CN114195613A - Indene extractive distillation purification method - Google Patents
Indene extractive distillation purification method Download PDFInfo
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- CN114195613A CN114195613A CN202010985208.9A CN202010985208A CN114195613A CN 114195613 A CN114195613 A CN 114195613A CN 202010985208 A CN202010985208 A CN 202010985208A CN 114195613 A CN114195613 A CN 114195613A
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- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 title claims abstract description 187
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000000895 extractive distillation Methods 0.000 title claims abstract description 31
- 238000000746 purification Methods 0.000 title claims abstract description 26
- 238000004821 distillation Methods 0.000 claims abstract description 52
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000605 extraction Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 238000005554 pickling Methods 0.000 claims description 22
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 10
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000011282 acid tar Substances 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000000295 fuel oil Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 21
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 14
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 12
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 12
- 239000012535 impurity Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- FWVOXSHLAYHOJS-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2CC=CC2=C1 FWVOXSHLAYHOJS-UHFFFAOYSA-N 0.000 description 1
- PJEKFSKIOOHJNR-UHFFFAOYSA-N 1h-indene;styrene Chemical compound C=CC1=CC=CC=C1.C1=CC=C2CC=CC2=C1 PJEKFSKIOOHJNR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 230000000798 anti-retroviral effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
- C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
- C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
- C07C7/08—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by extractive distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/14833—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds
- C07C7/1485—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds oxides; hydroxides; salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/17—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with acids or sulfur oxides
- C07C7/171—Sulfuric acid or oleum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides an indene extractive distillation purification method, which comprises the steps of primary distillation, acid washing and decoloration to obtain an indene-containing polymerized oil raw material. Secondly, distilling to remove various benzene substances in the polymerization oil raw material. Thirdly, adding an extracting agent N-methyl pyrrolidone NMP for extraction and rectification. Fourthly, the extractant is separated by distillation and can be recycled according to the situation. The invention improves the production process of indene from the product purification angle, obtains high-purity indene with high purity of more than 97 percent, meets the market demand and improves the application range of indene.
Description
Technical Field
The invention relates to an indene purification method, in particular to a method for purifying high-purity indene from heavy benzene, and specifically relates to a method for purifying high-purity indene from heavy benzene produced in a benzene hydrogenation device by using extractive distillation.
Background
INDENE (INDENE) molecular formula C9H8Molecular weight 116.1589, CAS number: 95-13-6, EINECS No.: 202-393-6, which belongs to aromatic hydrocarbon, and is colorless transparent oily liquid at normal temperature. Indene is an important basic organic chemical raw material and an organic chemical solvent, indene with low purity can be used for producing coumarone-indene resin and styrene-indene resin, and indene with high purity can be used for manufacturing high-end coating solvents and high-end optical resins, changing the surface property of polymers and being an antiretroviral medical intermediate.
Extractive distillation refers to the distillation separation of a feed stream by adding a third component, commonly referred to as an extractant, to the feed stream to alter the relative volatility of the original component. The main advantages of extractive distillation include relatively simple device, convenient operation, greatly reduced energy consumption, large throughput, etc.
In the prior art, the production process of high-purity indene mainly comprises a freezing crystallization purification method and a physical negative pressure rectification purification method, and patent CN 105967971A discloses a freezing crystallization purification method for cracking nonaindene carbonate, which comprises the following steps: taking a certain amount of indene enrichment liquid, and putting the indene enrichment liquid into a crystallizer; opening a constant-temperature water bath, cooling the material in the crystallizer by adopting refrigerating fluid to-20 to-10 ℃ until a crystallized product is separated out, separating a crystal and a mother solution at-20 to-10 ℃, and taking the crystal for later use; putting the crystals into a crystallizer again, keeping the temperature at-10-0 ℃ by adopting constant-temperature water, and keeping the temperature for 2 hours; and centrifuging again at the temperature of-10-0 ℃ to obtain crystals. The method can obtain indene with higher purity but has the main disadvantages of difficult industrial production caused by excessive operation difficulty, lower yield, relatively higher energy consumption and the like. Patent CN 110002945 a discloses an indene product extraction and purification method and a purification device system based on the method, which comprises the following steps: performing negative pressure rectification on the indene-containing material at the 1 st section, refluxing at the tower top, and collecting the light fraction enriched with indene components; performing negative pressure rectification on the light distillate enriched with indene components at the 2 nd working section, and fractionating to obtain crude indene with the purity of 70-85%; performing negative pressure rectification on the crude indene with the purity of 70-85% at the 3 rd section, refluxing and collecting the crude indene with the purity of 70-95% at the top of the tower, and performing fractionation to obtain refined indene with the purity of not less than 95%; and the 3 rd section negative pressure rectification is intermittent rectification. The major disadvantages of this process include the unstable purity of the product and the high energy consumption.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is that the invention provides a process method for purifying high-purity indene from heavy benzene. The method solves the demand of high-purity indene in the market, has simple and convenient operation, low energy consumption and small harm to the environment, and is suitable for industrial production.
The technical scheme of the invention is that the indene extractive distillation purification method comprises the following steps:
1) initial distillation of raw materials: cutting the raw material into a fraction at the temperature of 135-195 ℃ through a primary distillation tower D1, and removing light oil and heavy oil to obtain an indene-enriched component-containing stream 2;
2) and (3) removing pyridine and phenol: depyridinizing and dephenolizing in a pickling tank SW by a conventional pickling and alkali washing method, and further neutralizing to obtain an indene component enriched stream 3;
3) decoloring and distilling: the stream 3 enriched with indene-containing components passes through a decoloring tower D2, and heavy fractions containing naphthalene, acid tar, asphalt and the like are separated from the bottom of the tower; distilling an enriched indene-containing component stream 4 from the top of the column;
4) and (3) secondary distillation: passing the stream 4 enriched in indene-containing components through a distillation column D3, separating a light fraction containing various benzenes from the top of the column, and separating a stream 5 enriched in indene-containing components from the bottom of the column; the distillation conditions are as follows: number of trays: 10-30, reflux ratio: 5-25, bottom temperature: 100 ℃ and 200 ℃;
5) and (3) extraction and rectification: the stream enriched in indene-containing components 5 and the extractant N-methylpyrrolidone E1 are simultaneously passed through an extraction column D4, the extractant N-methylpyrrolidone is separated from the bottom of the column and passed through a mixer M1 into a tank J1; separating an enriched indene-containing component and a small amount of an extractant N-methylpyrrolidone stream 6 from the top of the tower; the conditions of the extraction and the rectification are as follows: molar ratio of extractant to feed: 0.5-5: 1, number of trays: 10-30, reflux ratio: 5-25, vacuum degree: 0.01-30 kPa;
6) final distillation: stream 6 is passed to distillation column D5 under the conditions of: number of trays: 10-20, reflux ratio: 5-25, bottom temperature: 80-280 ℃; high-purity indene with the purity of more than 97 percent is separated out from the top of the tower.
And (4) continuously distilling the light components obtained after decoloring in the step 3).
And in the process of the step 5), a certain amount of N-methyl pyrrolidone is used for extracting and rectifying heavy components obtained after distillation in the step 4).
And 5) distilling the mixture of high-purity indene and N-methyl pyrrolidone obtained after the extractive distillation in the step 6).
According to the indene extractive distillation purification method, the acid used in the acid washing in the step 2) is preferably one of a sulfuric acid solution, a hydrochloric acid solution or a nitric acid solution or a mixture of the sulfuric acid solution, the hydrochloric acid solution and the nitric acid solution.
Preferably, the alkali used in the alkali washing in the step 2) is one or a mixture of a sodium hydroxide solution, a sodium carbonate solution or a potassium hydroxide solution. Conventional acid and base types for acid or alkaline cleaning are used.
Further, the concentration of the sodium hydroxide solution is 1% -10%; further, the concentration of the sulfuric acid solution is 30% -60%.
According to the indene extractive distillation purification method, the distillation conditions in the step 4) are preferably as follows: number of trays: 10-20, reflux ratio: 5-20, bottom temperature: 120 ℃ and 180 ℃.
According to the indene extractive distillation purification method, the extraction distillation conditions in the step 5) are preferably as follows: molar ratio of extractant to feed: 0.5-4: 1, number of trays: 10-25, reflux ratio: 5-20, vacuum degree: 0.01-20 kPa.
According to the indene extractive distillation purification method, the distillation conditions in the step 6) are preferably as follows: number of trays: 10-18, reflux ratio: 5-20, bottom temperature: 100 ℃ and 250 ℃.
According to the indene extractive distillation purification method, the extractant N-methyl pyrrolidone is preferably separated from the bottom of the step 6) and is introduced into a tank J1 through a mixer M1.
The extractant may also be recycled as required. The operation is that the extraction agent is recycled: the extractant in tank J1 was controlled by valve V1 and passed through mixer M1 into tank J1; when valve V1 was opened as needed, the extractant in tank J1 and passed through mixer M1 into tank J1 would enter extraction column D4 through mixer M2.
Firstly, obtaining an indene-containing polymerized oil raw material through preliminary distillation, acid washing and decoloration;
secondly, distilling to remove various benzene substances in the polymerization oil raw material;
thirdly, adding an extracting agent N-methylpyrrolidone NMP for extraction and rectification;
fourthly, distilling and separating the extracting agent and recycling the extracting agent according to requirements.
The invention has the beneficial effects that:
based on the purity of the product and market demand, the indene production process is improved, and the indene with high purity of more than 97% is obtained from the product purification angle, which is obviously higher than that of the prior art (the purity of indene in the prior art is 75-95%), the market demand is met, and the use range of indene is enlarged. The preparation method for purifying indene from heavy benzene by extractive distillation is characterized in that a high-purity indene product which meets the market demand and is more than 97 percent is obtained by using the extractive distillation process on the basis of the traditional indene purification process. The product obtained by the method has high purity, simple and convenient operation, low energy consumption and environmental protection, and is suitable for industrial production.
Drawings
FIG. 1 is a flow chart of the production process of the present invention.
Detailed Description
The production process flow of the invention is shown in figure 1, and the raw materials are subjected to preliminary distillation, pyridine removal and phenol removal, decoloring distillation, secondary distillation, extractive distillation and final distillation to obtain high-purity indene.
In the figure, 1-raw, 2-enriched indene-containing component stream 2, 3-enriched indene-containing component stream 3, 4-enriched indene-containing component stream 4, 5-enriched indene-containing component stream 5, 6-stream 6.
The technical scheme of the invention is further illustrated by the following examples.
Example 1:
the raw material enters a distillation column D1, a crude coumarone fraction with a boiling point range of 135-195 ℃ is cut out from a distillation system, and a stream 2 is obtained at the top of the column. And (3) feeding the stream 2 into a pickling tank SW, circularly pickling by using 40% dilute sulfuric acid at normal temperature, neutralizing by using 10% NaOH after twice pickling, and washing by using water to obtain a neutral stream 3. And the washed stream 3 enters a decoloring tower D2, impurities such as naphthalene oil and the like in the materials are further removed at the temperature of 110 ℃ at the top of the tower and the pressure of 17.3kPa, and a stream 4 is obtained at the top of the tower. And the decolorized stream 4 enters a distillation column D3, impurities such as trimethylbenzene and the like in the material are further removed at the column bottom temperature of 138-142 ℃, the column number of 20 and the reflux ratio of 15, and a stream 5 is obtained at the column bottom. And (3) introducing the stream 5 into an extractive distillation column D4, and simultaneously adding a certain amount of N-methylpyrrolidone, wherein the molar ratio of the stream 5 to the N-methylpyrrolidone is 1: 2.02. the reflux ratio of the extraction and rectification tower is 15, the vacuum degree is 6.66kPa, and a mixture stream 6 of indene and the extracting agent is obtained at the tower top. The stream 6 enters a final distillation tower D5, the bottom temperature is 138-142 ℃, the number of plates is 20, the reflux ratio is 10, the extractant N-methylpyrrolidone is removed, the N-methylpyrrolidone obtained at the bottom of the tower is stored in a tank J1 through a mixer M1 and then returns to the circulation through a mixer M2. The final product was obtained at the top of the column, with an indene purity of 98.14% and an indene yield of 37.84%.
Comparative example 1:
the raw material enters a distillation column D1, a crude coumarone fraction with a boiling point range of 135-195 ℃ is cut out from a distillation system, and a stream 2 is obtained at the top of the column. And (3) feeding the stream 2 into a pickling tank SW, circularly pickling by using 40% dilute sulfuric acid at normal temperature, neutralizing by using 10% NaOH after twice pickling, and washing by using water to obtain a neutral stream 3. And the washed stream 3 enters a decoloring tower D2, impurities such as naphthalene oil and the like in the materials are further removed at the temperature of 110 ℃ at the top of the tower and the pressure of 17.3kPa, and a stream 4 is obtained at the top of the tower. And the decolorized stream 4 enters a distillation column D3, impurities such as trimethylbenzene and the like in the material are further removed at the column bottom temperature of 138-142 ℃, the column number of 20 and the reflux ratio of 15, and a stream 5 is obtained at the column bottom. And (3) introducing the stream 5 into an extractive distillation column D4, and simultaneously adding a certain amount of N-methylpyrrolidone, wherein the molar ratio of the stream 5 to the N-methylpyrrolidone is 1: 1. the reflux ratio of the extraction and rectification tower is 15, the vacuum degree is 6.66kPa, and a mixture stream 6 of indene and the extracting agent is obtained at the tower top. And the stream 6 enters a final distillation tower D5, the bottom temperature is 138-142 ℃, the number of plates is 20, the reflux ratio is 10, the extractant N-methyl pyrrolidone is removed, the N-methyl pyrrolidone obtained at the bottom of the tower is stored in a tank J1 through a mixer M1, and then the N-methyl pyrrolidone returns to the top of the circulating tower through a mixer M2 to obtain the final product, wherein the purity of indene is 40.23 percent, and the yield of indene is 18.99 percent.
Example 2:
the raw material enters a distillation column D1, a crude coumarone fraction with a boiling point range of 135-195 ℃ is cut out from a distillation system, and a stream 2 is obtained at the top of the column. And (3) feeding the stream 2 into a pickling tank SW, circularly pickling by using 40% dilute sulfuric acid at normal temperature, neutralizing by using 10% NaOH after twice pickling, and washing by using water to obtain a neutral stream 3. And the washed stream 3 enters a decoloring tower D2, impurities such as naphthalene oil and the like in the materials are further removed at the temperature of 110 ℃ at the top of the tower and the pressure of 17.3kPa, and a stream 4 is obtained at the top of the tower. And the decolorized stream 4 enters a distillation column D3, impurities such as trimethylbenzene and the like in the material are further removed at the column bottom temperature of 138-142 ℃, the column number of 20 and the reflux ratio of 15, and a stream 5 is obtained at the column bottom. And (3) introducing the stream 5 into an extractive distillation column D4, and simultaneously adding a certain amount of N-methylpyrrolidone, wherein the molar ratio of the stream 5 to the N-methylpyrrolidone is 1: 2.02. the reflux ratio of the extraction and rectification tower is 30, the vacuum degree is 6.66kPa, and a mixture stream 6 of indene and the extracting agent is obtained at the tower top. And the stream 6 enters a final distillation tower D5, the bottom temperature is 138-142 ℃, the number of plates is 20, the reflux ratio is 10, the extractant N-methyl pyrrolidone is removed, the N-methyl pyrrolidone obtained at the bottom of the tower is stored in a tank J1 through a mixer M1, and then the N-methyl pyrrolidone returns to the top of the circulating tower through a mixer M2 to obtain the final product, wherein the purity of indene is 98.15 percent, and the yield of indene is 9.23 percent.
Example 3:
the raw material enters a distillation column D1, a crude coumarone fraction with a boiling point range of 135-195 ℃ is cut out from a distillation system, and a stream 2 is obtained at the top of the column. And (3) feeding the stream 2 into a pickling tank SW, circularly pickling by using 40% dilute sulfuric acid at normal temperature, neutralizing by using 10% NaOH after twice pickling, and washing by using water to obtain a neutral stream 3. And the washed stream 3 enters a decoloring tower D2, impurities such as naphthalene oil and the like in the materials are further removed at the temperature of 110 ℃ at the top of the tower and the pressure of 17.3kPa, and a stream 4 is obtained at the top of the tower. And the decolorized stream 4 enters a distillation column D3, impurities such as trimethylbenzene and the like in the material are further removed at the column bottom temperature of 138-142 ℃, the column number of 20 and the reflux ratio of 15, and a stream 5 is obtained at the column bottom. And (3) introducing the stream 5 into an extractive distillation column D4, and simultaneously adding a certain amount of N-methylpyrrolidone, wherein the molar ratio of the stream 5 to the N-methylpyrrolidone is 1: 2.02. the reflux ratio of the extraction and rectification tower is 15, the vacuum degree is 30kPa, and a mixture stream 6 of indene and an extracting agent is obtained at the tower top. And the stream 6 enters a final distillation tower D5, the bottom temperature is 138-142 ℃, the number of plates is 20, the reflux ratio is 10, the extractant N-methyl pyrrolidone is removed, the N-methyl pyrrolidone obtained at the bottom of the tower is stored in a tank J1 through a mixer M1, and then the N-methyl pyrrolidone returns to the top of the circulating tower through a mixer M2 to obtain the final product, wherein the purity of indene is 97.25 percent, and the yield of indene is 36.56 percent.
Example 4:
the raw material enters a distillation column D1, a crude coumarone fraction with a boiling point range of 135-195 ℃ is cut out from a distillation system, and a stream 2 is obtained at the top of the column. And (3) feeding the stream 2 into a pickling tank SW, circularly pickling by using 40% dilute sulfuric acid at normal temperature, neutralizing by using 10% NaOH after twice pickling, and washing by using water to obtain a neutral stream 3. And the washed stream 3 enters a decoloring tower D2, impurities such as naphthalene oil and the like in the materials are further removed at the temperature of 110 ℃ at the top of the tower and the pressure of 17.3kPa, and a stream 4 is obtained at the top of the tower. And the decolorized stream 4 enters a distillation column D3, impurities such as trimethylbenzene and the like in the material are further removed at the column bottom temperature of 138-142 ℃, the column number of 20 and the reflux ratio of 15, and a stream 5 is obtained at the column bottom. And (3) introducing the stream 5 into an extractive distillation column D4, and simultaneously adding a certain amount of N-methylpyrrolidone, wherein the molar ratio of the stream 5 to the N-methylpyrrolidone is 1: 3. the reflux ratio of the extraction and rectification tower is 15, the vacuum degree is 6.66kPa, and a mixture stream 6 of indene and the extracting agent is obtained at the tower top. And the stream 6 enters a final distillation tower D5, the number of plates is 20, the reflux ratio is 10, an extracting agent N-methyl pyrrolidone is removed, the N-methyl pyrrolidone obtained at the bottom of the tower is stored in a tank J1 through a mixer M1, and then the N-methyl pyrrolidone returns to the top of the circulating tower through a mixer M2 to obtain a final product, wherein the purity of indene is 98.14%, and the yield of indene is 29.78%.
Example 5:
the raw material enters a distillation column D1, a crude coumarone fraction with a boiling point range of 135-195 ℃ is cut out from a distillation system, and a stream 2 is obtained at the top of the column. And (3) feeding the stream 2 into a pickling tank SW, circularly pickling by using 40% dilute sulfuric acid at normal temperature, neutralizing by using 10% NaOH after twice pickling, and washing by using water to obtain a neutral stream 3. And the washed stream 3 enters a decoloring tower D2, impurities such as naphthalene oil and the like in the materials are further removed at the temperature of 110 ℃ at the top of the tower and the pressure of 17.3kPa, and a stream 4 is obtained at the top of the tower. And the decolorized stream 4 enters a distillation column D3, impurities such as trimethylbenzene and the like in the material are further removed at the column bottom temperature of 138-142 ℃, the column number of 20 and the reflux ratio of 15, and a stream 5 is obtained at the column bottom. And (3) introducing the stream 5 into an extractive distillation column D4, and simultaneously adding a certain amount of N-methylpyrrolidone, wherein the molar ratio of the stream 5 to the N-methylpyrrolidone is 1: 2.02. the reflux ratio of the extraction and rectification tower is 12, the vacuum degree is 6.66kPa, and a mixture stream 6 of indene and the extracting agent is obtained at the tower top. And the stream 6 enters a final distillation tower D5, the number of plates is 20, the reflux ratio is 10, an extracting agent N-methyl pyrrolidone is removed, the N-methyl pyrrolidone obtained at the bottom of the tower is stored in a tank J1 through a mixer M1, and then the N-methyl pyrrolidone returns to the top of the circulating tower through a mixer M2 to obtain a final product, wherein the purity of indene is 97.02%, and the yield of indene is 39.27%.
Table one: summary of example parameters
As can be seen from the table above, the indene purity in the comparative example is significantly lower than in the examples. The indene purity of the invention reaches more than 97%.
Claims (8)
1. An indene extractive distillation purification method is characterized in that: the method comprises the following steps:
1) initial distillation of raw materials: cutting the raw material into a fraction at the temperature of 135-195 ℃ through a primary distillation tower D1, and removing light oil and heavy oil to obtain an indene-enriched component-containing stream 2;
2) and (3) removing pyridine and phenol: depyridinizing and dephenolizing in a pickling tank SW by a conventional pickling and alkali washing method, and further neutralizing to obtain an indene component enriched stream 3;
3) decoloring and distilling: the stream 3 enriched with indene-containing components passes through a decoloring tower D2, and heavy fractions containing naphthalene, acid tar, asphalt and the like are separated from the bottom of the tower; distilling an enriched indene-containing component stream 4 from the top of the column;
4) and (3) secondary distillation: passing the stream 4 enriched in indene-containing components through a distillation column D3, separating a light fraction containing various benzenes from the top of the column, and separating a stream 5 enriched in indene-containing components from the bottom of the column; the distillation conditions are as follows: number of trays: 10-30, reflux ratio: 5-25, bottom temperature: 100 ℃ and 200 ℃;
5) and (3) extraction and rectification: the stream enriched in indene-containing components 5 and the extractant N-methylpyrrolidone E1 are simultaneously passed through an extraction column D4, the extractant N-methylpyrrolidone is separated from the bottom of the column and passed through a mixer M1 into a tank J1; separating an enriched indene-containing component and a small amount of an extractant N-methylpyrrolidone stream 6 from the top of the tower; the conditions of the extraction and the rectification are as follows: molar ratio of extractant to feed: 0.5-5: 1, number of trays: 10-30, reflux ratio: 5-25, vacuum degree: 0.01-30 kPa;
6) final distillation: stream 6 is passed to distillation column D5 under the conditions of: number of trays: 10-20, reflux ratio: 5-25, bottom temperature: 80-280 ℃; high-purity indene with the purity of more than 97 percent is separated out from the top of the tower.
2. The indene extractive distillation purification method according to claim 1, characterized in that: and 2) acid used in the acid cleaning in the step 2) is one or a mixture of a sulfuric acid solution, a hydrochloric acid solution or a nitric acid solution.
3. The indene extractive distillation purification method according to claim 1, characterized in that: the alkali used in the alkali washing in the step 2) is one or a mixture of a sodium hydroxide solution, a sodium carbonate solution or a potassium hydroxide solution.
4. The indene extractive distillation purification method according to claim 2, characterized in that: the concentration of the sulfuric acid solution is 30-60%.
5. The indene extractive distillation purification method according to claim 1, characterized in that: the distillation conditions in the step 4) are as follows: number of trays: 10-20, reflux ratio: 5-20, bottom temperature: 120 ℃ and 180 ℃.
6. The indene extractive distillation purification method according to claim 1, characterized in that: the conditions of the extractive distillation in the step 5) are as follows: molar ratio of extractant to feed: 0.5-4: 1, number of trays: 10-25, reflux ratio: 5-20, vacuum degree: 0.01-20 kPa.
7. The indene extractive distillation purification method according to claim 1, characterized in that: the distillation conditions of the step 6) are as follows: number of trays: 10-18, reflux ratio: 5-20, bottom temperature: 100 ℃ and 250 ℃.
8. The indene extractive distillation purification method according to claim 1, characterized in that: step 6) the extractant N-methylpyrrolidone is separated off at the bottom and passed via a mixer M1 into a tank J1.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4280881A (en) * | 1980-07-02 | 1981-07-28 | Gulf Research & Development Company | Separating indene from unsaturated alkylaromatics |
| US20010023819A1 (en) * | 2000-01-26 | 2001-09-27 | Adchemco Corporation | Production process of indene |
| CN105294940A (en) * | 2014-06-23 | 2016-02-03 | 上海宝钢化工有限公司 | Method for removing mercaptan from coumarone resin |
| CN109553721A (en) * | 2017-09-25 | 2019-04-02 | 宝武炭材料科技有限公司 | Method for producing liquid coumarone resin and co-producing coumarone resin with high softening point |
| CN109627139A (en) * | 2017-10-09 | 2019-04-16 | 中国石化扬子石油化工有限公司 | Indane separation method in a kind of cracking carbon nine |
| CN110002945A (en) * | 2019-04-24 | 2019-07-12 | 刘思远 | The method for extraction and purification of indenes product and purifying plant system based on this method |
-
2020
- 2020-09-18 CN CN202010985208.9A patent/CN114195613A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4280881A (en) * | 1980-07-02 | 1981-07-28 | Gulf Research & Development Company | Separating indene from unsaturated alkylaromatics |
| US20010023819A1 (en) * | 2000-01-26 | 2001-09-27 | Adchemco Corporation | Production process of indene |
| CN105294940A (en) * | 2014-06-23 | 2016-02-03 | 上海宝钢化工有限公司 | Method for removing mercaptan from coumarone resin |
| CN109553721A (en) * | 2017-09-25 | 2019-04-02 | 宝武炭材料科技有限公司 | Method for producing liquid coumarone resin and co-producing coumarone resin with high softening point |
| CN109627139A (en) * | 2017-10-09 | 2019-04-16 | 中国石化扬子石油化工有限公司 | Indane separation method in a kind of cracking carbon nine |
| CN110002945A (en) * | 2019-04-24 | 2019-07-12 | 刘思远 | The method for extraction and purification of indenes product and purifying plant system based on this method |
Non-Patent Citations (4)
| Title |
|---|
| 卢金寿;: "高软化点古马隆-茚树脂的开发", 煤化工, no. 04, pages 44 - 49 * |
| 徐翰初, 韩永霞, 宫玉秀: "粗苯精制新技术", 山东冶金, no. 01, pages 15 - 17 * |
| 樊冬娌;曹宇锋;顾正桂;石健;单佳慧;: "萃取精馏法从加氢裂解C9芳烃中脱除茚满的模拟与优化（英文）", 计算机与应用化学, no. 12, pages 1507 - 1510 * |
| 王焕煜;王仁远;许振良;: "硫茚萃取精馏分离的模拟计算", 化学世界, no. 03, pages 148 - 151 * |
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