CN100448501C - Waste liquid separating method for tetrahydro methyl phthalic anhydride production process - Google Patents
Waste liquid separating method for tetrahydro methyl phthalic anhydride production process Download PDFInfo
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Abstract
The present invention relates to a separation method for waste liquid in the production processes of methyl tetrahydrophthalic anhydride. The waste liquid is a hydrocarbon mixture which comprises C5 paraffin hydrocarbon, C5 olefin and cis-form piperyene, and is prepared from the production process that division ring C5 made of a C5 distillation fraction which is a side product of ethene cracking after separating and eliminating dicyclopentadiene reacts with maleic anhydride to make the methyl tetrahydrophthalic anhydride. The separation process comprises the steps: 1) the waste liquid enters the rectifying tower for rectification to eliminating light components; 2) materials obtained from a tower kettle in the step 1 enters an extracting rectifying tower for extractive rectification, mixing C5 materials of cyclopentene and cyclopentane are obtained from a tower top, and an extracting agent is one of dimethylformamide, N-methyl pyrrolidone, acetonitrile or acetonitrile water solution with the water content of 5 to 15 wt%; 3) materials obtained from the tower kettle in the step 2 enter the rectifying tower for rectification to separate and recovery the extracting agent, the product of the cis-form piperyene is obtained from the tower top, and the extracting agent is obtained from the tower kettle and can be cyclically used. Various fine chemical products with high intrinsic value are obtained from the waste liquid after separating.
Description
Technical field
The present invention relates to the separation method of the waste liquid that produces in a kind of tetrahydro methyl phthalic anhydride production process, this waste liquid results from the production process of being made methyl tetrahydro phthalic anhydride by mixing carbon behind the cracking of ethylene by-product C 5 fraction separation removal dicyclopentadiene five and cis-butenedioic anhydride reaction.
Background technology
Methyl tetrahydro phthalic anhydride and methyl hexahydrophthalic anhydride all are the most frequently used epoxy curing agents.Methyl tetrahydro phthalic anhydride can be a raw material with the mixing carbon five (hereinafter to be referred as division ring carbon five) behind the Petrocarbon 5 distillate separation removal dicyclopentadiene, makes with the cis-butenedioic anhydride reaction.Methyl tetrahydro phthalic anhydride can make methyl hexahydrophthalic anhydride by further hydrogenation.
Division ring carbon Wuyuan material generates in the reaction of methyl tetrahydro phthalic anhydride with the cis-butenedioic anhydride reaction, with the cis-butenedioic anhydride reaction be mainly pentadiene and isoprene.Pentadiene and cis-butenedioic anhydride reaction directly generate methyl tetrahydro phthalic anhydride, and isoprene and cis-butenedioic anhydride reaction generate the 4-methyl tetrahydro phthalic anhydride, and then are methyl tetrahydro phthalic anhydride through being isomerizated into.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 division ring 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 division ring carbon Wuyuan material: between 1, the trans pentadiene, isoprene and the cyclopentadiene three total 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 C 5 alkane (pentane, isopentane and pentamethylene), carbon pentaene hydrocarbon (1-amylene, 2-amylene, iso-amylene and cyclopentene) and cis pentadiene, and remaining part is mainly the hydrocarbon compound of carbon more than six.
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, highly purified cis pentadiene product still is important fine chemical material, and C 5 alkane in the waste liquid and carbon pentaene hydrocarbon also all are of great value chemical products.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 the separation method of the waste liquid that produces in a kind of tetrahydro methyl phthalic anhydride production process, 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 highly purified cis pentadiene product, simultaneously by-product cyclopentene and pentamethylene mixing carbon five.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
The separation method of the waste liquid that produces in a kind of tetrahydro methyl phthalic anhydride production process, this waste liquid is the hydrocarbon mixture that contains pentamethylene, cyclopentene and cis pentadiene, and carbon five materials and cis-butenedioic anhydride that it results from behind the cracking of ethylene by-product C 5 fraction separation removal dicyclopentadiene react the production process of making methyl tetrahydro phthalic anhydride.
Separation process comprises:
1) waste liquid enters rectifying column rectifying and carries out rectifying to remove light component, the rectifying column operating pressure is 0～0.2MPa, tower still temperature is 40～70 ℃, tower top temperature is 30～50 ℃, reflux ratio is 2～10, cat head distillates light component material, and the tower still obtains containing the material of cis pentadiene, cyclopentene and pentamethylene;
2) process 1) material that obtains of tower still enters extractive distillation column and carries out extracting rectifying, the extractant feed temperature is 25～120 ℃, material is 1 with the feed weight ratio of extractant: (6～20), operating pressure is 0～0.2MPa, tower still temperature is 70～250 ℃, tower top temperature is 40～60 ℃, the cat head rate of distillating is 15～70%, reflux ratio is 1～30, cat head gets mixing carbon five materials of cyclopentene and pentamethylene, the tower still gets the material of cis 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%;
3) process 2) material that obtains of tower still enters rectifying column and carries out rectifying with separating and recovering extractant, operating pressure is 0～0.2MPa, tower still temperature is 70～180 ℃, tower top temperature is 38～60 ℃, reflux ratio is 0.5～5, cat head gets cis pentadiene product, and the tower still gets extractant, the extractant recycled.
Said process 1) described operating pressure is preferably normal pressure, and tower still temperature is preferably 45～60 ℃, and tower top temperature is preferably 30～40 ℃, and reflux ratio is preferably 3～6.
Said process 2) described extractant feed temperature is preferably 30～80 ℃; Material 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 ℃; Tower top temperature is preferably 43～48 ℃; It is the best with the percentage a little more than the mass content of cyclopentene in the raw material and pentamethylene that cat head distillates rate, generally is controlled between 45～55%; Reflux ratio is preferably 4～8; Extractant is that the acetonitrile solution of 5～15wt% is good with dimethyl formamide or water content.
Said process 3) described operating pressure is 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 main composed as follows of this tetrahydro methyl phthalic anhydride production process waste liquid is listed:
| Component | Content (wt%) |
| Trans-pentadiene | 0～3 |
| Cis-pentadiene | 10～15 |
| C 5 alkane (pentane, isopentane and pentamethylene) | 20～34 |
| Carbon pentaene hydrocarbon (1-amylene, 2-amylene, iso-amylene and cyclopentene) | 30～48 |
| Isoprene | 0～4 |
| C6 and other hydro carbons | Surplus |
As can be seen from the above table, cis pentadiene content is below 15% in the waste liquid, for alleviating the load of extracting rectifying, this method is taken off light rectifying earlier, remove the light component hydro carbons that boiling point is lower than pentadiene as far as possible, after taking off light rectifying, pentane, isopentane, 1-amylene, 2-amylene, iso-amylene and isoprene etc. all distillate from cat head basically.
Take off shown in light afterwards mixing carbon five tables composed as follows that the tower still obtains:
| Component | Content (wt%) |
| Trans-pentadiene | 0～5 |
| Cis-pentadiene | 20～50 |
| Cyclopentene | 20～35 |
| Pentamethylene | 3～15 |
| C6 and other hydro carbons | Surplus |
Other 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 2 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 process 3 is separated product with extractant, obtain product, and realize the recycled of extractant, to reduce the production cost that separates.Through these three processes, obtained highly purified cis pentadiene product (general purity can reach more than 85%), by-product obtains the mixing carbon five with cyclopentene and pentamethylene simultaneously.
The rectifying column of process 1 can be a packed tower, and its theoretical cam curve is 50～80.The extractive distillation column that process 2 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 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, the theoretical cam curve of rectifying column is generally 5～20.Obtained the very high high-purity cis pentadiene product of economic worth after the separation, the mixing carbon five of the cyclopentene that by-product obtains, pentamethylene can directly be made solvent, as obtaining higher cyclopentene of purity and pentamethylene after further being separated.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.In addition, process 1 isolated light component material is a kind of lightweight C5 fraction, and it can further be used by prior art, as directly being used as blowing agent, or obtain the mixture of pentane and isopentane by hydrogenation, obtain pentane and isopentane by separation then.
Positive effect of the present invention has been to provide a kind of desirable separation method, the tetrahydro methyl phthalic anhydride production process waste liquid has obtained the higher fine chemical product of multiple potential value after separating, compared with prior art, it has improved the value of tetrahydro methyl phthalic anhydride production process 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 | 1.2 |
| Cis-pentadiene | 12.7 |
| (pentane, isopentane are 29.4wt% to C 5 alkane; Pentamethylene is 2.5wt%) | 31.9 |
| (1-amylene, 2-amylene, iso-amylene are 39.9wt% to carbon pentaene hydrocarbon; Cyclopentene is 8.4wt%) | 48.3 |
| Isoprene | 2.9 |
| C6 and other hydro carbons | Surplus |
[embodiment 1～4]
Form MeTHPA production waste liquid as table 1 and enter and carry out rectifying in the rectifying column to remove light component, rectifying column is a packed tower, and theoretical cam curve is 60, and charging aperture is positioned at the 30th block of plate, and each embodiment distillation operation condition sees Table 2.Cat head distillates light component material, and the material composition that each embodiment tower still obtains sees Table 3.
Table 2.
| Reflux ratio | Tower still/tower top temperature (℃) | Operating pressure | |
| Embodiment 1 | 5 | 57/33 | Normal pressure |
| Embodiment 2 | 3 | 45/30 | Normal pressure |
| Embodiment 3 | 8 | 57/33 | Normal pressure |
| Embodiment 4 | 6 | 60/40 | 0.2MPa |
Table 3
[embodiment 5～10]
Form and to enter an extractive distillation column after material as the 1 tower still gained of embodiment in the table 3 is preheated to 40～50 ℃ and carry out extracting rectifying, extractive distillation column is a packed tower, and theoretical cam curve is 45.Material 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.Extractive distillation column is operated under normal pressure, and concrete extractant that uses of each embodiment and other operating condition see Table 4.The material of extracting rectifying column overhead discharging is mainly formed and is seen Table 5, and this is a kind of mixing carbon five based on cyclopentene and pentamethylene.
Table 4
| Extractant | The extractant feed temperature (℃) | Material/extractant (weight ratio) | Tower still/tower top temperature (℃) | Reflux ratio | D/F (％) | |
| Embodiment 5 | DMF | 30 | 16 | 125/48 | 20 | 42 |
| Embodiment 6 | DMF | 50 | 12 | 116/45 | 6 | 45 |
| Embodiment 7 | DMF | 80 | 10 | 114/45 | 4 | 48 |
| Embodiment 8 | DMF | 50 | 12 | 116/45 | 6 | 55 |
| Embodiment 9 | DMF | 60 | 8 | 98/43 | 8 | 50 |
| Embodiment 10 | Acetonitrile solution | 45 | 12 | 75/45 | 6 | 49 |
Annotate: DMF is a dimethyl formamide; The water content of acetonitrile solution is 10wt%.
Table 5.
| Cyclopentene (wt%) | Pentamethylene (wt%) | Trans pentadiene (wt%) | Cis pentadiene (wt%) | Other carbon five components | |
| Embodiment 5 | 71.9 | 22.8 | 0.7 | 0.8 | Surplus |
| Embodiment 6 | 68.9 | 21.5 | 1.1 | 1.1 | Surplus |
| Embodiment 7 | 66.2 | 20.4 | 1.3 | 1.7 | Surplus |
| Embodiment 8 | 61.1 | 18.8 | 4.6 | 5.6 | Surplus |
| Embodiment 9 | 63.2 | 19.6 | 2.0 | 2.4 | Surplus |
| Embodiment 10 | 63.7 | 19.6 | 3.3 | 3.7 | Surplus |
Extracting rectifying Tata still material enters subsequently and carries out rectifying in the rectifying column with separating and recovering extractant, rectifying column is a packed tower, and theoretical cam curve is 7, and charging aperture is positioned at the 5th block of plate, each embodiment rectifying column is operated under normal pressure, and other concrete operating condition sees Table 6.Rectifying Tata still obtains extractant, and extractant is sent the extractive distillation column recycled back to, and the material of cat head discharging is mainly formed and seen Table 7, and this is a kind of highly purified cis pentadiene product.
Table 6.
| Tower still/tower top temperature (℃) | Reflux ratio | |
| Embodiment 5 | 100/44 | 4 |
| Embodiment 6 | 110/44 | 2 |
| Embodiment 7 | 100/44 | 3 |
| Embodiment 8 | 100/44 | 1 |
| Embodiment 9 | 100/43 | 2 |
| Embodiment 10 | 80/40 | 4 |
Table 7.
| Cis pentadiene (wt%) | Trans pentadiene (wt%) | Cyclopentene (wt%) | Pentamethylene and other carbon five components (wt%) | |
| Embodiment 5 | 81.2 | 5.2 | 2.7 | Surplus |
| Embodiment 6 | 85.3 | 5.1 | 1.4 | Surplus |
| Embodiment 7 | 89.6 | 5.2 | 0.1 | Surplus |
| Embodiment 8 | 92.7 | 1.9 | Trace | Surplus |
| Embodiment 9 | 92.4 | 4.6 | 0.1 | Surplus |
| Embodiment 10 | 89.4 | 3.3 | 1.2 | Surplus |
Claims (10)
1, the separation method of the waste liquid that produces in a kind of tetrahydro methyl phthalic anhydride production process, this waste liquid is the hydrocarbon mixture that contains pentamethylene, cyclopentene and cis pentadiene, carbon five materials and cis-butenedioic anhydride that it results from behind the cracking of ethylene by-product C 5 fraction separation removal dicyclopentadiene react the production process of making methyl tetrahydro phthalic anhydride, and separation process comprises:
1) waste liquid enters rectifying column and carries out rectifying to remove light component, the rectifying column operating pressure is 0～0.2MPa, tower still temperature is 40～70 ℃, tower top temperature is 30～50 ℃, reflux ratio is 2～10, cat head distillates light component material, and the tower still obtains containing the material of cis pentadiene, cyclopentene and pentamethylene;
2) process 1) material that obtains of tower still enters extractive distillation column and carries out extracting rectifying, the extractant feed temperature is 25～120 ℃, material is 1 with the feed weight ratio of extractant: (6～20), operating pressure is 0～0.2MPa, tower still temperature is 70～250 ℃, tower top temperature is 40～60 ℃, the cat head rate of distillating is 15～70 quality %, reflux ratio is 1～30, cat head gets mixing carbon five materials of cyclopentene and pentamethylene, the tower still gets the material of cis 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%;
3) process 2) material that obtains of tower still enters rectifying column and carries out rectifying with separating and recovering extractant, operating pressure is 0～0.2MPa, tower still temperature is 70～180 ℃, tower top temperature is 38～60 ℃, reflux ratio is 0.5～5, cat head gets cis pentadiene product, and the tower still gets extractant, the extractant recycled.
2, the separation method of the waste liquid that produces in the tetrahydro methyl phthalic anhydride production process according to claim 1 is characterized in that process 1) described operating pressure is normal pressure, and tower still temperature is 45～60 ℃, and tower top temperature is 30～40 ℃, and reflux ratio is 3～6.
3, the separation method of the waste liquid that produces in the tetrahydro methyl phthalic anhydride production process according to claim 1 is characterized in that process 2) described extractant feed temperature is 30～80 ℃.
4, the separation method of the waste liquid that produces in the tetrahydro methyl phthalic anhydride production process according to claim 1 is characterized in that process 2) described material is 1 with the feed weight ratio of extractant: (8～16).
5, the separation method of the waste liquid that produces in the tetrahydro methyl phthalic anhydride production process according to claim 1 is characterized in that process 2) described operating pressure is normal pressure.
6, the separation method of the waste liquid that produces in the tetrahydro methyl phthalic anhydride production process according to claim 1 is characterized in that process 2) described tower still temperature is 75～125 ℃, tower top temperature is 43～48 ℃.
7, the separation method of the waste liquid that produces in the tetrahydro methyl phthalic anhydride production process according to claim 1 is characterized in that process 2) the described cat head rate of distillating is 45～55 quality %.
8, the separation method of the waste liquid that produces in the tetrahydro methyl phthalic anhydride production process according to claim 1 is characterized in that process 2) described reflux ratio is 4～8.
9, the separation method of the waste liquid that produces in the tetrahydro methyl phthalic anhydride production process according to claim 1 is characterized in that process 2) described extractant is that dimethyl formamide or water content are the acetonitrile solution of 5～15wt%.
10, the separation method of the waste liquid that produces in the tetrahydro methyl phthalic anhydride production process according to claim 1 is characterized in that process 3) described operating pressure is 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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| CN101497677B (en) * | 2008-12-11 | 2012-01-11 | 宁波职业技术学院 | Method for preparing C5 hydrocarbon resin from methyl tetrahydro benzoic anhydride production waste liquor |
| CN109305877A (en) * | 2017-07-26 | 2019-02-05 | 抚顺伊科思新材料有限公司 | Thick light dydrocarbon produces high alkene light dydrocarbon, pentane, isopentane and pentamethylene method |
| CN112661735B (en) * | 2021-01-15 | 2023-12-22 | 浙江正大新材料科技股份有限公司 | Continuous production system and method for methyltetrahydrophthalic anhydride |
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| 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 |
| US4431528A (en) * | 1981-07-14 | 1984-02-14 | Ec Erdolchemie Gmbh | Process for the hydrogenation of hydrocarbons |
| US4647344A (en) * | 1983-10-21 | 1987-03-03 | Basf Aktiengesellschaft | Recovery of isoprene from a C5 -hydrocarbon mixture |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4876840A (en) * | 1972-01-14 | 1973-10-16 | ||
| 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 |
| US4431528A (en) * | 1981-07-14 | 1984-02-14 | Ec Erdolchemie Gmbh | Process for the hydrogenation of hydrocarbons |
| US4647344A (en) * | 1983-10-21 | 1987-03-03 | Basf Aktiengesellschaft | Recovery of isoprene from a C5 -hydrocarbon mixture |
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