CN1762524A - 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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Abstract
A method for separating and using the discharge liquid from the production of methyl four hydrogen benzoic anhydride, the discharge liquid is the hydrocarbon mixture of pentadiene, cyclopentene and cyclopentane, generated in the course of producing the methyl four hydrogen benzoic anhydride by the reaction of hybrid carbon five and anhydride enriched with pentadiene which got from the separation of the carbon five cut fraction which is the by-product of the ethane cracking, the separating process comprises: 1) the discharge liquid being put into the extraction distillation column for extraction and distillation, getting the mixing carbon five material enriched with cyclopentene and cyclopentane in the top of the tower, getting the material enriched with pentadiene and extracting agent in the tower still; 2) the tower still material got in step 1) being put into the distillation tower for distillation, getting cis-pentadiene on the top of the tower, extracting agent in the tower still, the extracting agent can be reused; 3) mixing the material got on the tower top in step 1 with hydrogen gas, then carrying out the hydrogenation reaction in the fixed bed catalyst hydrogenation chamber and getting the hydrogenation product cyclopentane; 4)putting the hydrogenation product cyclopentane got in step 3 in the distillation tower for distillation, getting fine cyclopentane in the tower still. The invention improves the value of the discharge liquid greatly.
Description
Technical field
The present invention relates to the method that a kind of separation utilizes MeTHPA production waste liquid, the mixing carbon five that this waste liquid results to be separated the enrichment pentadiene that obtains by cracking of ethylene by-product C 5 fraction is 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.Pentamethylene in the waste liquid also is of great value chemical products, and it 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 the method that a kind of separation utilizes 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 the by-product pentamethylene.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of separation utilizes the method for MeTHPA production waste liquid, this waste liquid is the hydrocarbon mixture that contains pentadiene, cyclopentene and pentamethylene, and it results from the production process that cracking of ethylene by-product C 5 fraction separates mixing carbon five with the cis-butenedioic anhydride reaction manufacturing methyl tetrahydro phthalic anhydride of the enrichment pentadiene that obtains.
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 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 still material of process 1 enters rectifying column and carries out rectifying, and operating pressure is 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 with enter a fixed-bed catalytic hydrogenation reactor after hydrogen mixes and carry out hydrogenation reaction and obtain the hydrogenation products pentamethylene, catalyst is taken from Pd/ γ-Al
2O
3, a kind of in Pd/C or the Raney nickel, the volume charge ratio of hydrogen and cat head material is 3～5, air speed 4～6hr
-1, reaction pressure is 0.9～1.2MPa, reaction temperature is 65～70 ℃.
4) process 3 resulting hydrogenation products pentamethylene enter rectifying column and carry out rectifying, remove than the low-boiling component of pentamethylene, and operating pressure is a normal pressure, tower still temperature is 50～60 ℃, and tower top temperature is 40～45 ℃, and reflux ratio is 5～30, light component distillates from cat head, and the tower still gets the pentamethylene purified product.
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;
General olefin hydrogenation catalyst can use in the hydrogenation reaction of said process 3, and above-mentioned several catalyst are that the present invention recommends, and wherein preferably uses Pd/ γ-Al
2O
3
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 four 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 the recycled of realization extractant, process 3 is that mixing carbon five materials that will contain cyclopentene and pentamethylene carry out hydrogenation, makes cyclopentene be generated as pentamethylene.Through first three process, obtained the higher cis pentadiene product of purity, purity generally can reach more than 85%; By-product obtains purity at the pentamethylene more than 70% simultaneously, because therefore the pentane that impurity mainly is the pentadiene hydrogenation to be generated and the alkane of carbon six adopt known simple rectification process process 4 again, the purity of pentamethylene is reached more than 95%.
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 hydrogenation of the distillation process of process 2,4 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, both are separated or are relatively easy to, and the theoretical number of plates of rectifying tower that process 2 is used is generally 5～20.Process 3 is processes of a kind of hydrogenation of olefins system alkane of routine, and catalyst that it adopts and process conditions all are that this area is familiar with.Process 4 is conventional distillation operations, can adopt packed tower or sieve-plate tower, theoretical cam curve is between 30～50, generally can reach more than 95% through the cyclopentane product purity that obtains after the rectifying, can satisfy general service, if pentamethylene purity is had requirements at the higher level, can assign to realize by the reorganization that further rectifying removes in the product.
Positive effect of the present invention has been to provide a kind of desirable separation method, MeTHPA production waste liquid has obtained two 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 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: DMF is a dimethyl formamide; The water content of acetonitrile solution is 10wt%.
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 obtains by embodiment 1 process 1 with enter a fixed-bed catalytic hydrogenation reactor after hydrogen mixes and carry out hydrogenation reaction and obtain pentamethylene.Catalyst adopts Pd/ γ-Al
2O
3(Pd content is 0.5wt% in the catalyst, and catalyst is spherical, particle diameter 2～4mm).The process conditions that each embodiment adopts see Table 6.
Table 6.
| The volume charge ratio | Air speed (hr 1) | Reaction pressure (MPa) | Reaction temperature (℃) | Cyclopentene conversion ratio (%) | |
| Embodiment 7 | 5 | 3 | 1.2 | 65 | 99.5 |
| Embodiment 8 | 5 | 6 | 1.2 | 65 | 99.1 |
| Embodiment 9 | 5 | 3 | 1.2 | 70 | 99.7 |
| Embodiment 10 | 3 | 4 | 1.2 | 70 | 99.3 |
Annotate: the volume charge ratio is: hydrogen/cat head material
[embodiment 11～13]
Table 7 has been listed the hydrogenation products of embodiment 9 and has been formed.This product enters a rectifying column and carries out rectifying under 40 ℃, this rectifying column is a packed tower, and theoretical cam curve is 35.Hydrogenation products enters rectifying column with the flow of 100g/h from the 14th block of column plate.Rectifying column is operated under normal pressure, and the process conditions of employing see Table 7, and the light component material that cat head distillates and tower still cyclopentane product are formed and seen Table 8 and table 9 respectively.
Table 7.
| Tower still/tower top temperature (℃) | Reflux ratio | |
| Embodiment 11 | 51/43 | 15 |
| Embodiment 12 | 50/46 | 6 |
| Embodiment 13 | 51/43 | 25 |
Table 8.
| Isopentane (wt%) | Pentane (wt%) | Pentamethylene (wt%) | Carbon six above alkane | |
| Embodiment 11 | 12.3 | 17.2 | 69.6 | Surplus |
| Embodiment 12 | 9.1 | 9.0 | 80.8 | Surplus |
| Embodiment 13 | 12.3 | 20.0 | 66.8 | Surplus |
Table 9.
| Isopentane (wt%) | Pentane (wt%) | Pentamethylene (wt%) | Carbon six above alkane | |
| Embodiment 11 | Trace | 0.4 | 98.1 | Surplus |
| Embodiment 12 | 0.4 | 1.3 | 96.9 | Surplus |
| Embodiment 13 | Trace | Trace | 98.4 | Surplus |
Claims (9)
1, a kind of separation utilizes the method for MeTHPA production waste liquid, this waste liquid is the hydrocarbon mixture that contains pentadiene, cyclopentene and pentamethylene, it results from the production process that cracking of ethylene by-product C 5 fraction separates mixing carbon five with the cis-butenedioic anhydride reaction manufacturing methyl tetrahydro phthalic anhydride of the enrichment pentadiene that obtains, 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 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 still material of process 1 enters rectifying column and carries out rectifying, and operating pressure is 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 with enter a fixed-bed catalytic hydrogenation reactor after hydrogen mixes and carry out hydrogenation reaction and obtain the hydrogenation products pentamethylene, catalyst is taken from Pd/ γ-Al
2O
3, a kind of in Pd/C or the Raney nickel, the volume charge ratio of hydrogen and cat head material is 3～5, air speed 4～6hr
-1, reaction pressure is 0.9～1.2MPa, reaction temperature is 65～70 ℃;
4) process 3 resulting hydrogenation products pentamethylene enter rectifying column and carry out rectifying, remove than the low-boiling component of pentamethylene, and operating pressure is a normal pressure, tower still temperature is 50～60 ℃, and tower top temperature is 40～45 ℃, and reflux ratio is 5～30, light component distillates from cat head, and the tower still gets the pentamethylene purified product.
2, separation according to claim 1 utilizes the method for MeTHPA production waste liquid, it is characterized in that process 1 described extractant feed temperature is 30～80 ℃.
3, separation according to claim 1 utilizes the method for MeTHPA production waste liquid, it is characterized in that the process 1 described waste liquid and the feed weight ratio of extractant are 1: (8～16).
4, separation according to claim 1 utilizes the method for MeTHPA production waste liquid, it is characterized in that process 1 described operating pressure is a normal pressure.
5, separation according to claim 1 utilizes the method for MeTHPA production waste liquid, it is characterized in that process 1 described tower still temperature is 75～125 ℃, and tower top temperature is 43～48 ℃.
6, separation according to claim 1 utilizes the method for MeTHPA production waste liquid, it is characterized in that the process 1 described cat head rate of distillating is 40～50%, and reflux ratio is 4～8.
7, separation according to claim 1 utilizes the method for MeTHPA production waste liquid, it is characterized in that process 1 described extractant is that dimethyl formamide or water content are the acetonitrile solution of 5～15wt%.
8, separation according to claim 1 utilizes the method for MeTHPA production waste liquid, it 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.
9, separation according to claim 1 utilizes the method for MeTHPA production waste liquid, it is characterized in that process 3 described catalyst are Pd/ γ-Al
2O
3
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| JPS5529968B2 (en) * | 1972-01-14 | 1980-08-07 | ||
| DE2911394B1 (en) * | 1979-03-23 | 1980-04-30 | Basf Ag | Process for obtaining a conjugated diolefin from a C4 or C5 hydrocarbon mixture |
| DE2911393C2 (en) * | 1979-03-23 | 1984-07-19 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of a conjugated diolefin from a C 4 or C 5 hydrocarbon mixture |
| DE3127751A1 (en) * | 1981-07-14 | 1983-02-03 | EC Erdölchemie GmbH, 5000 Köln | METHOD FOR HYDROGENATING HYDROCARBONS |
| DE3338269A1 (en) * | 1983-10-21 | 1985-05-02 | Basf Ag, 6700 Ludwigshafen | METHOD FOR OBTAINING ISOPRENE FROM A C (DOWN ARROW) 5 (DOWN ARROW) HYDROCARBON MIXTURE |
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Cited By (1)
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| 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 |
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