ZA200900548B - Process for separating by-products in aqueous phase of a fischer-tropsch synthesis - Google Patents
Process for separating by-products in aqueous phase of a fischer-tropsch synthesis Download PDFInfo
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- ZA200900548B ZA200900548B ZA2009/00548A ZA200900548A ZA200900548B ZA 200900548 B ZA200900548 B ZA 200900548B ZA 2009/00548 A ZA2009/00548 A ZA 2009/00548A ZA 200900548 A ZA200900548 A ZA 200900548A ZA 200900548 B ZA200900548 B ZA 200900548B
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- 239000008346 aqueous phase Substances 0.000 title claims description 83
- 239000006227 byproduct Substances 0.000 title claims description 62
- 238000000034 method Methods 0.000 title claims description 58
- 238000003786 synthesis reaction Methods 0.000 title claims description 53
- 230000015572 biosynthetic process Effects 0.000 title claims description 51
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 615
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 369
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 213
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 188
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 178
- 239000007864 aqueous solution Substances 0.000 claims description 160
- 238000009835 boiling Methods 0.000 claims description 138
- 238000010992 reflux Methods 0.000 claims description 130
- 239000000203 mixture Substances 0.000 claims description 118
- 239000002904 solvent Substances 0.000 claims description 74
- 238000000926 separation method Methods 0.000 claims description 65
- 239000012071 phase Substances 0.000 claims description 52
- 239000003795 chemical substances by application Substances 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 238000000605 extraction Methods 0.000 claims description 41
- 239000011877 solvent mixture Substances 0.000 claims description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- 239000002351 wastewater Substances 0.000 claims description 28
- 150000001298 alcohols Chemical class 0.000 claims description 24
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 23
- 150000002576 ketones Chemical class 0.000 claims description 23
- 239000007791 liquid phase Substances 0.000 claims description 14
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002798 polar solvent Substances 0.000 claims description 12
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 7
- 229940011051 isopropyl acetate Drugs 0.000 claims description 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- GELMWIVBBPAMIO-UHFFFAOYSA-N 2-methylbutan-2-amine Chemical compound CCC(C)(C)N GELMWIVBBPAMIO-UHFFFAOYSA-N 0.000 claims description 4
- 150000003003 phosphines Chemical class 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 claims description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims 2
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 description 32
- 239000007789 gas Substances 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- -1 trimethylphosphine propanol Chemical compound 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- LRMLWYXJORUTBG-UHFFFAOYSA-N dimethylphosphorylmethane Chemical compound CP(C)(C)=O LRMLWYXJORUTBG-UHFFFAOYSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- KJUCPVIVNLPLEE-UHFFFAOYSA-N 2,6-difluoro-n-[2-fluoro-5-[5-[2-[(6-morpholin-4-ylpyridin-3-yl)amino]pyrimidin-4-yl]-2-propan-2-yl-1,3-thiazol-4-yl]phenyl]benzenesulfonamide Chemical compound S1C(C(C)C)=NC(C=2C=C(NS(=O)(=O)C=3C(=CC=CC=3F)F)C(F)=CC=2)=C1C(N=1)=CC=NC=1NC(C=N1)=CC=C1N1CCOCC1 KJUCPVIVNLPLEE-UHFFFAOYSA-N 0.000 description 1
- ISTJMQSHILQAEC-UHFFFAOYSA-N 2-methyl-3-pentanol Chemical compound CCC(O)C(C)C ISTJMQSHILQAEC-UHFFFAOYSA-N 0.000 description 1
- CLYAQFSQLQTVNO-UHFFFAOYSA-N 3-cyclohexylpropan-1-ol Chemical compound OCCCC1CCCCC1 CLYAQFSQLQTVNO-UHFFFAOYSA-N 0.000 description 1
- VGUJGODYQXGEAF-UHFFFAOYSA-N C(C)(=[O+][O-])O Chemical compound C(C)(=[O+][O-])O VGUJGODYQXGEAF-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000286819 Malo Species 0.000 description 1
- 241001608711 Melo Species 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Cwm
The present application claims the priority of the Chinese Patent Application Nos.
CN200810032926.3 filed on January 23, 2008, CN200810032927.8 filed on January 23, 2008, CN200810043253.1 filed on April 11, 2008 and CN200810043252.7 filed on April 11, 2008, which are incorporated herein by reference in their entirety and for all purposes.
The present invention relates to a process for separating by-products in aqueous phase of a Fischer-Tropsch synthesis. :
As a demand for petroleum-based liquid fuels is increasing and available reserves of petroleum source are decreasing, processes for producing useful liquid fuels from solid fuels, such as coal, draw increasing attention. A process well-known by those skilled in the art for producing liquid fuels from solid fuels is so-called Fischer-Tropsch synthesis process, which catalytically converts syngas comprising carbon monoxide and hydrogen and produced from carbonaceous material, such as coal, in the presence of an iron-based catalyst, a cobalt-based catalyst, or an iron and cobalt-based catalyst at a certain temperature under a certain pressure, into methane and hydrocarbons having more carbon atoms, with alcohols, other oxygenates, water, and the like being produced at the same time.
Water in Fischer-Tropsch synthesis reaction effluent can be easily separated from the hydrocarbons as main products of the Fischer-Tropsch synthesis, but the water separated from the Fischer-Tropsch synthesis reaction effluent will contain an amount of organic oxygenates such as alcohols, aldehydes, ketones, acids and the like because of the solubilities of said organic oxygenates in water.
Since the amount of water formed during the Fischer-Tropsch synthesis process is relatively large, direct disposal of the water is obviously uneconomical and does not comply with environmental protection regulations because of the presence of the organic oxygenates such as alcohols, aldehydes, ketones, acids and the like, which may cause corrosion and pollution. Patent Application CN 1696082A simply discloses a process for separating
Fischer-Tropsch synthesis by-products in aqueous phase, wherein the by-products in aqueous phase are separated through ordinary rectification into a mixture of light oxygenates such as alcohols and ketones containing a minor amount of water, and water containing oxygenates having higher boiling points, with the mixture obtained from the tower top being used as a fuel, and a kettle water being recycling back to syngas production stage to form a slurry with solids such as coal. The process disclosed in said patent application does not sufficiently make use of the basic organic materials included in the by-products in aqueous phase.
Therefore, there exists still a need for a process for separating Fischer-Tropsch synthesis by-products in aqueous phase, by which the Fischer-Tropsch synthesis by-products in aqueous phase can be utilized sufficiently and environmental pollution problem can be solved. : :
An object of the present invention is to provide a process for separating Fischer-Tropsch synthesis by-products in aqueous phase, comprising the steps of a) feeding the by-products in aqueous phase to an ordinary rectifying tower (1) at its middle portion, with a fraction stream I having a boiling range of from 50 to 120 °C being withdrawn as a side cut, light components having boiling points of less that 50°C being obtained from the tower top, and heavy components having boiling points of higher than 120°C being obtained from the kettle; : b) feeding the stream I to an acetic acid separation tower (2) at its middle portion, with. an alcohols and ketones-containing aqueous solution stream 11 having a boiling range of from 50 to 100°C being obtained from the tower top, and acetic acid aqueous solution stream III being obtained from the kettle; and : ~~ c) feeding the stream II to an ethanol separation tower (3) at its middle portion, with a methanol and acetone mixture stream IV being obtained from the tower top, and an aqueous solution stream of ethanol and n-propanol V being obtained from the kettle.
Another object of the present invention is to provide a process for separating Fischer-
Tropsch synthesis by-products in aqueous phase, comprising the steps of a) feeding the by-products in aqueous phase to an ordinary rectifying tower (201) at its middle portion, with a fraction stream I having a boiling range of from 50 to 120°C being withdrawn as a side cut, light components having boiling points of less that 50°C being obtained from the tower top, and heavy components having boiling points of higher than 120°C being obtained from the kettle; and b) feeding the stream I to one side of a divided tower (202) at its middle portion, with methanol/acetone mixture stream II being removed as a tower top distillate, an acetic acid aqueous solution stream III being removed from the kettle, ethanol as a side cut being withdrawn from the upper portion of the opposite side, and a n-propanol aqueous solution
: . stream IV as a side cut being withdrawn from the lower portion of the opposite side.
Figure 1 is a schematic flowchart of separation of Fischer-Tropsch synthesis by- products in aqueous phase according to an embodiment of the process of the first aspect of the invention. Co
Figure 2 is a schematic flowchart of separation of Fischer-Tropsch synthesis by- products in aqueous phase according to a preferred embodiment of the process of the first aspect of the invention.
Figure 3 is a schematic flowchart of separation of Fischer-Tropsch synthesis by- products in aqueous phase according to an embodiment of the process of the second aspect of the invention.
Figure 4 is a schematic flowchart of separation of Fischer-Tropsch synthesis by- products in aqueous phase according to a preferred embodiment of the process of the second aspect of the invention. _ Detailed description of the preferred embodiments :
In a first aspect, the present invention provides a process for separating Fischer-Tropsch synthesis by-products in aqueous phase (referred to as the process of the first aspect of the invention hereinafter), comprising the steps of : a) feeding the by-products in aqueous phase to an ordinary rectifying tower (1) at its middle portion, with a fraction stream I having a boiling range of from 50 to 120 °C being withdrawn as a side cut, light components having boiling points of less that 50°C being obtained from the tower top, and heavy components having boiling points of higher than 120°C being obtained from the kettle; b) feeding the stream I to an acetic acid separation tower (2) at its middle portion, with an alcohols and ketones-containing aqueous solution stream II having a boiling range of from 50 to 100°C being obtained from the tower top, and acetic acid aqueous solution stream III being obtained from the kettle; and ¢) feeding the stream II to an ethanol separation tower (3) at its middle portion, with a : methanol and acetone mixture stream IV being obtained from the tower top, and an aqueous solution stream of ethanol and n-propanol V being obtained from the kettle.
In this process, the ordinary rectifying tower 1 may have a theoretical plate number of from 10 to 60, a reflux ratio of from 1 to 12, a tower top temperature of not less than 40°C, “and a side-cut temperature of 80 to 90°C; the acetic acid separation tower 2 may have a theoretical plate number of from 10 to 50, a reflux ratio of from 1 to 8, and a kettle temperature of 104 to 108°C; and the ethanol separation tower 3 may have a theoretical plate number of from 20 to 80, a reflux ratio of from 2 to 10, and a tower top temperature of 60 to 64°C.
In a preferred embodiment, the process of the first aspect according to the invention further comprises the steps of d) feeding the stream III to an acetic acid extraction tower 4 at its top, with an acetic acid/extractant mixture stream VIII being obtained from the tower top, and waste water being obtained from the kettle, wherein the extractarit is at least one selected from the group
E consisting of organic phosphines and organic amines; and e) feeding the stream VIII to an extractant recovering tower 5 at its middle portion, with acetic acid being removed as a tower top distillate, and recovered extractant being obtained from the kettle.
The acetic acid extraction tower 4 may have a theoretical plate number of from 10 to 40, and may be operated at normal temperature. The extractant useful in the acetic acid extraction tower 4 is preferably at least one selected from the group consisting of tri(C1-C6- alkyl)phosphine oxides, triphenyl phosphine oxide, tert-butyl amine, n-butyl amine, and tert- amyl amine, and the weight ratio of the extractant to the stream III may be from 1 to 6. The extractant recovering tower 5 may have a theoretical plate number of from 10 to 50 and a reflux ratio of from 1 to 6. The extractant recovering tower 5 may be operated under atmospheric pressure or a reduced pressure, and preferably under a reduced pressure, and a tower top temperature may be set around the boiling point of acetic acid under the operation pressure, preferably in a range of said boiling point + 1.0 °C.
In a preferred embodiment, the process of the first aspect according to the invention : further comprises the steps of f) feeding the stream IV to an extractive rectifying tower 6 at its middle portion, and feeding a polar solvent to the extractive rectifying tower 6 above its middle point, with acetone being removed from the tower top, and a methanol/solvent mixture stream VI being removed from the kettle; and g) feeding the stream VI to a solvent recovering tower 7 at its middle portion, with methanol being removed from the tower top, and recovered solvent being obtained from the kettle
The extractive rectifying tower 6 may have a theoretical plate number of from 20 to 50, a reflux ratio of from 2 to 9, and a tower top temperature of 56 to 56.5°C. In the extractive rectifying tower 6, the weight ratio of the polar solvent to the stream IV may be from 2 to 10.
Examples of the polar solvent include, but are not limited to, water, ethylene glycol, N-
formoyl morpholine, tetramethylene sulfone, and monoethanolamine. The solvent recovering tower 7 may have a theoretical plate number of from 10 to 50, a reflux ratio of from 1 to 6, and a tower top temperature of 64.5 to 64.7°C.
In a preferred embodiment, the process of the first aspect according to the invention further comprises the steps of : h) feeding the stream V to a de-ethanolizing tower 8 at its middle portion, with ethanol being removed from the tower top, and a n-propanol aqueous solution stream VII being obtained from the kettle; and i) feeding the stream VII to an azeotrope rectifying tower 9 at its middle portion, and cofeeding an azeotrope forming agent, with the aqueous phase obtained in a phase separator at the tower top being withdrawn, the oil phase obtained in the phase separator being refluxed, and n-propanol being removed from the kettle, wherein the azeotrope forming agent is at least one which forms a lower boiling point azeotrope with water.
The de-ethanolizing tower 8 may have a theoretical plate number of from 10 to 60, a reflux ratio of from 1 to 8, and a tower top temperature of 68 to 68.5°C. The azeotrope rectifying tower 9 may have a theoretical plate number of from 15 to 60, a weight ratio of the azeotrope forming agent to the stream VII of from 0.2 to 1, and a kettle temperature of 96.8 to 97.5°C. Examples of the azeotrope forming agent include, but are not limited to, cyclohexane, benzene, toluene, isopropyl acetate and n-butyl acetate. : Since by-products in aqueous phase of a Fischer-Tropsch synthesis are complicated in composition, an ordinary rectification process may be first used to remove a minor amount of lighter components and a minor amount of heavier components, and to withdraw a major amount of middle components as a side-cut. More than 80wt% of the side-cut may be water.
In order to reduce energy consumption, a major amount of the water is removed as a heavy component from the kettle of the acetic acid separation tower. An extraction process may be utilized to separate acetic acid in the acetic acid aqueous solution obtained from the kettle of the acetic acid separation tower from the water. The components obtained from the tower top of the acetic acid separation tower may be separated in the ethanol separation tower 3 through conventional rectification into acetone/methanol mixture stream and ethanol/n- propanol aqueous solution stream. With the process of the first aspect of the invention, it is possible to separate well the by-products in aqueous phase of the Fischer-Tropsch synthesis, and good technical effect is achieved.
A specific embodiment of the process of the first aspect of the invention will be described in detail below with reference to the Figure 1.
In Figure 1, 1 is an ordinary rectifying tower, 2 is an acetic acid separation tower, 3 is an ethanol separation tower, 4 is an extraction tower, 5 is an extractant recovering tower, 10 is stream of by-products in aqueous phase, 11 is a stream of light components, 12 is a stream of heavy components, 13 is a side-cut stream, 14 is an alcohols and ketones-containing aqueous "solution stream, 15 is an acetic acid aqueous solution stream, 16 is an extractant stream, 17 is an methanol/acetone mixture stream, 18 is an ethanol/n-propanol aqueous solution stream, 19 is an acetic acid/extractant mixture stream, 20 is an acetic acid stream, 21 is a recovered extractant stream, 22 is a waste water stream.
As shown in the Figure 1, the stream 10 consisting of by-products in aqueous phase is fed to the ordinary rectifying tower 1 at its middle portion, with the light component stream 11 being obtained as a tower top distillate, a heavy component stream 12 being obtained from the kettle, and the stream 13 being withdrawn as a side-cut. The side-cut 13 is fed to the acetic acid separation tower 2 at its middle portion, with the aqueous solution stream 14 containing alcohols and ketones being obtained as a tower top distillate, and the acetic acid aqueous solution stream 15 being obtained from the kettle. The solution stream 14 containing alcohols and ketones is fed to the ethanol separation tower 3 at its middle portion, with the acetone/methanol mixture stream 17 being obtained as a tower top distillate, and the ethanol and n-propanol aqueous solution stream 18 being obtained from the kettle. The acetic acid aqueous solution stream 15 and the extractant stream 16 are fed at the tower top and the bottom of the extraction tower 4, respectively, with the mixture stream 19 of acetic acid and the extractant being obtained from the tower top, and waste water stream 22 being withdrawn from the kettle.
Figure 2 depicts another specific embodiment of the process of the first aspect of the invention. In Figure 2, 1 is an ordinary rectifying tower, 2 is an acetic acid separation tower, 3 isan ethanol separation tower, 4 is an extraction tower, 5 is an extractant recovering tower, "6 is an extractive rectifying tower, 7 is a solvent recovering tower, 8 is a de-ethanolizing tower, 9 is an azeotrope rectifying tower, 10 is a stream consisting of the by-products in aqueous phase, 11 is a light component stream, 12 is a heavy component stream, 13 is a side- cut stream, 14 is a stream of the aqueous solution containing alcohols and ketones, 15 is an acetic acid aqueous solution stream, 16 is an extractant stream, 17 is a methanol/acetone mixture stream, 18 is an ethanol and n-propanol aqueous solution stream, 19 is an acetic acid/extractant mixture stream, 20 is an acetic acid stream, 21 is a recovered extractant stream, 22 is a waste water stream, 23 is a solvent stream, 24 is an acetone stream, 25 is a methanol/solvent mixture stream, 26 is an ethanol (95%wt) stream, 27 is a n-propanol aqueous solution stream, 28 is a methanol stream, 29 is a recovered solvent stream, 301s an azeotropic water stream, and 31is a n-propanol stream.
As shown in the Figure 2, the stream 10 consisting of the by-products in aqueous phase is fed to the ordinary rectifying tower 1, with the light component stream 11 being obtained as a tower top distillate, the heavy component stream 12 being obtained from the kettle, and the stream 13 being obtained as a side-cut. The side-cut stream 13 is fed to the acetic acid separation tower 2, with the stream 14 of the aqueous solution containing alcohols and ketones being obtained as a tower top distillate, and the acetic acid aqueous solution stream being obtained from the kettle. The stream 14 is fed to the ethanol separation tower 3, with the acetone/methanol mixture stream 17 being obtained as a tower top distillate, and the ethanol and n-propanol aqueous solution stream 18 being obtained from the kettle. The acetic acid aqueous solution stream 15 and the extractant stream 16 are fed to the extraction tower 4 at its top and bottom, respectively, with the acetic acid/extractant mixture stream 19 being obtained from the tower top, and the waste water stream 22 being obtained from the kettle.
The methanol/acetone mixture stream 17 and the solvent stream 23 are fed to the extractive rectifying tower 6 at its middle portion and upper middle portion, respectively, with the acetone stream 24 being obtained as a tower top distillate, and the methanol/solvent mixture stream 25 being obtained from the kettle. The ethanol and n-propanol aqueous solution stream 18 is fed to the de-ethanolizing tower 8, with ethanol (95%wt) stream 26 being : obtained as a tower top distillate, and the n-propanol aqueous solution stream 27 being obtained from the kettle. The acetic acid/extractant mixture stream 19 is fed to the extractant recovering tower 5, with the acetic acid stream 20 being obtained as a tower top distillate, and the recovered extractant stream 21 being obtained from the kettle. T he methanol/solvent mixture stream 25 is fed to the solvent recovering tower 7, with the methanol stream 28 being obtained as a tower top distillate, and the recovered solvent stream 29 being obtained from the kettle. The n-propanol aqueous solution stream 27 is fed to the azeotrope rectifying tower 9, the azeotropic water 30 being withdrawn from the tower top, and the n-propanol stream 31 being obtained from the kettle.
In a second aspect, the present invention provides a process for separating Fischer-
Tropsch synthesis by-products in aqueous phase (referred to as the process of the second aspect of the invention hereinafter), comprising the steps of a) feeding the by-products in aqueous phase to an ordinary rectifying tower 201 at its middle portion, with a fraction stream I having a boiling range of from 50 to 120°C being withdrawn as a side cut, light components having boiling points of less that 50°C being obtained from the tower top, and heavy components having boiling points of higher than : 120°C being obtained from the kettle; and b) feeding the stream I to one side of a divided tower 202 at its middle portion, with methanol/acetone mixture stream II being removed as a tower top distillate, an acetic acid aqueous solution stream III being removed from the kettle, ethanol as a side cut being withdrawn from the upper portion of the opposite side, and a n-propanol aqueous solution stream IV as a side cut being withdrawn from the lower portion of the opposite side.
The ordinary rectifying tower 201 may have a theoretical plate number of from 10 to 60, a reflux ratio of from 1 to 12, a tower top temperature of not less than 40°C. The divided tower 202 may have a theoretical plate number of from 50 to 200, wherein the upper section may account for 1/6 to 1/3 of the theoretical plate number, the lower section may account for 1/6 to 1/3 of the theoretical plate number. Left side liquid phase in the upper section may have a distribution factor of from 0.3 to 0.7, and the left side gas phase in the lower section may have a distribution factor of from 0.3 to 0.7. The divided tower 202 may have a reflux ratio of from 5 to 30, a tower top temperature of 60 to 64°C, an upper side-cut temperature of 68 to 68.5°C, and a lower side-cut temperature of 87 to 93°C.
In a preferred embodiment, the process of the second aspect according to the invention further comprises the steps of c) feeding the stream IV to an azeotrope rectifying tower 203 at its middle portion, and co-feeding an azeotrope forming agent thereto, with an aqueous phase obtained in a tower : top phase separator being withdrawn and an oil phase being refluxed, and with n-propanol being withdrawn from the kettle, wherein the azeotrope forming agent is at least one which forms a lower boiling point azeotrope with water.
The azeotrope rectifying tower 203 may have a theoretical plate number of from 15 to 60, a weight ratio of the azeotrope forming agent to the stream IV of from 0.2 to 1, and a kettle temperature of 96.8 to 97.5°C. The azeotrope forming agent is preferably at least one from cyclohexane, benzene, toluene, isopropyl acetate and n-butyl acetate.
In a preferred embodiment, the process of the second aspect according to the invention further comprises the steps of d) feeding the stream III to the tower top of an acetic acid extraction tower 204, and an extractant to the tower bottom, with a mixture stream V of acetic acid and the extractant being withdrawn from the tower top, and waste water being withdrawn from the kettle, wherein the extractant is at least one selected from the group consisting of organic phosphines and organic amines; and e) feeding the stream V to an extractant recovering tower 205 at its middle portion, with acetic acid being withdrawn as tower top distillate, and recovered extractant being obtained from the kettle.
The acetic acid extraction tower 204 may have a theoretical plate number of from 10 to
40 and a weight ratio of the extractant to the stream III of from 1 to 6, and is operated at normal temperature. The extractant recovering tower 205 may have a theoretical plate number of from 10 to 50, and a reflux ratio of from 1 to 6. The extractant recovering tower a 205 may be operated under atmospheric pressure or a reduced pressure, and preferably under a reduced pressure. The extractant useful is preferably at least one selected from the group consisting of tri(C1-C6-alkyl)phosphine oxides, triphenyl phosphine oxide, tert-butyl amine, n-butyl amine, and tert-amyl amine. | :
In a preferred embodiment, the process of the second aspect according to the invention further comprises the steps of f) feeding the stream II to an extractive rectifying tower 206 at its middle portion, and a polar solvent at its upper section, with acetone being withdrawn as a tower top distillate, and a mixture stream VI of methanol and solvent being obtained from the kettle; and g) feeding the stream VI to a solvent recovering tower 207 at its middle portion, with methanol being withdrawn as a tower top distillate, and recovered solvent being obtained from the kettle.
The extractive rectifying tower 206 may have a theoretical plate number of from 20 to 50, a weight ratio of the polar solvent to the stream VI of from 2 to 10, a reflux ratio of from 2 to 9, and a tower top temperature of 56 to 56.5°C. The polar solvent is preferably at least "one from water, ethylene glycol, N-formoyl morpholine, tetramethylene sulfone, and monoethanolamine. The solvent recovering tower 207 may have a theoretical plate number of from 10 to 50, a reflux ratio of from 1 to 6, and a tower top temperature of 64.5 to 64.7°C.
Since by-products in aqueous phase of a Fischer-Tropsch synthesis are complicated in composition, an ordinary rectification process may be first used to remove a minor amount of lighter components and a minor amount of heavier components, and to withdraw a major amount of middle components as a side-cut stream. More than 80wt% of the side-cut stream may be water. In order to reduce energy consumption, a major amount of the water is removed as a heavy component from the kettle of the divided tower, acetone/methanol mixture is obtained from the tower top, ethanol is withdrawn as a upper side-cut, and n- propanol aqueous solution is withdrawn as a lower side-cut. An extraction process may be utilized to separate acetic acid in the acetic acid aqueous solution obtained from the kettle of the divided tower from the water. The n-propanol aqueous solution is separated through an azeotrope fractionation process. With the process of the second aspect of the invention, it is possible to separate well the by-products in aqueous phase of the Fischer-Tropsch synthesis, and good technical effect is achieved.
A specific embodiment of the process of the second aspect of the invention will be described in detail below with reference to the Figure 3.
In the Figure 3, 201 is an ordinary rectifying tower, 202 is a divided tower , 203 is an azeotrope rectifying tower, 204 is an acetic acid extraction tower, 205 is an extractant "recovering tower, 208 is a stream consisting of the F-T synthesis by-products in aqueous phase, 209 is a light component stream, 210 is a heavy component stream, 211 is a side-cut stream, 212 is a methanol/acetone mixture stream, 213 is an ethanol stream, 214 is a n- propanol aqueous solution stream, 215 is an acetic acid aqueous solution stream, 216 is an extractant stream, 217 is an azeotropic water stream, 218 is a n-propanol stream, 219 is an acetic acid/extractant mixture stream, 220 is a waste water stream, 221 is an acetic acid stream, and 222 is a recovered extractant stream.
As shown in the Figure 3, the stream 208 consisting of the by-products in aqueous phase is fed to the ordinary rectifying tower 201 at its middle portion, with the light component stream 209 being obtained as a tower top distillate, the heavy component stream 210 being obtained from the kettle, and the stream 211 being obtained as a side-cut. The side-cut 211 is fed to the divided tower 202 at its middle portion of its left side, with the acetone/methanol mixture stream 212 being obtained as a tower top distillate, the acetic acid aqueous solution : stream 215 being obtained from the kettle, the ethanol stream 213 being obtained as a side- cut from the upper portion of the right side, and the n-propanol aqueous solution stream 214 being obtained as a side-cut from the lower portion of the right side. The n-propanol aqueous solution stream 214 is fed to the azeotrope rectifying tower 203 at its middle portion, with : the azeotropic water stream 217 being withdrawn as a tower top aqueous phase, and the n- propanol stream 218 being obtained from the kettle. The acetic acid aqueous solution stream 215 and the extractant stream 216 are fed to the acetic acid extraction tower 204 at its upper and lower portion, respectively, with acetic acid/extractant mixture stream 219 being obtained from the tower top, and the waste water stream 220 being obtained from the kettle.
The acetic acid/extractant mixture stream 219 is fed to the extractant recovering tower 205 at its middle portion, with the acetic acid stream 221 being obtained as a tower top distillate, and the recovered extractant stream 222 being obtained from the kettle.
In the Figure 4, 201 is an ordinary rectifying tower, 202 is a divided tower, 203 is an azeotrope rectifying tower, 204 is an acetic acid extraction tower, 205 is an extractant recovering tower, 206 is an extractive rectifying tower, 207 is a solvent recovering tower, 208 is a stream consisting of the by-products in aqueous phase, 209 is a light component stream, 210 is a heavy component stream, 211 is a side-cut, 212 is a methanol/acetone mixture stream, 213 is an ethanol stream, 214 is a n-propanol aqueous solution stream, 215 is an acetic acid aqueous solution stream, 216 is an extractant stream, 217 is an azeotropic water stream, 218 is a n-propanol stream, 219 is an acetic acid/extractant mixture stream, 220 is a waste water stream, 221 is an acetic acid stream, 222 is a recovered extractant stream, 223 is a solvent stream, 224 is an acetone stream, 225 is a methanol/solvent mixture stream, 226 is a methanol stream, and 227 is a recovered solvent stream.
As shown in the Figure 4, the stream 208 consisting of the by-products in aqueous phase : is fed to the ordinary rectifying tower 201 at its middle portion, with the light component stream 209 being obtained as a tower top distillate, the heavy component stream 210 being obtained from the kettle, and the stream 211 being withdrawn as a side-cut. The side-cut stream 211 is fed to the divided tower 202 at its middle portion of the left side, with acetone/methanol mixture stream 212 being obtained as a tower top distillate, acetic acid aqueous solution stream 215 being obtained from the kettle, the ethanol stream 213 being obtained as a side-cut from the upper portion of the right side of the tower, and the n- propanol aqueous solution stream 214 being obtained as a side-cut from the lower portion of the right side. The solvent stream 223 and the acetone/methanol mixture stream 212 are fed to the extractive rectifying tower 206 at its upper portion and middle portion, respectively, with the acetone stream 224 being obtained as a tower top distillate, and methanol/solvent mixture stream 225 being obtained from the kettle. The n-propanol aqueous solution stream 214 is fed to the azeotrope rectifying tower 203 at its middle portion, with the azeotropic water stream 217 being withdrawn as a tower top aqueous phase, and n-propanol stream 218 being obtained from the kettle. The acetic acid aqueous solution stream 215 and the extractant stream 216 are fed to the acetic acid extraction tower 204 at its upper portion and lower portion, respectively, with the acetic acid/extractant mixture stream 219 being obtained from the tower top, and the waste water stream 220 being withdrawn from the kettle. The methanol/solvent mixture stream 225 is fed to the solvent recovering tower 207 at its middle portion, with the methanol stream 226 being obtained as a tower top distillate, and recovered solvent stream 227 being obtained from the kettle. The acetic acid/extractant mixture stream 219 is fed to the extractant recovering tower 205 at its middle portion, with acetic acid 221 being obtained as a tower top distillate, and recovered extractant 222 being obtained from the kettle.
The following examples are given for further illustrating the invention, but do not make limitation to the invention in any way.
Example 1 - As shown in the Figure 1, a stream 10 consisting of Fischer-Tropsch synthesis by-
products in aqueous phase (comprising S5wt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 1 having a theoretical plate number of 15 at the 7" theoretical plate, the tower 1 being operated at a reflux ratio of 12 and a tower top temperature of 40°C. A side-cut 13 having a boiling range of from 50 to 120°C was withdrawn from the 8™ theoretical plate and fed to an acetic acid separation tower 2 having a theoretical plate number of 15 at the 8™ theoretical plate. The tower 2 was operated at a reflux ratio of 8 and a kettle temperature of from 104 to 108°C, with an aqueous solution stream 14 containing alcohols and ketones being obtained as a tower top distillate, and acetic acid aqueous solution stream 15 being obtained from the kettle. The stream 14 was fed to an ethanol separation tower 3 having a theoretical plate number of 20 at the 9" theoretical plate. The ethanol separation tower 3 was operated at a reflux ratio of 10 and a tower top temperature of from 60 to 64°C, with methanol/acetone mixture stream 17 being obtained as a tower top distillate, and ethanol and n-propanol aqueous solution stream 18 being obtained from the kettle. The stream 15 from the kettle of the acetic acid separation tower and an extractant 16 were fed to an acetic acid extraction tower 4 having a theoretical plate number of 10 at its top and bottom, respectively. The extractant was tert-butyl amine, and weight ratio of the extractant to the stream 15 was 5. The : acetic acid extraction tower 4 was operated at a temperature of 35°C, acetic acid/extractant mixture 19 was obtained from the top of the acetic acid extraction tower, and waste water 22 was obtained from the kettle. The acetic acid/extractant mixture 19 was fed to an extractant recovering tower 5 having a theoretical plate number of 10 at the 4™ theoretical plate. The extractant recovering tower 5 was operated at a reflux ratio of 6 and a tower top temperature of from 115 to 118°C, with acetic acid 20 being obtained as a tower top distillate, and recovered extractant 21 being obtained from the kettle. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the
Table 1.
Table 1 Analysis data (wt%) for the streams of individual towers stream | acetone | methanol | ethanol n- acetic water tert- propanol | acid k butyl 2 3 | os | 16 | 27 | 11 | 88 | 850 | 0 14 | os | 195 | 39 | 134 | 0 [ 244 | 0 | 0 | o | oo | 96 [0a] 0 6 | o | o | o [ o | o | o | 10 7 | 335 | 66s | o | o | o | o | o
18 | 0 | o [sas [ass | o | w0 | 0 9 | o | o | o | o | 1s [ o | os 2» | 0 | o | o | o [os | os | 0
CT [oo oo |ws| o [oa 2 | 0 | o | o [of of o | w
Example 2
As shown in the Figure 1, a stream 10 consisting of Fischer-Tropsch synthesis by- products in aqueous phase (comprising S5wt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 1 having a theoretical plate number of 60 at the 35" theoretical plate. The tower 1 was operated at a reflux ratio of 1 and a tower top temperature of 40°C. A side-cut 13 having a boiling range of from 50 to 120°C was withdrawn from the 40" theoretical plate and fed to an acetic acid separation tower 2 having a theoretical plate number of 50 at the 30 theoretical plate. The tower 2 was operated at a reflux ratio of 8 and a kettle temperature of from 104 to 108°C, with an aqueous solution stream 14 containing alcohols and ketones being obtained as a tower top distillate, and an acetic acid aqueous solution stream 15 being obtained from the kettle. The aqueous stream 14 was fed to an ethanol separation tower 3 having a theoretical plate number of 80 at the 50™ theoretical plate. The ethanol separation tower 3 was operated at a reflux ratio of 2 and a tower top temperature of from 60 to 64°C, with methanol/acetone mixture stream17 being obtained as a tower top distillate, and ethanol and n-propanol aqueous solution stream 18 being obtained from the kettle. The stream 15 from the kettle of the acetic acid separation tower and an extractant 16 were fed to an acetic "acid extraction tower 4 having a theoretical plate number of 40 at its top and bottom, respectively. The extractant was n-butyl amine, and a weight ratio of the extractant to the stream 15 was 1. The acetic acid extraction tower was operated at a temperature of 35°C, acetic acid/extractant mixture 19 was obtained from the top of the acetic acid extraction tower, and waste water 22 was obtained from the kettle. The acetic acid/extractant mixture 19 was fed to an extractant recovering tower 5 having a theoretical plate number of 50 at the 20™ theoretical plate. The extractant recovering tower 5 was operated at a reflux ratio of 1 and a tower top temperature of from 115 to 118 °C, with acetic acid 20 being obtained as a tower top distillate, and extractant 21 being obtained from the kettle. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 2.
Table 2 Analysis data (wt%) for the streams of individual towers propanol | acid amine 3 | 08 | 16 | 27 [ 11 [ ss | 850 | 0 14 | 104 | 208 [30 | 143 [ 0 [10a | 0 is | o | o [| o | o [os | os | o 6 | 0 | o | o [ o [0 | o | 10 “17 | ss | ees | o | o | 0 | o | o is | o | o | so] 20s | o | 282] o ww | o | o | o | o [or | o | oso 2 | 0 | o | o | o [os | 5 | o 0 | o | o | o | o [ws] o | 0 2 | 0 | o | o [oo | o | w
Example 3
As shown in the Figure 1, a stream 10 consisting of Fischer-Tropsch synthesis by- products in aqueous phase (comprising Swt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying : tower 1 having a theoretical plate number of 30 at the 17" theoretical plate. The tower 1 was operated at a reflux ratio of 3 and 1 tower top temperature of 40 °C. A side-cut 13 having a boiling range of from 50 to 120 °C was withdrawn from the 20™ theoretical plate and fed to an acetic acid separation tower 2 having a theoretical plate number of 30 at the 17° theoretical plate. The tower 2 was operated at a reflux ratio of 4 and a kettle temperature of from 104 to 108 °C, with an aqueous solution stream 14 containing alcohols and ketones being obtained as a tower top distillate, and an acetic acid aqueous solution stream 15 being obtained from the kettle. The stream 14 was fed to an ethanol separation tower 3 having a theoretical plate number of 40 at the 25" theoretical plate. The tower 3 was operated at a reflux ratio of 4 and a tower top temperature of from 60 to 64 °C, with methanol/acetone mixture stream 17 being obtained as a tower top distillate, and an ethanol and n-propanol aqueous solution stream 18 being obtained from the kettle. The stream 15 from the kettle of - the acetic acid separation tower and an extractant 16 were fed to an acetic acid extraction tower 4 having a theoretical plate number of 20 at its top and bottom, respectively. The extractant was trimethylphosphine oxide, and a weight ratio of the extractant to the stream 15 was 2. The tower 4 was operated at a temperature of 35 °C, acetic acid/extractant mixture 19 was obtained from tower top, and waste water 22 was obtained from the kettle. The acetic acid/extractant mixture 19 was fed to an extractant recovering tower 5 having a theoretical plate number of 25 at the 10™ theoretical plate. The tower 5 was operated at a reflux ratio of 3, and a tower top temperature of from 115 to 118 °C, with acetic acid 20 being obtained as a tower top distillate, and extractant 21 being obtained from the kettle. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 3.
Table 3 analysis data for the streams of individual towers (wt%) propanol | acid oxide 3 | os | 16 | 27 | 11 | 88 | 850 | 0 14 | 101 | 203 | 32 | wo | 0 [as] 0 15s | 0 | o | o | o | 96 [o0a] 0 6 | 0 | o | o | o | oo | o] 0 17 | 35 | ees | 0 | o | o | 0 | 0 8 | o | o [a1 20 | o [309] 0 w | 0 | o | o | o Jas | o | 9s » | o | o | o | o | o7 | 3] 0 20 | o | o | o | o [es] 0 | os 2 | 0 | o | o | o [oo] 0 | 10
Example 4
The procedure as described in Example 3 was followed, except that triphenyl phosphine - oxide was used as the extractant in the acetic acid extraction tower 4. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 4. : Table 4 Analysis data (wt%) for the streams of individual towers stream | acetone | methanol | ethanol n- acetic water | triphenylphosphine
Fd rl le s | os | 16 | 27 | 11 | ss | 850 | 0 0 | 101 | 203 | 42 | 139 [ 0 [215 0 1 | 0 | o | o | o [os | oa] 0 2 | o | o | o | o [oo [ of 3 | 35 | es | 0 | o [ o | o 0 4 | 0 | o [a1] 200] o [309 0 5s | o | o | o | o [as] o | 96s 6 | 0 | o | o | o [| 16 [esa 0 7 | o | o | o | o Jes] o | os 8s | o | o | o | o [of o | 10
Example 5 :
The procedure as described in Example 3 was followed, except that the Fischer-Tropsch synthesis by-products in aqueous phase had a composition of: 7wt% of a component having a boiling point of less than 50°C, 84wt% of a component having a boiling range of from 50 to 120°C, and 9wt% of a component having a boiling point of larger than 120°C. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 5. . Table 5 Analysis data (wt%) for the streams of individual towers stream trimethylphosphine propanol acid oxide 8 0 0 [154 | 124 | 196 | 289 | 0 [m7] 0 nu | o | o [of o Jerfos| oo 2 | 0 | o | o | o [oo] wm 1 [ms] e@2 | o | o [oo oo 4 | 0 | o [wes | sof 0 me] oo is | o | o | o | o |as| o | oss 6 | o | o | o | o [ores] oo vo | oo Jo] o [ss] o| os os] oo [oo] olofo] ow
Example 6
As shown in the Figure 2, a stream 10 consisting of Fischer-Tropsch synthesis by- products in aqueous phase (comprising 5wt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 1 having a theoretical plate number of 15 at the 7" theoretical plate. The tower 1 was operated at a reflux ratio of 12 and a tower top temperature of 40 °C. A side-cut 13 having a boiling range of from 50 to 120 °C was withdrawn from the 8™ theoretical plate and fed to an acetic acid separation tower 2 having a theoretical plate number of 15 at the 8™ theoretical plate. The tower 2 was operated at a reflux ratio of 8 and a kettle temperature of from 104 to 108 °C, with an aqueous solution stream 14 containing alcohols and ketones being obtained as a tower top distillate and an acetic acid aqueous solution stream 15 being obtained from the kettle. The stream 14 ‘was fed to an ethanol separation tower 3 having a theoretical plate number of 20 at the 9" theoretical plate.
The tower 3 was operated at a reflux ratio of 10 and a tower top temperature of from 60 to 64 °C, with methanol/acetone mixture stream 17 being obtained as a tower top distillate, and an ethanol and n-propanol aqueous solution stream 18 being obtained from the kettle.
The methanol/acetone mixture stream 17 was fed to an extractive rectifying tower 6 having a theoretical plate number of 20 at the 12™ theoretical plate, and water 23 as solvent was co-fed at the 5" theoretical plate.
The tower 6 was operated at a weight ratio of the solvent to the stream 17 of 10, a reflux ratio of 9, and a tower top temperature of from 56 to 56.5 °C, with acetone 24 being obtained as a tower top distillate, and methanol/solvent mixture 25 being obtained from the kettle.
The methanol/solvent mixture 25 was fed to a solvent recovering tower 7 having a theoretical plate number of 10 at the 5™ theoretical plate.
The tower 7 was operated at a reflux ratio of 6 and a tower top temperature of from 64.5 to 64.7°C, with methanol 28 being obtained as a tower top distillate, and recovered solvent 29 being obtained from the kettle.
The stream 18 from the ethanol separation tower 3 was fed to a de-ethanolizing tower 8 having a theoretical plate number of 15 at the 10" theoretical plate, and the tower 8 was operated at a reflux ratio of 8 and a tower top temperature of from 68 to 68.5 °C, with ethanol 26 being obtained as a tower top distillate, and n-propanol aqueous solution 27 being obtained from the kettle.
The n-propanol aqueous solution 27 was fed to an azeotrope rectifying tower 9 having a theoretical plate number of 20 at the 12" theoretical plate, and cyclohexane as an azeotrope forming agent was co-fed.
In the tower 9, a weight ratio of the azeotrope forming agent to the n-propanol aqueous solution 27 was 0.9, and kettle temperature was from 96.8 to 97.5 °C, with aqueous phase obtained in an tower top phase separator being withdrawn as a stream 30 and oil phase being refluxed, and n-propanol 31 being withdrawn from the kettle.
The stream from the acetic acid separation tower 2 was fed to an acetic acid extraction tower 4 having a theoretical plate number of 10, and tert-butyl amine was co-fed as an extractant.
The tower 4 was operated at a weight ratio of the extractant to the stream 15 of 5 and an operation temperature of 35 °C, with acetic acid/extractant mixture 19 being obtained from the tower top, and waste water 22 being obtained from the kettle.
The acetic acid/extractant mixture 19 was fed to an extractant recovering tower 5 having a theoretical plate number of 10 at the 4m theoretical plate, and the tower 5 was operated at a reflux ratio of 6 and a tower top temperature of from 115 to 118 °C, with acetic acid 20 being obtained as a tower top distillate, and recovered extractant 21 being obtained from the kettle.
Upon the operation was stable, analysis data for the streams of individual towers were acquired.
The results are shown in the Table 6.
Table 6 Analysis data (wt%) for the streams of individual towers stream | acetone | methanol | ethanol n- acetic | water | tert- | cyclohexane propanol | acid butyl amine © i os [we | 22 | 1 les [sso] 0 | o 1 | 98 | 195 | mo | pa | 0 [2a] 0 | 0 is | 0 | 0 | o | o [os oa] 0 | o is | 0 | o [oo [of ow] o v | 3s | es | 0 | 0 [of of 0 | o no | o [of ololw|ol] o is | o | o [ss |oas | 0 [wo] 0 | o o | 0 | o | o Jul oo] o 2 | 0 | o | oo [es|ws| oo] 2 [wo | oa | o | o [ol ool o | o | 67 | o | o [oles] oo] o % | 0 | o Joo] o [oso] oo] 0 vw | 0 | o | o [ss | o |eal 0 | © 0 | 0 | o | oo [os] ool 0 2 | 0 | o ol o [of owl] o % | 0 [ws | 0 | o | ofol oo] o » | 0 | 0 | o | o [ow] oo] 0 | o | o | o | o [oo Jws| oo | os 5 | 0 | o | o [oso Jos] ol o : Example 7
As shown in the Figure 2, a stream 10 consisting of Fischer-Tropsch synthesis by- products in aqueous phase (comprising 5wt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 1 having a theoretical plate number of 60 at the 35" theoretical plate. The tower 1 was operated at a reflux ratio of 1 and a tower top temperature of 40 °C. A side-cut 13 having a boiling range of from 50 to 120 °C was withdrawn from the 40™ theoretical plate and fed to an acetic acid separation tower 2 having a theoretical plate number of 50 at the 30" theoretical plate. The tower 2 was operated at a reflux ratio of 8 and a kettle temperature of from 104 to 108 °C, with an aqueous solution stream 14 containing alcohols and ketones being obtained as a tower top distillate, and an acetic acid aqueous solution stream 15 being obtained from the kettle. The stream 14 was fed to an ethanol separation tower 3 having a theoretical plate number of 80 at the 50™ theoretical plate. The tower 3 was operated at a reflux ratio of 2 and a tower top temperature of from 60 to 64 °C, with methanol/acetone mixture stream 17 being obtained as a tower top distillate, and ethanol and n-propanol aqueous solution stream 18 being obtained from the kettle. The methanol/acetone mixture stream 17 was fed to extractive rectifying tower 6 having a theoretical plate number of 50 at the 20™ theoretical plate, and monoethanolamine 23 as solvent was co-fed at the 3rd theoretical plate. The tower 6 was operated at a weight ratio of the solvent to the stream 17 of 2, a reflux ratio of 2, and a tower top temperature of from 56 to 56.5°C, with acetone 24 being obtained as a tower top distillate, and methanol/solvent mixture 25 being obtained from the kettle. The methanol/solvent mixture 25 was fed to solvent recovering tower 7 having a theoretical plate number of 50 at the 20 theoretical plate. The tower 7 was operated at a reflux ratio of 1.5 and a tower top temperature of from 64.5 to 64.7 °C, with methanol 28 being obtained as a tower top distillate, and recovered solvent 29 being obtained from the kettle. The ethanol and n-propanol aqueous solution 18 from the ethanol separation tower 3 was fed to de-ethanolizing tower 8 having a theoretical plate number of 60 at the 40™ theoretical plate. The tower 8 was operated at a reflux ratio of 2 and a tower top temperature of from 68 to 68.5 °C, with ethanol 26 being obtained as a tower top distillate, and n- propanol aqueous solution 27 being obtained from the kettle. The n-propanol aqueous solution 27 was fed to an azeotrope rectifying tower 9 having a theoretical plate number of 60 at the 35" theoretical plate, and n-butyl acetate as an azeotrope forming agent was co-fed.
In the tower 9, a weight ratio of the azeotrope forming agent to the n-propanol aqueous solution 27 was 0.2, and a kettle temperature was from 96.8 to 97.5 °C, with aqueous phase obtained in an tower top phase separator being withdrawn as a stream 30 and oil phase being refluxed, and n-propanol 31 being withdrawn from the kettle. The acetic acid aqueous solution stream 15 from the acetic acid separation tower 2 was fed to an acetic acid "extraction tower 4 having a theoretical plate number of 40, and n-butyl amine was co-fed as an extractant. The tower 4 was operated at a weight ratio of the extractant to the stream 15 of 1 and an operation temperature of 35 °C, with acetic acid/extractant mixture 19 being obtained from the tower top, and waste water 22 being obtained from the kettle. The acetic acid/extractant mixture 19 was fed to an extractant recovering tower 5 having a theoretical plate number of 50 at the 20™ theoretical plate, and the tower 5 was operated at a reflux ratio of 1 and a tower top temperature of from 115 to 118 °C, with acetic acid 20 being obtained as a tower top distillate, and recovered extractant 21 being obtained from the kettle. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 7.
Table 7 Analysis data (wt%) for the streams of individual towers propanol | acid amine amine | acetate [os | ws | 27 | wu [ssleol o [oo w [0a | 208 [asa | ws [0 [wel o | o | oo solo [oo Teslms[ oo [oo wl oo [ol oTolo] o [wm] o 7 [sms | ees | 0 | 0 Jo of o | oo 5] 0 | o | oo lolol w |ol]eo 5 | 0 | o |so| ws | 0 [ma] o | 0 oo | o lo] o Jorlol o [os] o » | 0 | o | o | o loslws|[ o [ol] 2 999 | or | 0 | 0 Joo o [oo ss | 0 [asa | 0 | o [ome] o [ol a | 0 [0 [eso] 0 [oso o [oo [0 7] 0 | o | o [ax | o [sso] o [oo 0] 0 | 0 | o | o [ws[o] o Joa] wo | 0 ol o Jolol o [wl] s | 0 | ws | 0 | 0 Joo] ow [0] o wo | 0 | oo o [ole] w |ofeo 0 | 0 | o | o | o [ofa o [os wo | o Jo ws [oo] o Jolfez
Example 8 Co
As shown in the Figure 2, a stream 10 consisting of Fischer-Tropsch synthesis by- products in aqueous phase (comprising Swt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 1 having a theoretical plate number of 30 at the 17" theoretical plate. The tower 1 was operated at a reflux ratio of 3 and a tower top temperature of 40 °C. A side-cut 13 having a boiling range of from 50 to 120 °C was withdrawn from the 20" theoretical plate, and fed to an acetic acid separation tower 2 having a theoretical plate number of 30 at the 17th theoretical plate.
The tower 2 was operated at a reflux ratio of 4 and a kettle temperature of from 104 to 108 °C, with an aqueous solution stream 14 containing alcohols and ketones being obtained as a tower top distillate, and an acetic acid aqueous solution stream 15 being obtained from the kettle.
The stream 14 was fed to an ethanol separation tower 3 having a theoretical plate number of 40 at the 25th theoretical plate.
The tower 3 was operated at a reflux ratio of 4 and a tower top temperature of from 60 to 64 °C, with methanol/acetone mixture stream 17 being obtained as a tower top distillate, and ethanol and n-propanol aqueous solution stream 18 being obtained from the kettle.
The methanol/acetone mixture stream 17 was fed to an extractive rectifying tower 6 having a theoretical plate number of 30 at the 17th theoretical plate, and ethylene glycol 23 as a solvent was co-fed at the 3rd theoretical plate.
The tower 6 was operated at a weight ratio of the solvent to the stream 17 of 4, a reflux ratio of 4, and a tower top temperature of from 56 to 56.5 °C, with acetone 24 being obtained as a tower top distillate, and methanol/solvent mixture 25 being obtained from the kettle.
The methanol/solvent mixture 25 was fed to a solvent recovering tower 7 having a theoretical plate number of 25 at the 10th theoretical plate.
The tower 7 was operated at a reflux ratio of 3 and a tower top temperature of from 64.5 to 64.7°C, with methanol 28 being obtained as a tower top distillate, and recovered solvent 29 being obtained from the kettle.
The ethanol and n-propanol aqueous solution 18 from the ethanol separation tower was fed to a de-ethanolizing tower 8 having a theoretical plate number of 30 at the 20th theoretical plate.
The tower 8 was operated at a reflux ratio of 4 and a tower top temperature of from 68 to 68.5 °C, with ethanol 26 being obtained as a tower top distillate, and n-propanol aqueous solution 27 being obtained from the kettle.
The n-propanol aqueous solution 27 was fed to an azeotrope rectifying tower 9 having a theoretical plate number of at the 17th theoretical plate, and isopropyl acetate as an azeotrope forming agent was co- fed.
In the tower 9, a weight ratio of the azeotrope forming agent to the n-propanol aqueous solution 27 was 0.5, and a kettle temperature was from 96.8 to 97.5 °C, with aqueous phase obtained in an tower top phase separator being withdrawn as a stream 30 and oil phase being refluxed, and n-propanol 31 being withdrawn from the kettle.
The: acetic acid aqueous solution stream 15 from the acetic acid separation tower 2 was fed to an acetic acid extraction tower 4 having a theoretical plate number of 20, and trimethylphosphine oxide was co-fed as an extractant.
The tower 4 was operated at a weight ratio of the extractant to the stream 15 of 2 and an operation temperature of 35 °C, with acetic acid/extractant mixture 19 being obtained from the tower top, and waste water 22 being obtained from the kettle.
The acetic acid/extractant mixture 19 was fed to an extractant recovering tower 5 having a theoretical plate number of 25 at the 10th theoretical plate, and the tower 5 was operated at a reflux ratio of 3 and a tower top temperature of from 115 to 118 °C, with acetic acid 20 being : obtained as a tower top distillate, and recovered extractant 21 being obtained from the kettle.
Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 8.
Table 8 Analysis data (wt%) for the streams of individual towers propanol | acid glycol oxide acetate
Cw los | we [er | uw Jesfme] oo | 0] oo w [tox | 203 [waa | wo Jo fms] 0 [0 | 0
Ts loo [oo Jeefoel 0 | 0 | 0 6 o | o [oo lolol oo ww | o ov [ms | es | 0 | 0 [ool o | oo | oo ol o lol oololm|[ o w | 0 | o [wa] wo |olsmsl o | oo | 0 wo | o | o | o |as[ol 0 | os [ 0 2] 0 | o | o| 0 Jorjes| o | oo | o w | ws | 02 | 0 | 0 [olo| o | oo | o
Tso lw oo {ole oo | oo lo w | 0 | 0 [oso] o olse| oo | 0 | oo nl 0 | 0 | o [moos] o | o w | 0 | 0 [oo [wslol o | os | o nl ol ooo lolol of w wo [we | 0 | o Joelle [| oo | oo
Cw lol ool oo lolol m|[ o w | 0 | 0 | 0 | o lols o | 0 | a wo | o | o Jor ole] of o | o
Example 9 ~The procedure as described in Example 8 was followed, except that triphenyl phosphine : oxide was used as the extractant in the acetic acid extraction tower 4. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 9.
Table 9 Analysis data (wt%) for the streams of individual towers stream | acetone | methanol | ethanol n- acetic | water | ethylene | triphenyl isopropyl propanol acid glycol phosphine acetate oxide 5s [os | 16 | 27 | 11 [ssfso] o | o | o w oa | 03 [saz | wo [ous] 0 | 0 | 0 s | o | o | o | o [oslmel o [ o | o 6 | o | o | oo ole of ww | o ov [ss | ws | 0 | 0 [oof of o | o slo o lol oololw] o | o | 0 | o [au] 20 [0 lwsf o | o | o oo | o | oo] o Jsslol of oss | o no | 0 [oo [welomel o | o | o w los | 02 | o | 0 [olol o| o | o s | o [ws | o | o [oles] o | o | o 6 | o | o [oso] 0 [oso] o | o plo] o | o [moo sw] of o | o w | 0 | 0 | o | o Jerfol o | es | o wl ol o [oo Jolol oo] ww o w | 0 |» | 0 | 0 [olol ou] o | o wo | o | oo [ololwm| o [ o wo | o | o| o [oleae] 0 | o | a no | o | o wr |ofoa] of o | o
Example 10
The procedure as described in Example 8 was followed, except that the Fischer-Tropsch synthesis by-products in aqueous phase had a composition of: 7wt% of a component having a boiling point of less than 50°C, 84wt% of a component having a boiling range of from 50 to 120°C, and 9wt% of a component having a boiling point of larger than 120°C. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 10.
Table 10 Analysis data (wt%) for the streams of individual towers stream | acetone | methanol | ethanol n- acetic | water | ethylene | Trialkyl | isopropyl propanol | acid glycol | phosphine | acetate oxide
Co La | us as | as Jss[wmol o [0 | o w | usa | 1a | we | mo | o [mr] o | 0 | o 5s | o | o | o | o Jerfwal o | o | o 6 | 0 | o | o | o lol o] of uw | o
Cu ws lee | 0 | 0 [ole of oo
Lo o [ol] o [olol wl of oo s | 0 | o Jos | ws lo ms] o | o | o o | o | o | o | o las| o| o [oss] o 2 | ol o | o | o Jorlws] of o | o w |x | 02 [0 | o Lolo] of oo ss Lo ws | 0 | o Jolewr| of of} o 6 | 0 | 0 [sso] o [ose] oo 7 Lo | 0 | o | a [osm] ol o w | 0 | o | o | o |wsl oo o | os | o wl oo lol o [olol owl] o w | 0 | mw | o | o [ol] ol oo] ol o wo | o lo o [oo [wl ol 0 w | oo | o | o [olos| ol o | a
Tal ole Tow [ole] oo]
Example 11
As shown in the Figure 3, a stream 208 consisting of Fischer-Tropsch synthesis by- products in aqueous phase (comprising 5wt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 201 having a theoretical plate number of 15 at the 7th theoretical plate. The tower 201 was operated at a reflux ratio of 12 and a tower top temperature of 40 °C, with a side-cut 211 having a boiling range of from 50 to 120 °C being withdrawn from the 8th theoretical plate.
The side-cut 211 was fed to a divided tower 202 having a theoretical plate number of 50, in which the upper section accounted for a theoretical plate. number of 10, the lower section also accounted for a theoretical plate number of 10, left side liquid phase in the upper section had a distribution factor of 0.7, and the left side gas phase in the lower section had a distribution factor of 0.68. The divided tower 202 was operated at a reflux ratio of 30, a tower top temperature of from 60 to 64 °C, an upper side-cut temperature of 68 to 68.5 °C, and a lower side-cut temperature of 87 to 93 °C, with acetone/methanol mixture 212 being withdrawn as a tower top distillate, ethanol 213 as a side-cut being withdrawn from upper portion of the divided tower, n-propanol aqueous solution stream 214 as a side-cut being withdrawn from lower portion of the divided tower, and acetic acid aqueous solution 215 being obtained from the kettle. The n-propanol aqueous solution stream 214 was fed to an azeotrope rectifying tower 203 having a theoretical plate number of 20 at the 12th theoretical plate, and cyclohexane as an azeotrope forming agent was co-fed. The tower 203 was operated at a weight ratio of the azeotrope forming agent to the stream 214 of 0.9 and a kettle temperature of from 96.8 to 97.5 °C, with aqueous phase obtained in an tower top phase separator being withdrawn as a stream 217 and oil phase being refluxed, and n-propanol 2138 being withdrawn from the kettle. The acetic acid aqueous solution 215 from the divided tower 202 was fed to an acetic acid extraction tower 204 having a theoretical plate number of 10, and tert-butyl amine as an extractant was co-fed. The tower 204 was operated at a weight ratio of the extractant to the acetic acid aqueous solution 215 of 5 and an operation temperature of 35 °C, with acetic acid/extractant mixture stream 219 being obtained from the tower top, and waste water 220 being obtained from the kettle. The acetic acid/extractant mixture 219 was fed to an extractant recovering tower 205 having a theoretical plate number of 10 at the 4th theoretical plate. The tower 205 was operated at a reflux ratio of 6 and a tower top temperature of from 115 to 118 °C, with acetic acid 221 being obtained as a tower top distillate, and recovered extractant 222 being obtained from the kettle. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 11.
Table 11 Analysis data (wt%) for the streams of individual towers propanol acid butyl amine on | os | te | 27 | wm | ss [wo] o | oo mo | ws [es | 0 | 0 | o | 0 | o | o wm | 0 | 0 [eo] o | o [soo] we | 0 | o | o [ses | o [wal o | o ws | 0 | o | o | o [se ]os] o | a
So I I ES A A I on | 0 | o | o [oo [0 [ws] 0 | os as | 0 | o | o Jos | o los | 0 wo | 0 | 0 | oo [aslo Jam] o m | 0 | o | o | o [es [ws] 0 | 0 2 | 0 | o | o [oo [ws] o oa] o wm | 0 | 0 [ooo] o fw] o
Example 12
As shown in the Figure 3, a stream 208 consisting of Fischer-Tropsch synthesis by- products in aqueous phase (comprising Swt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 201 having a theoretical plate number of 60 at the 35th theoretical plate. The tower 201 was operated at a reflux ratio of 1 and a tower top temperature of 40 °C, with a side-cut 211 having a boiling range of from 50 to 120 °C being withdrawn from the 40th theoretical plate.
The side-cut 211 was fed to a divided tower 202 having a theoretical plate number of 200, in which the upper section accounted for a theoretical plate number of 40, the lower section accounted also for a theoretical plate number of 60, left side liquid phase in the upper section had a distribution factor of 0.31, and left side gas phase in the lower section had a distribution factor of 0.3. The divided tower 202 was operated at a reflux ratio of 30, a tower top temperature of 60 to 64 °C, an upper side-cut temperature of 68 to 68.5 °C, and a lower side-cut temperature of 87 to 93 °C, with acetone and methanol mixture 212 being withdrawn as a tower top distillate, ethanol 213 as a side-cut being withdrawn from upper portion of the divided tower, n-propanol aqueous solution stream 214 as a side-cut being withdrawn from lower portion of the divided tower, and acetic acid aqueous solution 215 being obtained from the kettle. The n-propanol aqueous solution stream 214 was fed to an azeotrope rectifying tower 203 having a theoretical plate number of 60 at the 35th theoretical plate, and n-butyl acetate as an azeotrope forming agent was co-fed. The tower 203 was operated at a weight ratio of the azeotrope forming agent to the stream 214 of 0.2 and a kettle temperature of from 96.8 to 97.5 °C, with aqueous phase obtained in an tower top phase separator being withdrawn as a stream 217 and oil phase being refluxed, and n-propanol 218 being withdrawn from the kettle. The acetic acid aqueous solution 215 from the divided tower 202 was fed to an acetic acid extraction tower 204 having a theoretical plate number of 40, and tert-butyl amine as an extractant was co-fed. The tower 204 was operated at a weight ratio of the extractant to the acetic acid aqueous solution 215 of 1 and an operation temperature of 35 °C, with acetic acid/extractant mixture stream 219 being obtained from the tower top, and waste water 220 being obtained from the kettle. The acetic acid/extractant mixture 219 was fed to an extractant recovering tower 205 having a theoretical plate number of 50 at the 20th theoretical plate. The tower 205 was operated at a reflux ratio of 1 and a tower top temperature of from 115 to 118 °C, with acetic acid 221 being obtained as a tower top distillate, and extractant 222 being obtained from the kettle. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 12.
Table 12 Analysis data (wt%) for the streams of individual towers propanol acid amine acetate on | os | we | 27 | wu ss feel o [ 0 wo | a | ws | 0 | 0 [oo] o ws | o | o [ool o | oso o | o
Tae 0 | 0 [0 Jano [se 0 | oo ss | 0 | o | o | o [os [ons] o | o © awl oo [oo [elo] ww [| oo 0 | o | o | oo mal o ss | 0 | 0 | o [es | o fos] o | o wo | 0 | o | o | o [oro] | 0 m0 | 0 | 0 | o | o [os ws] 0
CT lo [0 [oo [melo ee m | 0] o | o | ol ofo] mw] o
Example 13
As shown in the Figure 3, a stream 208 consisting of Fischer-Tropsch synthesis by- products in aqueous phase (comprising 5wt% of a component having a boiling point of less
Co than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 201 having a theoretical plate number of 30 at the 17th theoretical plate. The tower 201 was operated at a reflux ratio of 3 and a tower top temperature of 40 °C, with a side-cut 211 having a boiling range of from 50 to 120 °C being withdrawn from the 20th theoretical plate.
The side-cut 211 was fed to a divided tower 202 having a theoretical plate number of 120, in which the upper section accounted for a theoretical plate number of 20, the lower section accounted for a theoretical plate number of 30, left side liquid phase in the upper section had a distribution factor of 0.52, and left side gas phase in the lower section had a distribution factor of 0.5. The divided tower 202 was operated at a reflux ratio of 12, a tower top temperature of 60 to 64 °C, an upper side-cut temperature of 68 to 68.5 °C, and a lower side- cut temperature of 87 to 93 °C, with acetone/methanol mixture 212 being withdrawn as a oo tower top distillate, ethanol 213 as a side-cut being withdrawn from upper portion of the divided tower, n-propanol aqueous solution stream 214 as a side-cut being withdrawn from lower portion of the divided tower, and acetic acid aqueous solution 215 being obtained from the kettle. The n-propanol aqueous solution stream 214 was fed to an azeotrope rectifying tower 203 having a theoretical plate number of 30 at the 17th theoretical plate, and isopropyl acetate as an azeotrope forming agent was co-fed. The tower 203 was operated at a weight ratio of the azeotrope forming agent to the stream 214 of 0.5 and a kettle temperature of from 96.8 to 97.5 °C, with aqueous phase obtained in an tower top phase separator being withdrawn as a stream 217 and oil phase being refluxed, and n-propanol 218 being withdrawn from the kettle. The acetic acid aqueous solution 215 from the divided tower 202 was fed to an acetic acid extraction tower 204 having a theoretical plate number of 20, and trimethylphosphine oxide as an extractant was co-fed. The tower 204 was operated at a weight ratio of the extractant to the acetic acid aqueous solution 215 of 2 and an operation temperature of 35 °C, with acetic acid/extractant mixture stream 219 being obtained from the tower top, and waste water 220 being obtained from the kettle. The acetic acid/extractant mixture 219 was fed to an extractant recovering tower 205 having a theoretical plate number of 25 at the 10th theoretical plate. The tower 205 was operated at a reflux ratio of 3 and a tower top temperature of from 115 to 118 °C, with acetic acid 221 being obtained as a tower top distillate, and recovered extractant 222 being obtained from the kettle. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The : results are shown in the Table 13.
Table 13 Analysis data (wt%) for the streams of individual towers propanol | acid oxide acetate on | os | te | a1 | ur Jesse] 0 | oo oz | ws | es | 0 | 0 lolol oo wm | 0 | o Jomo] o Jose] oo | oo we | 0 | 0 | o [aw oso] oo [0 ws | 0 | o | o | o Joesles] oo | oo me | 0 | o [oo [olol wo [| o
0 | 0 [oo [ofa] 0 | a wo | 0 | o | o |e ofol 0 | oo wo | 0 | o | o | o [aslo] ess | oo m | 0 | 0 | o | o lorem] oo m | 0 | o | o | o lws[o] 02 | oo
Tm oo [oo ole we | oo
Example 14 :
The procedure as described in Example 13 was followed, except that the Fischer-
Tropsch synthesis by-products in aqueous phase had a composition of: 7wt% of a component having a boiling point of less than 50°C, 84wt% of a component having a boiling range of from 50 to 120°C, and 9wt% of a component having a boiling point of larger than 120°C.
Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 14.
Table 14 Analysis data (wt%) for the streams of individual towers propanol | acid oxide acetate on | 12 | 19 [2s | 20 [ss lmo| oo oi as | ez | 0 | o | olol oo Lo 0 | o lwo] o [ose 0 | 0 we | 0 | 0 | o |e [om] 0} ws | 0 | 0 | o | o |erlsma| 0 we | 0 | 0 | o | o Jolol wm 0 | 0 oo [oles] o | w we | 0 | 0 | o |r loo] o | 0 ws | 0 | 0 | o | o [aslol ws | 0 m0 | 0 | 0 | o | o lerlws| oo | 0 wi | 0 | 0 | o | o [wslo| os | 0 wm 0 | 0 [oo] o [oo] w | 0 . Example 15
As shown in the Figure 4, a stream 208 consisting of Fischer-Tropsch synthesis by- products in aqueous phase (comprising 5wt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% oo 2 of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 201 having a theoretical plate number of 15 at the 7th theoretical plate. The tower 201 was operated at a reflux ratio of 12 and a tower top temperature of 40 °C, with a side-cut 211 having a boiling range of from 50 to 120 °C being withdrawn from the 8th theoretical plate.
The side-cut 211 was fed to a divided tower 202 having a theoretical plate number of 50, in which the upper section accounted for a theoretical plate number of 10, the lower section accounted also for a theoretical plate number of 10, left side liquid phase in the upper section had a distribution factor of 0.7, and left side gas phase in the lower section had a distribution factor of 0.68. The divided tower 202 was operated at a reflux ratio of 30, a tower top temperature of 60 to 64 °C, an upper side-cut temperature of 68 to 68.5 °C, and a lower side- cut temperature of 87 to 93 °C, with acetone/methanol mixture 212 being withdrawn as a : tower top distillate, ethanol 213 as a side-cut being withdrawn from upper portion of the divided tower, n-propanol aqueous solution stream 214 as a side-cut being withdrawn from lower portion of the divided tower, and acetic acid aqueous solution 215 being obtained from the kettle. The acetone/methanol mixture 212 and water 223 as solvent were fed to an extractive rectifying tower 206 having a theoretical plate number of 20 at the 12th and 5th theoretical plate, respectively. The tower 206 was operated at a weight ratio of the solvent to the acetone/methanol mixture 212 of 10, a reflux ratio of 9, and a tower top temperature of : from 56 to 56.5 °C, with acetone 224 being obtained as a tower top distillate, and _ methanol/solvent mixture 225 being obtained from the kettle. The methanol/solvent mixture 225 was fed to a solvent recovering tower 207 having a theoretical plate number of 10 at the 5th theoretical plate. The tower 207 was operated at a reflux ratio of 6 and a tower top temperature of from 64.5 to 64.7 °C, with methanol 226 being obtained as a tower top distillate, and recovered solvent 227 being obtained from the kettle. The n-propanol aqueous solution 214 from the divided tower 202 was fed to an azeotrope rectifying tower 203 having a theoretical plate number of 20 at the 12th theoretical plate, and cyclohexane as an azeotrope forming agent was co-fed. The tower 203 was operated at a weight ratio of the azeotrope forming agent to the stream 214 of 0.9 and a kettle temperature of from 96.8 to 97.5 °C, with aqueous phase obtained in an tower top phase separator being withdrawn as a stream 217 and oil phase being refluxed, and n-propanol 218 being withdrawn from the kettle. The acetic acid aqueous solution 215 from the divided tower 202 was fed to an acetic acid extraction tower 204 having a theoretical plate number of 10, and tert-butyl amine as an extractant was co-fed. The tower 204 was operated at a weight ratio of the extractant to the acetic acid aqueous solution 215 of 5 and an operation temperature of 35 °C, with acetic acid/extractant mixture stream 219 being obtained from the tower top, and waste water 220 being obtained from the kettle. The acetic acid/extractant mixture 219 was fed to an extractant recovering tower 205 having a theoretical plate number of 10 at the 4th theoretical - plate. The tower 205 was operated at a reflux ratio of 6 and a tower top temperature of from 115 to 118 °C, with acetic acid 221 being obtained as a tower top distillate, and recovered extractant 222 being obtained from the kettle. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 15. :
Table 15 Analysis data (wt%) for the streams of individual towers stream | acetone | methanol | ethanol n- acetic water tert- cyclohexane propanol | acid butyl * amine on | os | 16 | ar | uu [es [wo] 0 in | 3s | ws | 0 | o | o [oo | ol 0 is | 0 | o Joo] o [0 [solo] o ie | 0 | o | 0 [ses | o [ea] 0 | o is | 0 | o | 0 | o [es [we] 0 | o we | 0 | 0 | o | oo] om] wm | 0 | o | o | oo lw]| of o pe | 999 | 00 | 0 | o | oo | oo | o 2 | 0 |e | 0 | 0 | 0 [malo | oo wr | o | o | 0 | o | o [ms] o | os ms | o | o | o los | o los | ol 0 wo | 0 | o | o | o [us| oo Ja] o m | 0 | o | 0 | o [os [sms] 0 | o me | 0 | ws | o | o | o Jaf 0] o “wr | 0 | 0 [oo [0 fw] 0] o wr | 0 | 0 | o | o [ws] 0 [0a] o wm | 0 | o | ol ooo [ww] o
Example 16
As shown in the Figure 4, a stream 208 consisting of Fischer-Tropsch synthesis by- products in aqueous phase (comprising Swt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 201 having a theoretical plate number of 60 at the 35th theoretical plate. The tower 201 was operated at a reflux ratio of 1 and a tower top temperature of 40 °C, with a side-cut 211 having a boiling range of from 50 to 120 °C being withdrawn from the 40th theoretical plate.
The side-cut 211 was fed to a divided tower 202 having a theoretical plate number of 200, in which the upper section accounted for a theoretical plate number of 40, the lower section accounted for a theoretical plate number of 60, left side liquid phase in the upper section had a distribution factor of 0.31, and left side gas phase in the lower section had a distribution factor of 0.3. The divided tower 202 was operated at a reflux ratio of 30, a tower top temperature of 60 to 64 °C, an upper side-cut temperature of 68 to 68.5 °C, and a lower side- cut temperature of 87 to 93 °C, with acetone/methanol mixture 212 being withdrawn as a tower top distillate, ethanol 213 as a side-cut being withdrawn from upper portion of the divided tower, n-propanol aqueous solution stream 214 as a side-cut being withdrawn from lower portion of the divided tower, and acetic acid aqueous solution 215 being obtained from the kettle. The acetone/methanol mixture 212 and monoethanolamine 223 as solvent were fed to an extractive rectifying tower 206 having a theoretical plate number of 50 at the 20th and 3rd theoretical plate, respectively. The tower 206 was operated at a weight ratio of the solvent to the acetone/methanol mixture 212 of 2, a reflux ratio of 2, and a tower top temperature of from 56 to 56.5 °C, with acetone 224 being obtained as a tower top distillate, and methanol/solvent mixture 225 being obtained from the kettle. The methanol/solvent mixture 225 was fed to a solvent recovering tower 207 having a theoretical plate number of 50 at the 20th theoretical plate. The tower 207 was operated at a reflux ratio of 1.5 and a tower top temperature of from 64.5 to 64.7 °C, with methanol 226 being obtained as a tower top distillate, and recovered solvent 227 being obtained from the kettle. The n-propanol aqueous solution 214 from the divided tower 202 was fed to an azeotrope rectifying tower © 203 having a theoretical plate number of 60 at the 35th theoretical plate, and n-butyl acetate as an azeotrope forming agent was co-fed. The tower 203 was operated at a weight ratio of the azeotrope forming agent to the stream 214 of 0.2 and a kettle temperature of from 96.8 to 97.5 °C, with aqueous phase obtained in an tower top phase separator being withdrawn as a stream 217 and oil phase being refluxed, and n-propanol 218 being withdrawn from the kettle. The acetic acid aqueous solution 215 from the divided tower 202 was fed to an acetic . acid extraction tower 204 having a theoretical plate number of 40, and tert-butyl amine as an extractant was co-fed. The tower 204 was operated at a weight ratio of the extractant to the acetic acid aqueous solution 215 of 1 and an operation temperature of 35 °C, with acetic acid/extractant mixture stream 219 being obtained from the tower top, and waste water 220 being obtained from the kettle. The acetic acid/extractant mixture 219 was fed to an extractant recovering tower 205 having a theoretical plate number of 50 at the 20th theoretical plate. The tower 205 was operated at a reflux ratio of 1 and a tower top temperature of from 115 to 118 °C, with acetic acid 221 being obtained as a tower top "distillate, and recovered extractant 222 being obtained from the kettle. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 16.
Table 16 Analysis data (wt%) for the streams of individual towers stream | acetone | methanol | ethanol n- acetic | water | Monoethanol | tert- n-butyl : propanol | acid -amine butyl acetate amine wn | os | 16 | 27 | ues sel o [0 wz | ma es | 0 | 0 |olol o [of 0 m | o | o sso] 0 [ose] o [ol o me | 0 | 0 | o [wa ose] o [0] ws | 0 | 0 | o | o Josfos| o [0] ms | 0 | o | 0 | 0 lolol o [uw] o mo | o | o| o [olol w [o}o 2 | 9 | or | 0 | 0 Joo o [ol] ms | 0 | asa | 0 | 0 [ome] o lo} o ro | o | o | o [ofa] o [ol ws | 0 | o | o [ms | olos| o [ol wo | 0 | 0 | o | o [oalol o oo} o mo | 0 | o | o | o |osles] o [ol 226 “0 [9 | 0 | 0 |ofo| au |o 0 wm | 0 | o | o | 0 Jolol w [oles a | 0 | 0 | o | 0 |wslol o [ool o wm 0 | 0 | o] o Jolol o [wm]
Example 17 :
As shown in the Figure 4, a stream 208 consisting of Fischer-Tropsch synthesis by- products in aqueous phase (comprising 5wt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 201 having a theoretical plate number of 30 at the 17th theoretical plate. The tower 201 was operated at a reflux ratio of 3 and a tower top temperature of 40 °C, with a side-cut 211 having a boiling range of from 50 to 120 °C being withdrawn from the 20th theoretical plate.
The side-cut 211 was fed to a divided tower 202 having a theoretical plate number of 120, in which the upper section accounted for a theoretical plate number of 20, the lower section accounted for a theoretical plate number of 30, left side liquid phase in the upper section had a distribution factor of 0.52, and left side gas phase in the lower section had a distribution factor of 0.5. The divided tower 202 was operated at a reflux ratio of 12, a tower top temperature of 60 to 64 °C, an upper side-cut temperature of 68 to 68.5 °C, and a lower side- cut temperature of 87 to 93 °C, with acetone/methanol mixture 212 being withdrawn as a tower top distillate, ethanol 213 as a side-cut being withdrawn from upper portion of the divided tower, n-propanol aqueous solution stream 214 as a side-cut being withdrawn from lower portion of the divided tower, and acetic acid aqueous solution 215 being obtained from the kettle. The acetone and methanol mixture 212 and ethylene glycol 223 as solvent were fed to an extractive rectifying tower 206 having a theoretical plate number of 30 at the 17th and 3rd theoretical plate, respectively. The tower 206 was operated at a weight ratio of the solvent to the acetone/methanol mixture 212 of 4, a reflux ratio of 4, and a tower top temperature of from 56 to 56.5 °C, with acetone 224 being obtained as a tower top distillate, and methanol/solvent mixture 225 being obtained from the kettle. The methanol/solvent - mixture 225 was fed to a solvent recovering tower 207 having a theoretical plate number of at the 10th theoretical plate. The tower 207 was operated at a reflux ratio of 3 and a tower top temperature of from 64.5 to 64.7 °C, with methanol 226 being obtained as a tower top distillate, and recovered solvent 227 being obtained from the kettle. The n-propanol aqueous solution 214 from the divided tower 202 was fed to an azeotrope rectifying tower 203 having : a theoretical plate number of 30 at the 17th theoretical plate, and isopropyl acetate as an azeotrope forming agent was co-fed. The tower 203 was operated at a weight ratio of the azeotrope forming agent to the stream 214 of 0.5 and a kettle temperature of from 96.8 to 97.5 °C, with aqueous phase obtained in an tower top phase separator being withdrawn as a stream 217 and oil phase being refluxed, and n-propanol 218 being withdrawn from the kettle. The acetic acid aqueous solution 215 from the divided tower 202 was fed to an acetic acid extraction tower 204 having a theoretical plate number of 20, and trimethylphosphine oxide as an extractant was co-fed. The tower 204 was operated at a weight ratio of the extractant to the acetic acid aqueous solution 215 of 2 and an operation temperature of 35 °C, with acetic acid/extractant mixture stream 219 being obtained from the tower top, and waste water 220 being obtained from the kettle. The acetic acid/extractant mixture 219 was fed to an extractant recovering tower 205 having a theoretical plate number of 25 at the 10th theoretical plate. The tower 205 was operated at a reflux ratio of 3 and a tower top temperature of from 115 to 118 °C, with acetic acid 221 being obtained as a tower top distillate, and recovered extractant 222 being obtained from the kettle. Upon the operation ~ was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 17. * Table 17 Analysis data (wt%) for the streams of individual towers propanol | acid | glycol oxide acetate © Tan Jos [we ar | ou Jssfse] o | 0 an ms | ws | 0 | 0 Jolol oo] oo | oo ws] o | 0 |sso| o [oso o | oo | oo me | 0 | 0 | 0 [wo |olsol oo | oo ws | 0 | o | o | o |os|oa| o | 0 we | 0 | 0 | o | o [ool of wo | oo wm 0 | 0 | o | o Jololm]|[ oo
Taw [ws | 02 | 0 | 0 lolol 0 | 0 | oo ws | 0 |ws | 0 | 0 [oer] oo | 0 | oo 0 | o | oo [ole] oo | 0 as | 0 | o | o [wile] ol oo | oo wo | 0 | 0 | o | o aslo of os | o
Tao [0 | 0 [oo lorfews| 0 | 0 | oo ms | 0 | ws | 0 | 0 Jo ola oo wm] 0 | o [oo [oom] o a] 0 | 0 | o | o [ws|ol o | 02 [oo wm] 0 | o [ol oo Jolol ol w | o
Example 18
The procedure as described in Example 17 was followed, except that the Fischer-
Tropsch synthesis by-products in aqueous phase had a composition of: 7wt% of a component having a boiling point of less than 50°C, 84wt% of a component having a boiling range of from 50 to 120°C, and 9wi% of a component having a boiling point of larger than 120°C.
Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 18. :
Table 18 Analysis data (wt%) for the streams of individual towers propanol | acid glycol oxide acetate m | 12 | 1s [as | 2 |sslwmel o | 0 ma [ws | oa | 0 | 0 [ool o | o oo mo | o [sso] o [oso o | 0 Lo we | 0 | 0 | o las [ols] o | 0 | oo ws 0 | 0 [oo oro] o | o woo | 0 [ol o [ole of wm | o wm | 0 | 0 | oo [ololwm| o | o oe [ws | 02 | 0 | 0 Joo] o| o Lo ws | 0 | os | 0 | o Joe] o | o Jo wl ol o [oo [oles] oo 0 [
I I I I I Ee EC wl o | o | oo [esol of sss [0 wo] 0 | 0 | ol o Jorlows| o | 0 | 0 me 0 Ls | 0 | o Jololoul o wr | 0 | 0 loo |ololml o | o mo | 0 lo] o [ms|ol o | os | 0 ml oo lol o [olol ol w [o
Example 19 :
As shown in a part of the Figure 1, a stream 10 consisting of Fischer-Tropsch synthesis by-products in aqueous phase (comprising 5wt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 1 having a theoretical plate number of 60 at the 35" theoretical plate, the tower 1 being operated at a reflux ratio of 1 and a tower top temperature of 40°C. A side-cut 13 having a boiling range of from 50 to 120°C was withdrawn from the 40™ theoretical plate and fed to an acetic acid separation tower 2 having a theoretical plate number of 50 at the 30" theoretical plate. The tower 2 was operated at a reflux ratio of 8 and a kettle temperature of from 104 to 108°C, with an aqueous solution stream 14 containing alcohols and ketones being obtained as a tower top distillate, and acetic acid aqueous solution stream 15 being obtained from the kettle. The stream 14 was fed to an ethanol separation tower 3 having a theoretical plate number of 80 at the 50™ theoretical plate. The ethanol separation tower 3 was operated at a reflux ratio of 2 and a tower top temperature of from 60 to 64°C, with methanol/acetone mixture stream 17 being obtained as a tower top distillate, and ethanol and n-propanol aqueous solution stream 18 being obtained from the kettle. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 19.
Table 19 Analysis data (wt%) for the streams of individual towers : acid 3 | os | 16 | 27 | 11 | ss | 850 1a | 104 | 20s | 351 | ws [ 0 | 104 5s | 0 | o | o | o | os | 0s 17 | 3s | es | 0 | o | o Lo | 0 | o | so | 208 [ o [282
Example 20
As shown in a part of the Figure 3, a stream 208 consisting of Fischer-Tropsch synthesis by-products in aqueous phase (comprising 5wt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary : rectifying tower 201 having a theoretical plate number of 15 at the 7th theoretical plate. The tower 201 was operated at a reflux ratio of 12 and a tower top temperature of 40 °C, with a side-cut 211 having a boiling range of from 50 to 120 °C being withdrawn from the 8th theoretical plate. The side-cut 211 was fed to a divided tower 202 having a theoretical plate number of 50, in which the upper section accounted for a theoretical plate number of 10, the lower section also accounted for a theoretical plate number of 10, left side liquid phase in the upper section had a distribution factor of 0.7, and the left side gas phase in the lower section had a distribution factor of 0.68. The divided tower 202 was operated at a reflux ratio of 30, a tower top temperature of from 60 to 64 °C, an upper side-cut temperature of 68 to 68.5 °C, and a lower side-cut temperature of 87 to 93 °C, with acetone/methanol mixture 212 being withdrawn as a tower top distillate, ethanol 213 as a side-cut being withdrawn from upper portion of the divided tower, n-propanol aqueous solution stream 214 as a side-cut being withdrawn from lower portion of the divided tower, and acetic acid aqueous solution 215 being obtained from the kettle. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 20.
Table 20 Analysis data (wt%) for the streams of individual towers acid an | os | 16 | 27 | 11 | ss | 850 2 | 335 | 665 | o | 0 | 0 | 0 a3 | 0 | 0 [eso] o | 0 [50
Example 21
As shown in a part of the Figure 3, a stream 208 consisting of Fischer-Tropsch synthesis by-products in aqueous phase (comprising 5wt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 201 having a theoretical plate number of 60 at the 35th theoretical plate. The tower 201 was operated at a reflux ratio of 1 and a tower top temperature of 40 °C, with a side-cut 211 having a boiling range of from 50 to 120 °C being withdrawn from the 40th theoretical plate. The side-cut 211 was fed to a divided tower 202 having a theoretical plate number of 200, in which the upper section accounted for a theoretical plate number of 40, the
Jower section accounted also for a theoretical plate number of 60, left side liquid phase in the upper section had a distribution factor of 0.31, and left side gas phase in the lower section had a distribution factor of 0.3. The divided tower 202 was operated at a reflux ratio of 30, a tower top temperature of 60 to 64 °C, an upper side-cut temperature of 68 to 68.5 °C, and a lower side-cut temperature of 87 to 93 °C, with acetone and methanol mixture 212 being withdrawn as a tower top distillate, ethanol 213 as a side-cut being withdrawn from upper portion of the divided tower, n-propanol aqueous solution stream 214 as a side-cut being withdrawn from lower portion of the divided tower, and acetic acid aqueous solution 215 being obtained from the kettle. The n-propanol aqueous solution stream 214 was fed to an azeotrope rectifying tower 203 having a theoretical plate number of 60 at the 35th theoretical plate, and n-butyl acetate as an azeotrope forming agent was co-fed. The tower 203 was operated at a weight ratio of the azeotrope forming agent to the stream 214 of 0.2 and a kettle temperature of from 96.8 to 97.5 °C, with aqueous phase obtained in an tower top phase separator being withdrawn as a stream 217 and oil phase being refluxed, and n-propanol 218 being withdrawn from the kettle. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 21.
Table 21 Analysis data (wt%) for the streams of individual towers acid _ acetate
Tou [os | 16 [27 | 11 | ss [sso] oo 22 | 34 | 666 | 0 | 0 | 0 [0] oo a3 | 0 | o [eso] o | oo [so] 0 24 | 0 | o | o | wr | oo [sso] 0 us | 0 | o | o | o [os [os] 0 wr | 0 | o | o | o | o [ess] 1 8 | 0 | 0 | o [9s [0 Jos] oo
Example 22
As shown in a part of the Figure 4, a stream 208 consisting of Fischer-Tropsch synthesis by-products in aqueous phase (comprising 5wt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 201 having a theoretical plate number of 15 at the 7th theoretical plate. The tower 201 was operated at a reflux ratio of 12 and a tower top temperature of 40 °C, with a side-cut 211 having a boiling range of from 50 to 120 °C being withdrawn from the 8th theoretical plate. The side-cut 211 was fed to a divided tower 202 having a theoretical plate number of 50, in which the upper section accounted for a theoretical plate number of 10, the - lower section accounted also for a theoretical plate number of 10, left side liquid phase in the upper section had a distribution factor of 0.7, and left side gas phase in the lower section had a distribution factor of 0.68. The divided tower 202 was operated at a reflux ratio of 30, a tower top temperature of 60 to 64 °C, an upper side-cut temperature of 68 to 68.5 °C, and a lower side-cut temperature of 87 to 93 °C, with acetone/methanol mixture 212 being withdrawn as a tower top distillate, ethanol 213 as a side-cut being withdrawn from upper portion of the divided tower, n-propanol aqueous solution stream 214 as a side-cut being withdrawn from lower portion of the divided tower, and acetic acid aqueous solution 215 being obtained from the kettle. The acetic acid aqueous solution 215 was fed to an acetic acid extraction tower 204 having a theoretical plate number of 10, and tert-butyl amine as an extractant was co-fed. The tower 204 was operated at a weight ratio of the extractant to the acetic acid aqueous solution 215 of 5 and “an operation temperature of 35 °C, with acetic acid/extractant mixture stream 219 being obtained from the tower top, and waste water 220 being obtained from the kettle. The acetic acid/extractant mixture 219 was fed to an extractant recovering tower 205 having a theoretical plate number of 10 at the 4th theoretical plate. The tower 205 was operated at a reflux ratio of 6 and a tower top temperature of from 115 to 118 °C; with acetic acid 221 being obtained as a tower top distillate, and recovered extractant 222 being obtained from the kettle. Upon the operation was stable, analysis data ~ for the streams of individual towers were acquired. The results are shown in the Table 22.
Table 22 Analysis data (wt%) for the streams of individual towers acid | | amine ar | os | 16 | 27 | 11 | 88 | 850 | 0
Tom | ms | ees | 0 | o [ol o | oo 3 | 0 | o [oso] o | o [so] 0 na | 0 | o | o [ss | 0 [e2] 0 as | 0 | 0 | o | o | os [sal 0 26 | 0 | 0 | o | o | o [ o | 10 | o | 0 | o | o [19] o | os 20 | 0 | 0 | o | o [os [os] o 2 | 0 | o | o | o [ows| o | 02 m | 0 | o | o | o [of o | wo Example23 oo
As shown in a part of the Figure 4, a stream 208 consisting of Fischer-Tropsch synthesis by-products in aqueous phase (comprising 5wt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 201 having a theoretical plate number of 60 at the 35th theoretical plate. The tower 201 was operated at a reflux ratio of 1-and a tower top temperature of 40 °C, with a side-cut 211 having a boiling range of from 50 to 120 °C being withdrawn from the 40th theoretical plate. The side-cut 211 was fed to a divided tower 202 having a theoretical plate number of 200, in which the upper section accounted for a theoretical plate number of 40, the lower section accounted for a theoretical plate number of 60, left side liquid phase in the upper section had a distribution factor of 0.31, and left side gas phase in'the lower section had a distribution factor of 0.3. The divided tower 202 was operated at a reflux ratio of 30, a tower top temperature of 60 to 64 °C, an upper side-cut temperature of 68 to 68.5 °C, and a lower side-cut temperature of 87 to 93 °C, with acetone/methanol mixture 212 being withdrawn as a tower top distillate, ethanol 213 as a side-cut being withdrawn from upper portion of the divided tower, n-propanol aqueous solution stream 214 as a side-cut being withdrawn from lower portion of the divided tower, and acetic acid aqueous solution 215 being obtained from the kettle. The acetone/methanol mixture 212 and monoethanolamine 223 as solvent were fed to an extractive rectifying tower 206 having a theoretical plate number of 50 at the 20th and 3rd theoretical plate, respectively. The tower 206 was operated at a weight ratio of the solvent to the acetone/methanol mixture 212 of 2, a reflux ratio of 2, and a tower top temperature of from 56 to 56.5 °C, with acetone 224 being obtained as a tower top distillate, and methanol/solvent mixture 225 being obtained from the kettle. The methanol/solvent mixture 225 was fed to a solvent recovering tower 207 having a theoretical plate number of 50 at the 20th theoretical plate. The tower 207 was operated at a reflux ratio of 1.5 and a tower top temperature of from 64.5 to 64.7 °C, with methanol 226 being obtained as a tower top distillate, and recovered solvent 227 being obtained from the kettle.
Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 23.
Table 23 Analysis data (wt%) for the streams of individual towers acid -amine a1 | os | 16 [27 | 11 [88 [sso] 0 22 | 334 | 666 | 0 | 0 [0 of o 23 | 0 | o Jesol o lo lsof oo 24 | 0 | 0 | o | a1 |o [ss] 0 | 0 | 0 [0 | o Jos[os| o 23 0 | o [o[ o [ofo] 10 24 [999 | or | 0 | o [ool o 25 | 0 | 251 | o | o [oo [ms] o 26 | 0 | 999 | 0 | o [oo] o1 27] 0 | o J of o [ofo] 10 _ Example 24
As shown in a part of the Figure 4, a stream 208 consisting of Fischer-Tropsch synthesis by-products in aqueous phase (comprising 5wt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 201 having a theoretical plate number of 15 at the 7th theoretical plate. The tower 201 was operated at a reflux ratio of 12 and a tower top temperature of 40 °C, with a side-cut 211 having a boiling range of from 50 to 120 °C being withdrawn from the 8th theoretical plate. The side-cut 211 was fed to a divided tower 202 having a theoretical plate number of 50, in which the upper section accounted for a theoretical plate number of 10, the lower section accounted also for a theoretical plate number of 10, left side liquid phase in the upper section had a distribution factor of 0.7, and left side gas phase in the lower section had a distribution factor of 0.68. The divided tower 202 was operated at a reflux ratio of 30, a tower top temperature of 60 to 64 °C, an upper side-cut temperature of 68 to 68.5 °C, and a : lower side-cut temperature of 87 to 93 °C, with acetone/methanol mixture 212 being withdrawn as a tower top distillate, ethanol 213 as a side-cut being withdrawn from upper portion of the divided tower, n-propanol aqueous solution stream 214 as a side-cut being: withdrawn from lower portion of the divided tower, and acetic acid aqueous solution 215 : being obtained from the kettle. The acetone/methanol mixture 212 and water 223 as solvent were fed to an extractive rectifying tower 206 having a theoretical plate number of 20 at the 12th and 5th theoretical plate, respectively. The tower 206 was operated at a weight ratio of the solvent to the acetone/methanol mixture 212 of 10, a reflux ratio of 9, and a tower top temperature of from 56 to 56.5 °C, with acetone 224 being obtained as a tower top distillate, and methanol/solvent mixture 225 being obtained from the kettle. The methanol/solvent mixture 225 was fed to a solvent recovering tower 207 having a theoretical plate number of at the 5th theoretical plate. The tower 207 was operated at a reflux ratio of 6 and a tower top temperature of from 64.5 to 64.7 °C, with methanol 226 being obtained as a tower top distillate, and recovered solvent 227 being obtained from the kettle. The n-propanol aqueous . solution 214 from the divided tower 202 was fed to an azeotrope rectifying tower 203 having a theoretical plate number of 20 at the 12th theoretical plate, and cyclohexane as an azeotrope forming agent was co-fed. The tower 203 was operated at a weight ratio of the azeotrope forming agent to the stream 214 of 0.9 and a kettle temperature of from 96.8 to 97.5 °C, with aqueous phase obtained in an tower top phase separator being withdrawn as a stream 217 and oil phase being refluxed, and n-propanol 218 being withdrawn from the kettle. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 24. -
Table 24 Analysis data (wt%) for the streams of individual towers acid an | os | 16 | 27 | 11 | 88 | sso] 0 22 | 335 | es | 0 | o [oo] o a3 | 0 | 0 [eso] o [oo |sof 0 a4 | 0 | 0 | o [368 | o ea] 0 a5 | 0 | o | o | o [os |oosa] o 2 | 0 | 0 | o | o [0 [100] o 24 | 999] or | o [ o [of oo] o
| 0 | 67 | o | o [0 [e3] o ar | 0 | 0 | o | o [0 [os] os 28 | o | o | o [ees [0 [os | o “aw oo [ol oo fw] o
Example 25 :
As shown in a part of the Figure 4, a stream 208 consisting of Fischer-Tropsch synthesis by-products in aqueous phase (comprising Swt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 201 having a theoretical plate number of 60 at the 35th theoretical plate. The tower 201 was operated at a reflux ratio of 1 and a tower top temperature of 40 °C, with a side-cut 211 having a boiling range of from 50 to 120 °C being withdrawn from the 40th theoretical plate. The side-cut 211 was fed to a divided tower 202 having a theoretical plate number of 200, in which the upper section accounted for a theoretical plate number of 40, the lower section accounted for a theoretical plate number of 60, left side liquid phase in the upper section had a distribution factor of 0.31, and left side gas phase in the lower section had a distribution factor of 0.3. The divided tower 202 was operated at a reflux ratio of 30, a tower top temperature of 60 to 64 °C, an upper side-cut temperature of 68 to 68.5 °C, and a lower side-cut temperature of 87 to 93 °C, with acetone/methanol mixture 212 being withdrawn as a tower top distillate, ethanol 213 as a side-cut being withdrawn from upper portion of the divided tower, n-propanol aqueous solution stream 214 as a side-cut being withdrawn from lower portion of the divided tower, and acetic acid aqueous solution 215 x being obtained from the kettle. The acetone/methanol mixture 212 and monoethanolamine 723 as solvent were fed to an extractive rectifying tower 206 having a theoretical plate number of 50 at the 20th and 3rd theoretical plate, respectively. The tower 206 was operated at a weight ratio of the solvent to the acetone/methanol mixture 212 of 2, a reflux ratio of 2, and a tower top temperature of from 56 to 56.5 °C, with acetone 224 being obtained as a tower top distillate, and methanol/solvent mixture 225 being obtained from the kettle. The methanol/solvent mixture 225 was fed to a solvent recovering tower 207 having a theoretical plate number of 50 at the 20th theoretical plate. The tower 207 was operated at a reflux ratio of 1.5 and a tower top temperature of from 64.5 to 64.7 °C, with methanol 226 being i obtained as a tower top distillate, and recovered solvent 227 being obtained from the kettle.
The acetic acid aqueous solution 215 from the divided tower 202 was fed to an acetic acid extraction tower 204 having a theoretical plate number of 40, and tert-butyl amine as an extractant was co-fed. The tower 204 was operated at a weight ratio of the extractant to the acetic acid aqueous solution 215 of 1 and an operation temperature of 35 °C, with acetic acid/extractant mixture stream 219 being obtained from the tower top, and waste water 220 being obtained from the kettle. The acetic acid/extractant mixture 219 was fed to an extractant recovering tower 205 having a theoretical plate number of 50 at the 20th theoretical plate. The tower 205 was operated at a reflux ratio of 1 and a tower top temperature of from 115 to 118 °C, with acetic acid 221 being obtained as a tower top distillate, and recovered extractant 222 being obtained from the kettle. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 25.
Table 25 Analysis data (wt%) for the streams of individual towers stream | acetone | methanol | ethanol | n-propanol | acetic | water tert-butyl
Fd oe aii | os | 16 | 27 | 11 [sss] o | 0 a2 | 334 | ess | 0 | 0 [oo] o | 0 as | 0 | o [oso] o [oso] o | 0 aa | 0 | o | o | er |o [sso] o | 0 as | 0 | o | o | o loess] o | 0 a6] 0 | o | o | o [ofol o [iw wm 0 | 0 [oo | o [olo] 10 | 0 a [999 | or | 0 | o [olo] o [0 ms | 0 | asi | 0 | o ome] o | 0 ao | 0 | o | o | o [oro] o | 09 m0 | 0 | 0 | o | o Joss] o | 0 © Tams] 0 [woo] o Jolof 01 | 0 wr | 0 | o | o | o |olo] ww [0 wi 0 | o | o | o [ws[of o Jo2 0 | 0 | o] o [ofol o [0
Example 26 :
As shown in a part of the Figure 2, a stream 10 consisting of Fischer-Tropsch synthesis by-products in aqueous phase (comprising 5wt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 1 having a theoretical plate number of 15 at the 7™ theoretical plate. The tower 1 was operated at a reflux ratio of 12 and a tower top temperature of 40 °C. A side-cut
13 having a boiling range of from 50 to 120 °C was withdrawn from the 8" theoretical plate and fed to an acetic acid separation tower 2 having a theoretical plate number of 15 at the 8" theoretical plate. The tower 2 was operated at a reflux ratio of 8 and a kettle temperature of from 104 to 108 °C, with an aqueous solution stream 14 containing alcohols and ketones being obtained as a tower top distillate and an acetic acid aqueous solution stream 15 being obtained from the kettle. The stream 14 was fed to an ethanol separation tower 3 having a theoretical plate number of 20 at the 9" theoretical plate. The tower 3 was operated at a reflux ratio of 10 and a tower top temperature of from 60 to 64 °C, with methanol/acetone mixture stream 17 being obtained as a tower top distillate, and an ethanol and n-propanol aqueous solution stream 18 being obtained from the kettle. The methanol/acetone mixture stream 17 was fed to an extractive rectifying tower 6 having a theoretical plate number of 20 at the 12% theoretical plate, and water 23 as solvent was co-fed at the 5" theoretical plate.
The tower 6 was operated at a weight ratio of the solvent to the stream 17 of 10, a reflux ratio of 9, and a tower top temperature of from 56 to 56.5 °C, with acetone 24 being obtained as a tower top distillate, and methanol/solvent mixture 25 being obtained from the kettle. The methanol/solvent mixture 25 was fed to a solvent recovering tower 7 having a theoretical plate number of 10 at the 5% theoretical plate. The tower 7 was operated at a reflux ratio of 6 and a tower top temperature of from 64.5 to 64.7°C, with methanol 28 being obtained as a tower top distillate, and recovered solvent 29 being obtained from the kettle. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 26.
Table 26 Analysis data (wt%) for the streams of individual towers acid amine “3 [os | 16 | 27 | 11 [ss [sso] 0 14 | os | 195 | 20 | 13a | 0 [24] o 5s | 0 | o | o | o os al o 17 | 3s | 665 | 0 | o | oo | 0 » | 0 | o | o | o | of} o 8 | 0 | o | sas | 4s | o [wo] ©
Te [oo | or | 0 | oo Jol | 0 » | 0 | 67 | o | o [0 Jes] 0 | 0 | o | o | o [ows] o | o2 a | 0 | o | o | o [oo] ol 10 2 | 0 | 9 | o | o [0 Joi} o 9 | 0 | o | o | o [oo Jw] o
Example 27
As shown in a part of the Figure 2, a stream 10 consisting of Fischer-Tropsch synthesis by-products in aqueous phase (comprising Swi% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 1 having a theoretical plate number of 60 at the 35™ theoretical plate. The tower 1 was operated at a reflux ratio of 1 and a tower top temperature of 40 °C. A side-cut 13 having a boiling range of from 50 to 120 °C was withdrawn from the 40™ theoretical plate, and fed to an acetic acid separation tower 2 having a theoretical plate number of 50 at the 30™ theoretical plate. The tower 2 was operated at a reflux ratio of 8 and a kettle temperature of from 104 to 108 °C, with an aqueous solution stream 14 containing alcohols . and ketones being obtained as a tower top distillate, and an acetic acid aqueous solution stream 15 being obtained from the kettle. The stream 14 was fed to an ethanol separation tower 3 having a theoretical plate number of 80 at the 50™ theoretical plate. The tower 3 was operated at a reflux ratio of 2 and a tower top temperature of from 60 to 64 °C, with methanol/acetone mixture stream 17 being obtained as a tower top distillate, and ethanol and n-propanol aqueous solution stream 18 being obtained from the kettle. The ethanol and n- propanol aqueous solution 18 was fed to a de-ethanolizing tower 8 having a theoretical plate number of 60 at the 40™ theoretical plate. The tower 8 was operated at a reflux ratio of 2 and . a tower top temperature of from 68 to 68.5 °C, with ethanol 26 being obtained as a tower top distillate, and n-propanol aqueous solution 27 being obtained from the kettle. The n-propanol aqueous solution 27 was fed to an azeotrope rectifying tower 9 having a theoretical plate : number of 60 at the 35T theoretical plate, and n-butyl acetate as an azeotrope forming agent was co-fed. In the tower 9, a weight ratio of the azeotrope forming agent to the n-propanol aqueous solution 27 was 0.2, and a kettle temperature was from 96.8 to 97.5 °C, with aqueous phase obtained in an tower top phase separator being withdrawn as a stream 30 and oil phase being refluxed, and n-propanol 31 being withdrawn from the kettle. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 27. :
Table 27 Analysis data (wt%) for the streams of individual towers acid amine acetate | 08 | te | 27 | 11 lss|ssol o | o 14 | 104 | 208 [351] 143 | 0 [194] 0 |} 0 5s] 0 | o [o o [os|ss[ o [ 0
17 [335] es | 0 [ o [ofo] o [| o
To To [oo [oo] ww 1s | 0 | o [sw] 20s |ofasal o | 0 0 | 0 | o | o| o [ofsms| o | 1 50] 0 | o | oes [ofos|] o | o
Example 28
As shown in a part of the Figure 2, a stream 10 consisting of Fischer-Tropsch synthesis by-products in aqueous phase (comprising Swt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 1 having a theoretical plate number of 15 at the 7" theoretical plate. The tower 1 was operated at a reflux ratio of 12 and a tower top temperature of 40 °C. A side-cut 13 having a boiling range of from 50 to 120 °C was withdrawn from the 8" theoretical plate, and fed to an acetic acid separation tower 2 having a theoretical plate number of 15 at the g™ theoretical plate. The tower 2 was operated at a reflux ratio of 8 and a kettle temperature of from 104 to 108 °C, with an aqueous solution stream 14 containing alcohols and ketones being obtained as a tower top distillate and an acetic acid aqueous solution stream 15 being obtained from the kettle. The stream 14 was fed to an ethanol separation tower 3 having a theoretical plate number of 20 at the 9™ theoretical plate. The tower 3 was operated at a reflux ratio of 10 and a tower top temperature of from 60 to 64 °C, with methanol/acetone : mixture stream 17 being obtained as a tower top distillate, and an ethanol and n-propanol oe aqueous solution stream 18 being obtained from the kettle. The methanol/acetone mixture stream 17 was fed to an extractive rectifying tower 6 having a theoretical plate number of 20 at the 12" theoretical plate, and water 23 as solvent was co-fed at the 5" theoretical plate.
The tower 6 was operated at a weight ratio of the solvent to the stream 17 of 10, a reflux ratio of 9, and a tower top temperature of from 56 to 56.5 °C, with acetone 24 being obtained as a tower top distillate, and methanol/solvent mixture 25 being obtained from the kettle. The ~ methanol/solvent mixture 25 was fed to a solvent recovering tower 7 having a theoretical N plate number of 10 at the 5™ theoretical plate. The tower 7 was operated at a reflux ratio of 6 and a tower top temperature of from 64.5 to 64.7°C, with methanol 28 being obtained as a tower top distillate, and recovered solvent 29 being obtained from the kettle. The stream 15 from the acetic acid separation tower 2 was fed to an acetic acid extraction tower 4 having a theoretical plate number of 10, and tert-butyl amine was co-fed as an extractant. The tower 4 was operated at a weight ratio of the extractant to the stream 15 of 5 and an operation temperature of 35 °C, with acetic acid/extractant mixture 19 being obtained from the tower top, and waste water 22 being obtained from the kettle. The acetic acid/extractant mixture 19 was fed to an extractant recovering tower 5 having a theoretical plate number of 10 at the 4™ theoretical plate, and the tower 5 was operated at a reflux ratio of 6 and a tower top temperature of from 115 to 118 °C, with acetic acid 20 being obtained as a tower top ~~ distillate, and recovered extractant 21 being obtained from the kettle. Upon the operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 28.
Table 28 Analysis data (wt%) for the streams of individual towers acid | amine 3 | os | 16 | 27 | 11 | ss [sso] o 14 | 08 | 195 | 20 | 134 | 0 oma] 0 is | o | o | o | o Jos |sal 0 6 | 0 | o | o | o Jo] ol] 10 7 | 35 | ees | o | oo | o | o | o » | 0 | 0 | o | o [oo [ww] o 8 | o | o [as | as | o Joo] © 9 | 0 | o | o | o [19] o | om
Tm [oo [oo los [ews] 0 © Ta [ws [or | 0 | o J olo} o | o | er | 0 | o [oo [esl 0 2 | 0 | o | o | o [ws oo | o a | o | o [oo [of 0 | wo 2 | 0 | wo | o | o [oo [or] o 2» | 0 | o | o | o [ofw] of
Example 29
As shown in a part of the Figure 2, a stream 10 consisting of Fischer-Tropsch synthesis by-products in aqueous phase (comprising SWt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 1 having a theoretical plate number of 60 at the 35 theoretical plate. The tower 1 was operated at a reflux ratio of 1 and a tower top temperature of 40 °C. A side-cut 13 having a boiling range of from 50 to 120 °C was withdrawn from the 40™ theoretical plate, and fed to an acetic acid separation tower 2 having a theoretical plate number of 50 at the 30™ theoretical plate. The tower 2 was operated at a reflux ratio of 8 and a kettle temperature of from 104 to 108 °C, with an aqueous solution stream 14 containing alcohols and ketones being obtained as a tower top distillate, and an acetic acid aqueous solution stream 15 being obtained from the kettle. The stream 14 was fed to an ethanol separation tower 3 having a theoretical plate number of 80 at the 50" theoretical plate. The tower 3 was operated at a reflux ratio of 2 and a tower top temperature of from 60 to 64 °C, with methanol/acetone mixture stream 17 being obtained as a tower top distillate, and ethanol and n-propanol aqueous solution stream 18 being obtained from the kettle. The ethanol and n- propanol aqueous solution 18 was fed to a de-ethanolizing tower 8 having a theoretical plate number of 60 at the 40" theoretical plate. The tower 8 was operated at a reflux ratio of 2 and a tower top temperature of from 68 to 68.5 °C, with ethanol 26 being obtained as a tower top distillate, and n-propanol aqueous solution 27 being obtained from the kettle. The n-propanol aqueous solution 27 was fed to an azeotrope rectifying tower 9 having a theoretical plate number of 60 at the 35 theoretical plate, and n-butyl acetate as an azeotrope forming agent was co-fed. In the tower 9, a weight ratio of the azeotrope forming agent to the n-propanol aqueous solution 27 was 0.2, and a kettle temperature was from 96.8 to 97.5 °C, with ‘aqueous phase obtained in an tower top phase separator being withdrawn as a stream 30 and oil phase being refluxed, and n-propanol 31 being withdrawn from the kettle. The acetic acid . aqueous solution stream 15 from the acetic acid separation tower 2 was fed to an acetic acid extraction tower 4 having a theoretical plate number of 40, and n-butyl amine was co-fed as an extractant. The tower 4 was operated at a weight ratio of the extractant to the stream 15 of 1 and an operation temperature of 35 °C, with acetic acid/extractant mixture 19 being obtained from the tower top, and waste water 22 being obtained from the kettle. The acetic © acid/extractant mixture 19 was fed to an extractant recovering tower 5 having a theoretical plate number of 50 at the 20™ theoretical plate, and the tower 5 was operated at a reflux ratio of 1 and a tower top temperature of from 115 to 118 °C, with acetic acid 20 being obtained as a tower top distillate, and recovered extractant 21 being obtained from the kettle. Upon the -
Co operation was stable, analysis data for the streams of individual towers were acquired. The results are shown in the Table 29.
Table 29 Analysis data (wt%) for the streams of individual towers acid amine acetate | os | 16 | 27 | 11 [ss [sso] o | 0 1a | 104] 208 [351 | 143 [0 [194] 0 | 0 5s | 0 | o | o | o [os[ss[ o | o 6 | 0 | o | o| o Jolofwm] o
17 [335 [es | 0 | o [ool o | o 18 | 0 | o [sw] 208 [0 [m2] o | 0 woo [ol o [oro se] 0 2 o | o [of o Tos|oes| o | o 26 | 0 | o [oso] o Jolso] ol o 27 | 0 | 0 | o [41 Jolsso]l o[ 0 | o | o | o| o Joslojoa] © 2 0 | o [oo] o [ololwo] o 0 | o | o | ol o [oles] ol] 17 si] o | o [ol ws Joos] o | o
Example 30
As shown in a part of the Figure 2, a stream 10 consisting of Fischer-Tropsch synthesis by-products in aqueous phase (comprising SWt% of a component having a boiling point of less than 50°C, 85wt% of a component having a boiling range of from 50 to 120°C, and 10wt% of a component having a boiling point of larger than 120°C) was fed to an ordinary rectifying tower 1 having a theoretical plate number of 60 at the 35" theoretical plate. The tower 1 was operated at a reflux ratio of 1 and a tower top temperature of 40 °C. A side-cut 13 having a boiling range of from 50 to 120 °C was withdrawn from the 40" theoretical plate, and fed to an acetic acid separation tower 2 having a theoretical plate number of 50 at the 30" theoretical plate. The tower 2 was operated at a reflux ratio of 8 and a kettle temperature of from 104 to 108 °C, with an aqueous solution stream 14 containing alcohols and ketones being obtained as a tower top distillate, and an acetic acid aqueous solution stream 15 being obtained from the kettle. The stream 14 was fed to an ethanol separation tower 3 having a theoretical plate number of 80 at the 50" theoretical plate. The tower 3 was operated at a reflux ratio of 2 and a tower top temperature of from 60 to 64 °C, with methanol/acetone mixture stream 17 being obtained as a tower top distillate, and ethanol and n-propanol aqueous solution stream 18 being obtained from the kettle. The methanol/acetone. mixture stream 17 was fed to extractive rectifying tower 6 having a theoretical plate number of 50 at the 20" theoretical plate, and monoethanolamine 23 as solvent was co-fed at the 3rd theoretical plate. The tower 6 was operated at a weight ratio of the solvent to the stream 17 of 2, a reflux ratio of 2, and a tower top temperature of from 56 to 56.5°C, with acetone 24 being obtained as a tower top distillate, and methanol/solvent mixture 25 being obtained from the kettle. The methanol/solvent mixture 25 was fed to solvent recovering tower 7 having a theoretical plate number of 50 at the 20™ theoretical plate. The tower 7 was operated at a reflux ratio of 1.5 and a tower top temperature of from 64.5 to 64.7 °C, with methanol 28 being obtained as a tower top distillate, and recovered solvent 29 being obtained from the kettle. The ethanol and n-propanol aqueous solution 18 from the ethanol separation tower 3 was fed to a de-ethanolizing tower 8 having a theoretical plate number of 60 at the 40" theoretical plate. The tower 8 was operated at a reflux ratio of 2 and a tower top temperature of from 68 to 68.5 °C, with ethanol 26 being obtained as a tower top distillate, and n- propanol aqueous solution 27 being obtained from the kettle. The n-propanol aqueous solution 27 was fed to an azeotrope rectifying tower 9 having a theoretical plate number of 60 at the 35" theoretical plate, and n-butyl acetate as an azeotrope forming agent was co-fed.
In the tower 9, a weight ratio of the azeotrope forming agent to the n-propanol aqueous solution 27 was 0.2, and a kettle temperature was from 96.8 to 97.5 °C, with aqueous phase obtained in an tower top phase separator being withdrawn as a stream 30 and oil phase being refluxed, and n-propanol 31 being withdrawn from the kettle. Upon the operation was: stable, analysis data for the streams of individual towers were acquired. The results are shown in the
Table 30.
Table 30 Analysis data (wt%) for the streams of individual towers ~ stream | acetone | methanol | ethanol | n-propanol | acetic | water | Monoethanol- n-butyl acid amine acetate 3 | 08 | 16 | 27 | 11 |ss|sso[ 0 | 0 14 | 104 | 208 [351 | 143 | 0 [194] 0 1 0 15 | 0 | o | o | o Josfoeos] 0 | 0 17 | 335 | 665 | 0 | 0 Jo [0] 0 | 0 3 | 0 | 0 | o | o [ool 10 | 0 8 | 0 | 0 [sto] 208 | oJ22] 0 | 0 24 | 99 | oi | o | 0 [oflof[ o | 0 | 0 | 251 | 0 | o | o [749] oo | © 26 | 0 | o [90] o [oso oo | 0 27 | 0 | 0 [| o | a1 [0 [559] 0 | 0 2% | 0 [99 [o [ o [o}of[ of | 0 9 0 | o | o | o To lo] 100 [| 0 3 | 0 | o | o | o [ofoe3] o | 17 31 | 0 | 0 | 0 | 95 [ofJos[ o [ 0
While the invention has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. Therefore, the invention is not limited to the particular embodiments disclosed as the best mode contemplated for carrying out this invention, but the invention will include all embodiments falling within the scope of the appended claims.
Claims (8)
1. A process for separating by-products in aqueous phase of a Fischer-Tropsch synthesis, comprising the steps of a) feeding the by-products in aqueous phase to an ordinary rectifying tower (1) at its middle portion, with a fraction stream I having a boiling range of from 50 to 120 °C being withdrawn as a side cut, light components having boiling points of less that 50°C being obtained from the tower top, and heavy components having boiling points of higher than 120°C being obtained from the kettle; b) feeding the stream I to an acetic acid separation tower (2) at its middle portion, with an alcohols and ketones-containing aqueous solution stream II having a boiling range of from 50 to 100°C being obtained from the tower top, and acetic acid aqueous solution stream III being obtained from the kettle; and ¢) feeding the stream II to an ethanol separation tower (3) at its middle portion, with a methanol and acetone mixture stream IV being obtained from the tower top, and an aqueous solution stream of ethanol and n-propanol V being obtained from the kettle.
2. The process of claim 1, wherein the ordinary rectifying tower (1) has a theoretical plate number of from 10 to 60, a reflux ratio of from 1 to 12, a tower top temperature of not less than 40°C, and a side-cut temperature of from 80 to 90 °C; the acetic acid separation tower (2) has a theoretical plate number of from 10 to 50, a reflux ratio of from 1 to 8, a kettle temperature of from 104 to 108 °C; and the ethanol separation tower (3) has a theoretical plate number of from 20 to 80, a reflux ratio of from 2 to 10, and a tower top temperature of from 60 to 64°C. oC
3. The process of claim 1 or 2, further comprising the steps of : d) feeding the stream III to an acetic acid extraction tower (4) at its top, with an acetic acid/extractant mixture stream VIII being obtained from the tower top, and waste water being obtained from the kettle, wherein the extractant is at least one selected from the group consisting of organic phosphines and organic amines; and e) feeding the stream VIII to an extractant recovering tower (5) at its middle portion, with acetic acid being removed as a tower top distillate, and recovered extractant being obtained from the kettle. .
: 4. The process of claim 3, wherein the acetic acid extraction tower (4) has a theoretical plate number of from 10 to 40 and is operated at normal temperature; the weight ratio of the : extractant to the stream III is in a range of from 1 to 6; the extractant recovering tower (5) has a theoretical plate number of from 10 to 50 and a reflux ratio of from 1 to 6, and is operated under atmospheric pressure or a reduced pressure, and its tower top temperature is set around the boiling point of acetic acid under the operation pressure, and preferably in a range of said boiling point + 1.0 °C.
5. The process of claim 3, wherein the extractant is at least one selected from the group consisting of tri(C1-C6-alkyl)phosphine oxides, tripheny] phosphine oxide, tert-butyl amine, n-butyl amine, and tert-amyl amine.
6. The process of any of claims 1 to 5, further comprises the steps of ~ f) feeding the stream IV to an extractive rectifying tower (6) at its middle portion, and feeding a polar solvent to the extractive rectifying tower (6) above its middle point, with : acetone being removed from the tower top, and a methanol/solvent mixture stream VI being removed from the kettle; and g) feeding the stream VI to a solvent recovering tower (7) at its middle portion, with methanol being removed from the tower top, and recovered solvent being obtained from the kettle. ’
7. The process of claim 6, wherein the extractive rectifying tower (6) has a theoretical plate number of from 20 to 50, a reflux ratio of from 2 to 9, and a tower top temperature of from 56 to 56.5°C; in the extractive rectifying tower (6), a weight ratio of the polar solvent to the stream IV is from 2 to 10; the polar solvent is at least one selected from water, ethylene glycol, N-formoyl morpholine, tetramethylene sulfone, and monoethanolamine; the solvent recovering tower (7) has a theoretical plate number of from 10 to 50, a reflux ratio of from'1 to 6, and a tower top temperature of 64.5 to 64.7°C. .
8. The process of any of claims 1 to 7, further comprises the steps of h) feeding the stream V to a de-ethanolizing tower (8) at its middle portion, with ethanol being removed from the tower top, and a n-propanol aqueous solution stream VII being obtained from the kettle; and i) feeding the stream VII to an azeotrope rectifying tower (9) at its middle portion, and cofeeding an azeotrope forming agent, with the aqueous phase obtained in a phase separator at the tower top being withdrawn, the oil phase obtained in the phase separator being refluxed, and n-propanol being removed from the kettle, wherein the azeotrope forming agent is at least one which forms a lower boiling point azeotrope with water.
9. The process of claim 8, wherein the de-ethanolizing tower (8) has a theoretical plate number of from 10 to 60, a reflux ratio of from 1 to 8, and a tower top temperature of 68 to
68.5°C; the azeotrope rectifying tower (9) has a theoretical plate number of from 15 to 60, a weight ratio of the azeotrope forming agent to the stream VII of from 0.2 to 1, and a kettle temperature of 96.8 to 97.5°C; and the azeotrope forming agent is selected from the group consisting of cyclohexane, benzene, toluene, isopropyl acetate, n-butyl acetate and mixture thereof. :
10. A process for separating Fischer-Tropsch synthesis by-products in aqueous phase, comprising the steps of a) feeding the by-products in aqueous phase to an ordinary rectifying tower (201) at its middle portion, with a fraction stream I having a boiling range of from 50 to 120°C being withdrawn as a side cut, light components having boiling points of less that 50°C being obtained from the tower top, and heavy components having boiling points of higher than 120°C being obtained from the kettle; and _ b) feeding the stream I to one side of a divided tower (202) at its middle portion, with a methanol/acetone mixture stream II being removed as a tower top distillate, an acetic acid : aqueous solution stream III being removed from the kettle, ethanol as a side cut being ~ withdrawn from the upper portion of the opposite side, and a n-propanol aqueous solution stream IV as a side cut being withdrawn from the lower portion of the opposite side.
11. The process of claim 10, wherein the ordinary rectifying tower (201) has a theoretical plate number of from 10 to 60, a reflux ratio of from 1 to 12, and a tower top temperature of not less than 40°C; the divided tower (202) has a theoretical plate number of from 50 to 200, wherein the upper section accounts for 1/6 to 1/3 of the theoretical plate - number, the lower section accounts for 1/6 to 1/3 of the theoretical plate number, feeding side liquid phase in the upper section has a distribution factor of from 0.3 to 0.7, feeding side gas phase in the lower section has a distribution factor of from 0.3 to 0.7; and the divided tower (202) has a reflux ratio of from 5 to 30, a tower top temperature of 60 to 64°C, an upper side- cut temperature of 68 to 68.5°C, and a lower side-cut temperature of 87 to 93°C.
12. The process of claim 10 or 11, further comprises the steps of ¢) feeding the stream IV to an azeotrope rectifying tower (203) at its middle portion, and co-feeding an azeotrope forming agent, with an aqueous phase obtained in a tower top phase separator being withdrawn and an oil phase being refluxed, and with n-propanol being withdrawn from the kettle, wherein the azeotrope forming agent is at least one which forms a lower boiling point azeotrope with water.
13. The process of claim 12, wherein the azeotrope rectifying tower (203) has a theoretical plate number of from 15 to 60, a weight ratio of the azeotrope forming agent to the stream IV of from 0.2 to 1, and a kettle temperature of 96.8 to 97.5°C; and wherein the azeotrope forming agent is at least one selected from cyclohexane, benzene, toluene, isopropyl acetate and n-butyl acetate.
14. The process of any of claims 10 to 13, further comprises the steps of d) feeding the stream III to the tower top of an acetic acid extraction tower (204), and an extractant to the tower bottom, with a mixture stream V of acetic acid and the extractant being withdrawn from the tower top, and waste water being withdrawn from the kettle, wherein the extractant is at least one selected from the group consisting of organic phosphines and organic amines; and e) feeding the stream V to an extractant recovering tower (205) at its middle portion, with acetic acid being withdrawn as a tower top distillate, and recovered extractant being obtained from the kettle.
15. The process of claim 14, wherein the acetic acid extraction tower (204) has a theoretical plate number of from 10 to 40 and a weight ratio of the extractant to the stream III of from 1 to 6, and is operated at normal temperature; the extractant recovering tower (205) : has a theoretical plate number of from 10 to 50 and a reflux ratio of from 1 to 6, and is operated under atmospheric pressure or a reduced pressure; and the extractant is at least one selected from the group consisting of tri(C1-C6-alkyl)phosphine oxides, triphenyl phosphine : oxide, tert-butyl amine, n-butyl amine, and tert-amyl amine.
16. The process of any of claims 10 to 15, further comprises the steps of f) feeding the stream II to an extractive rectifying tower (206) at its middle portion, and co-feeding a polar solvent to the tower (206) at its upper portion, with acetone being withdrawn as a tower top distillate, and a mixture stream VI of methanol and solvent being obtained from the kettle; and oo g) feeding the stream VI to a solvent recovering tower (207) at its middle portion, with methanol being withdrawn as a tower top distillate, and recovered solvent being obtained from the kettle.
17. The process of claim 16, wherein the extractive rectifying tower (206) has a : theoretical plate number of from 20 to 50, a weight ratio of the polar solvent to the stream II of from 2 to 10, a reflux ratio of from 2 to 9, and a tower top temperature of 56 to 56.5°C; the polar solvent is at least one selected from the group consisting of water, ethylene glycol, N- formoyl morpholine, tetramethylene sulfone, and monoethanolamine; and the solvent recovering tower (207) has a theoretical plate number of from 10 to 50, a reflux ratio of from 1 to 6, rma tower top temperature of 64.5 to 64.7°C.
8. The process of claim 1, substantially as herein described. DA \ S| 23%° DAY OF JANUARY 2009 i SPOOR|& FISHER APPLICANTS PATENT ATTORNEYS
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100329278A CN101492332B (en) | 2008-01-23 | 2008-01-23 | Process for the separation of aqueous phase by-product of fischer-tropsch synthesis reaction |
| CN2008100329263A CN101492360B (en) | 2008-01-23 | 2008-01-23 | Process for the separation of aqueous phase by-product of fischer-tropsch synthesis reaction |
| CN2008100432531A CN101555194B (en) | 2008-04-11 | 2008-04-11 | Method for separating aqueous phase byproduct from Fischer-Tropsch synthesis reaction |
| CN2008100432527A CN101555193B (en) | 2008-04-11 | 2008-04-11 | Separating method of aqueous phase byproduct from Fischer-Tropsch synthesis |
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| JP4499557B2 (en) * | 2002-06-18 | 2010-07-07 | サソール テクノロジー（プロプライエタリー）リミテッド | Fischer-Tropsch derived water purification method |
| CN1297523C (en) * | 2005-04-01 | 2007-01-31 | 上海兖矿能源科技研发有限公司 | Method for treating water reacted from Fischer-Tropsch synthesis |
| CN100395315C (en) * | 2005-04-29 | 2008-06-18 | 中国石油化工股份有限公司 | Hydrogenation purifying combined process for Fischer-Tropsch synthetic substance |
| CN100523132C (en) * | 2007-06-13 | 2009-08-05 | 中国石油天然气集团公司 | Method for carrying Fischer-Tropsch synthesis by using fixed bed device |
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