CN1272408C - Composite solvent in use for extracting, rectifying and separating arene and method of application - Google Patents
Composite solvent in use for extracting, rectifying and separating arene and method of application Download PDFInfo
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- CN1272408C CN1272408C CN 200410004476 CN200410004476A CN1272408C CN 1272408 C CN1272408 C CN 1272408C CN 200410004476 CN200410004476 CN 200410004476 CN 200410004476 A CN200410004476 A CN 200410004476A CN 1272408 C CN1272408 C CN 1272408C
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- aromatic hydrocarbons
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- 239000002904 solvent Substances 0.000 title claims abstract description 117
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims description 35
- 239000002131 composite material Substances 0.000 title abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000011084 recovery Methods 0.000 claims abstract description 26
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- -1 sulfone compound Chemical class 0.000 claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000000895 extractive distillation Methods 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 16
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 15
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical group C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 8
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 8
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- ZAYITQDIKSBHDD-UHFFFAOYSA-N benzene methane Chemical compound C.C1=CC=CC=C1.C1=CC=CC=C1 ZAYITQDIKSBHDD-UHFFFAOYSA-N 0.000 claims description 6
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 6
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 claims description 5
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 150000003457 sulfones Chemical class 0.000 claims description 5
- RJTJVVYSTUQWNI-UHFFFAOYSA-N 2-ethylnaphthalene Chemical compound C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 claims description 4
- 241000282326 Felis catus Species 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- KQVDKQHGEHIKIE-UHFFFAOYSA-N methane 1,2-xylene Chemical group C.C=1(C(=CC=CC1)C)C KQVDKQHGEHIKIE-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 12
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000006184 cosolvent Substances 0.000 abstract 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000000605 extraction Methods 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- TZZQGQMZDLEJFR-UHFFFAOYSA-N 1-ethylnaphthalene;2-ethylnaphthalene Chemical compound C1=CC=CC2=CC(CC)=CC=C21.C1=CC=C2C(CC)=CC=CC2=C1 TZZQGQMZDLEJFR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000003797 solvolysis reaction Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a composite solvent for extracting, rectifying and separating arene. The present invention comprises 68 to 98.8 wt% of prime solvent, 1 to 30 wt% of cosolvent and 0.2 to 2.0 wt% of water, wherein the prime solvent is selected from a sulfone compound, a glycerol compound, N-formylmorpholine or N-methyl pyrrolidone; the cosolvent is selected from hydrocarbon provided with two benzene rings, and the two benzene rings are mutually connected to form a condensed ring and can be connected by single chemical bond. The composite solvent has the advantages of wide application range, high purity mixing arene recovery from raw materials with low arene content, high arene yield, less cosolvent loss and low energy consumption.
Description
Technical field
The present invention is used double solvents and a using method of a kind of extracting rectifying aromatics separation, specifically, is that a kind of extracting rectifying that utilizes reclaims used double solvents of high purity aromatic hydrocarbons and using method from hydrocarbon mixture.
Background technology
At present, the method for aromatics separation mainly contains liquid liquid extraction process and extraction fractional distillation from hydrocarbon mixtures such as catalytic reforming gasoline or cracking hydrogenated gasoline.Liquid liquid extraction process is most widely used mainly contains with the glycols and is the Udex, Tetra technology of solvent and is the Sulfolane method of solvent with the tetramethylene sulfone.The extracting of liquid liquid can obtain high purity BTX product with higher yields.Extracting rectifying is to utilize solvent method of aromatics separation to the difference of each component relative volatility of hydro carbons influence and from hydrocarbon mixture.Comparatively speaking, extracting rectifying is suitable for handling high aroamtic hydrocarbon raw material, and solvent for use is generally simple N-formyl morpholine, N-Methyl pyrrolidone, tetramethylene sulfone etc.
US5310480 has proposed a kind of technology of extracting rectifying aromatics separation.Characteristics are only with an extraction distillation column and a cyclonic separator that contains reboiler the aromatic hydrocarbons in the raw material to be separated with non-aromatics, adopt water-containing solvent, and the solvent recuperation process is by means of the water vapour stripping.The solvent that this method is selected is aqueous sulfone class, glycol, glycol ethers etc.Though this method flow process is simpler relatively, owing to be subjected to the deliquescent restriction of water-containing solvent, implement to show when adopting reasonable solvent ratio, easily in two liquid phases of extractive distillation column top formation, not only influence operation control, and can the remarkable rate of recovery that reduces aromatic hydrocarbons.
US2003/0042125A1 discloses a kind of method of mixed extractant solvent rectifying and separating aromatic hydrocarbons, described mixed solvent is made of main solvent tetramethylene sulfone and at least a solubility promoter, solubility promoter comprises 3-methyl sulfolane, N-N-methyl-2-2-pyrrolidone N-, methyl phenyl ketone, the happy ketone of different fluorine and morpholine, and solubility promoter is 0.1: 1～20: 1 with the ratio of the content of main solvent.Therefore the effect that this kind mixed solvent improves the relative volatility of normal heptane/benzene significantly is better than each simple solvent, helps separating of aromatic hydrocarbons and non-aromatics.But owing to after the mixing of dissimilar organic solvents,, there is the problem of thermochemistry instability, the aggravation of solvent deterioration, even influences normal running in system, circulating under the comparatively high temps.
CN1393507A has proposed a kind of method of extractive distillation aromatics separation and the double solvents of use, and double solvents comprises main solvent and solubility promoter, also has properties-correcting agent.Described solubility promoter is selected from C
8～C
11When any one in the aromatic hydrocarbons or two kinds of mixtures with different carbon number aromatic hydrocarbons, this double solvents are used for extractive distillation recovery aromatic hydrocarbons, can significantly relax the solvent recuperation operational condition, improve aromatic recovery rate, and can make the aromatic hydrocarbons that obtains be neutral.But the selectivity of this solubility promoter itself is still not ideal enough, and boiling point is on the low side, is generally 140～200 ℃, is being used for C
6～C
7Waste during cut extractive distillation aromatics separation is bigger, and is inapplicable than the extractive distillation of wide fraction to boiling spread.
Existing extraction rectification technique has certain requirement to aromaticity content in the raw material, generally can not be lower than 50 quality %, otherwise two liquid phases are easily formed at extractive distillation column top, and plate efficiency seriously descends, and operates restive.Use single selective solvent in extraction rectification technique, in the solvent recuperation process, owing to be subjected to the restriction of solvent thermal decomposition temperature, be difficult to solvent is thoroughly separated with aromatic hydrocarbons, aromatic recovery rate can not be very high.In addition, because the solvolysis that the local superheating that produces in operating process causes causes aromatic hydrocarbons to pollute, the purity of aromatic hydrocarbons is affected.
Summary of the invention
The purpose of this invention is to provide a kind of extracting rectifying aromatics separation used double solvents and using method, described double solvents has higher solvability and selectivity, and in use be easy to regulation and control, under maintenance high aromatics yield and quality, can reduce the material consumption and the energy consumption of extracting rectifying operation.
The used double solvents of extracting rectifying aromatics separation provided by the invention comprises the main solvent of 68～98.8 quality %, the solubility promoter of 1～30 quality % and the water of 0.2～2.0 quality %; described main solvent is selected from sulfone compound, glycols compound, N-formyl morpholine or N-Methyl pyrrolidone; solubility promoter is selected from the hydrocarbon compound with two phenyl ring; two phenyl ring can be interconnected to form condensed ring, also can link to each other by single chemical bond.
The present invention adds the compound that contains two phenyl ring on a small quantity in the extracting rectifying selective solvent of routine be solubility promoter, significantly strengthened the dissolving power of solvent to aromatic hydrocarbons, therefore, can handle boiling spread broad, raw material that aromaticity content is lower.Compare with the extracting rectifying that carries out with single solvent, double solvents provided by the invention can reduce solvent load, improves aromatic recovery rate.
Description of drawings
Fig. 1 carries out the schematic flow sheet of extracting rectifying for the present invention uses double solvents.
Embodiment
Double solvents provided by the invention comprises main solvent, solubility promoter and water.Main solvent occupies the majority in double solvents, and the main character of decision double solvents contains less water and can make the choice of Solvent raising in the main solvent.Solubility promoter is the key ingredient in the mixed solvent, make double solvents have some special nature, as strengthening solvability to aromatic hydrocarbons and non-aromatics, reduce extracting rectifying vapour-liquid phase interface tension force, improve mass-transfer performance etc., thereby improve extraction rectification technique effectively, improve the aromatic hydrocarbons quality, improve aromatics yield.
Main solvent sulfone compound, glycols compound, N-formyl morpholine or N-Methyl pyrrolidone in the double solvents of the present invention, wherein sulfone compound is selected from tetramethylene sulfone, 3-methyl sulfolane, dimethyl sulfone or di sulfone, preferred tetramethylene sulfone; The glycols compound is selected from triglycol or Tetraglycol 99.
Described solubility promoter is the hydrocarbon compound with two phenyl ring, and two phenyl ring can be interconnected to form condensed ring, as naphthalene or alkylnaphthalene; Two phenyl ring also can link to each other by single chemical bond, as biphenyl, ditan, diphenylethane or dialkyl benzene methane.Alkyl in the alkyl of alkylnaphthalene and the dialkyl benzene methane is the alkyl of preferred C1～C3 respectively.Preferred solubility promoter is 1-methylnaphthalene, 2-methylnaphthalene, 1-ethylnaphthalene, 2-ethylnaphthalene, biphenyl, ditan or diphenylethane.
Preferred 5～20 quality % of the content of solubility promoter in the double solvents, preferred 78～98.8 quality % of main solvent content.The water that also contains 0.2～2.0 quality % in the double solvents of the present invention, the water of trace has obviously strengthened the selectivity of mixed solvent, thereby extracting rectifying is separable goes out highly purified benzene, toluene and dimethylbenzene.
Use double solvents of the present invention to carry out the method for extracting rectifying aromatics separation, comprise the steps:
(1) will contain the C of aromatic hydrocarbons
6～C
8Hydrocarbon mixture is introduced the middle part of extractive distillation column; contact with the double solvents of introducing from extractive distillation column top and to carry out extracting rectifying; the rich solvent that is rich in aromatic hydrocarbons of discharging at the bottom of the extracting rectifying Tata is introduced solvent recovery tower from the middle part; overhead stream obtains non-aromatics and water through separation; non-aromatics is discharged system; described double solvents comprises the main solvent of 68～98.8 quality %; the water of the solubility promoter of 1～30 quality % and 0.2～2.0 quality %; described main solvent is selected from tetramethylene sulfone; the 3-methyl sulfolane; dimethyl sulfone; the di sulfone; triglycol; Tetraglycol 99; N-formyl morpholine or N-Methyl pyrrolidone; preferred tetramethylene sulfone; solubility promoter is selected from the hydrocarbon compound with two phenyl ring; two phenyl ring can be interconnected to form condensed ring; also can link to each other by single chemical bond; preferred 1-methylnaphthalene; the 2-methylnaphthalene; 1-ethylnaphthalene; 2-ethylnaphthalene; biphenyl; ditan or diphenylethane
(2) described rich solvent of (1) step is separated in solvent recovery tower, aromatic hydrocarbons and water are isolated in the logistics that cat head is discharged after condensation, aromatic hydrocarbons is discharged system, and the lean solvent that obtains at the bottom of the recovery tower returns extractive distillation column and recycles.The content of solubility promoter is 5～20 quality % in the double solvents, and main solvent content is 78～98.8 quality %.
Above-mentioned steps (1) is in the step, and the suitable theoretical plate number of extractive distillation column is 30～65, and double solvents is gone into 90～125 ℃ of tower temperature, 140～175 ℃ of column bottom temperatures, pressure tower 0.10～0.3MPa, and solvent ratio 2.8～5.0, reflux ratio are 0.2～1.0.To introduce the recovery tower bottom as water stripping from the isolated water in extracting rectifying top.
(2) the suitable theoretical plate number of solvent recovery tower is 8～28 in the step, tower top pressure 0.035～0.05MPa, and reflux ratio is 0.4～1.0, and tower top temperature is 50～80 ℃, and column bottom temperature is 160～185 ℃.The water that cat head is told is introduced the recovery tower bottom as water stripping.In this step, by the amount of water stripping in the control solvent recuperation process, the service temperature of tower and pressure are controlled the water-content in the double solvents.
Double solvents provided by the invention is applicable to that extracting rectifying reclaims aromatic hydrocarbons from the lower raw material of aromaticity content.Raw material C
6～C
8The content of aromatic hydrocarbons is 30～98 quality % in the hydrocarbon mixture.Suitable raw material with double solvents extracting rectifying aromatics separation of the present invention is catalytic reforming gasoline and cracking hydrogenated gasoline.
Further specify the present invention below in conjunction with accompanying drawing.Among Fig. 1, the raw material that is rich in aromatic hydrocarbons enters interchanger 101 by pipeline 1, enters extractive distillation column 102 by pipeline 4 after the heat exchange, and double solvents enters extractive distillation column 102 through pipeline 15 from top.Through extracting rectifying, non-aromatics steam enters return tank 103 by pipeline 5 after condensation, and the non-aromatics product is through pipeline 6 carrying devices behind the standing demix, and less water flows into solvent recovery tower 104 bottoms through pipeline 8.The rich solvent that is rich in aromatic hydrocarbons at the bottom of the extracting rectifying Tata enters solvent recovery tower 104 through pipeline 7, after the distillation of water vapor decompression stripping, aromatic hydrocarbons and water enter return tank 105 standing separation by pipeline 9 after condensation, aromatic hydrocarbons is by pipeline 10 carrying devices, the water of telling enters interchanger 106 heat exchange through pipeline 11 earlier as the stripping medium, enters solvent recovery tower 104 bottoms through pipeline 12 again.Obtain lean solvent at the bottom of the recovery tower and enter interchanger 106 and water stripping heat exchange, enter interchanger 101 and raw material heat exchange by pipeline 14 again, enter the recycle of extracting rectifying top of tower by pipeline 15 at last by pipeline 13.
Further specify the present invention below by example, but the present invention is not limited only to this.
Example 1
With reformation de-pentane oil C6～C7 fraction is raw material, and its composition is listed in table 1.Carry out extracting rectifying and separating benzene and toluene by flow process shown in Figure 1, the selective solvent of use is a double solvents of the present invention, wherein contains the tetramethylene sulfone of 84 quality %, the 1-methylnaphthalene of 15 quality % and the water of 1.0 quality %.The operational condition of extracting rectifying, solvent recovery tower sees Table 2, and separating resulting sees Table 3.
Example 2
Carry out the operation of extracting rectifying and separating benzene and toluene by the method for example 1, different is that used double solvents is the tetramethylene sulfone of 84 quality %, the ditan of 15 quality % and the water of 1.0 quality %.The operational condition of extracting rectifying, solvent recovery tower sees Table 2, and separating resulting sees Table 3.
Comparative Examples
Carry out extracting rectifying and separating benzene and toluene by the method with CN1393507A, use raw material with example 1, the double solvents of use is the tetramethylene sulfone of 84 quality %, the C9 aromatic hydrocarbons of 14 quality % and the properties-correcting agent N-formyl morpholine of 2.0 quality %.The operational condition of extracting rectifying, solvent recovery tower sees Table 2, and separating resulting sees Table 3.
As shown in Table 3, the present invention compares with the extraction rectification technique of the CN1393507A that uses double solvents, lower in solvent ratio, each tower operating parameters is comparatively under the demulcent condition, the aromatic hydrocarbon product yield is further improved, reach 99.85～99.91%, also make the purity of aromatic hydrocarbon product bring up to 99.98% by 99.80%.In addition, the inventive method is separated in the BTX aromatics and non-aromatic component that obtains, and the content of solubility promoter significantly reduces than Comparative Examples, illustrates that the hydrotropy dosage that loses in the sepn process reduces greatly.
Table 1
| Component | Content, quality % |
| Alkane C 5 C 6 C 7 C 8 | 1.00 11.45 9.94 5.00 |
| Naphthenic hydrocarbon C 5 C 6 C 7 C 8 | 0.51 1.20 1.27 0.83 |
| Aromatic hydrocarbons C 6 C 7 C 8 | 19.80 46.20 2.80 |
| Amount to | 100.00 |
Table 2
| Project | Example 1 | Example 2 | Comparative Examples | |||
| Extractive distillation column | Solvent recovery tower | Extractive distillation column | Solvent recovery tower | Extractive distillation column | Solvent recovery tower | |
| Number of theoretical plate solvent (quality) is gone into the tower temperature than solvent, ℃ trim the top of column (quality) is than cat head working pressure, the MPa tower top temperature, ℃ water stripping (quality) is than column bottom temperature, ℃ | 40 3.2 110 0.4 0.15 101 - 163 | 16 - - 0.6 0.045 65 0.015 172 | 40 3.2 110 0.4 0.15 101 - 164 | 16 - - 0.6 0.045 65 0.015 173 | 40 4.0 110 0.4 0.15 103 - 175 | 16 - - 1.0 0.045 75 - 179 |
Table 3
| Project | Example 1 | Example 2 | Comparative Examples |
| BTX aromatics purity, % is non-aromatic, the ppm solubility promoter, the ppm yield, quality % | 99.98 200 10 99.91 | 99.98 180 2 99.85 | 99.80 1900 95 99.13 |
| The non-aromatics solubility promoter, ppm aromatic hydrocarbons, quality % | 25 0.19 | 10 0.32 | 120 1.87 |
Claims (11)
1, the used double solvents of a kind of extracting rectifying aromatics separation; comprise the main solvent of 68～98.8 quality %, the solubility promoter of 1～30 quality % and the water of 0.2～2.0 quality %; described main solvent is selected from sulfone compound, glycols compound, N-formyl morpholine or N-Methyl pyrrolidone; solubility promoter is selected from the hydrocarbon compound with two phenyl ring, and two phenyl ring are interconnected to form condensed ring or continuous by single chemical bond.
2, according to the described double solvents of claim 1, the content that it is characterized in that solubility promoter in the double solvents is 5～20 quality %, and main solvent content is 78～98.8 quality %.
3, according to claim 1 or 2 described double solventss, it is characterized in that sulfone compound is selected from tetramethylene sulfone, 3-methyl sulfolane, dimethyl sulfone or di sulfone in the described main solvent, the glycols compound is selected from triglycol or Tetraglycol 99, and solubility promoter is selected from alkylnaphthalene, biphenyl, ditan, diphenylethane or dialkyl benzene methane.
4, according to claim 1 or 2 described double solventss, it is characterized in that described main solvent is selected from tetramethylene sulfone, the alkyl in the alkyl of solubility promoter alkylnaphthalene and the dialkyl benzene methane is selected from the alkyl of C1～C3 respectively.
5, according to claim 1 or 2 described double solventss, it is characterized in that described alkylnaphthalene is selected from 1-methylnaphthalene, 2-methylnaphthalene, 1-ethylnaphthalene or 2-ethylnaphthalene, dialkyl benzene methane is selected from dimethyl benzene methane.
6, a kind of method of extracting rectifying aromatics separation comprises the steps:
(1) will contain the C of aromatic hydrocarbons
6～C
8Hydrocarbon mixture is introduced the middle part of extractive distillation column; contact with the double solvents of introducing from extractive distillation column top and to carry out extracting rectifying; the rich solvent that is rich in aromatic hydrocarbons of discharging at the bottom of the extracting rectifying Tata is introduced solvent recovery tower from the middle part; overhead stream obtains non-aromatics and water through separation; non-aromatics is discharged system; described double solvents comprises the main solvent of 68～98.8 quality %; the water of the solubility promoter of 1～30 quality % and 0.2～2.0 quality %; described main solvent is selected from tetramethylene sulfone; the 3-methyl sulfolane; dimethyl sulfone; the di sulfone; triglycol; Tetraglycol 99; N-formyl morpholine or N-Methyl pyrrolidone; solubility promoter is selected from the hydrocarbon compound with two phenyl ring; two phenyl ring are interconnected to form condensed ring or continuous by single chemical bond
(2) described rich solvent of (1) step is separated in solvent recovery tower, aromatic hydrocarbons and water are isolated in the logistics that cat head is discharged after condensation, aromatic hydrocarbons is discharged system, and the lean solvent that obtains at the bottom of the recovery tower returns extractive distillation column and recycles.
7, in accordance with the method for claim 6, the content that it is characterized in that solubility promoter in the double solvents is 5～20 quality %, and main solvent content is 78～98.8 quality %.
8, in accordance with the method for claim 6, it is characterized in that described main solvent is selected from tetramethylene sulfone, solubility promoter is selected from alkylnaphthalene, biphenyl, ditan, diphenylethane or dialkyl benzene methane.
9, in accordance with the method for claim 6, the theoretical plate number that it is characterized in that extractive distillation column in (1) step is 30～65, and double solvents is gone into 90～125 ℃ of tower temperature, 140～175 ℃ of column bottom temperatures, pressure tower 0.10～0.3MPa, solvent ratio 2.8～5.0, reflux ratio are 0.2～1.0.
10, in accordance with the method for claim 6, it is characterized in that the theoretical plate number of solvent recovery tower in (2) step is 8～28, tower top pressure 0.035～0.05MPa, reflux ratio is 0.4～1.0, and tower top temperature is 50～80 ℃, and column bottom temperature is 160～185 ℃.
11, in accordance with the method for claim 6, it is characterized in that described C
6～C
8The content of aromatic hydrocarbons is 30～98 quality % in the hydrocarbon mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410004476 CN1272408C (en) | 2004-02-27 | 2004-02-27 | Composite solvent in use for extracting, rectifying and separating arene and method of application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410004476 CN1272408C (en) | 2004-02-27 | 2004-02-27 | Composite solvent in use for extracting, rectifying and separating arene and method of application |
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| CN1272408C true CN1272408C (en) | 2006-08-30 |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101468938B (en) * | 2007-12-28 | 2012-09-05 | 中国石油化工股份有限公司 | Composite solvent for extracting, distilling and separating styrene in hydrocarbons mixture, and method therefor |
| CN101759520B (en) * | 2008-12-25 | 2012-12-12 | 中国石油化工股份有限公司 | Method for extracting, rectifying and separating phenylethylene from hydrocarbon mixture |
| CN101531921B (en) * | 2009-04-09 | 2012-08-29 | 吉林大学 | Complex solvent for extracting and separating aromatic hydrocarbon in gasoline or hydrocarbon mixture |
| CN101875592B (en) * | 2009-04-30 | 2013-07-31 | 中国石油化工股份有限公司 | Regeneration method of extracting solvent for extracting, rectifying and separating styrene |
| CN103160310A (en) * | 2013-03-15 | 2013-06-19 | 西南石油大学 | Composite solvent and extraction method for extracting and separating aromatic hydrocarbons |
| CN104031674A (en) * | 2014-06-20 | 2014-09-10 | 西南石油大学 | Composite solvent for extracting and separating aromatics in low-aromatic naphtha |
| CN104926605A (en) * | 2015-05-21 | 2015-09-23 | 济南大学 | Benzene-propanol azeotrope rectification separation method based on choline chloride further-co-melting solvent |
| CN105219422B (en) * | 2015-10-30 | 2017-05-03 | 西北大学 | Composite extracting agent suitable for coal-based naphtha and method for preparing solvent naphtha |
| CN110105159A (en) | 2018-02-01 | 2019-08-09 | 中国石油化工股份有限公司 | The method of separation of extractive distillation aromatic hydrocarbons |
| CN108558604B (en) * | 2018-02-28 | 2021-09-03 | 中国天辰工程有限公司 | Method and device for separating cyclohexanol and n-hexanol by extractive distillation |
| CN110357760A (en) * | 2019-07-31 | 2019-10-22 | 黄河三角洲京博化工研究院有限公司 | A kind of technique of extraction rectifying method production high-purity mixed xylenes |
| CN111072173A (en) * | 2019-12-30 | 2020-04-28 | 江苏盈天化学有限公司 | Biphenyl thermal extraction sewage treatment process |
| CN112920162A (en) * | 2021-01-29 | 2021-06-08 | 临涣焦化股份有限公司 | Solvent regenerating unit |
| CN115992014B (en) * | 2021-10-19 | 2024-05-17 | 中国石油化工股份有限公司 | Method for producing light white oil and increasing BTX yield |
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