CN101139277A - Method for reclaiming terephthalic acid residue - Google Patents
Method for reclaiming terephthalic acid residue Download PDFInfo
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- CN101139277A CN101139277A CNA2007100705708A CN200710070570A CN101139277A CN 101139277 A CN101139277 A CN 101139277A CN A2007100705708 A CNA2007100705708 A CN A2007100705708A CN 200710070570 A CN200710070570 A CN 200710070570A CN 101139277 A CN101139277 A CN 101139277A
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 228
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000007787 solid Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims description 42
- 238000002425 crystallisation Methods 0.000 claims description 32
- 230000008025 crystallization Effects 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 19
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 18
- 238000011084 recovery Methods 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 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- -1 Fluorenone class carboxylic acid Chemical class 0.000 claims description 9
- 238000007701 flash-distillation Methods 0.000 claims description 8
- 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 claims description 8
- DYNFCHNNOHNJFG-UHFFFAOYSA-N 2-formylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=O DYNFCHNNOHNJFG-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 239000002440 industrial waste Substances 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
- 239000012965 benzophenone Substances 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- 239000002245 particle Substances 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000007670 refining Methods 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 230000029087 digestion Effects 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 13
- 238000001914 filtration Methods 0.000 description 11
- 239000007790 solid phase Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 150000003504 terephthalic acids Chemical class 0.000 description 4
- 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
- 238000010219 correlation analysis Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 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
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-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
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229920004935 Trevira® Polymers 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The present invention provides a method of reclaiming the terephthalic acid residue. In the method, water is used as the solvent to dissolve, crystallize, and separate the solid and liquid of the terephthalic acid residue under the high-temperature condition. At first, the solid residue of the terephthalic acid is dissolved in water at the temperature between 150 and 350 DEG C; the aqueous solution is gradually flashed and crystallized to get the solid slurry containing the solid terephthalic acid; the terephthalate product of high purity and the aqueous solution full of the impurities can be got through the solid-liquid separation; the reclaimed terephthalic acid can be returned to the oxidation system or directly sent to the refining unit. The use of the method can not only lower the discharge of the solid waste in the PTA production process and protect the environment, but also can reduce the consumption of raw materials and the production cost, and improve the economic benefit.
Description
Technical field
The present invention relates to a kind of method of the terephthaldehyde's of recovery acid residue.
Background technology
Pure terephthalic acid (PTA) is the important source material of producing trevira and polyester material.PTA production mainly is made up of two main processes: the production of crude terephthalic acid (CTA) and the refining purification of CTA.CTA mainly by p-Xylol (PX) by liquid-phase air oxidation production (US2833816, US4243636).Because the not pure and mild PX oxidizing reaction of raw material is incomplete, contain plurality of impurities in the CTA product, as to carboxyl benzaldehyde (4-CBA), p-methylbenzoic acid (PTAcid), phenylformic acid (BA) etc., the total concn of this class impurity in CTA up to 5000ppm about, this class impurity can influence the follow-up method that directly contracts and produce polyester and spinning process, can remove by treating process.On the other hand, other side reaction in the PX oxidising process also can generate multiple foreign pigment, as Fluorenone carboxylic acid derivative, anthraquinone carboxylic acids derivative etc., though this class impurity content in CTA very low (＜10ppm), but can directly worsen the chromaticity index of follow-up polyester product, must remove by treating process.At present, the CTA process for purification that adopts in the industry mainly contains hydrofining method (US4467111, US5159109) and multi-stage oxidizing method (CN02810929, US7074954), also has partial monopoly to disclose the technology (CN96195921, CN98810798, US6013835, US5961935) that adopts organic solvent dissolution crystallization process purification CTA in addition.
In PTA device operational process,, must strictly control the CTA quality product of removing refined unit because the processing power of CTA treating process is limited.In order to control the impurity concentration of CTA, adopt extraction part circulating reaction mother liquor to carry out impurity and purification in the industry usually and handle (US4939297, CN200410045270).In mother liquor removal of impurities process, can produce a certain amount of terephthalic acid solid residue, a part of 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 CN200310103432, CN200310103435, CN01127075, CN98114453, CN97103884 etc.Because the composition of terephthalic acid solid residue is very complicated, except contain a large amount of TA, phenylformic acid (BA), p-methylbenzoic acid (PT), to carboxyl benzaldehyde (4-CBA), m-phthalic acid (IPA), phthalic acid (OPA), the trimellitic acid aromatic carboxylic acid such as (TMA), also contain a spot of bromobenzene, biphenyl, benzophenone carboxylic acid's derivative and colored Fluorenone, anthraquinone carboxylic acids derivative, contain a spot of cobalt-manganese catalyst 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.
CN200310103432 and CN200310103435 disclose a kind of method that adopts the esterification method to reclaim terephthalic acid and p-methylbenzoic acid in the TA solid residue; CN01127075 and CN98114453 disclose a kind of employing dissolving, crystallization and rectifying and have reclaimed benzoic method in the TA solid residue; CN97103884 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.Terephthaldehyde's acid residue that this several method all is aimed at specific composition proposes.
Summary of the invention
The object of the invention is to improve existing terephthalic acid solid draff processing method, proposes a kind of method that reclaims terephthaldehyde's acid residue, to reduce waste discharge, cuts down the consumption of raw materials, and increases economic efficiency.
Basic ideas of the present invention are to adopt high-temperature water dissolving terephthalic acid solid residue, and classified then crystallization and liquid-solid sepn process are reclaimed and obtained the higher TA product of purity and the aqueous solution of other aromatic carboxylic acid of enrichment.
The concrete steps that reclaim terephthaldehyde's acid residue method are as follows:
1) terephthalic acid solid residue and water are joined heating for dissolving in the high pressure dissolver together, dissolving obtains the aqueous solution of terephthalic acid solid residue under 150～350 ℃, 1.0～25Mpa condition, and the mass percent of residue and water is 5～50%;
2) the above-mentioned aqueous solution is sent into progressively flash distillation decrease temperature crystalline of crystallizer, obtained containing the slurry of terephthalic acid solid particle;
3) slurry is got the aqueous solution of terephthalic acid and enrichment impurity through solid-liquid separation;
4) terephthalic acid of Hui Shouing returns oxidation system or directly enters refined unit;
5) aqueous solution of enrichment impurity enters the sewage disposal unit, or obtains the aromatic carboxylic acid series products through further separating to purify.
Among the present invention, said terephthalic acid solid residue is to derive from p xylene oxidation reaction mother liquor removal of impurities process or the sedimentary industrial waste that contains terephthalic acid of PTA wastewater.
Among the present invention, said terephthalic acid solid residue contains terephthalic acid, Fluorenone class carboxylic acid and anthraquinone class carboxylic acid foreign pigment, 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.
Among the present invention, said heating for dissolving process can adopt high-temperature water vapor direct heating, electrically heated or high-temperature medium indirect heating.
Among the present invention, the crystallization of the said terephthalic acid solid residue aqueous solution can be adopted 1～5 grade of flash crystallization, preferred 2～3 grades of crystallizations; Adopt the two-stage flash crystallization: the temperature of first step crystallizer is 150～250 ℃, and preferred 190～230 ℃, the temperature of second stage crystallizer is 50～150 ℃, preferred 90～130 ℃; Adopt three grades of flash crystallizations: the temperature of first step crystallizer is 200～230 ℃, and the temperature of second stage crystallizer is 130～160 ℃, and the temperature of third stage crystallizer is 60～90 ℃, and temperature is determined by regulating crystallizer pressure.
Among the present invention, the solid-liquid separation of said TA slurry can adopt Pressure Centrifuges or filter-press.
Among the present invention, said aromatic carboxylic acid series products is phenylformic acid, p-methylbenzoic acid, in the middle of carboxyl benzaldehyde and the m-phthalic acid one or more.
Feasibility of the present invention is mainly based on following 3 considerations: the variation that at first is the solubility with temperature of terephthalic acid in high-temperature water is comparatively responsive, all dissolvings in high temperature, can most of crystallization separate out again under higher temperature, table 1 has been listed the dissolubility data of terephthalic acid in high-temperature water; Next is that the dissolubility difference of other aromatic carboxylic acid component in water in terephthalic acid and the residue is bigger, and by the crystallization separate easily, table 1 has been listed the dissolubility data of other main aromatic carboxylic acid component in water in the residue; At last, be that the concentration of foreign pigment is lower, and the solubleness in the high-temperature water is bigger, the solid-liquid separation under comparatively high temps can effectively reduce its residual in terephthalic acid solid.
The dissolubility data of component in water in the table 1TA residue
| Temperature (℃) | Dissolubility data (g/100gH under the condition of different temperatures 2O) | ||||||
| TA | BA | PT | 4-CBA | IPA | OPA | TMA | |
| 20 | - | 0.29 | - | 0.08 | - | - | - |
| 40 | - | 0.55 | - | 0.13 | - | - | - |
| 60 | - | 1.2 | 0.03 | 0.28 | 0.036 | 6.5 | 0.85 |
| 80 | - | 2.7 | 0.20 | 0.65 | 0.12 | 18 | 1.6 |
| 100 | 0.034 | 6.9 | 1.0 | 1.5 | 0.24 | 38 | 4.2 |
| 120 | 0.070 | - | 5.6 | - | 0.86 | 57 | - |
| 150 | 0.23 | - | - | - | 1.9 | 147 | - |
| 180 | 0.45 | - | - | - | 6.5 | - | - |
| 200 | 1.8 | - | - | - | 30 | - | - |
| 220 | 3.5 | - | - | - | - | - | - |
| 250 | 11 | - | - | - | - | - | - |
| 280 | 35 | - | - | - | - | - | - |
No matter be the TA residue of different PTA factory, the TA residue that still same PTA factory produces under different technology conditions can effectively reclaim wherein TA and other aromatic carboxylic acid component according to the present invention.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 adopts the double flash evaporation crystallization to reclaim the process flow sheet of terephthaldehyde's acid residue.
Fig. 2 adopts three grades of flash crystallizations to reclaim the process flow sheet of terephthaldehyde's acid residue.
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 1～5, any local improvement to these methods can not change feature of the present invention yet.
Embodiment 1
Present embodiment is furnished with in dissolving, crystallization and the filtering experimental installation at one and carries out.This device is a high pressure cylindrical chamber, and container is furnished with the heating temperature control facility outward.The space is divided into two districts up and down by a sintered metal filtration sheet in the container: filtrate district and high-temperature digestion crystallizing field.High-temperature digestion crystallizing field volume is 200ml, in be furnished with a temperature sensor; The sintered metal filtration sheet is sealingly fastened between high-temperature digestion crystallizing field and the filtrate district, can bear the filtration pressure difference of 1MPa, and its maximum diameter of hole is 5 μ m; Filtrate district volume also is 200ml, also is furnished with a temperature sensor, also is furnished with a gas outlet in addition and leads to outside the container; Gas outlet is through the emptying of pin type snifting valve, and gas outlet is mainly used in step-down flash distillation cooling operation.When carrying out the operation of high-temperature digestion and flash crystallization, the filtrate district is last, and the high-temperature digestion crystallizing field is following; When carrying out the high temperature filtration operation, this installs inversion, and the high-temperature digestion crystallizing field is last, and the filtrate district is following.For convenience of description, can be called for short this device and be " the dissolving crystallized strainer of high pressure ".The handled TA residue of present embodiment mainly consists of: TA (89.77wt%), 4-CBA (4.18wt%), PT (2.60wt%), BA (1.13wt%), IPA (0.86wt%), other component is about 1.46wt%.For sake of convenience, can be called for short this TA residue and be " TA residue first ".
Earlier 10.213g " TA residue first " and 100ml water are joined the high-temperature digestion crystallizing field of the dissolving crystallized strainer of high pressure, the dissolving crystallized strainer of high pressure is just put; Setting the dissolving crystallized strainer target temperature of high pressure is 250 ℃, heat temperature raising, and constant temperature is 2 hours when temperature arrives 250 ℃, allows the dissolving of TA residue fully; The target setting temperature is 200 ℃ then, opens snifting valve and emits portion water steam, allows the dissolving crystallized strainer of high pressure be cooled to 200 ℃ in 10 minutes, 200 ℃ of following constant temperature 1 hour, allows the complete crystallization of TA; Then the dissolving crystallized strainer of high pressure is inverted, is filtered under 200 ℃, filtration time is 1 hour, separates with the aqueous solution fully in order to guarantee the TA solid, can keep some pressure reduction by the TA filter cake by crack snifting valve in the filtration later stage; At last the dissolving crystallized strainer of high pressure is cooled to normal temperature, take out solid drying, the analysis of weighing in the high-temperature digestion crystallizing field, take out the solidliquid mixture in the filtrate district, filter out solid and dry, the analysis of weighing, and further analyze the composition and the form and aspect index of various solid phases.The TA solid masses that is reclaimed by crystallizing field is 5.453g, and containing solid masses in the enrichment water impurity solution by the recovery of filtrate district is 4.175g, and remaining is the loss of liquid phase loss and experiment collection process.
The composition of each solid phase adopts the Agilent1100 liquid-phase chromatographic analysis, is 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 0.1g solid is dissolved in 10ml, measure the absorbance A of this solution under wavelength 340nm (λ=340nm) then.The correlation analysis data results in contrast to table 2.
Embodiment 2
Carry out the high-temperature digestion crystallization filtration treatment of " TA residue first " with the mode identical with embodiment 1.Different is add the high-temperature digestion crystallizing field be 24.936g " TA residue first " and 100ml water, solvent temperature is 280 ℃, the crystallization filtration temperature is 220 ℃.The TA solid masses that is reclaimed by crystallizing field is 17.384g, and the solid masses that is reclaimed by the filtrate district is 6.947g, and the correlation analysis data results in contrast to table 2.
The TA product contrast that table 2 is reclaimed by " TA residue first "
| Analysis project | TA residue first | Embodiment 1 | Embodiment 2 | ||
| TA residue first 10.213g | TA residue first 24.936g | ||||
| Crystallizing field | The filtrate district | Crystallizing field | The filtrate district | ||
| TA(wt％) | 89.77 | 99.44 | 81.01 | 99.37 | 67.88 |
| 4-CBA(wt％) | 4.18 | 0.42 | 8.89 | 0.36 | 13.90 |
| PT(wt％) | 2.60 | 0.10 | 5.75 | 0.14 | 8.91 |
| BA(wt％) | 1.13 | ＜0.01 | 1.42 | 0.05 | 3.17 |
| IPA(wt％) | 0.86 | ＜0.01 | 1.96 | 0.05 | 2.97 |
| Other (wt%) | 1.46 | ＜0.01 | 0.79 | 0.03 | 3.17 |
| A(λ＝340nm) | 0.420 | 0.126 | 0.715 | 0.105 | 0.720 |
| Solid masses (g) | - | 5.453 | 4.175 | 17.384 | 6.947 |
Comparative example 1 and 2 result as can be known, " the TA residue first " of high TA concentration can be by the recyclable higher TA product of purity that obtains of single-stage high-temperature digestion crystallization, i.e. the TA solid (TA purity is greater than 99.3%) that is reclaimed by crystallizing field.4-CBA in this TA product and PT acid impurity concentration all lower (4-CBA is less than 5000ppm, and PT is less than 1000ppm); (λ=340nm) illustrates that the concentration of its foreign pigment is also very low to A about 0.1, have chromaticity index preferably.The TA product of this recovery is Returning oxidation reactor or be recovered as the PTA product by refined unit directly.And the aqueous solution of the enrichment impurity that is obtained by the filtrate district can further reclaim wherein useful component by multistage crystallization.
Embodiment 3
Carry out the high-temperature digestion crystallization filtration treatment of TA residue with the mode similar to embodiment 1.Just in the handled TA residue of present embodiment difference, mainly consisting of of this TA residue: TA (12.43wt%), 4-CBA (4.01wt%), IPA (14.33wt%), PT (20.06wt%), BA (24.08wt%), water (18.91wt%), acetic acid (0.65wt%), other component is about 5.53wt%.Can be called for short this TA residue and be " TA residue second ".
In this embodiment, what add the high-temperature digestion crystallizing field is 9.975g " TA residue second " and 100ml water, and solvent temperature is 200 ℃, and the crystallization filtration temperature is 150 ℃.The TA solid masses that is reclaimed by crystallizing field is 0.952g, and the solid masses that is reclaimed by the filtrate district is 5.668g.The correlation analysis data results in contrast to table 3.
The TA product contrast that table 3 is reclaimed by " TA residue second "
| Analysis project | TA residue second | Embodiment 3 | |
| TA residue first 9.975g | |||
| Crystallizing field TA | The filtrate district | ||
| TA(wt％) | 12.43 | 92.67 | 4.98 |
| 4-CBA(wt％) | 4.01 | 0.57 | 4.69 |
| PT(wt％) | 20.06 | 2.27 | 33.68 |
| BA(wt％) | 24.08 | 2.69 | 31.32 |
| IPA(wt％) | 14.33 | 1.80 | 24.28 |
| Other (wt%) | 5.53 | ＜0.01 | 1.05 |
| A(λ＝340nm) | 0.739 | 0.321 | 0.787 |
| Quality (g) | - | 0.952 | 5.668 |
Embodiment 4
Present embodiment will be narrated and adopt technology shown in Figure 1 to recycle the specific embodiment of " TA residue first ".
" TA residue first " and the water of High Temperature High Pressure are joined in the dissolver, and " TA residue first " add-on is 1.3 * 10
3Kg/h, the high-temperature water add-on is 13 * 10
3Kg/h obtains TA residue high-temperature water solution 250 ℃ of following TA residue dissolvings; This aqueous solution is introduced in the first crystallizer step-down flash crystallization, and mould temperature is 210 ℃; The steam of crystallizer flash distillation is behind the heat exchange recovered energy, and a part of lime set is used for solid-liquid separation I TA washing filter cakes, and a part is used as the water solvent of dissolver after heating and pressurizing; The TA crystalline slurry that contains that is obtained by first crystallizer enters solid-liquid separation I, can have the TA product of higher degree after carrying out solid-liquid separation and wash under hot conditions; Solution by solid-liquid separation I outlet is introduced in the further step-down flash crystallization of second crystallizer, and mould temperature is 120 ℃; The steam of this crystallizer flash distillation is behind the heat exchange recovered energy, and a part of lime set is used for solid-liquid separation II washing filter cakes, and a part is used as the water solvent of dissolver after heating and pressurizing; Contain TA crystalline slurry through solid-liquid separation II by what second crystallizer obtained, reclaim the solid phase that is rich in TA, this solid is back to further recovery TA wherein of dissolver; The aqueous solution by solid-liquid separation II outlet can further reclaim other component, or the decontaminated water processing unit.The TA parameter of each unitary processing parameter and recovery is listed in table 4,5 respectively.
Each cell process parameter of table 4. embodiment 4
| Processing parameter | Temperature (℃) | Pressure (MPa) | The residence time (min) |
| Dissolver | 250℃ | 4.0 | 60 |
| First crystallizer | 210℃ | 2.2 | 60 |
| Solid-liquid separation I | 200℃ | 2.2 | - |
| Second crystallizer | 120℃ | 0.4 | 30 |
| Solid-liquid separation II | 120℃ | 0.4 | - |
The TA correlation parameter contrast that table 5. embodiment 4 reclaims
| Correlation parameter | TA residue first | The TA that embodiment 4 reclaims |
| TA purity | 89.77wt％ | ＞99.5 |
| 4-CBA concentration | 4.18wt％ | ＜3000ppm |
| PT concentration | 2.60wt％ | ＜500ppm |
| BA concentration | 1.13wt％ | ＜10ppm |
| IPA concentration | 0.86wt％ | ＜10ppm |
| Other | 1.46wt％ | ＜10ppm |
| Reclaim the TA amount | 1.11×10 3kg/h | |
| The TA rate of recovery | ＞95wt％ | |
Embodiment 5
Present embodiment will be narrated and adopt technology shown in Figure 2 to recycle the specific embodiment of " TA residue second ".
" TA residue second " and the water of High Temperature High Pressure are joined in the dissolver, and " TA residue second " add-on is 1 * 10
3Kg/h, the high-temperature water add-on is 2 * 10
3Kg/h obtains TA residue high-temperature water solution 250 ℃ of following TA residue dissolvings; This aqueous solution is introduced in the first crystallizer step-down flash crystallization, and mould temperature is 20 ℃; The steam of crystallizer flash distillation is behind the heat exchange recovered energy, and a part of lime set is used for solid-liquid separation I TA washing filter cakes, and a part is used as the water solvent of dissolver after heating and pressurizing; The TA crystalline slurry that contains that is obtained by first crystallizer enters solid-liquid separation I, can have the TA product of higher degree after carrying out solid-liquid separation and wash under hot conditions; Solution by solid-liquid separation I outlet is introduced in the further step-down flash crystallization of second crystallizer, and mould temperature is 120 ℃; The steam of this crystallizer flash distillation is behind the heat exchange recovered energy, and a part of lime set is used for solid-liquid separation II washing filter cakes, and a part is used as the water solvent of dissolver after heating and pressurizing; Contain IPA crystalline slurry through solid-liquid separation II by what second crystallizer obtained, reclaim the solid phase that is rich in IPA; Solution by solid-liquid separation II outlet is introduced in the further step-down flash crystallization of the 3rd crystallizer, and mould temperature is 40 ℃; The steam of this crystallizer flash distillation lime set behind the heat exchange recovered energy is mainly used in washing filter cakes among the solid-liquid separation III; The slurry that contains PT acid, 4-CBA and BA that is obtained by the 3rd crystallizer passes through solid-liquid separation II, the solid phase of PT acid, 4-CBA and BA is rich in recovery, can claim that this solid phase is the BA solid phase, the BA solid phase can reclaim wherein PT acid, 4-CBA and BA respectively by follow-up sepn process; The aqueous solution by solid-liquid separation III outlet can further reclaim other component, or the decontaminated water processing unit.The TA and the lA parameter of each unitary processing parameter, recovery are listed in table 6,7 respectively.
Each cell process parameter of table 6 embodiment 5
| Processing parameter | Temperature (℃) | Pressure (MPa) | The residence time (min) |
| Dissolver | 250℃ | 4.0 | 60 |
| First crystallizer | 200℃ | 1.7 | 60 |
| Solid-liquid separation I | 200℃ | 1.7 | - |
| Second crystallizer | 120℃ | 0.4 | 30 |
| Solid-liquid separation II | 120℃ | 0.4 | - |
| The 3rd crystallizer | 40℃ | 0.1 | 30 |
| Solid-liquid separation III | 40℃ | 0.1 | - |
The TA that table 7. embodiment 5 reclaims and the parameter comparison of IPA solid phase
| Correlation parameter | TA residue first | The TA that reclaims | The IPA that reclaims |
| TA purity | 12.43wt％ | ＞99.0wt％ | ＜1.0wt％ |
| 4-CBA concentration | 4.01wt％ | ＜5000ppm | ＜1.0wt％ |
| PT concentration | 20.06wt％ | ＜500ppm | ＜1000ppm |
| BA concentration | 24.08wt％ | ＜100ppm | ＜1000ppm |
| IPA concentration | 14.33wt％ | ＜1000ppm | ＞96wt％ |
| Other | 5.53wt％ | ＜100ppm | ＜1000ppm |
| The solid yield | 100kg/h | 120kg/h | |
Claims (8)
1. method that reclaims terephthaldehyde's acid residue is characterized in that step is as follows:
1) terephthalic acid solid residue and water are joined heating for dissolving in the high pressure dissolver together, dissolving obtains the aqueous solution of terephthalic acid solid residue under 150～350 ℃, 1.0～25Mpa condition, and the mass percent of residue and water is 5～50%;
2) the above-mentioned aqueous solution is sent into progressively flash distillation decrease temperature crystalline of crystallizer, obtained containing the slurry of terephthalic acid solid particle;
3) slurry is got the aqueous solution of terephthalic acid and enrichment impurity through solid-liquid separation;
4) terephthalic acid of Hui Shouing returns oxidation system or directly enters refined unit;
5) aqueous solution of enrichment impurity enters the sewage disposal unit, or obtains the aromatic carboxylic acid series products through further separating to purify.
2. the method for recovery terephthaldehyde acid residue according to claim 1 is characterized in that said terephthalic acid solid residue is to derive from p xylene oxidation reaction mother liquor removal of impurities process or the sedimentary industrial waste that contains terephthalic acid of PTA wastewater.
3. the method for recovery terephthaldehyde acid residue according to claim 1, it is characterized in that said terephthalic acid solid residue contains terephthalic acid, Fluorenone class carboxylic acid and anthraquinone class carboxylic acid foreign pigment, 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.
4. the method for recovery terephthaldehyde acid residue according to claim 1 is characterized in that said heating for dissolving process can adopt high-temperature water vapor direct heating, electrically heated or high-temperature medium indirect heating.
5. the method for recovery terephthaldehyde acid residue according to claim 1 is characterized in that 2～5 grades of flash crystallizations are adopted in the crystallization of the said terephthalic acid solid residue aqueous solution.
6. the method for recovery terephthaldehyde acid residue according to claim 5, the two-stage flash crystallization is adopted in the crystallization that it is characterized in that the said terephthalic acid solid residue aqueous solution: the temperature of first step crystallizer is 150～250 ℃, and the temperature of second stage crystallizer is 50～150 ℃.
7. the method for recovery terephthaldehyde acid residue according to claim 5, three grades of flash crystallizations are adopted in the crystallization that it is characterized in that the said terephthalic acid solid residue aqueous solution: the temperature of first step crystallizer is 200～230 ℃, the temperature of second stage crystallizer is 130～160 ℃, and the temperature of third stage crystallizer is 60～90 ℃.
8. the method for recovery according to claim 1 terephthaldehyde acid residue, it is characterized in that said aromatic carboxylic acid series products be phenylformic acid, p-methylbenzoic acid, in the middle of carboxyl benzaldehyde and the m-phthalic acid one or more.
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| CNA2007100705708A CN101139277A (en) | 2007-08-28 | 2007-08-28 | Method for reclaiming terephthalic acid residue |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102381953A (en) * | 2011-09-07 | 2012-03-21 | 山西大学 | Method for extracting and purifying fluorenone from industrial wastes generated in production of benzoic acid |
| CN107176745A (en) * | 2016-03-09 | 2017-09-19 | 王仲甫 | The method for biologically treating wastewater of polybasic carboxylic acid residue |
| WO2018171028A1 (en) * | 2017-03-22 | 2018-09-27 | 天华化工机械及自动化研究设计院有限公司 | Method for recycling mother liquor in pta refined unit |
| CN112358393A (en) * | 2020-10-23 | 2021-02-12 | 珠海鑫通化工有限公司 | PTA waste recovery device and recovery method |
| CN116265044A (en) * | 2021-12-16 | 2023-06-20 | 中国科学院大连化学物理研究所 | Method for treating paraxylene liquid phase oxidation residues |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102381953A (en) * | 2011-09-07 | 2012-03-21 | 山西大学 | Method for extracting and purifying fluorenone from industrial wastes generated in production of benzoic acid |
| CN102381953B (en) * | 2011-09-07 | 2013-07-10 | 山西大学 | Method for extracting and purifying fluorenone from industrial wastes generated in production of benzoic acid |
| CN107176745A (en) * | 2016-03-09 | 2017-09-19 | 王仲甫 | The method for biologically treating wastewater of polybasic carboxylic acid residue |
| WO2018171028A1 (en) * | 2017-03-22 | 2018-09-27 | 天华化工机械及自动化研究设计院有限公司 | Method for recycling mother liquor in pta refined unit |
| CN108623065A (en) * | 2017-03-22 | 2018-10-09 | 天华化工机械及自动化研究设计院有限公司 | The recoverying and utilizing method of PTA refined unit mother liquors |
| US20190225569A1 (en) * | 2017-03-22 | 2019-07-25 | Tianhua Institute of Chemical Machinery and Automation Co., Ltd | Method of recycling mother liquid of pta refining unit |
| JP2019534854A (en) * | 2017-03-22 | 2019-12-05 | 天華化工機械及自動化研究設計院有限公司Ｔｉａｎｈｕａ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｃｈｅｍｉｃａｌ Ｍａｃｈｉｎｅｒｙ Ａｎｄ Ａｕｔｏｍａｔｉｏｎ Ｃｏ．，Ｌｔｄ． | Recovery and use of PTA purification unit mother liquor |
| US10787411B2 (en) * | 2017-03-22 | 2020-09-29 | Tianhua Institute of Chemical Machinery and Automation Co., Ltd | Method of recycling mother liquid of pure terephthalic acid (PTA) refining unit |
| CN112358393A (en) * | 2020-10-23 | 2021-02-12 | 珠海鑫通化工有限公司 | PTA waste recovery device and recovery method |
| CN116265044A (en) * | 2021-12-16 | 2023-06-20 | 中国科学院大连化学物理研究所 | Method for treating paraxylene liquid phase oxidation residues |
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