CN100467389C - Waste liquid separating process for tetrahydromethyl phthalic anhydride prduction process - Google Patents
Waste liquid separating process for tetrahydromethyl phthalic anhydride prduction process Download PDFInfo
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Abstract
The process of separating waste liquid from the tetrahydromethyl phthalic anhydride producing process includes the following steps: 1. rectifying waste liquid to eliminate light components; 2. extracting and rectifying the cauldron material of the step 1 with the extractant dimethyl formamide, N-mehtyl pyrrolidone, acetonitrile or water solution of acetonitrile with water content of 5-15 wt%; 3. rectifying the cauldron material of the step 2 to separate and recover extractant in the cauldron for reuse while obtaining cis-piperyene product; 4. hydrogenating the tower top material of the step 2 to obtain hydrogenated product cyclopentane; and 5. rectifying the hydrogenated product cyclopentane to eliminate low boiling point components and obtain refined cyclopentane product in the cauldron. The waste liquid separating process obtain valuable cis-piperyene product in high purity and co-product cyclopentane.
Description
Technical field
The present invention relates to a kind of separation method of tetrahydro methyl phthalic anhydride production process waste liquid, this waste liquid results from the production process of being made methyl tetrahydro phthalic anhydride by mixing carbon after 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) after 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 m-pentadiene and isoprene.M-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, m-pentadiene has cis and trans two kinds of isomer, in the reaction of m-pentadiene and cis-butenedioic anhydride generation, have only trans m-pentadiene to participate in reaction, the cis m-pentadiene then with division ring carbon five in other component of not participating in reaction from reaction 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 m-pentadiene is in (1.5～3) in the division ring carbon Wuyuan material: between 1, the trans m-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 major ingredient of waste liquid is C 5 alkane (Skellysolve A, iso-pentane and pentamethylene), carbon pentaene hydrocarbon (1-amylene, 2-amylene, isopentene and cyclopentenes) and cis m-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 m-pentadiene except that can as the m-pentadiene raw material equally be used to produce the hydrocarbon resin, highly purified cis m-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 Chemicals.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 separation method of tetrahydro methyl phthalic anhydride production process 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 highly purified cis m-pentadiene product, 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 method of tetrahydro methyl phthalic anhydride production process waste liquid, the division ring carbon five that this waste liquid results from after the cracking of ethylene by-product C 5 fraction separation removal dicyclopentadiene reacts the production process of making methyl tetrahydro phthalic anhydride with cis-butenedioic anhydride, and it is the hydrocarbon mixture that contains C 5 alkane, carbon pentaene hydrocarbon and cis m-pentadiene.
Sepn process comprises:
1) waste liquid enters rectifying tower and carries out rectifying to remove light component, and the rectifying tower working pressure is 0～0.2MPa, and tower still temperature is 40～70 ℃, tower top temperature is 30～50 ℃, reflux ratio is 2～10, and cat head distillates light component material, and the tower still obtains the material of cis m-pentadiene, cyclopentenes and pentamethylene;
2) material that obtains of process 1 tower still enters extractive distillation column and carries out extracting rectifying, the extractant feed temperature is 25～120 ℃, material is 1:(6～20 with the feed weight ratio of extraction agent), working 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 cyclopentenes and pentamethylene, the tower still gets the material of m-pentadiene and extraction agent, and extraction agent is a dimethyl formamide, N-Methyl pyrrolidone, acetonitrile or water-content are any in the acetonitrile solution of 5～15wt%;
3) material that obtains of process 2 tower stills enters rectifying tower and carries out rectifying with separating and recovering extractant, working 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 m-pentadiene product, and the tower still gets extraction agent, the extraction agent recycled;
4) mixing carbon five materials that obtain of process 2 cats head with enter a fixed-bed catalytic hydrogenator after hydrogen mixes and carry out hydrogenation reaction, obtain the hydrogenation products pentamethylene, catalyzer is taken from Pd/ γ-Al
20
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, temperature of reaction is 65～70 ℃;
5) process 4 resulting hydrogenation products pentamethylene enter rectifying tower and carry out rectifying, remove than the low-boiling component of pentamethylene, and working 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 constituent distillates from cat head, and the tower still gets the pentamethylene purified product.
Said process 1 described working 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 are preferably 30～80 ℃; Waste liquid is preferably 1:(8～16 with the feed weight ratio of extraction agent); Working 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 ratio a little more than the mass content of cyclopentenes in the raw material and pentamethylene that cat head distillates rate, generally is controlled between 45～55%; Reflux ratio is preferably 4～8; Extraction agent is that the acetonitrile solution of 5～15wt% is good with dimethyl formamide or water-content.
Said process 3 described working 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 4, and above-mentioned several catalyzer are that the present invention recommends, and wherein preferably uses Pd/ γ-Al
2O
3
Usually, the table main composed as follows of this tetrahydro methyl phthalic anhydride production process waste liquid is listed:
| Component | Content (wt%) |
| Trans-m-pentadiene | 0～3 |
| Cis-m-pentadiene | 10～15 |
| C 5 alkane (Skellysolve A, iso-pentane and pentamethylene) | 20～34 |
| Carbon pentaene hydrocarbon (1-amylene, 2-amylene, isopentene and cyclopentenes) | 30～48 |
| Isoprene | 0～4 |
| C6 and other hydro carbons | Surplus |
As can be seen from the above table, the heavy cis m-pentadiene of waste liquid content is below 15%, for alleviating the load of extracting rectifying, present method is taken off light rectifying earlier, remove the light component hydro carbons that boiling point is lower than m-pentadiene as far as possible, after taking off light rectifying, Skellysolve A, iso-pentane, 1-amylene, 2-amylene, isopentene 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-m-pentadiene | 0～5 |
| Cis-m-pentadiene | 20～50 |
| Cyclopentenes | 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 m-pentadiene are approaching, but differ bigger with cyclopentenes 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 m-pentadiene and cyclopentenes is 0.2 ℃ only, and the separation between them is very difficult.
Technical scheme provided by the invention has mainly comprised five processes, wherein process 2 is the most key, the present invention is by having selected ideal extraction agent and suitable extracting rectifying operational condition, realized the separation of MeTHPA production waste liquid well, the rectifying of process 3 is separated product with extraction agent, obtain product, and realize the recycled of extraction agent, to reduce isolating production cost.Through this first three process, obtained highly purified cis m-pentadiene product (general purity can reach more than 85%), by-product obtains the mixing carbon five based on cyclopentenes/pentamethylene simultaneously.Process 4 is by hydrogenation reaction the cyclopentenes in cyclopentenes/pentamethylene mixing carbon five to be converted into pentamethylene, and the pentamethylene purity of hydrogenated products is more than 70%.Impurity in the hydrogenated products mainly is the Skellysolve A of m-pentadiene hydrogenation generation and the alkane of carbon six, therefore adopt simple rectifying 5 again, the purity of pentamethylene is reached more than 95%, can satisfy general use, if pentamethylene purity is had requirements at the higher level, can assign to realize by the reorganization that further rectifying removes in the product.
The rectifying tower of process 1 can be a packing tower, and its theoretical plate number is 50～80.The extractive distillation column that process 2 adopts can be packing tower or sieve-tray tower, and the theoretical plate number of extractive distillation column is generally 40～80.Comparatively speaking, the rectifying of process 3 is comparatively simple, because the boiling point of the extraction agent that the present invention selects is all apparently higher than the boiling point of m-pentadiene, the theoretical plate number of rectifying tower is generally 5～20.Process 5 can adopt packing tower or sieve-tray tower, and theoretical plate number is between 30～50.
Waste liquid has obtained the very high high purity cis m-pentadiene product of economic worth after separating, and by-product obtains the higher pentamethylene of purity.Pentamethylene is harmless to atmospheric ozonosphere, can substitute halogenated hydrocarbon (CFCs) and make whipping 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 whipping agent, or obtain the mixture of Skellysolve A and iso-pentane by hydrogenation, obtain Skellysolve A and iso-pentane by separation then.
Positive effect of the present invention is to provide a kind of ideal 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 utility 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:
Embodiment
The MeTHPA production waste liquid that each embodiment uses is formed listed as table 1.
Table 1.
| Component | Content (wt%) |
| Trans-m-pentadiene | 1.2 |
| Cis-m-pentadiene | 12.7 |
| (Skellysolve A, iso-pentane are 29.4wt% to C 5 alkane; Pentamethylene is 2.5wt%) | 31.9 |
| (1-amylene, 2-amylene, isopentene are 39.9wt% to carbon pentaene hydrocarbon; Cyclopentenes 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 tower to remove light component, rectifying tower is a packing tower, and theoretical plate number is 60, and opening for feed 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 (℃) | Working 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 packing tower, and theoretical plate number is 45.Material enters extractive distillation column with the speed of 400g/h from the 32nd block of column plate, and extraction agent is from the 4th column plate charging.Extractive distillation column is operated under normal pressure, and concrete extraction agent that uses of each embodiment and other operational 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 cyclopentenes and pentamethylene.
Table 4
| Extraction agent | The extractant feed temperature (℃) | Material/extraction agent (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.
| Cyclopentenes (wt%) | Pentamethylene (wt%) | Trans m-pentadiene (wt%) | Cis m-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 tower with separating and recovering extractant, rectifying tower is a packing tower, and theoretical plate number is 7, and opening for feed is positioned at the 5th block of plate, each embodiment rectifying tower is operated under normal pressure, and other concrete operational condition sees Table 6.Rectifying Tata still obtains extraction agent, and extraction agent 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 m-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 m-pentadiene (wt%) | Trans m-pentadiene (wt%) | Cyclopentenes (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 |
[embodiment 11～14]
The cat head material (composition sees Table 5) that embodiment 5 obtains with enter a fixed-bed catalytic hydrogenator after hydrogen mixes and carry out hydrogenation reaction and obtain pentamethylene.Catalyzer adopts Pd/ γ-Al
2O
3(Pd content is 0.5wt% in the catalyzer, and catalyzer is spherical, particle diameter 2～4mm).The processing condition that each embodiment adopts see Table 8.
Table 8.
| The volume charge ratio | Air speed (hr -1) | Reaction pressure (MPa) | Temperature of reaction (℃) | Cyclopentenes transformation efficiency (%) | |
| Embodiment 11 | 5 | 4 | 1.2 | 70 | 99.6 |
| Embodiment 12 | 5 | 6 | 1.2 | 65 | 99.2 |
| Embodiment 13 | 3 | 4 | 0.9 | 70 | 99.6 |
| Embodiment 14 | 5 | 4 | 1.2 | 70 | 99.7 |
Annotate: the volume charge ratio is: hydrogen/cat head material
[embodiment 15～17]
The hydrogenation products of embodiment 12 enters a rectifying tower and carries out rectifying under 40 ℃, the composition of this hydrogenation products sees Table 9:
Table 9.
| Component | Content (wt%) |
| Iso-pentane | 1.3 |
| Skellysolve A | 2.1 |
| Pentamethylene | 94.1 |
| Carbon six | Surplus |
Rectifying tower is a packing tower, and theoretical plate number is 35.Hydrogenation products enters rectifying tower with the flow of 100g/h from the 14th block of column plate.Rectifying tower is operated under normal pressure, and the processing condition of employing see Table 10, and the tower still obtains cyclopentane product, and its composition sees Table 11.
Table 10.
| Tower still/tower top temperature (℃) | Reflux ratio | |
| Embodiment 15 | 55/40 | 15 |
| Embodiment 16 | 50/45 | 6 |
| Embodiment 17 | 60/43 | 30 |
Table 11.
| Iso-pentane (wt%) | Skellysolve A (wt%) | Pentamethylene (wt%) | Carbon six above alkane | |
| Embodiment 15 | Trace | Trace | 98.4 | Surplus |
| Embodiment 16 | Trace | 0.8 | 97.8 | Surplus |
| Embodiment 17 | Trace | 0.2 | 98.2 | Surplus |
Claims (10)
1, a kind of separation method of tetrahydro methyl phthalic anhydride production process waste liquid, the division ring carbon five that this waste liquid results from after the cracking of ethylene by-product C 5 fraction separation removal dicyclopentadiene reacts the production process of making methyl tetrahydro phthalic anhydride with cis-butenedioic anhydride, it is the hydrocarbon mixture that contains C 5 alkane, carbon pentaene hydrocarbon and cis m-pentadiene, and sepn process comprises:
1) waste liquid enters rectifying tower and carries out rectifying to remove light component, and the rectifying tower working pressure is 0～0.2MPa, and tower still temperature is 40～70 ℃, tower top temperature is 30～50 ℃, reflux ratio is 2～10, and cat head distillates light component material, and the tower still obtains the material of cis m-pentadiene, cyclopentenes and pentamethylene;
2) material that obtains of process 1 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 extraction agent: (6～20), working 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 cyclopentenes and pentamethylene, the tower still gets the material of m-pentadiene and extraction agent, and extraction agent is a dimethyl formamide, N-Methyl pyrrolidone, acetonitrile or water-content are any in the acetonitrile solution of 5～15wt%;
3) material that obtains of process 2 tower stills enters rectifying tower and carries out rectifying with separating and recovering extractant, working 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 m-pentadiene product, and the tower still gets extraction agent, the extraction agent recycled;
4) mixing carbon five materials that obtain of process 2 cats head with enter a fixed-bed catalytic hydrogenator after hydrogen mixes and carry out hydrogenation reaction, obtain the hydrogenation products pentamethylene, catalyzer 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, temperature of reaction is 65～70 ℃;
5) process 4 resulting hydrogenation products pentamethylene enter rectifying tower and carry out rectifying, remove than the low-boiling component of pentamethylene, and working 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 constituent distillates from cat head, and the tower still gets the pentamethylene purified product.
2, the separation method of tetrahydro methyl phthalic anhydride production process waste liquid according to claim 1 is characterized in that process 1 described working pressure is a 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 tetrahydro methyl phthalic anhydride production process waste liquid according to claim 1 is characterized in that process 2 described extractant feed temperature are 30～80 ℃.
4, the separation method of tetrahydro methyl phthalic anhydride production process waste liquid according to claim 1 is characterized in that the process 2 described waste liquids and the feed weight ratio of extraction agent are 1: (8～16).
5, the separation method of tetrahydro methyl phthalic anhydride production process waste liquid according to claim 1 is characterized in that process 2 described working pressures are normal pressure.
6, the separation method of tetrahydro methyl phthalic anhydride production process waste liquid according to claim 1 is characterized in that process 2 described tower still temperature are 75～125 ℃, and tower top temperature is 43～48 ℃.
7, the separation method of tetrahydro methyl phthalic anhydride production process waste liquid according to claim 1 is characterized in that the process 2 described cat head rates of distillating are 45～55%, and reflux ratio is 4～8.
8, the separation method of tetrahydro methyl phthalic anhydride production process waste liquid according to claim 1 is characterized in that process 2 described extraction agents are that dimethyl formamide or water-content are the acetonitrile solution of 5～15wt%.
9, the separation method of tetrahydro methyl phthalic anhydride production process waste liquid according to claim 1 is characterized in that process 3 described working pressures are normal pressure, and tower still temperature is 80～110 ℃, and tower top temperature is 40～44 ℃, and reflux ratio is 1～4.
10, the separation method of tetrahydro methyl phthalic anhydride production process waste liquid according to claim 1 is characterized in that process 4 described catalyzer are Pd/ γ-Al
2O
3
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| CN1453273A (en) * | 2002-04-22 | 2003-11-05 | 衣守志 | Benzene anhydride recovering and refining method from rectified residue |
| CN1462729A (en) * | 2003-06-19 | 2003-12-24 | 上海交通大学 | Treatment process for two stage recycling alkali waste liquid drained off by process system of synthesizing octanol |
| JP2004255351A (en) * | 2003-02-28 | 2004-09-16 | Kuraray Co Ltd | Method for removing neutral metal |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1453273A (en) * | 2002-04-22 | 2003-11-05 | 衣守志 | Benzene anhydride recovering and refining method from rectified residue |
| JP2004255351A (en) * | 2003-02-28 | 2004-09-16 | Kuraray Co Ltd | Method for removing neutral metal |
| CN1462729A (en) * | 2003-06-19 | 2003-12-24 | 上海交通大学 | Treatment process for two stage recycling alkali waste liquid drained off by process system of synthesizing octanol |
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