range of the first-stage fraction is 59-140 ℃, wherein the content of alpha-olefin is 72.96 wt%, the content of normal alkane is 22.01 wt%, the content of alcohol in the oxygen-containing compound is 2.44 wt%, the content of aldehyde and ketone is 0.59 wt%, and the content of acid and ester is 0.13 wt%;
the second stage fraction had a distillation range of greater than 140 ℃ and not greater than 240 ℃, wherein the content of α -olefin was 68.69% by weight, the content of n-alkane was 24.01% by weight, the content of alcohol in the oxygen-containing compound was 3.58% by weight, the content of aldehyde and ketone was 0.76% by weight, and the content of acid and ester was 0.13% by weight;
the distillation range of the third stage fraction is a fraction of more than 240 ℃ and not more than 380 ℃, wherein the content of alpha-olefin is 52.23 wt%, the content of normal alkane is 38.07 wt%, the content of alcohol in the oxygen-containing compound is 3.42 wt%, the content of aldehyde and ketone is 0.62 wt%, and the content of acid and ester is 0.11 wt%;
(2) taking 1000g of the first-stage fraction, and carrying out multi-stage countercurrent extraction in a first extraction tower by using 85 wt% methanol aqueous solution, wherein the extraction temperature is 30 ℃, the dosage of the methanol aqueous solution is 4000g, and the extraction theoretical stage number is 3, so as to obtain an extract phase 1 and a raffinate phase 1. Introducing raffinate phase 1 at the top of the first extraction tower into a first water washing tower, washing methanol off by a water washing method, taking out hydrocarbon phase 1 as a tower top product, returning a tower bottom product (methanol aqueous solution) to the first extraction tower for recycling, and obtaining 941.3g of hydrocarbon phase 1, wherein the recovery rate of the hydrocarbon phase 1 is 97.2%, the alpha-olefin content in the hydrocarbon phase 1 is 73.81 wt%, the normal alkane content is 23.21 wt%, and the oxygen-containing compound content is 70ppm (the alcohol content is 0ppm, the aldehyde and ketone content is 52ppm, and the acid and ester content is 18ppm) through gas chromatography detection. Introducing an extraction phase 1 at the bottom of a first extraction tower into a first rectifying tower, obtaining methanol at the top of the first rectifying tower, introducing a kettle bottom product of the first rectifying tower into a first decanter, recovering an aqueous solvent at the bottom of the first decanter, preparing the aqueous solvent and the methanol obtained at the top of the first rectifying tower to obtain a methanol aqueous solution with the concentration of 85 weight percent, returning the methanol aqueous solution to the first extraction tower for recycling, and obtaining an organic phase 1 at the top of the first decanter;
and taking 1000g of the second-stage fraction, and carrying out multi-stage countercurrent extraction in a second extraction tower by using 80 wt% ethanol aqueous solution at the extraction temperature of 30 ℃, wherein the dosage of the ethanol aqueous solution is 4000g, and the extraction theoretical stage number is 3, so as to obtain an extract phase 2 and a raffinate phase 2. Introducing the raffinate phase 2 at the top of the second extraction tower into a second water washing tower, washing off ethanol by a water washing method, taking out the hydrocarbon phase 2 as a tower top product, returning a tower bottom product (ethanol aqueous solution) to the second extraction tower for recycling to obtain 937.1g of the hydrocarbon phase 2, wherein the recovery rate of the hydrocarbon phase 2 is 98.1%, and the alpha-olefin content in the hydrocarbon phase 2 is 69.26% by weight, the normal alkane content is 24.96% by weight, and the oxygen-containing compound content is 73ppm (the alcohol content is 0ppm, the aldehyde and ketone content is 58ppm, and the acid and ester content is 15ppm) through gas chromatography detection. Introducing an extraction phase 2 at the bottom of a second extraction tower into a second rectification tower, obtaining an azeotrope of ethanol and water at the top of the second rectification tower, introducing a kettle bottom product of the second rectification tower into a second decanter, recovering a water solvent at the bottom of the second decanter, preparing the azeotrope of ethanol and water obtained at the top of the second rectification tower with the water solvent to obtain an ethanol aqueous solution with the concentration of 80 weight percent, returning the ethanol aqueous solution to the second extraction tower for recycling, and obtaining an organic phase 2 at the top of the second decanter;
and taking 1000g of the third-stage fraction, and carrying out multi-stage countercurrent extraction in a third extraction tower by using an aqueous solution of 80 wt% diethylene glycol monobutyl ether, wherein the extraction temperature is 30 ℃, the dosage of an extracting agent is 4000g, and the extraction theoretical stage number is 3, so as to obtain an extract phase 3 and a raffinate phase 3. Introducing the raffinate phase 3 at the top of the third extraction tower into a third water washing tower, washing off the diethylene glycol monobutyl ether by a water washing method, taking out the hydrocarbon phase 3 as a tower top product, returning a tower bottom product (an aqueous solution of the diethylene glycol monobutyl ether) to the third extraction tower for recycling to obtain 921.1g of the hydrocarbon phase 3, wherein the recovery rate of the hydrocarbon phase 3 is 96.1%, and the alpha-olefin content in the hydrocarbon phase 3 is 53.15 wt%, the normal paraffin content is 38.89 wt%, and the oxygen-containing compound content is 60ppm (the alcohol content is 0ppm, the aldehyde and ketone content is 41ppm, and the acid and ester content is 19ppm) through gas chromatography detection. Introducing an extraction phase 3 at the bottom of a third extraction tower into a third rectifying tower, obtaining an azeotrope of diethylene glycol monobutyl ether and water at the top of the third rectifying tower, introducing a kettle bottom product of the third rectifying tower into a third decanter, recovering an aqueous solvent at the bottom of the third decanter, preparing the aqueous solvent with the azeotrope of the diethylene glycol monobutyl ether and water obtained at the top of the third rectifying tower to obtain an aqueous solution of the diethylene glycol monobutyl ether with the concentration of 80 weight percent, returning the aqueous solution to the third extraction tower for recycling, and obtaining an organic phase 3 at the top of the third decanter;
in summary, the content of the oxygen-containing compounds in the hydrocarbon phase 1, the hydrocarbon phase 2 and the hydrocarbon phase 3 is 70ppm, 73ppm and 60ppm, that is, the content of the oxygen-containing compounds in the deoxygenated refined Fischer-Tropsch synthesis oil is less than 100 ppm.
Comparative example 1
1000g of Fischer-Tropsch synthesis oil shown in Table 1 was subjected to multistage countercurrent extraction with 69% aqueous ethanol at 20 ℃ with an extractant amount of 1000g and a theoretical extraction stage number of 7, to obtain 873.0g of a hydrocarbon phase 1 having a recovery rate of 90.9%, and as determined by gas chromatography, the hydrocarbon phase contained 61.9 wt% of α -olefin, 32.2 wt% of n-alkane and 200ppm of oxygen-containing compound (40 ppm of alcohol, 120ppm of aldehyde and ketone and 40ppm of acid and ester).
Comparative example 2
1000g of Fischer-Tropsch synthesis oil shown in Table 1 was subjected to multistage countercurrent extraction with a 65% methanol aqueous solution at an extraction temperature of 20 ℃, an extractant amount of 1000g, and a theoretical stage number of extraction of 7, to obtain 953.0g of a hydrocarbon phase 1 having a recovery rate of 99.2%, and as determined by gas chromatography, the hydrocarbon phase had an α -olefin content of 61.8 wt%, a normal paraffin content of 32.3 wt%, and an oxygen-containing compound content of 900ppm (an alcohol content of 300ppm, aldehyde and ketone contents of 400ppm, and acid and ester contents of 200 ppm).
Comparative example 3
1000g of Fischer-Tropsch synthesis oil shown in the table 1 is taken, multi-stage countercurrent extraction is carried out by using 65% of ethylene glycol monomethyl ether aqueous solution, the extraction temperature is 20 ℃, the dosage of an extracting agent is 1000g, the extraction theoretical stage is 7 stages, 855.0g of hydrocarbon phase 1 is obtained, the recovery rate of the hydrocarbon phase is 89.0%, the content of alpha-olefin in the hydrocarbon phase is 61.36 wt%, the content of normal alkane is 32.36 wt%, and the content of oxygen-containing compounds is 70ppm (the content of alcohol is 0ppm, the content of aldehyde and ketone is 53ppm, and the content of acid and ester is 17ppm) through gas chromatography detection.
Comparative example 4
The process of example 1 was followed except that the aqueous methanol solution in step (2) was replaced with an aqueous ethanol solution. That is, 1000g of the first stage fraction was taken, and subjected to multistage countercurrent extraction with an aqueous ethanol solution having a concentration of 65% by weight in a first extraction column to obtain 869.8g of a hydrocarbon phase 1, the recovery rate of the hydrocarbon phase 1 was 90.0%, and the content of α -olefin in the hydrocarbon phase 1 was 72.1% by weight, the content of n-paraffin was 23.12% by weight, and the content of oxygen-containing compound was 75ppm (the alcohol content was 0ppm, the aldehyde and ketone contents were 52ppm, and the acid and ester contents were 23ppm) as determined by gas chromatography.
Comparative example 5
The process of example 1 was followed except that the aqueous methanol solution in step (2) was replaced with water. That is, 1000g of the first stage fraction was taken and subjected to multistage countercurrent extraction with water in a first extraction column to obtain 1000g of a hydrocarbon phase 1, the recovery rate of the hydrocarbon phase was 100%, and the content of α -olefin in the hydrocarbon phase 1 was 71.29% by weight, the content of n-paraffin was 22.02% by weight, the content of alcohol in the oxygen-containing compound was 2.60% by weight, the content of aldehyde and ketone was 0.62% by weight, and the content of acid and ester was 0.14% by weight, as measured by gas chromatography.
Comparative example 6
The procedure of example 1 was followed, except that the aqueous ethanol solutions in step (2) were each replaced with an aqueous methanol solution. That is to say that the first and second electrodes,
taking 1000g of the second-stage fraction, and carrying out multi-stage countercurrent extraction on the second-stage fraction by using a 69 wt% methanol aqueous solution in a second extraction tower to obtain 961.0g of a hydrocarbon phase 2, wherein the recovery rate of the hydrocarbon phase 2 is 99.2%, and the content of alpha-olefin, n-alkane and oxygen-containing compounds in the hydrocarbon phase 2 is 67.69 wt%, 22.83 wt% and 1.29 wt% (the content of alcohol is 1.01 wt%, the content of aldehyde and ketone is 0.22 wt%, and the content of acid and ester is 0.06 wt%) according to gas chromatography detection;
1000g of the third fraction were subjected to multistage countercurrent extraction with an aqueous methanol solution having a concentration of 80% by weight in a third extraction column to obtain 975.8g of a hydrocarbon phase 3, the recovery rate of the hydrocarbon phase 3 was 99.6%, and the content of α -olefin, the content of n-paraffin, and the content of oxygen-containing compound in the hydrocarbon phase 3 were 45.96% by weight, 46.03% by weight, and 1.94% by weight, respectively, as measured by gas chromatography (the content of alcohol was 1.65% by weight, the content of aldehyde and ketone was 0.22% by weight, and the content of acid and ester was 0.07% by weight).
It can be seen from the examples and comparative examples that not only the content of alpha-olefins is maintained during the process of removing the oxygenates, but also the content of the oxygenates in the Fischer-Tropsch synthesis oil after deoxygenation refining is reduced to below 100 ppm. The content of the oxygen-containing compound was high in the case of using only an aqueous ethanol solution (comparative example 1), an aqueous methanol solution (comparative example 2), a method according to the present invention in which the aqueous methanol solution in step (2) was replaced with water (comparative example 5), and a method according to the present invention in which the aqueous ethanol solution in step (2) was replaced with an aqueous methanol solution (comparative example 6). Furthermore, using only an aqueous solution of ethylene glycol monomethyl ether (comparative example 3), and the process according to the invention but replacing the aqueous methanol solution in step (2) with an aqueous ethanol solution (comparative example 4), the oxygenate content in the deoxygenated refined Fischer-Tropsch synthesis oil could reach 100ppm or less, but the recovery of the hydrocarbon phase was only 89.0%, 90.0%, significantly lower than the process of the invention.
In conclusion, the method not only maintains the content of the alpha-olefin in the process of removing the oxygen-containing compound, but also reduces the content of the oxygen-containing compound in the deoxidized and refined Fischer-Tropsch synthetic oil to be less than 100ppm and has high oil recovery rate.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (17)
1. A Fischer-Tropsch synthetic oil deoxidation refining method is characterized by comprising the following steps:
(1) carrying out atmospheric and vacuum fractionation on Fischer-Tropsch synthetic oil to obtain a first-stage fraction, a second-stage fraction and a third-stage fraction, wherein,
the above-mentionedThe distillation range of the first stage fraction is IBP-T a The temperature is less than or equal to 140 ℃ and T is less than or equal to a ≤170℃；
The distillation range of the second-stage fraction is more than T a And is not more than T b The temperature is less than or equal to 240 ℃ and T is less than or equal to b ≤300℃；
The distillation range of the third-stage fraction is more than T b ℃；
(2) Carrying out first extraction on the first-stage fraction by using a methanol aqueous solution to obtain an extract phase 1 and a raffinate phase 1, wherein the concentration of the methanol aqueous solution is not more than 85 wt%; performing second extraction on the second-stage fraction by using an ethanol aqueous solution to obtain an extract phase 2 and a raffinate phase 2, wherein the concentration of the ethanol aqueous solution is not more than 80 wt%; performing third extraction on the third-stage fraction by using an aqueous solution of glycol ethers to obtain an extract phase 3 and a raffinate phase 3, wherein the concentration of the aqueous solution of the glycol ethers is not more than 80 wt%, and the glycol ethers are selected from one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether and diethylene glycol monobutyl ether;
(3) washing the raffinate phase 1, the raffinate phase 2 and the raffinate phase 3 respectively to obtain deoxidized and refined Fischer-Tropsch synthetic oil;
the Fischer-Tropsch synthetic oil comprises 0.1-10 wt% of oxygen-containing compounds by total weight of the Fischer-Tropsch synthetic oil, wherein the oxygen-containing compounds comprise alcohols, ketones, aldehydes, acids and esters.
2. The process according to claim 1, wherein in step (1), the distillation range of the first stage fraction is IBP-T a Fraction at 150 ℃ or lower, wherein T is not more than 150 ℃ a ≤160℃；
The distillation range of the second-stage fraction is more than T a And is not more than T b The temperature is less than or equal to 260 ℃ and T is more than or equal to b ≤280℃；
The distillation range of the third-stage fraction is more than T b ℃。
3. The method according to claim 1 or 2, wherein, in the step (2), the concentration of the methanol aqueous solution is 60 to 75 wt%; the amount of the methanol aqueous solution is 0.5-4 times of the weight of the first-stage distillate.
4. A process according to claim 3, wherein the aqueous methanol solution is used in an amount of 0.8 to 2 times the weight of the first stage fraction.
5. The method according to claim 1 or 2, wherein, in the step (2), the concentration of the ethanol aqueous solution is 60 to 75 wt%; the dosage of the ethanol water solution is 0.5-4 times of the weight of the second-stage fraction.
6. The method according to claim 5, wherein the amount of the ethanol aqueous solution is 0.8 to 2 times the weight of the second-stage fraction.
7. The method according to claim 1 or 2, wherein in step (2), the concentration of the aqueous solution of glycol ethers is 60-70 wt%; the dosage of the glycol ether aqueous solution is 0.5-4 times of the weight of the third-stage fraction.
8. A process according to claim 5, wherein the aqueous solution of glycol ethers is used in an amount of 0.8 to 2 times the weight of the third fraction.
9. The process according to claim 1 or 2, wherein the temperature of the first extraction is 15-50 ℃; the first extraction method is a multi-stage countercurrent extraction method; the theoretical stage number of the first extraction is 3-10.
10. The method of claim 9, wherein the temperature of the first extraction is 20-50 ℃; the theoretical stage number of the first extraction is 5-7.
11. The process according to claim 1 or 2, wherein the temperature of the second extraction is 15-50 ℃; the second extraction method is a multi-stage countercurrent extraction method; the theoretical stage number of the second extraction is 3-10.
12. The method of claim 11, wherein the temperature of the second extraction is 20-50 ℃; the theoretical stage number of the second extraction is 5-7.
13. The process according to claim 1 or 2, wherein the temperature of the third extraction is 15-50 ℃; the third extraction method is a multi-stage countercurrent extraction method; and the theoretical stage number of the third extraction is 3-10.
14. The method of claim 13, wherein the temperature of the third extraction is 20-50 ℃; the theoretical stage number of the third extraction is 5-7.
15. The process of claim 1 or claim 2, wherein the Fischer-Tropsch oil has a boiling range of IBP-380 ℃.
16. The process of claim 15, wherein the fischer-tropsch synthesis oil has a boiling range of IBP to 350 ℃.
17. The process of claim 1 or 2, further comprising subjecting the extract phase 1, extract phase 2 and extract phase 3 to solvent separation to obtain oxygenates and recycled solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910214756.9A CN111718746B (en) | 2019-03-20 | 2019-03-20 | Method for deoxidizing and refining Fischer-Tropsch synthetic oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910214756.9A CN111718746B (en) | 2019-03-20 | 2019-03-20 | Method for deoxidizing and refining Fischer-Tropsch synthetic oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111718746A CN111718746A (en) | 2020-09-29 |
| CN111718746B true CN111718746B (en) | 2022-08-02 |
Family
ID=72563571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910214756.9A Active CN111718746B (en) | 2019-03-20 | 2019-03-20 | Method for deoxidizing and refining Fischer-Tropsch synthetic oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111718746B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625732B (en) * | 2020-12-25 | 2023-01-24 | 国家能源集团宁夏煤业有限责任公司 | Composite extractant for extracting oxygen-containing compounds in C5 hydrocarbon raw material and method for treating oxygen-containing compounds in C5 hydrocarbon |
| CN113621402B (en) * | 2021-07-14 | 2022-09-20 | 上海兖矿能源科技研发有限公司 | Separation method of Fischer-Tropsch synthetic oil |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6559248B2 (en) * | 2001-08-31 | 2003-05-06 | Exxonmobil Chemical Patents Inc. | Process of removing contaminants from an olefin stream using extractive distillation |
| US8058498B2 (en) * | 2004-10-29 | 2011-11-15 | Sandra Jensen | Device for removing oxygen-containing organic compounds from mixtures of various hydrocarbon compounds |
| EP2338864A1 (en) * | 2009-12-22 | 2011-06-29 | Total Petrochemicals Research Feluy | Process for removing oxygenated contaminants from an hydrocarbon stream |
| CN101891589B (en) * | 2010-06-21 | 2013-06-12 | 中国海洋石油总公司 | Method for extracting fatty alcohols |
| CN109022027B (en) * | 2017-06-12 | 2020-10-02 | 神华集团有限责任公司 | Method for producing poly alpha-olefin from Fischer-Tropsch synthesis light oil and poly alpha-olefin obtained by method |
-
2019
- 2019-03-20 CN CN201910214756.9A patent/CN111718746B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111718746A (en) | 2020-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111718748A (en) | Method for removing oxygen-containing compounds from Fischer-Tropsch synthetic oil | |
| CN111718746B (en) | Method for deoxidizing and refining Fischer-Tropsch synthetic oil | |
| CN109627137B (en) | A kind of separation method for coal base Fischer-Tropsch olefins | |
| CN107915612B (en) | Method for preparing purified MIBK from industrial byproduct waste liquid acetone | |
| CN101333144B (en) | Method for removing dimethyl ether from olefin stream | |
| CN114409496A (en) | Method and device for separating 1-octene from Fischer-Tropsch synthetic oil | |
| CN100383096C (en) | Extraction of oxygenates from a hydrocarbon stream | |
| CN107973687B (en) | Method for removing oxygen-containing compounds in mixed aromatics of methanol aromatization product | |
| CN112745913B (en) | Method for removing oxygen-containing compounds in Fischer-Tropsch synthetic oil | |
| CN112745912B (en) | Method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil | |
| US6483000B2 (en) | Process for the manufacture in pure form of 1-pentene or an alpha-olefin lower than 1-pentene | |
| CN110787719A (en) | Method and system for preparing surfactant by using Fischer-Tropsch synthesis heavy distillate oil | |
| CN113621402B (en) | Separation method of Fischer-Tropsch synthetic oil | |
| CN100413824C (en) | Production of linear alkyl benzene | |
| CN112625732A (en) | Composite extractant for extracting oxygen-containing compound in C5 hydrocarbon raw material and method for processing oxygen-containing compound in C5 hydrocarbon | |
| CN107721829A (en) | A kind of method that dimethyl ether is removed from the feed stream comprising propane and dimethyl ether | |
| US2537658A (en) | Recovery of fatty acids from dilute aqueous solutions | |
| CN115612521A (en) | Process for removing oxygenates from a hydrocarbon-containing stream | |
| CN115491229B (en) | Separation method of high-temperature Fischer-Tropsch synthesis light oil | |
| AU2003297339A1 (en) | Process for separating linear alpha olefins from saturated hydrocarbons | |
| CN114478169A (en) | Method and device for separating and purifying 1-hexene from Fischer-Tropsch synthetic oil | |
| CN116286085A (en) | Fischer-Tropsch synthesis naphtha deoxygenation method | |
| CN115612522A (en) | Method and system for reducing oxygenates in a hydrocarbon-containing stream | |
| CN213232061U (en) | Apparatus for purifying 1-hexene | |
| CN116064091A (en) | Fischer-Tropsch oil deoxygenation device and method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 100011 Beijing Dongcheng District, West Binhe Road, No. 22 Applicant after: CHINA ENERGY INVESTMENT Corp.,Ltd. Applicant after: Beijing low carbon clean energy Research Institute Address before: 100011 Beijing Dongcheng District, West Binhe Road, No. 22 Applicant before: CHINA ENERGY INVESTMENT Corp.,Ltd. Applicant before: NATIONAL INSTITUTE OF CLEAN-AND-LOW-CARBON ENERGY |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |