CN101302152B - Method for recovering terephthalic acid from coloured terephthalic acid residue by complexation-crystallization - Google Patents
Method for recovering terephthalic acid from coloured terephthalic acid residue by complexation-crystallization Download PDFInfo
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- CN101302152B CN101302152B CN200810062425XA CN200810062425A CN101302152B CN 101302152 B CN101302152 B CN 101302152B CN 200810062425X A CN200810062425X A CN 200810062425XA CN 200810062425 A CN200810062425 A CN 200810062425A CN 101302152 B CN101302152 B CN 101302152B
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 305
- 238000002425 crystallisation Methods 0.000 title claims abstract description 57
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 33
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 23
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- 239000002253 acid Substances 0.000 claims description 19
- 238000001953 recrystallisation Methods 0.000 claims description 19
- 239000000049 pigment Substances 0.000 claims description 16
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- DYNFCHNNOHNJFG-UHFFFAOYSA-N 2-formylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=O DYNFCHNNOHNJFG-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 4
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 239000002440 industrial waste Substances 0.000 claims description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- ILYSAKHOYBPSPC-UHFFFAOYSA-N 2-phenylbenzoic acid Chemical class OC(=O)C1=CC=CC=C1C1=CC=CC=C1 ILYSAKHOYBPSPC-UHFFFAOYSA-N 0.000 claims description 2
- 229910020632 Co Mn Inorganic materials 0.000 claims description 2
- 229910020678 Co—Mn Inorganic materials 0.000 claims description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Chemical class CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004056 anthraquinones Chemical class 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000004927 fusion Effects 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008247 solid mixture Substances 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 51
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 12
- 238000010219 correlation analysis Methods 0.000 description 12
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- 150000003504 terephthalic acids Chemical class 0.000 description 3
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- POPBYCBXVLHSKO-UHFFFAOYSA-N 9,10-dioxoanthracene-1-carboxylic acid Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(=O)O POPBYCBXVLHSKO-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
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- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 2
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229920004935 Trevira® Polymers 0.000 description 1
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- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 239000011549 crystallization solution Substances 0.000 description 1
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Abstract
The invention discloses a method for reclaiming terephthalic acid from colored terephthalic acid residue by adopting complex crystallization. The method is as follows: firstly, the terephthalic acid residue and complex crystallization solvent are mixed in a complex crystallizer, then the temperature is controlled to be between 10 and 120 DEG C to ensure that a pure terephthalic acid product is precipitated in the form of solvent complex crystallization, and colored impurities are enriched in solution. The method can effectively remove the colored impurities in the terephthalic acid residue, and the reclaimed terephthalic acid product has higher color quality. The method can effectively reduce the discharge of solid waste during the production process of PTA, protect the environment, can also reduce the consumption of raw materials and production cost, and improve the economic benefit.
Description
Technical field
The present invention relates to a kind ofly from coloured terephthaldehyde's acid residue, reclaim method of terephthalic acid, especially adopt the complexing crystallization from coloured terephthaldehyde's acid residue, to reclaim method of terephthalic acid.
Background technology
Pure terephthalic acid (PTA) is the important source material of producing trevira and polyester material, is mainly made by p-Xylol (PX) air liquid phase catalytic oxidation.In pure terephthalic acid (PTA) production process, chromaticity index is one of key index of PTA quality product, and the control of PTA product colourity (as the b value) and the removal of foreign pigment are closely related.In PTA device operational process,, must strictly control crude terephthalic acid (CTA) quality product of removing refined unit because treating process is limited to the foreign pigment processing power.In order to control the concentration of the foreign pigment among the CTA, the method that adopts usually in the industry is to extract part circulating reaction mother liquor to carry out impurity and purification processing (US4939297, CN1572765).In mother liquor removal of impurities process, though removed most foreign pigment, also can produce a certain amount of coloured terephthalic acid solid residue simultaneously, this residue part terephthalic acid (TA) product will be discarded with the form of solid residue in CTA removal of impurities process.The quantity discharged of the terephthalic acid solid residue of PTA factory is about 0.5% of PTA output, with scale is that 600,000 tons/year PTA factory is an example, the terephthalic acid solid residue quantity discharged of annual discharging reaches 3000 tons, and wherein the depleted terephthalic acid reaches more than 2000 ton.Because the discharging of a large amount of terephthalic acid solid residues can cause the serious environmental pollution, adopt incinerating method to handle in the industry usually.Though this method has solved environmental problem, also wasted a large amount of Nonrenewable resources, be necessary to improve.
Be worth in view of such solid residue has higher recycling, occurred a lot of relevant patented technologies in recent years.As CN1611481, CN1611482, CN1332145, CN1253942, CN1195660 etc.Because the composition of terephthalic acid solid residue is very complicated, except containing a large amount of TA, phenylformic acid (BA), p-methylbenzoic acid (PT), to the content of carboxyl benzaldehyde (4-CBA), m-phthalic acid (IPA), phthalic acid (OPA), trimellitic acid aromatic carboxylic acid such as (TMA) also than higher, contain a spot of bromobenzene, biphenyl, benzophenone carboxylic acid's derivative and colored Fluorenone, anthraquinone carboxylic acids derivative in addition.And the composition of the terephthalic acid solid residue that produces of the PTA factory that adopts different patented technologies differs greatly.So adopt the method that separating purifies reclaims one by one to all components very difficult, and existing patented technology all is to develop at the TA waste residue of a certain specific composition, the mentioned target pure substance with recovery value generally also has only one to two kind.CN1611481 and CN1611482 disclose a kind of method that adopts the esterification method to reclaim terephthalic acid and p-methylbenzoic acid in the TA solid residue; CN1332145 and CN1253942 disclose a kind of employing dissolving, crystallization and rectifying and have reclaimed benzoic method in the TA solid residue; CN1195660 also discloses a kind of method that is rich in acetic acid and catalyst cobalt manganese in the TA solid residue waste liquid that adopts evaporation, rectifying, extraction to wait to reclaim.
Impurity in coloured terephthaldehyde's acid residue can divide two classes: a class is the impurity that is easy to remove such as phenylformic acid, p-methylbenzoic acid, to carboxyl benzaldehyde, m-phthalic acid, phthalic acid, trimellitic acid etc., though the content of such impurity than higher, is easy to remove by reaction in the technology and crystallisation process; Another kind of is colored Fluorenone, anthraquinone carboxylic acids class impurity, though the concentration of such impurity very low usually (＜50ppm), extremely low concentration (＜still have a strong impact on the colourity quality of product under 1ppm).This also is a reason of constantly strengthening mother liquor removal of impurities and the coloured terephthaldehyde's acid residue of a large amount of dischargings during PTA produces.
Summary of the invention
The objective of the invention is to improve existing terephthalic acid solid draff processing method, propose a kind of employing complexing crystallization and from coloured terephthaldehyde's acid residue, reclaim method of terephthalic acid,, reduce PTA raw material consumption to reduce waste discharge.
Basic ideas of the present invention are to select suitable complexing recrystallisation solvent system for use, utilize the solvent complex properties difference of terephthalic acid and foreign pigment to realize removing of foreign pigment, have the terephthalic acid solid of good chromaticity index thereby reclaim.At first colored terephthalic acid solid residue and complexing recrystallisation solvent are mixed, the TA in the residue, 4-CBA, PT acid, BA etc. and foreign pigment can both combine fast with solvent and form the complex compound dissolving; Wherein, because the solvent complex thing solubleness of TA is less, TA solvent complex thing can be separated out by rapid crystallization; In like manner, the solvent complex thing of carboxylic acids such as 4-CBA, PT acid, BA also can be separated out in company with TA complex compound crystallising part; Because the solvent complex thing crystallographic property and the TA complex compound of the foreign pigment in the residue differ greatly, and concentration is very low, foreign pigment can not separated out with the crystallization of TA complex compound, thereby realizes foreign pigment and TA product separation.
With the complexing crystallisation process of terephthalic acid (TA) in dimethyl formamide (DMF) solvent is example.Under the certain temperature condition, DMF is a kind of good solvent of TA, and solvent DMF can form the complex compound of TA with the quick complexing of TA in the dissolution process of TA.Stable TA complex structure also can change with temperature is different, and as under 10～60 ℃, stable complex structure is TA2DMF, and promptly each TA molecule is in conjunction with the DMF of 2 molecules; And when being higher than 80 ℃, stable complex structure is TADMF; When temperature was higher than 120 ℃, the structure of any complex compound all was unsettled, and the crystallization of TA in the DMF solvent all exists with the TA of pure molecular state.Detailed process is seen formula (1), (2).
Dissolving crystallized:
Stable crystalline is with variation of temperature:
(2)
(10～60℃)..............(＞80℃)..............................(＞120℃)
Because the TA complex structure also can change with temperature is different, and under hot conditions, the TA complex compound all can be transformed into stable TA.Therefore, the complexing recrystallisation solvent all can be removed by the intensification fusion-crystallization.
Employing complexing crystallization of the present invention is reclaimed method of terephthalic acid from coloured terephthaldehyde's acid residue, its step is as follows:
1) the coloured terephthalic acid solid residue of exsiccant is put into the complexing crystallizer, add the complexing recrystallisation solvent, the mass ratio of complexing recrystallisation solvent and coloured terephthalic acid solid residue is 0.5～50, mixes;
2) mixture under 10～120 ℃ of temperature, stopped 0.5～200 minute in the complexing crystallizer, and the solvent complex thing crystallization of terephthalic acid is separated out, and the foreign pigment in the residue solid is dissolved in the mother liquor that is rich in the complexing recrystallisation solvent;
3) with the solidliquid mixture in the complexing crystallizer through solid-liquid separation, washing, obtain terephthaldehyde's acid complex crystallization of white; 4) with the crystallization of terephthaldehyde's acid complex 50～250 ℃ of following fusions, form the liquid-solid mixture slurry of terephthalic acid solid and mother liquor;
5) with terephthalic acid slurry through solid-liquid separation, washing, drying, reclaim terephthalate product.
Among the present invention, said coloured terephthalic acid solid residue is the industrial waste that contains a large amount of terephthalic acids, can derive from the removal of impurities process of PX oxidizing reaction mother liquor or the throw out in the PTA waste water.Coloured terephthalic acid solid residue is except that containing terephthalic acid, Fluorenone class carboxylic acid and anthraquinone class carboxylic acid foreign pigment, also contain phenylformic acid, p-methylbenzoic acid, to one or more the industrial waste in carboxyl benzaldehyde, m-phthalic acid, phthalic acid, trimellitic acid, bromo aromatic carboxylic acid, biphenyl carboxylic acids and the benzophenone carboxylic acid's derivative, also can contain acetic acid, water and Co-Mn metal catalyzer in the residue.
Among the present invention, said complexing recrystallisation solvent is one or more mixtures in sulfone class or the amide solvent.The sulfone kind solvent can be selected from one or more mixtures in sulfone class dimethyl sulfoxide (DMSO) (DMSO), ring fourth sulfoxide, tetramethylene sulfone and the dimethyl sulfone, preferred DMSO.Amide solvent can be selected from N-Methyl pyrrolidone (NMP), N-ethyl pyrrolidone (NEP), N, dinethylformamide (DMF), N,N-dimethylacetamide (DMA) and N, one or more mixtures in the N-diethyl acetamide.Preferred DMA and NMP.
Among the present invention, said adding complexing recrystallisation solvent and terephthaldehyde's acid residue mass ratio are 0.5～50, preferred 1～10.
Among the present invention, the container that said complexing crystallizer stirs for band, the temperature of complexing crystallizer is 10～120 ℃, preferred 40～100 ℃, the residence time of mixture in the complexing crystallizer is 0.5～200 minute, preferred 5～60 minutes.
Among the present invention, the temperature of said fusion-crystallization is 80～250 ℃, preferred 100～150 ℃.
The present invention is in the process that reclaims terephthalic acid, and the mother liquor after step 3) and the step 5) solid-liquid separation all can return the recycle of complexing crystallizer.
Beneficial effect of the present invention is:
Can be according to the present invention to the processing of decolouring of coloured terephthalic acid solid residue, efficiently remove wherein micro-foreign pigment, efficient recovery TA component wherein, the terephthalate product of recovery has higher quality of colour.Use the present invention not only can reduce the discharging of solid waste in the PTA production process, the protection environment can also be cut down the consumption of raw materials, and reduces production costs, and increases economic efficiency.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Further specify the present invention below in conjunction with embodiment and accompanying drawing.Need to prove that method provided by the invention is not limited to processing condition and the flow process configuration that provides among the embodiment, any local improvement to these methods can not change feature of the present invention yet.
The concrete technical process of the inventive method as shown in Figure 1.
Embodiment 1
The handled TA residue of present embodiment derives from CTA mother liquor impurity removed system, mainly consist of: TA (90.15wt%), 4-CBA (4.05wt%), PT (2.44wt%), BA (1.21wt%), IPA (0.75wt%), other component is about 1.40wt%, and the chromaticity index b value of this TA residue is 17.0.
The coloured terephthalic acid solid residue of exsiccant 100.0g is put into the complexing crystallizer, add 400.0gN, N-N,N-DIMETHYLACETAMIDE (DMA) mixes; Mixture under 70 ℃ of temperature, stopped 20 minutes in the complexing crystallizer, and the TA complexing crystallization of adularescent generates, and mother liquor also is transformed into yellow by clear, colorless.Filter, and, obtain white TA complexing crystalline solid at last, be weighed as 117.8g with the complexing crystallization solution washing of saturated TA.
Adopt the mass fraction of solvent DMA in the crystallization of gas chromatographic analysis TA complex compound, the DMA mass fraction is 49.4%, and promptly the molecule number of DMA and TA ratio is 1.86: 1, also is that a TA molecule is combined with 2 DMA molecules approximately in the TA complexing crystallization.Take by weighing the crystallization of 50.0gTA complex compound and carry out vacuum-drying under 120 ℃ of conditions, can obtain the about 25.0g of TA solid after 2 hours, the DMA residual quantity in the TA solid is less than 0.5% (wt%).4-CBA in the TA solid phase, PT acid concentration adopt the Agilentl100 liquid-phase chromatographic analysis, be furnished with DAD detector and quaternary pump, chromatographic column be Agilent-ZORBAK-SB-C18 (post of 150mm * 4.6mm/5um), moving phase is the ternary gradient elution of water, methyl alcohol and acetonitrile; (analysis of UV757CRT ultraviolet-visible pectrophotometer is adopted in the analysis of λ=340nm) to the 340nm absorbance A, usually get the 0.2mol/L potassium hydroxide solution that the 0.1gTA solid is dissolved in 10ml, measure the absorbance A of this solution under wavelength 340nm (λ=340nm) then.
Embodiment 2
Carry out the processing of TA residue with the mode similar to embodiment 1.Be N in quality such as the complexing solvent that present embodiment adopted are, dinethylformamide (DMF), the DMF complexing crystalline solid 102.0g of acquisition TA.The mass fraction of solvent DMF is 46.0% in the DMF complexing crystallization of employing gas chromatographic analysis TA, and promptly the molecule number of DMF and TA ratio is 1.94: 1, also is that a TA molecule is combined with 2 DMF molecules approximately in the TA complexing crystallization.Vacuum-drying is carried out in this complex compound crystallization remove DMF solvent acquisition TA solid under 120 ℃ of conditions, analyze foreign matter content and chromaticity index that TA reclaims, the correlation analysis data results in contrast to table 1.
Embodiment 3
Carry out the processing of TA residue with the mode similar to embodiment 1.Just, obtain the NMP complexing crystalline solid 88.7g of TA at the N-Methyl pyrrolidone (NMP) of quality such as the complexing solvent that present embodiment adopted is.The mass fraction of solvent NMP is 54.2% in the NMP complexing crystallization of employing gas chromatographic analysis TA,, promptly the molecule number of NMP and TA ratio is 1.98: 1, also is that a TA molecule is combined with 2 NMP molecules approximately in the TA complexing crystallization.Vacuum-drying is carried out in this complex compound crystallization obtain the TA solid under 120 ℃ of conditions, analyze foreign matter content and chromaticity index that TA reclaims, the correlation analysis data results in contrast to table 1.
Embodiment 4
Carry out the processing of TA residue with the mode similar to embodiment 1.At the complexing solvent that present embodiment adopted is the dimethyl sulfoxide (DMSO) (DMSO) of 400.0g, and the TA residue of processing is 200.0g.Its reason is to consider that the solubleness of TA in DMSO is more much bigger than DMA, NMP and DMF.Obtain the DMSO complexing crystalline solid 121.7g of TA.The mass fraction of solvent DMSO is 34.7% in the DMSO complexing crystallization of employing gas chromatographic analysis TA, and promptly the molecule number of DMSO and TA ratio is 1.13: 1, also is that a TA molecule is combined with 1 DMSO molecule approximately in the TA complexing crystallization.Vacuum-drying is carried out in this complex compound crystallization obtain the TA solid under 120 ℃ of conditions, analyze foreign matter content and chromaticity index that TA reclaims, the correlation analysis data results in contrast to table 1.
The TA index that the different complexing recrystallisation solvents of table 1 reclaim
| Embodiment | Solvent | Crystallization (g) | Solvent/TA (mol) | TA yield (wt%) | ?4-CBA ?(wt％) | ?A ?(λ＝340nm) |
| 1 | ?DMA | ?117.8 | ?1.86 | ?66.2 | ?0.85 | ?0.025 |
| 2 | ?DMF | ?102.0 | ?1.94 | ?61.2 | ?1.26 | ?0.073 |
| 3 | ?NMP | ?88.7 | ?1.98 | ?45.2 | ?0.93 | ?0.081 |
| 4 | ?DMSO | ?121.7 | ?1.13 | ?44.1 | ?1.95 | ?0.115 |
| The TA residue | ?—— | ?—— | ?—— | ?—— | ?4.05 | ?0.450 |
Comparative example 1～4 result adopts the complexing crystallization process can remove foreign pigment in the TA residue effectively as can be known, and the TA product chromaticity index of recovery is very good, and the concentration of 4-CBA also reduces significantly.In the complexing recrystallisation solvent of being investigated, with the best results of DMA, the result of DMF and NMP is also good, and the effect of DMSO is relatively poor.
Embodiment 5
Carry out the processing of TA residue with the mode similar to embodiment 1.Be 5 minutes just, obtain the DMA complexing crystalline solid 109.9g of TA at the complexing crystallization time that present embodiment adopted.The correlation analysis data results in contrast to table 2.
Embodiment 6
Carry out the processing of TA residue with the mode similar to embodiment 1.Be 40 minutes just, obtain the DMA complexing crystalline solid 116.3g of TA at the complexing crystallization time that present embodiment adopted.The correlation analysis data results in contrast to table 2.
Embodiment 7
Carry out the processing of TA residue with the mode similar to embodiment 1.Be 40 ℃ in the complexing Tc that present embodiment adopted just, the complexing crystallization time is 40 minutes, obtains the DMA complexing crystalline solid 137.8g of TA.The correlation analysis data results in contrast to table 2.
Embodiment 8
Carry out the processing of TA residue with the mode similar to embodiment 1.Be 40 ℃ in the complexing Tc that present embodiment adopted just, the complexing crystallization time is 20 minutes, obtains the DMA complexing crystalline solid 141.8g of TA.The correlation analysis data results in contrast to table 2.
Embodiment 9
Carry out the processing of TA residue with the mode similar to embodiment 1.Be 100 ℃ in the complexing Tc that present embodiment adopted just, the complexing crystallization time is 20 minutes, obtains the DMA complexing crystalline solid 40.1g of TA.The correlation analysis data results in contrast to table 2.
The different condition contrast of TA process is reclaimed in the crystallization of table 2 DMA solvent complex
| Embodiment | Temperature (℃) | Time (min) | Crystallization (g) | Solvent/TA (mol) | TA yield (wt%) | ?4-CBA ?(wt％) | A (λ＝340nm) |
| ?1 | ?70 | ?20 | ?117.8 | ?1.86 | ?66.2 | ?0.85 | 0.025 |
| ?5 | ?70 | ?5.0 | ?45.6 | ?1.60 | ?66.4 | ?0.98 | 0.056 |
| ?6 | ?70 | ?40 | ?50.8 | ?1.97 | ?63.6 | ?0.56 | 0.036 |
| ?7 | ?40 | ?40 | ?51.0 | ?1.99 | ?75.1 | ?0.75 | 0.123 |
| ?8 | ?40 | ?20 | ?50.6 | ?1.95 | ?77.9 | ?1.06 | 0.156 |
| ?9 | ?100 | ?20 | ?23.5 | ?0.59 | ?34.1 | ?1.23 | 0.278 |
Comparative example 1 and 5～9 result as can be known, temperature and time is very big to the influence of DMA solvent complex crystallisation process.Too high temperature as Tc during greater than 100 ℃, because the solubleness increase can make one way TA yield significantly reduce, because TA complexing crystallization can not stable existence under the too high temperature condition, makes the quality index severe exacerbations such as TA colourity of recovery simultaneously.Because the crystallization rate of this process is very fast, the influence of crystallization time is less.
Embodiment 10
Carry out the processing of TA residue with the mode similar to embodiment 3.The complexing recrystallisation solvent that adopts also is NMP, and just the complexing Tc that adopts at present embodiment is 40 ℃, and the complexing crystallization time is 20 minutes, obtains the NMP complexing crystalline solid 131.7g of TA.The correlation analysis data results in contrast to table 3.
Embodiment 11
Carry out the processing of TA residue with the mode similar to embodiment 3.The complexing recrystallisation solvent that adopts also is NMP, is 100 ℃ in the complexing Tc that present embodiment adopted just, and the complexing crystallization time is 20 minutes, obtains the NMP complexing crystalline solid 23.8g of TA.The correlation analysis data results in contrast to table 3.
Temperature and time is to the influence of TA quality in the table 3.NMP solvent complex crystallisation process
| Embodiment | Temperature (℃) | Time (min) | Crystallization (g) | Solvent/TA (mol) | TA yield (wt%) | 4-CBA (wt％) | ?A ?(λ＝340nm) |
| 3 | 70 | ?20 | 88.7 | 1.98 | 45.2 | 0.93 | ?0.081 |
| 10 | 40 | ?20 | 131.7 | 53.4 | 1.921 | 1.15 | ?0.116 |
| 11 | 100 | ?20 | 23.8 | 36.9 | 0.981 | 1.63 | ?0.225 |
Comparative example 3,10 and 11 result as can be known, temperature and time to nmp solvent complexing crystallisation process to influence rule similar with DMA solvent complex crystallisation process.
Embodiment 12
Carry out the processing of TA residue with the mode similar to embodiment 1.Just the TA residue of handling in the present embodiment is 200.0g, and the DMA complexing recrystallisation solvent of employing is 400.0g, obtains the DMA complexing crystalline solid 283.6g of TA.The correlation analysis data results in contrast to table 4.
Embodiment 13
Carry out the processing of TA residue with the mode similar to embodiment 3.Just the TA residue of handling in the present embodiment is 200.0g, and the NMP complexing recrystallisation solvent of employing is 400.0g, obtains the NMP complexing crystalline solid 264.5g of TA.The correlation analysis data results in contrast to table 4.
The comparison of TA process is reclaimed in the complexing crystallization under the table 4. different solvents amount condition
| Embodiment | Solvent | Solvent/residue | Crystallization (g) | Solvent/TA (mol) | TA yield (wt%) | ?4-CBA ?(wt％) | ?A ?(λ＝340nm) |
| 1 | ?DMA | ?4/1 | ?117.8 | ?1.86 | ?66.2 | ?0.85 | ?0.025 |
| 3 | ?NMP | ?4/1 | ?88.7 | ?1.98 | ?45.2 | ?0.93 | ?0.081 |
| 12 | ?DMA | ?2/1 | ?283.6 | ?2.01 | ?76.7 | ?1.00 | ?0.056 |
| 13 | ?NMP | ?2/1 | ?264.5 | ?1.74 | ?72.1 | ?1.13 | ?0.105 |
Comparative example 1,3,12 and 13 result as can be known, in handling TA residue process, the complexing recrystallisation solvent amount that is adopted is also important.When increasing solvent ratio,, can reduce one way TA yield significantly simultaneously though the TA quality product that reclaims is slightly improved.Therefore under TA quality product situation up to standard, can suitably reduce solvent ratio.
Claims (4)
1. adopt the complexing crystallization from coloured terephthaldehyde's acid residue, to reclaim method of terephthalic acid, it is characterized in that step is as follows:
1) the coloured terephthalic acid solid residue of exsiccant is put into the complexing crystallizer, add the complexing recrystallisation solvent, the mass ratio of complexing recrystallisation solvent and coloured terephthalic acid solid residue is 0.5～50, mixes;
2) mixture under 10～120 ℃ of temperature, stopped 0.5～200 minute in the complexing crystallizer, and the solvent complex thing crystallization of terephthalic acid is separated out, and the foreign pigment in the residue solid is dissolved in the mother liquor that is rich in the complexing recrystallisation solvent;
3) with the solidliquid mixture in the complexing crystallizer through solid-liquid separation, washing, obtain terephthaldehyde's acid complex crystallization of white;
4) with the crystallization of terephthaldehyde's acid complex 50～250 ℃ of following fusions, form the liquid-solid mixture slurry of terephthalic acid solid and mother liquor;
5) with terephthalic acid slurry through solid-liquid separation, washing, drying, reclaim terephthalate product;
Above-mentioned complexing recrystallisation solvent is dimethyl sulfoxide (DMSO), ring fourth sulfoxide, tetramethylene sulfone, dimethyl sulfone, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, N-ethyl pyrrolidone, N, N-diethylformamide and N, one or more mixtures in the N-diethyl acetamide;
Above-mentioned coloured terephthalic acid solid residue also contains phenylformic acid, p-methylbenzoic acid, to one or more the industrial waste in carboxyl benzaldehyde, m-phthalic acid, phthalic acid, trimellitic acid, bromo aromatic carboxylic acid, biphenyl carboxylic acids and the benzophenone carboxylic acid's derivative except that containing terephthalic acid, Fluorenone class carboxylic acid and anthraquinone class carboxylic acid foreign pigment.
2. according to claim 1ly from coloured terephthaldehyde's acid residue, reclaim method of terephthalic acid, it is characterized in that said terephthalic acid solid residue also contains acetic acid, water and Co-Mn metal catalyzer.
3. according to claim 1ly from coloured terephthaldehyde's acid residue, reclaim method of terephthalic acid, it is characterized in that the mother liquor after the step 3) solid-liquid separation is returned the recycle of complexing crystallizer.
4. according to claim 1ly from coloured terephthaldehyde's acid residue, reclaim method of terephthalic acid, it is characterized in that the mother liquor after the step 5) solid-liquid separation is returned the recycle of complexing crystallizer.
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