CN100364633C - Method for separating and utilizing MeTHPA production waste liquid - Google Patents
Method for separating and utilizing MeTHPA production waste liquid Download PDFInfo
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- CN100364633C CN100364633C CNB2004100673652A CN200410067365A CN100364633C CN 100364633 C CN100364633 C CN 100364633C CN B2004100673652 A CNB2004100673652 A CN B2004100673652A CN 200410067365 A CN200410067365 A CN 200410067365A CN 100364633 C CN100364633 C CN 100364633C
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Abstract
The present invention relates to a method for separating and utilizing waste liquid produced by methyl tetrahydrophthalic anhydride, wherein the waste liquid is a hydrocarbon mixture containing pentadiene, cyclopentene and cyclopentane and is generated in the production process that mixed carbon 5 enriched with pentadiene and obtained by the distillation fraction separation of the by-product carbon 5 split by ethene and maleic anhydride generate reaction to manufacture the methyl tetrahydrophthalic anhydride. The separating process comprises: 1, the waste liquid enters an extraction and distillation tower for extraction and distillation, a mixed carbon 5 material enriched with the cyclopentene and the cyclopentane is obtained at the top of the tower, a material enriched with the pentadiene and an extracting agent is obtained in the tower still, and the extracting agent is one of dimethyl formamide, N-methyl pyrrolidone, acetonitrile and an acetonitrile water solution with the water content of 5 wt% to 15 wt%; 2, the material obtained in the tower still in process 1 enters a rectifying tower for rectification, a cis-form pentadiene product is obtained at the top of the tower; 3, the material obtained at the top of the tower in process 1 enters the rectifying tower for rectification, the cyclopentene is obtained at the top of the tower, and the cyclopentane is obtained in the tower still. Three fine chemical products with high potential values are obtained by separating the waste liquid.
Description
Technical field
The present invention relates to a kind of method of separating MeTHPA production waste liquid, mixing carbon five materials that this waste liquid results to be separated the enrichment pentadiene that obtains by cracking of ethylene by-product C 5 fraction are raw material, with the production process of cis-butenedioic anhydride reaction manufacturing methyl tetrahydro phthalic anhydride.
Background technology
Methyl tetrahydro phthalic anhydride and methyl hexahydrophthalic anhydride all are the most frequently used epoxy curing agents.Methyl tetrahydro phthalic anhydride is a raw material with the mixing carbon five (hereinafter to be referred as pentadiene mixing carbon five) that is separated the enrichment pentadiene that obtains by cracking of ethylene by-product C 5 fraction generally, makes with the cis-butenedioic anhydride reaction.Methyl tetrahydro phthalic anhydride can make methyl hexahydrophthalic anhydride by further hydrogenation.
Pentadiene mixing carbon five generates in the reaction of methyl tetrahydro phthalic anhydride with the cis-butenedioic anhydride reaction, with the pentadiene that is mainly of cis-butenedioic anhydride reaction.In addition, the a small amount of cyclopentadiene that contains in the raw material also similarly reacts with cis-butenedioic anhydride and generates the Na Dike acid anhydride, because the Na Dike acid anhydride also is a kind of good epoxy curing agent, allows the Na Dike acid anhydride be present in the methyl tetrahydro phthalic anhydride product in therefore producing usually and do not handled.It is to be noted, pentadiene has cis and trans two kinds of isomers, in the reaction of pentadiene and cis-butenedioic anhydride generation, have only trans pentadiene to participate in reaction, the cis pentadiene then with mix carbon five in other component of not participating in reaction from product, be separated in process of production by distillation, become the production waste liquid of methyl tetrahydro phthalic anhydride.Generally speaking, the ratio of the trans and cis of pentadiene is in (1.5～3) in the pentadiene mixing carbon five: between 1, the trans pentadiene and the cyclopentadiene that participate in reaction account for 30～50% of raw material total amount, therefore, the production process of methyl tetrahydro phthalic anhydride will produce a considerable amount of waste liquids, the Main Ingredients and Appearance of waste liquid is cis pentadiene, cyclopentene and pentamethylene, and remaining part mainly is 2-methyl-2-butene and a spot of other C5 hydro carbons and the above hydrocarbon compound of C6.
At present, this MeTHPA production waste liquid is only done the utilization of low value usually, as acts as a fuel and solvent etc.But in fact, a lot of components in this waste liquid all have been widely used, the cis pentadiene except that can as the pentadiene raw material equally be used to produce the hydrocarbon resin, the higher cis pentadiene product of purity still is important fine chemical material.Cyclopentene in the waste liquid and pentamethylene also all are of great value chemical products, and cyclopentene is a kind of important polymerization single polymerization monomer and fine chemical material, and pentamethylene is harmless to the ozone layer of atmosphere, can substitute halogenated hydrocarbon (CFCs) and make blowing agent.Therefore, the production waste liquid of methyl tetrahydro phthalic anhydride is separated and utilizes better, will have very big economic benefit.
Summary of the invention
The invention provides a kind of method of separating MeTHPA production waste liquid, the technical problem that it will solve is that this waste liquid is carried out the more utilization of high value, separated the back by extraction and distillation technology and obtained the higher cis pentadiene product of purity, simultaneously by-product cyclopentene and pentamethylene.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of method of separating MeTHPA production waste liquid, this waste liquid is the hydrocarbon mixture that contains pentadiene, cyclopentene and pentamethylene, and it results from cracking of ethylene by-product C 5 fraction and separates mixing carbon five materials of the enrichment pentadiene that obtains and the production process that methyl tetrahydro phthalic anhydride is made in the cis-butenedioic anhydride reaction.
Separation process comprises:
1) waste liquid enters extractive distillation column and carries out extracting rectifying, the extractant feed temperature is 25～120 ℃, waste liquid is 1 with the feed weight ratio of extractant: (6～20), operating pressure is gauge pressure 0～0.2MPa, tower still temperature is 70～250 ℃, tower top temperature is 40～60 ℃, and the cat head rate of distillating is 30～60%, and reflux ratio is 2～30.Cat head gets mixing carbon five materials of enrichment cyclopentene and pentamethylene, and the tower still gets the material of enrichment pentadiene and extractant, and extractant is that dimethyl formamide, N-methyl pyrrolidone, acetonitrile or water content are any in the acetonitrile solution of 5～15wt%;
2) the tower still material of process 1 enters first rectifying column and carries out rectifying, and operating pressure is gauge pressure 0～0.2MPa, and tower still temperature is 70～180 ℃, and tower top temperature is 38～60 ℃, and reflux ratio is 0.5～5.Cat head gets cis pentadiene product, and the tower still gets extractant, the extractant recycled;
3) the cat head material of process 1 enters second rectifying column and carries out rectifying, and operating pressure is a normal pressure, and tower still temperature is 50～60 ℃, and tower top temperature is 40～45 ℃, and reflux ratio is 5～50, and cat head gets cyclopentene, and the tower still gets pentamethylene.
Said process 1 described extractant feed temperature is preferably 30～80 ℃, and waste liquid is preferably 1 with the feed weight ratio of extractant: (8～16); Operating pressure is preferably normal pressure, tower still temperature is preferably 75～125 ℃, and tower top temperature is preferably 43～48 ℃, and the cat head rate of distillating is preferably 40～50%, reflux ratio is preferably 4～8, and extractant is preferably dimethyl formamide or water content is the acetonitrile solution of 5～15wt%;
Said process 2 described operating pressures are preferably normal pressure, and tower still temperature is preferably 80～110 ℃, and tower top temperature is preferably 40～44 ℃, and reflux ratio is preferably 1～4.
Usually, the table composed as follows of above-mentioned MeTHPA production waste liquid is listed:
| Component | Content (wt%) |
| Trans-pentadiene | 0～3 |
| Cis-pentadiene | 20～50 |
| Cyclopentene | 10～28 |
| Pentamethylene | 3～18 |
| Other C5 hydro carbons and the above hydro carbons of C6 | Surplus |
Other C5 hydro carbons is C 5 monoolefin and alkane such as 2-methyl-2-butene in the table, and their content is generally very low, and boiling point and trans pentadiene are approaching, but differ bigger with cyclopentene and pentamethylene etc.Owing to the boiling point that each component in the waste liquid is mutual is more approaching, particularly the boiling-point difference of cis pentadiene and cyclopentene is 0.2 ℃ only, and the separation between them is very difficult.
Technical scheme provided by the invention has mainly comprised three processes, wherein process 1 is the most key, the present invention is by having selected desirable extractant and suitable extracting rectifying operating condition, realized the separation of MeTHPA production waste liquid well, the distillation process of the 2nd process is separated cis pentadiene product with extractant, obtain cis pentadiene product, and realize the recycled of extractant.Process 3 is common distillation process, has realized separating pentamethylene and cyclopentene.Through these three processes, obtained the higher cis pentadiene product of purity, by-product obtains cyclopentene and pentamethylene simultaneously.The purity of cyclopentene and cyclopentane product can reach more than 90%, can satisfy general application requirements, if purity is had higher requirement, and can be by further refining realization.
The extractive distillation column that process 1 adopts can be packed tower or sieve-plate tower, and the theoretical cam curve of extractive distillation column is generally 40～80.Comparatively speaking, the distillation process of process 2 and process 3 is comparatively simple, because the boiling point of the extractant that the present invention selects is all apparently higher than the boiling point of pentadiene.And the boiling point of cyclopentene and pentamethylene is respectively 44.2 ℃ and 49.3 ℃, both are separated or is relatively easy to by precise distillation.The theoretical number of plates of rectifying tower that process 2 is used is generally 5～20, and the theoretical cam curve of the rectifying column that process 3 is used is generally 50～80.
Positive effect of the present invention has been to provide a kind of desirable separation method, MeTHPA production waste liquid has obtained three kinds of fine chemical products that potential value is higher after separating, compared with prior art, it has improved the value of MeTHPA production waste liquid greatly.
Below will the invention will be further described by specific embodiment.
In an embodiment, cat head distillates rate D/F and is defined as:
The specific embodiment
The MeTHPA production waste liquid that each embodiment uses is formed listed as table 1:
Table 1.
| Component | Content (wt%) |
| Trans-pentadiene | 3 |
| Cis-pentadiene | 50 |
| Cyclopentene | 26 |
| Pentamethylene | 16 |
| Other C5 hydro carbons and the above hydro carbons of C6 | Surplus |
[embodiment 1～6]
Form and to enter an extractive distillation column after MeTHPA production waste liquid as table 1 is preheated to 40～50 ℃ and carry out extracting rectifying, extractive distillation column is a packed tower, and theoretical cam curve is 45.Waste liquid enters extractive distillation column with the speed of 400g/h from the 32nd block of column plate, and extractant is from the 4th column plate charging.The concrete extractant that uses of each embodiment, waste liquid are operated under normal pressure with feed weight ratio, the extractive distillation column of extractant, tower still and tower top temperature see Table 2, the main composition of extracting rectifying column overhead discharging material sees Table 3, and this is a kind of mixing carbon five materials based on cyclopentene and pentamethylene.
Extracting rectifying Tata still material enters subsequently and carries out rectifying in the rectifying column, and rectifying column is a packed tower, and theoretical cam curve is 7, and charging aperture is positioned at the 5th block of plate, and each embodiment rectifying column is operated under normal pressure, and other operating condition sees Table 4.Rectifying Tata still obtains extractant, and extractant is sent the extractive distillation column recycled back to, and the main composition of cat head discharging material sees Table 5, and this is the higher cis pentadiene product of a kind of purity.
Table 2
| Extractant | The extractant feed temperature (℃) | Waste liquid/extractant (weight ratio) | Tower still/tower top temperature (℃) | Reflux ratio | D/F (％) | |
| Embodiment 1 | DMF | 30 | 16 | 125/48 | 20 | 42 |
| Embodiment 2 | DMF | 50 | 12 | 116/47 | 6 | 45 |
| Embodiment 3 | DMF | 80 | 10 | 114/46 | 6 | 48 |
| Embodiment 4 | DMF | 50 | 12 | 116/46 | 6 | 52 |
| Embodiment 5 | DMF | 60 | 8 | 98/46 | 8 | 50 |
| Embodiment 6 | Acetonitrile solution | 45 | 12 | 79/45 | 6 | 49 |
Annotate: 1) DMF is a dimethyl formamide; The water content of acetonitrile solution is 10wt%;
2) data of " waste liquid/extractant (weight ratio) " are in the table: when the weight portion of waste liquid is 1, and the weight portion of extractant.
Table 3.
| Cyclopentene (wt%) | Pentamethylene (wt%) | Trans pentadiene (wt%) | Cis pentadiene (wt%) | Other carbon five components | |
| Embodiment 1 | 57.6 | 38.0 | 1.0 | 1.0 | Surplus |
| Embodiment 2 | 57.7 | 35.6 | 2.2 | 1.8 | Surplus |
| Embodiment 3 | 54.1 | 33.3 | 2.5 | 6.9 | Surplus |
| Embodiment 4 | 50.0 | 30.7 | 4.2 | 8.3 | Surplus |
| Embodiment 5 | 52.0 | 32.0 | 3.6 | 7.4 | Surplus |
| Embodiment 6 | 51.2 | 32.6 | 2.0 | 8.6 | Surplus |
Table 4.
| Tower still/tower top temperature (℃) | Reflux ratio | |
| Embodiment 1 | 100/44 | 4 |
| Embodiment 2 | 101/44 | 2 |
| Embodiment 3 | 100/44 | 3 |
| Embodiment 4 | 100/44 | 2 |
| Embodiment 5 | 100/44 | 2 |
| Embodiment 6 | 80/44 | 4 |
Table 5.
| Cis pentadiene (wt%) | Trans pentadiene (wt%) | Cyclopentene (wt%) | Pentamethylene and other carbon five components | |
| Embodiment 1 | 85.5 | 4.5 | 3.1 | Surplus |
| Embodiment 2 | 89.5 | 3.6 | 0 | Surplus |
| Embodiment 3 | 89.8 | 3.4 | 0.5 | Surplus |
| Embodiment 4 | 95.2 | 1.7 | 0 | Surplus |
| Embodiment 5 | 92.6 | 2.4 | 0 | Surplus |
| Embodiment 6 | 89.8 | 4.1 | 1.8 | Surplus |
[embodiment 7～10]
The cat head material (form and see Table 3) that is obtained by embodiment 1 process 1 enters and carries out rectifying in the rectifying column, rectifying column is a packed tower, theoretical cam curve is 50, charging aperture is positioned at the 28th block of plate, each embodiment rectifying column is operated under normal pressure, to distillate rate D/F be 0.60 in control, and other process conditions see Table 6, and cat head and tower still product are formed and seen Table 7 and table 8 respectively.
Table 6
| Tower still/tower top temperature (℃) | Reflux ratio | |
| Embodiment 7 | 51/44 | 20 |
| Embodiment 8 | 50/45 | 12 |
| Embodiment 9 | 51/44 | 30 |
| Embodiment 10 | 55/44 | 45 |
Table 7.
| Trans pentadiene (wt%) | Cis pentadiene (wt%) | Pentamethylene (wt%) | Cyclopentene (wt%) | Carbon six and other carbon five components | |
| Embodiment 7 | 1.7 | 1.4 | 3.5 | 91.3 | Surplus |
| Embodiment 8 | 1.6 | 1.4 | 6.2 | 88.6 | Surplus |
| Embodiment 9 | 1.7 | 1.5 | 2.5 | 92.3 | Surplus |
| Embodiment 10 | 1.7 | 1.5 | 2.0 | 92.9 | Surplus |
Table 8.
| Trans pentadiene (wt%) | Cis pentadiene (wt%) | Pentamethylene (wt%) | Cyclopentene (wt%) | Carbon six and other carbon five components | |
| Embodiment 7 | Trace | Trace | 90.0 | 7.0 | Surplus |
| Embodiment 8 | Trace | 0.1 | 86.0 | 11.1 | Surplus |
| Embodiment 9 | Trace | Trace | 91.5 | 6.5 | Surplus |
| Embodiment 10 | Trace | Trace | 92.3 | 4.7 | Surplus |
Claims (8)
1. method of separating MeTHPA production waste liquid, this waste liquid is the hydrocarbon mixture that contains pentadiene, cyclopentene and pentamethylene, it results from cracking of ethylene by-product C 5 fraction and separates mixing carbon five materials of the enrichment pentadiene that obtains and the production process that methyl tetrahydro phthalic anhydride is made in the cis-butenedioic anhydride reaction, and separation process comprises:
1) waste liquid enters extractive distillation column and carries out extracting rectifying, the extractant feed temperature is 25～120 ℃, waste liquid is 1 with the feed weight ratio of extractant: (6～20), operating pressure is gauge pressure 0～0.2MPa, tower still temperature is 70～250 ℃, tower top temperature is 40～60 ℃, the cat head rate of distillating is 30～60%, reflux ratio is 2～30, cat head gets mixing carbon five materials of enrichment cyclopentene and pentamethylene, the tower still gets the material of enrichment pentadiene and extractant, and extractant is a dimethyl formamide, the N-methyl pyrrolidone, acetonitrile or water content are any in the acetonitrile solution of 5～15wt%;
2) the tower still material of process 1 enters first rectifying column and carries out rectifying, and operating pressure is gauge pressure 0～0.2MPa, and tower still temperature is 70～180 ℃, tower top temperature is 38～60 ℃, and reflux ratio is 0.5～5, and cat head gets cis pentadiene product, the tower still gets extractant, the extractant recycled;
3) the cat head material of process 1 enters second rectifying column and carries out rectifying, and operating pressure is a normal pressure, and tower still temperature is 50～60 ℃, and tower top temperature is 40～45 ℃, and reflux ratio is 5～50, and cat head gets cyclopentene, and the tower still gets pentamethylene.
2. the method for separation MeTHPA production waste liquid according to claim 1 is characterized in that process 1 described extractant feed temperature is 30～80 ℃.
3. the method for separation MeTHPA production waste liquid according to claim 1 is characterized in that the process 1 described waste liquid and the feed weight ratio of extractant are 1: (8～16).
4. the method for separation MeTHPA production waste liquid according to claim 1 is characterized in that process 1 described operating pressure is a normal pressure.
5. the method for separation MeTHPA production waste liquid according to claim 1 is characterized in that process 1 described tower still temperature is 75～125 ℃, and tower top temperature is 43～48 ℃.
6. the method for separation MeTHPA production waste liquid according to claim 1 is characterized in that the process 1 described cat head rate of distillating is 40～50%, and reflux ratio is 4～8.
7. the method for separation MeTHPA production waste liquid according to claim 1 is characterized in that process 1 described extractant is that dimethyl formamide or water content are the acetonitrile solution of 5～15wt%.
8. the method for separation MeTHPA production waste liquid according to claim 1 is characterized in that process 2 described operating pressures are normal pressure, and tower still temperature is 80～110 ℃, and tower top temperature is 40～44 ℃, and reflux ratio is 1～4.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3686349A (en) * | 1968-08-23 | 1972-08-22 | Bayer Ag | Process for recovering cyclopentene, isoprene and a diolefin stream from the c{11 -cut obtained by petroleum cracking |
| US4277315A (en) * | 1979-03-23 | 1981-07-07 | Basf Aktiengesellschaft | Isolation of a conjugated diolefin from a C4 - or C5 -hydrocarbon mixture |
| US4278504A (en) * | 1979-03-23 | 1981-07-14 | Basf Aktiengesellschaft | Isolation of a conjugated diolefin from a C4 - or C5 -hydrocarbon mixture |
| US4647344A (en) * | 1983-10-21 | 1987-03-03 | Basf Aktiengesellschaft | Recovery of isoprene from a C5 -hydrocarbon mixture |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3686349A (en) * | 1968-08-23 | 1972-08-22 | Bayer Ag | Process for recovering cyclopentene, isoprene and a diolefin stream from the c{11 -cut obtained by petroleum cracking |
| US4277315A (en) * | 1979-03-23 | 1981-07-07 | Basf Aktiengesellschaft | Isolation of a conjugated diolefin from a C4 - or C5 -hydrocarbon mixture |
| US4278504A (en) * | 1979-03-23 | 1981-07-14 | Basf Aktiengesellschaft | Isolation of a conjugated diolefin from a C4 - or C5 -hydrocarbon mixture |
| US4647344A (en) * | 1983-10-21 | 1987-03-03 | Basf Aktiengesellschaft | Recovery of isoprene from a C5 -hydrocarbon mixture |
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