CN101747172B - Method for recycling acetic acid and catalysts in preparation process of 2,6-naphthalene dicarboxylic acid - Google Patents
Method for recycling acetic acid and catalysts in preparation process of 2,6-naphthalene dicarboxylic acid Download PDFInfo
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- CN101747172B CN101747172B CN2009102659883A CN200910265988A CN101747172B CN 101747172 B CN101747172 B CN 101747172B CN 2009102659883 A CN2009102659883 A CN 2009102659883A CN 200910265988 A CN200910265988 A CN 200910265988A CN 101747172 B CN101747172 B CN 101747172B
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- acetic acid
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- naphthalene dicarboxylic
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 237
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract 4
- 238000004064 recycling Methods 0.000 title abstract 2
- 238000000926 separation method Methods 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000012452 mother liquor Substances 0.000 claims description 42
- 238000011084 recovery Methods 0.000 claims description 29
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 2
- -1 for input port Substances 0.000 claims 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 abstract description 18
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 11
- 239000010941 cobalt Substances 0.000 abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 abstract description 9
- 239000011572 manganese Substances 0.000 abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052748 manganese Inorganic materials 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 9
- 229910052794 bromium Inorganic materials 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000001427 coherent effect Effects 0.000 description 2
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- FUPMSLTYEIZSLZ-UHFFFAOYSA-N cobalt;naphthalene-1-carboxylic acid Chemical compound [Co].C1=CC=C2C(C(=O)O)=CC=CC2=C1 FUPMSLTYEIZSLZ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a device and a method for recycling acetic acid and catalysts in the preparation process of 2,6-naphthalene dicarboxylic acid and relates to a device and a method which can effectively recover acetic acid and catalysts, wherein the acetic acid and the catalysts are acetic acid and catalysts in mother liquid discharged after steps of oxidation, oxidation and solid-liquid separation in the preparation process of naphthalene dicarboxylic acid. In the preparation of naphthalene dicarboxylic acid, in the presence of oxygen-contained gas and an acetic acid solvent, by using a catalyst system prepared from cobalt, manganese and other transition metal and bromine compounds, dimethylnaphthalene is subject to oxidization to prepare naphthalene dicarboxylic acid.
Description
The application divides an application, and the denomination of invention of its original application is " the recovery apparatus and method of the acetic acid in the manufacturing process of 2,6-naphthalene dicarboxylic acids and catalyzer ", and the applying date is on June 20th, 2006, and application number is 200610093085.8.
Technical field
The present invention relates to the apparatus and method for efficient recovery acetic acid and catalyzer, described acetic acid and catalyzer are in the series-operation of making naphthalene dicarboxylic acids, through acetic acid and the catalyzer in the mother liquor of discharging behind oxidation operation and crystallization step and the solid-liquid separation process, during above-mentioned manufacturing naphthalene dicarboxylic acids, in the presence of oxygen-containing gas and acetic acid solvent, the catalyst system that utilize to use the such transition metal of cobalt, manganese and bromine based compound to make makes dimethylnaphthalene generation oxidizing reaction make naphthalene dicarboxylic acids.
Background technology
Usually, in order to be recovered in employed acetic acid and catalyzer in the operation, can adopt multiple separation circuit.
Usually, in the acetic acid recovery process, use distillation method as the method that reclaims acetic acid, but the method is unfavorable at economic aspect, in addition, filtration method is not suitable for separating of acetic acid and catalyzer with absorption process.Therefore, various other methods that be used for to reclaim acetic acid and catalyzer have been proposed.Patent documentation 1 shows the operation of utilizing extracting process to reclaim acetic acid, and it is that tertiary amine and organic thinner are used with solvent as the extraction of acetic acid, reclaims acetic acid from the acetic acid solution that contains the metallicity material.But such method is not suitable as acetic acid and the catalyzer in the manufacturing process that recovery method reclaims naphthalene dicarboxylic acids.This is because in the method for using extraction, after the separated from acetic acid recovery, carry out postprocessing working procedures, so must consider the extraction reactivity of solvent and catalyst for oxidation reaction.
As the recovery method of catalyzer, incineration method, vacuum filtration process, electrochemical process etc. are arranged, but these are in also not by the state of commercialization.
No. the 4th, 883,912, [patent documentation 1] United States Patent (USP)
Summary of the invention
The present invention is for solving the problems referred to above point and the drawback of prior art, provides a kind of and can more economical and effectively be recovered in acetic acid in the mother liquor of discharging in the manufacturing process of naphthalene dicarboxylic acids and the apparatus and method of catalyzer.
In order to achieve the above object, the invention provides a kind of acetic acid in the mother liquor of discharging in the manufacturing process of naphthalene dicarboxylic acids and apparatus and method of catalyzer of being recovered in.
According to preferred implementation of the present invention, the recovery device of a kind of acetic acid and catalyzer is provided, its be from the manufacturing process of naphthalene dicarboxylic acids, discharge, contain in acetic acid, catalyzer and other organism mother liquors recovery device that reclaims acetic acid and catalyzer, comprise: mother liquor acceptance division, this mother liquor acceptance division have for input port, acetic acid relief outlet and the catalyzer and the organism relief outlet that drop into mother liquor or caustic soda; Heating unit, described heating unit is used for heating described mother liquor acceptance division; The filtering membrane of bottom, the filtering membrane of this bottom is connected separating catalyst from organism with described catalyzer with the organism relief outlet; And stirrer, this stirrer is for the inside of stirring described mother liquor acceptance division.
According to another preferred implementation of the present invention, it is characterized in that described heating unit is the sleeve pipe that is assemblied on the mother liquor acceptance division outer wall, has steam input port and condensed water discharge outlet.
According to another preferred implementation of the present invention, described mother liquor acceptance division also can comprise the caustic soda input port.
According to another preferred implementation of the present invention, it is characterized in that the recovery device of described acetic acid and catalyzer is taper shape or truncated cone shape.
According to another preferred implementation of the present invention, it is characterized in that the vacuum tightness of the filtering membrane of described bottom is 50mmHg～150mmHg, total filtration area is 0.3m
2～0.7m
2, and the mesh opening of filtering membrane is 20 μ m～80 μ m.
According to another preferred implementation of the present invention, the recovery method of a kind of acetic acid and catalyzer is provided, it is the method that reclaims acetic acid and catalyzer the separation circuit of naphthalene dicarboxylic acids from the mother liquor of discharging, and comprises the steps: to receive the mother liquor of discharging behind the separation circuit of naphthalene dicarboxylic acids; Heat the described mother liquor that receives, reclaim acetic acid with gaseous state; And in the rear residual residuum of acetic acid recovery, drop into caustic soda, precipitated catalyst is separated rear the recovery.
According to another preferred implementation of the present invention, with respect to residual acetic acid, can drop into the described caustic soda of 2 times of % by weight～3 times % by weight.
According to another preferred implementation of the present invention, it is characterized in that, in order to reclaim described catalyzer, adopt vacuum filtration process.
According to another preferred implementation of the present invention, method of the present invention adopts the recovery device of the above-mentioned acetic acid of mentioning and catalyzer, is made of the integrated operation of integral body.Herein, an integrated operation refers to, reclaims the coherent operation of acetic acid and catalyzer and does not use the in addition separated device of opening, and adopt a device to carry out.
The retrieving arrangement of acetic acid of the present invention and catalyzer, different from existing mode, can reclaim with a device the coherent operation of acetic acid and catalyzer, therefore have on the operation very easily advantage.And, need not other refining step, i.e. the recyclable acetic acid that can be recycled and catalyzer, very economical material benefit.
Description of drawings
Fig. 1 is in one embodiment of the invention, the sketch chart of the acetic acid in the mother liquor of discharging in the manufacturing process of recovery 2,6-naphthalene dicarboxylic acids and the device of catalyzer.
Nomenclature
A mother liquor acceptance division; The B stirrer; 1 mother liquor input port; 2 catalyzer and organism relief outlet; 3 acetic acid relief outlets; 4 steam input ports; 5 condensed water discharge outlets; 6 caustic soda input ports; The filtering membrane of 7 bottoms.
Embodiment
Fig. 1 is the sketch chart of one embodiment of the invention, and the below describes the present invention in detail according to Fig. 1.
Top at mother liquor acceptance division A has mother liquor input port 1, receives the mother liquor of discharging in the manufacturing process of naphthalene dicarboxylic acids.By the indirect heating unit the described mother liquor that receives is heated, at this moment, the acetic acid gasification is discharged from acetic acid relief outlet 3.Acetic acid is discharged rear residual residuum and is comprised of catalyzer and other organism, drops into caustic soda in described residuum, makes catalyst precipitation.Described caustic soda also can be from other input port 6 drops into, but also can be from the mother liquor input port 1 drops into.After the described catalyzer that precipitates was discharged by catalyzer and organism relief outlet 2, by the filtering membrane 7 of bottom, this catalyzer and separating organic matters also were recovered.
The mother liquor acceptance division has the residuum etc. that stirrer B be used for to stir mother liquor and contains catalyzer, and described stirrer is preferably anchor type (Anchor).
As described mother liquor heating unit, for example drop into 170 ℃～190 ℃ steam to the steam input port 4 of playing the effect of heat supplying opening, to add the mother liquor in the hot mother liquor acceptance division, input steam is condensed, and discharges from bottom condensed water discharge outlet 5.
As the catalyzer that is used for dimethylnaphthalene is oxidized to naphthalene dicarboxylic acids, use is by the complex catalyst system that constitutes of cobalt composition, manganese composition and bromine composition, the compound that wherein can be used as the use of cobalt composition has cobaltous acetate, naphthoic acid cobalt and cobaltous carbonate etc., amount for described cobalt composition, cobalt atom is 0.02～0.15 with respect to the ratio of dimethylnaphthalene, preferred 0.04～0.12, more preferably 0.06～0.1.
The compound that can be used as the use of manganese composition has manganous acetate, manganese naphthenate, manganous carbonate and manganese bromide, and take cobalt atom as benchmark, the amount of manganese composition is 0.05～1.0, and preferred 0.15～0.4.The amount of total metal catalyst, being cobalt and manganese composition sum, take atom as benchmark, is 0.03～0.25 with respect to dimethylnaphthalene, preferred 0.05～0.2.If not in described scope, then can not obtain desirable highly purified naphthalene dicarboxylic acids, when the usage quantity of cobalt composition and manganese composition is very few, can not carry out as 2 of the intermediate product of oxidizing reaction, the conversion of 6-naphthaldehyde acid causes the yield of ultimate aim product to reduce, and uses when too much, form coordination compound with the trimellitic acid as impurity, the purity of naphthalene dicarboxylic acids descends.
In order the bromine composition to be provided, can to use at least a kind of compound in the group that is selected from Manganese dibromide, cobaltous bromide, Sodium Bromide, brometo de amonio and tetrabromoethane composition, take cobalt atom as benchmark, the ratio of bromine composition is 0.8～2.0, preferred 1.0～1.5.When using the bromine composition that surpasses described scope, the amount of the transition metal complex compound of the naphthalene dicarboxylic acids of finally deriving reduces, and the amount of bromine compounds increases, and the load of refining step increases, and is with coloured impurity to increase, and is therefore undesirable.And, when adopting the operation that the bromine composition is re-used, need recovery process, therefore produce additional financial loss.On the other hand, use when not reaching the bromine composition of above-mentioned scope, cause the amount of transition metal complex compound in the naphthalene dicarboxylic acids to increase.
With reactant, be dimethylnaphthalene with 1: 5 to 1: 15 ratio solvent in acetic acid, preferably in 1: 10 to 1: 12 ratio, dissolve, drop into the oxidizing reaction machine.
Through the resultant of described oxidizing reaction operation in by crystallization step, the form of the form of dividing with the solid phase with a certain size crystallization and the paste-like of acetic acid is transported to solid-liquid separation process, is separated into resultant and the mother liquor (containing catalyzer and organic acetic acid solution) that solid phase is divided by the separation circuit device.The invention is characterized in that the employing effective means will be through the acetic acid in the mother liquor of solid-liquid separation process and catalyst separating.
Retrieving arrangement by acetic acid of the present invention and catalyzer, acetic acid is to evaporate to reclaim by the steam that drops into as the heat medium, catalyzer in the solution that is not evaporated is by dropping into caustic soda, make after the catalyst precipitation, adopting vacuum filtration process to reclaim.
The recovery of acetic acid of the present invention and catalyzer is adopted the heat medium with in the device as the mother liquor heating unit that is used for evaporation of acetic acid, for this reason preferred mounting bush on outer wall.
And, with respect to residual acetic acid, preferably drop into the caustic soda of 2 times of % by weight～3 times % by weight, thereby suitably with residual acetic acid and organism neutralization.
And total filtration area of employed filtering membrane is 0.3m in the vacuum filtration process
2～0.7m
2, the opening of mesh is 20 μ m～80 μ m, vacuum keep is 50mmHg～150mmHg.
Embodiment
Below, further describe the present invention according to embodiment, but the present invention is not limited to this embodiment.
[embodiment 1]
In the titanyl reaction machine that catalyzer and the reactant of ratio of components shown in the table 1 are together put into 300L, this titanyl reaction machine comprises cooler, heater, stirrer and recirculation acetic acid drum.
Table 1
| Material | Input amount |
| Cobalt | 6.21 % by weight (wt%) |
| Manganese | 1.58 % by weight |
| Bromine | 3.87 % by weight |
| Distilled water | 25.0 % by weight |
| Acetic acid | In right amount |
Temperature of reaction is adjusted to 200 ℃, reaction pressure is adjusted to 20kg/cm
2Afterwards, stirrer is set as 700rpm, so that input reactant gases suitably disperses.Be 10% reaction soln with dimethylnaphthalene with respect to the weight ratio of acetic acid, supply with catalyzer with the speed of 93kg/hr, to carry out successive reaction.
After the reaction, the mother liquor that will discharge behind crystallization step and separation circuit is injected in the retrieving arrangement of acetic acid and catalyzer.The retrieving arrangement internal capacity of acetic acid and catalyzer is 107L and is formed by stainless material, is equipped with on the outer wall be used to the sleeve pipe that makes the medium flowing of supplying with heat, and inside is provided with anchor type stirrer.Medium as supplying with heat uses 10 atmospheric steam, supplies with until evaporate more than or equal to 70% acetic acid.After the acetic acid evaporation, when temperature is maintained 60 ℃, drop into the caustic soda of 50L.After about 2 hours, filter and vacuum pump are connected on catalyzer and the organism relief outlet, organism and solution are filtered, reclaim residual catalyzer.
Obtain following result: the cobalt catalyst metal recovery rate is 95%, and the Mn catalyst metal recovery rate is 90%, and the bromine rate of recovery is 10%, and the acetic acid rate of recovery is 65%.
Can prove according to the above embodiments, when reclaiming acetic acid and catalyzer by device of the present invention, be highly profitable economically.
Claims (4)
1. the recovery method of an acetic acid and catalyzer, it is from reclaiming the method for acetic acid and catalyzer in the mother liquor of discharging in the separation circuit of 2,6-naphthalene dicarboxylic acids, comprising the steps:
The mother liquor that reception is discharged behind the separation circuit of 2,6-naphthalene dicarboxylic acids;
Heat the described mother liquor that receives, reclaim acetic acid with gaseous state; And
After reclaiming acetic acid, in the residual residuum, drop into caustic soda, will reclaim after the catalyst separating that precipitate.
2. the recovery method of acetic acid according to claim 1 and catalyzer is characterized in that, with respect to residual acetic acid, drops into and counts 2 times～3 times described caustic soda with % by weight.
3. the recovery method of acetic acid according to claim 1 and catalyzer is characterized in that, in order to reclaim described catalyzer, adopts vacuum filtration process.
4. the recovery method of acetic acid according to claim 1 and catalyzer, it is characterized in that, adopt following acetic acid and the recovery device of catalyzer, consisted of by the integrated operation of integral body, the recovery device of described acetic acid and catalyzer is from 2, reclaim the recovery device of acetic acid and catalyzer in the mother liquor of discharging in the manufacturing process of 6-naphthalene dicarboxylic acids, contain acetic acid, catalyzer and other organism in the described mother liquor, the recovery of described acetic acid and catalyzer comprises with device:
The mother liquor acceptance division, this mother liquor acceptance division has for input port, acetic acid relief outlet and the catalyzer and the organism relief outlet that drop into mother liquor and caustic soda, and perhaps this mother liquor acceptance division has for the input port of dropping into mother liquor, for input port, acetic acid relief outlet and the catalyzer and the organism relief outlet that drop into caustic soda;
Heating unit, this heating unit is used for heating described mother liquor acceptance division;
The filtering membrane of bottom, this filtering membrane is connected with the organism relief outlet with described catalyzer, is used for from the organism separating catalyst; And
Stirrer, this stirrer is for the inside of stirring described mother liquor acceptance division.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102659883A CN101747172B (en) | 2006-06-20 | 2006-06-20 | Method for recycling acetic acid and catalysts in preparation process of 2,6-naphthalene dicarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102659883A CN101747172B (en) | 2006-06-20 | 2006-06-20 | Method for recycling acetic acid and catalysts in preparation process of 2,6-naphthalene dicarboxylic acid |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006100930858A Division CN101092341B (en) | 2006-06-20 | 2006-06-20 | Recovery installation and method for acetic acid and catalyst in process of preparing 2.6 naphthalic carboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101747172A CN101747172A (en) | 2010-06-23 |
| CN101747172B true CN101747172B (en) | 2013-03-27 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4883912A (en) * | 1982-07-06 | 1989-11-28 | Daicel Chemical Industries, Ltd. | Process for the recovery of acetic acid |
| CN2762859Y (en) * | 2004-12-27 | 2006-03-08 | 济南倍力粉技术工程有限公司 | Extraction separator |
-
2006
- 2006-06-20 CN CN2009102659883A patent/CN101747172B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4883912A (en) * | 1982-07-06 | 1989-11-28 | Daicel Chemical Industries, Ltd. | Process for the recovery of acetic acid |
| CN2762859Y (en) * | 2004-12-27 | 2006-03-08 | 济南倍力粉技术工程有限公司 | Extraction separator |
Non-Patent Citations (1)
| Title |
|---|
| 王沛.2，6－萘二甲酸的合成及含二氮杂萘酮结构新型聚芳酰胺的.《大连理工大学博士学位论文》.2006, * |
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| CN101747172A (en) | 2010-06-23 |
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Effective date of registration: 20181210 Address after: Seoul, South Kerean Patentee after: Xiaoxing Chemistry (strain) Address before: Gyeonggi Do, South Korea Patentee before: Hyosung Corp. |