CN105001073B - Low energy consumption material consumption, the PTA production methods and system of few waste discharge - Google Patents
Low energy consumption material consumption, the PTA production methods and system of few waste discharge Download PDFInfo
- Publication number
- CN105001073B CN105001073B CN201510380472.9A CN201510380472A CN105001073B CN 105001073 B CN105001073 B CN 105001073B CN 201510380472 A CN201510380472 A CN 201510380472A CN 105001073 B CN105001073 B CN 105001073B
- Authority
- CN
- China
- Prior art keywords
- acetic acid
- extractant
- water
- tower
- oxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 238000005265 energy consumption Methods 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 27
- 239000002699 waste material Substances 0.000 title claims abstract description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 586
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 162
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 135
- 230000003647 oxidation Effects 0.000 claims abstract description 120
- 239000012452 mother liquor Substances 0.000 claims abstract description 93
- 238000005406 washing Methods 0.000 claims abstract description 90
- 238000000605 extraction Methods 0.000 claims abstract description 84
- 239000002002 slurry Substances 0.000 claims abstract description 76
- 238000011084 recovery Methods 0.000 claims abstract description 74
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 49
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 46
- 239000012065 filter cake Substances 0.000 claims abstract description 41
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 17
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 17
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000006227 byproduct Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 126
- 239000007789 gas Substances 0.000 claims description 120
- 239000012071 phase Substances 0.000 claims description 70
- 230000008676 import Effects 0.000 claims description 44
- 239000007791 liquid phase Substances 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 40
- 239000000706 filtrate Substances 0.000 claims description 34
- 238000007599 discharging Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 27
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- 238000004140 cleaning Methods 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 12
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 12
- 229940011051 isopropyl acetate Drugs 0.000 claims description 12
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 12
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 12
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 12
- 239000010865 sewage Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 11
- 239000012141 concentrate Substances 0.000 claims description 11
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 239000007792 gaseous phase Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 5
- 208000021302 gastroesophageal reflux disease Diseases 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 36
- 230000008569 process Effects 0.000 abstract description 26
- 239000002351 wastewater Substances 0.000 abstract description 9
- 239000005416 organic matter Substances 0.000 abstract description 8
- 229960000583 acetic acid Drugs 0.000 description 160
- 239000003054 catalyst Substances 0.000 description 34
- 239000002253 acid Substances 0.000 description 21
- 238000005984 hydrogenation reaction Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 239000006096 absorbing agent Substances 0.000 description 14
- 229960004365 benzoic acid Drugs 0.000 description 14
- 239000000052 vinegar Substances 0.000 description 13
- 235000021419 vinegar Nutrition 0.000 description 13
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 11
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 10
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000007670 refining Methods 0.000 description 9
- 239000010409 thin film Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- -1 carboxyl benzaldehyde Chemical compound 0.000 description 7
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 230000006837 decompression Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000010612 desalination reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000035611 feeding Effects 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000010533 azeotropic distillation Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000007701 flash-distillation Methods 0.000 description 3
- 238000005360 mashing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 210000005056 cell body Anatomy 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical group CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RLLPVAHGXHCWKJ-IEBWSBKVSA-N (3-phenoxyphenyl)methyl (1s,3s)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@@H]1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-IEBWSBKVSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- YNCRBFODOPHHAO-YUELXQCFSA-N Phaseic acid Natural products CC(=CC(=O)O)C=C[C@@H]1[C@@]2(C)CO[C@@]1(C)CC(=O)C2 YNCRBFODOPHHAO-YUELXQCFSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- ZBICJTQZVYWJPB-UHFFFAOYSA-N [Mn].[Co].[Br] Chemical compound [Mn].[Co].[Br] ZBICJTQZVYWJPB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- IZGYIFFQBZWOLJ-UHFFFAOYSA-N neophaseic acid Natural products C1C(=O)CC2(C)OCC1(C)C2(O)C=CC(C)=CC(O)=O IZGYIFFQBZWOLJ-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- IZGYIFFQBZWOLJ-CKAACLRMSA-N phaseic acid Chemical compound C1C(=O)C[C@@]2(C)OC[C@]1(C)[C@@]2(O)C=CC(/C)=C\C(O)=O IZGYIFFQBZWOLJ-CKAACLRMSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of low energy consumption material consumption, the PTA production methods and system of few waste discharge, Acetic Acid Recovering Column recovery of acetic acid is sent into the output of oxidation reactor tail gas after first order steam generator byproduct steam, refinement mother liquor is back to Acetic Acid Recovering Column, replace former vacuum filter with filter-press, and filter cake is directly beaten supply refinement, by extraction and recovery acetic acid, oxidation mother liquor treatment is carried out by extraction, will eliminate the acetic acid recovery tower top phegma after methyl acetate for aoxidize with the Washing of Filter Cake and the slurry preparation of refinement of refinement.The present invention not only can effectively control the acetic acid consumption in tail gas, waste water, the organic matter of high efficiente callback refinement mother liquor simultaneously realizes the recycling of water, reduce steam, power consumption, reduce waste discharge, and also add the byproducts such as benzoic acid, mixed phthalic acid, and technological process is short, workable, low production cost, plant investment are low.
Description
Technical field
The present invention relates to a kind of PTA production methods, compared to traditional its raw material of PTA production methods, process solvent, catalyst
It is a kind of new PTA production technologies of the low material consumption of low energy consumption and steam consumption is significantly reduced.
Background technology
P-phthalic acid（Purified Terephthalic Acid, abbreviation PTA）It is production polyester fiber and resin
Primary raw material, be nonpoisonous and tasteless white crystal or powder under normal temperature, be important large chemical products, it is daily with the people
Life is closely bound up.
PTA mainly uses paraxylene at present（P-Xylene, abbreviation PX）Air oxidation process is produced, and technical process is mainly wrapped
Oxidation and refined Liang Ge workshop sections are included, and a whole set of technique system is formed with the process matched therewith such as oxidation mother liquor treatment and oxidized tail gas treatment
System, Fig. 2 is the flow chart of one embodiment of traditional PTA production technologies.
（1）Oxidation
Raw material PX300 in the oxidation reactor 201 with acetic acid as solvent under the effect of cobalt manganese bromine catalyst 302 with air
In 301 there is oxidation reaction generation terephthalic acid (TPA) TA in oxygen, and most of terephthalic acid (TPA) crystallizes out to be formed in the reactor
Slurry；Slurry after oxidizing and crystallizing device 202-204 step by step decrease temperature and pressure flash distillation and crystallization by sending into oxidation filter 205（Generally
It is rotary vaccum filter）, slurry is sequentially completed filtering, Washing of Filter Cake, blow dried totally three processes in filter：First
Filtered, will most of liquid phase separated with TA crystal, in 28wt%, filtrated stock is 91% vinegar for rate of cake moisture content control
Acid, in addition to small part delivers to mother liquid disposal subsystem, most of mother liquor is back to oxidation reactor；Then filter cake is washed
Wash, washing process is washed using the acetum containing 10% water together；Blow dried is finally carried out, dry gas are dried
Oxidized tail gas, filter filter cake out obtains intermediate products crude terephthalic acid after being dried through drying machine 206（Abbreviation CTA）,
Intermediate bunker 207 is delivered to blast system, it is oxidation mother liquor that filter 205 is filtrated to get major part Returning oxidation reactor, few
Extract out and go to carry out oxidation mother liquor treatment in part.
（2）It is refined
Beaten in refined slurry blend tank 208 from the crude terephthalic acid powder out of intermediate bunker 207 and hot water
Slurry obtains slurry, slurry by six grades of refined paste heater 209-214 stepped heatings, by the slurry that heats in hydrogenation reaction
Carry out hydrogenation reaction in device 215 with hydrogen 303, catalyst for hydrogenation is palladium charcoal solid particle, hydrogenation reaction makes miscellaneous in CTA
Confrontation carboxyl benzaldehyde（Abbreviation 4-CBA）Reacted with hydrogen and be reduced to PT acid more soluble in water（That is p-methylbenzoic acid,
It is also another impurity component in CTA）, the discharging of hydrogenation reactor 215 carries out decrease temperature and pressure sudden strain of a muscle through refining crystallization device 216-220
Steam, crystallize, the bottom discharge of refining crystallization device 220 delivers to refined filter-press 221 and carries out separation of solid and liquid, by refined pressure mistake
Filtering successively in filter 221, the gentle body of Washing of Filter Cake are dried to obtain filter cake and refinement mother liquor（By filter liquor and washing filtrate
Composition）, filter cake turns into PTA products 304 after being dried through PTA drying machines 222, refinement mother liquor is successively through flash distillation, cooling, at filtering
Reason, filtrate is directly discharged to sewage plant in the form of refined wastewater.
（3）Solvent recovery
From the top of oxidation reactor 201, oxidized tail gas out sequentially pass through steam generator 231-234 condensations and by-product
Water vapour, then dereaction device return tank 236 carries out gas-liquid separation after desalination water cooler 235 continues to cool down again, flows back
Tank is exported sends to oxidized tail gas treatment after gas phase is cooled down through cooler 237（Into high pressure absorber 238）, return tank 236 exports
Liquid phase（Water-containing acetic acid）A part removes dehydrating tower 251（Entrainer is n-butyl acetate）Azeotropic distillation dehydration is carried out, remaining returns oxygen
Change reactor 201；The outlet at bottom liquid phase of dehydrating tower 251 is back to oxidation reactor 201 on a small quantity, is mainly used as device spray acid,
A part of flushing acetic acid 306 as whole system, remaining delivers to high pressure absorber 238 as the washing condensed device 252 of acetic acid；
The top gaseous phase of dehydrating tower 251 realizes the separation of oil phase and water phase in decanter 254 after being cooled down through cooler 253, oil phase is returned
Recycled to dehydrating tower, water mutually sends into entrainer recovery tower 255, and methyl acetate is stripped from the tower top of entrainer recovery tower 255
Discharge is recycled to oxidation reactor 201 through the cooling of subcooler 256, and decanter 254, tower bottoms are delivered in the entrainer extraction of tower middle part
Sewage Disposal 257 is delivered to as waste water discharging device.
（4）Oxidized tail gas treatment
The purpose of oxidized tail gas treatment is to carry out purification utilization to oxidized tail gas, and processing procedure is：From cooler 237
Oxidized tail gas enter the bottom of towe of high pressure absorber 238, and high pressure absorber middle part is using cold through cooler 252 from the bottom of dehydrating tower 251
But the dense acetic acid spray after, top is sprayed using demineralized water 305, and high pressure absorber top exit gas phase removes tail gas CIU
239 purifications, the tail gas after purification goes the decompression acting of off-gas expander 240, and the tail gas after decompression acting goes tail gas washing tower 241 to pass through
It is finally exhausted in air after alkali cleaning.
（5）Oxidation mother liquor treatment
Oxidation mother liquor first passes through the concentrate of acetic acid stripper 261 recovery of acetic acid simultaneously, and the discharging of acetic acid stripping tower bottom is residual for mother liquor
Slurry material, mother liquor residue slurry enters thin film evaporator 262, and recovery of acetic acid, equipment bottom are further evaporated in thin film evaporator
Portion's discharge mother liquor residue enters catalyst water extractor 263, while be stirred to addition water in catalyst water extractor 263,
Water carrys out fresh food frozen water 307, and the discharging of catalyst water extractor goes residue centrifuge 264 to isolate oxidation residua 308 to transport outward, liquid phase
Catalyst recycling can 266 is delivered to after being heated into concentrate heater 265, is back to after being beaten in catalyst recycling can
Oxidation reactor 201 is recycled.
Traditional PTA technological process of productions are long, energy consumption and material consumption are high.As a example by producing 1200000 tons of PTA devices per year, PTA per ton
Products material PX unit consumption 655-657kg/tPTA, acetic acid unit consumption 38-40kg/tPTA, steam mono-consumption 0.7-1.0t/tPTA, desalination
Water unit consumption 2.2-3.0t/tPTA, the pond waste material that especially detention tank is pulled out just has 2000-4000 tons/year, converts into PX mono-
Consumption 1.2-2.4kg/tPTA, up to 3,600,000 tons/year, COD is discharged up to 1.5 ten thousand tons/year full factory's sewage quantity, and equivalent ton products C OD is
12.5kg/tPTA。
The disadvantage of traditional PTA techniques is in particular in following five aspects：
（1）Oxidation section uses vacuum filter+drying mode, high energy consumption.Oxidation subsystem uses rotary vaccum filter
Filtering and acetic acid mode of washing, filter discharging use drying machine drying with recovery of acetic acid, and the CTA obtained after drying is sent by wind
To intermediate bunker storage.So, be that the supporting vacuum system of filter needs power consumption 8-12KW/tPTA, drying machine consume 5barG with
Upper pressure steam 0.1-0.2t/tPTA, blast system consumes high pressure exhaust gas so as to reduce tail gas expansion work about 5KW/tPTA.
（2）Dewatering system high energy consumption.It is the addition water for generating water and high pressure absorber washing tail gas of removing oxidation reaction,
Need to set acetic acid dehydration system.But because the relative volatility of acetic acid and water is close to 1, therefore typically taken off using azeotropic distillation
Water, removing water per ton need to consume water vapour 1.4-2.0t, and steam high energy consumption causes plant energy consumption higher.
（3）Oxidation mother liquor dedoping step high energy consumption.It is control PTA product qualities, it is necessary to extraction section oxidation mother liquor goes mother
To remove the impurity in mother liquor, the mother liquor is first through acetic acid stripping tower concentrate, then further reclaims vinegar through thin film evaporator for liquid treatment
Acid, thin film evaporator need to consume extraneous high steam to heat, and increased the steam consumption 0.03t/tPTA of device.
（4）Oxidation residua is not utilized effectively.Acetic acid and catalyst in thin film evaporator blanking residue are not reclaimed, and are made
Into acetic acid consumption 0.5-1.0kg/tPTA, cobalt consumption 0.01kg/tPTA, manganese consumption 0.02kg/tPTA；Thin film evaporator blanking is residual
Slag is directly outer after water is beaten and cools down to be arranged, and benzoic acid therein, terephthalic acid (TPA), M-phthalic acid, cobalt manganese are unrecovered
Utilize, conversion PX unit consumption about 2-3kg/tPTA, cobalt unit consumption 0.03kg//tPTA, manganese unit consumption 0.03kg//tPTA, acetic acid unit consumption
2kg/tPTA。
（5）Refinement mother liquor does not obtain effective recycling.Refinement mother liquor generally using first flash distillation be cooled to 101 DEG C, again
The scheme for being cooled to about 45 DEG C and then filtering is processed, and filtrate is directly discharged to sewage plant in the form of refined wastewater, discharge
The equivalent 2-3t/tPTA of refined wastewater, while also containing 300-600ppm in water（Mass concentration）Acetic acid, 300-600ppm
PT acid, the TA of the 4-CBA of 10ppmw and 200-500ppmw；In addition, the impurity such as PT acid in refinement mother liquor is in mother liquor cooling procedure
In, meeting fouling in equipment and pipeline has a strong impact on the continuous operation of device, meanwhile, PT acid can be caused in cleaning process
Loss, converts into PX consumption and is about 0.5kg/tPTA.Also there are Chinese patent CN201210382308.8, CN201210428330.1
Propose to be exchanged using adion respectively and extraction mode reclaim organic matter, waste water recycling it is relatively costly, it is difficult to actual motion.
To sum up, in view of tradition PTA energy consumption in production process, material consumption are higher, it is necessary to find brand-new process program to drop
The consumption such as low raw material PX, process solvent acetic acid and water, steam energy consumption and catalyst, promotes clean manufacturing and energy-saving.
The content of the invention
In order to overcome the drawbacks described above under prior art, it is an object of the invention to provide a kind of low energy consumption material consumption, few useless
The PTA production methods and system of thing discharge, the method and system not only can effectively control the acetic acid consumption in tail gas, waste water, high
Effect reclaims the organic matter of refinement mother liquor and realizes the recycling of water, reduces steam, power consumption, reduces waste discharge, and
Also add the byproducts such as benzoic acid, mixed phthalic acid, and technological process is short, workable, low production cost, plant investment
It is low.
The technical scheme is that：
A kind of low energy consumption material consumption, the PTA production methods of few waste discharge, including oxidation section and refinement, the oxygen
The oxidation reactor top of chemical industry section oxidized tail gas out are introduced into first order steam generator byproduct steam, first order steam
The thermal medium outlet gas phase of generator enters Acetic Acid Recovering Column from bottom of towe, and the Acetic Acid Recovering Column top gaseous phase discharging is sequentially passed through
The steam generator group that multiple steam generators are composed in series carries out multi-stage condensing and byproduct steam, the Acetic Acid Recovering Column it is big
Part bottom of towe liquid phase is back to the tower top dewatering period of the oxidation reactor, and the refinement mother liquor of the refinement is from the acetic acid
Enter the Acetic Acid Recovering Column on one piece of the top tower tray of recovery tower.
The low energy consumption material consumption, the PTA production methods of few waste discharge also include the fraction to the Acetic Acid Recovering Column
The solvent recovery of bottom of towe liquid phase, the solvent recovery can include that extraction, extractant are reclaimed and extractant rectification step, the extraction
It is the pending liquid through cooling down to be carried out extraction oil phase and aqueous phase extracted is obtained by extraction to take step, and extractant preferably uses acetic acid first
The mixture of any one or a few the arbitrary proportion in ester, isopropyl acetate, n-butyl acetate, isobutyl acetate, it is described
Extractant recycling step is to the further isolated gaseous state extractant of the aqueous phase extracted and water, wherein gaseous state extractant cooling
After be back to use the extraction step, the extractant rectification step is that gas phase mixture and dense is obtained to the extraction oil phase rectifying
Acetic acid, wherein gas phase mixture carry out water-oil separating after cooling, obtain oil phase extractant and are back to use the extraction step, obtain
Aqueous phase substance is back to the extractant recycling step, and the dense acetic acid is back to use in oxidation reaction and/or as whole system
Flushing acetic acid.
Oxidation reaction described in the oxidation section generation terephthalic acid crystals separate out to form slurry, the slurry according to
The secondary feeding filter-press after some crystallizers are crystallized is filtered successively, filtration cakes torrefaction and the multistage washing of filter cake obtain thick
Terephthalic acid (TPA) wet cake, oxidation mother liquor and washing filtrate, the crude terephthalic acid wet cake directly send as primary raw material
Going refinement carries out slurry preparation, and most of oxidation mother liquor is back into the oxidation reaction, oxygen described in remainder
Change mother liquor and send to oxidation mother liquor treatment, dry with gas preferably using in dried oxidized tail gas, fresh nitrogen or water vapour
One or more, the washing filtrate is back to the Acetic Acid Recovering Column and carries out acetic acid recovery, in the multistage washing of the filter cake most
Rear stage is washed and slurry preparation liquid uses water, and the water is preferably using the gas phase of steam generator group output
Through the liquid phase obtained by gas-liquid separation.
Afterbody washing liquid, the slurry preparation of refinement are used in the multistage washing of the filter cake of oxidation section
P-phthalic acid's Washing of Filter Cake liquid of liquid and refinement can be the gas phase of steam generator group output through gas
The liquid phase that liquid is isolated is again through removing the liquid phase obtained after methyl acetate, it is preferred to use gas stripping process removes methyl acetate, and vapour
The portion of lime set and afterbody crystallizer after crystallizer flash steam heating slurry preheater of the thermal source for carrying from refinement
Divide gas phase.
The step of oxidation mother liquor is processed can be：Oxidation mother liquor first passes through acetic acid stripper concentrate recovery of acetic acid, carries
The mother liquor residue slurry obtained after dense is diluted with water and puts into extractant and extracted, and the bottom slurry after extraction is filtered
To filter cake and filtrate, filter cake obtains mixed phthalic acid coarse fodder through dried recovered acetic acid and extractant, and filtrate obtains through water-oil separating
Oil phase and water phase, extractant is first reclaimed to oil phase to carry out rectification and purification and cools down to obtain benzoic acid product again, the extraction reclaimed
The extraction of oxidation mother liquor is returned to after agent cooling, water is mutually back to the oxidation reaction.
Further, acetate concentration preferably reaches 60-85wt%, extraction used in the mother liquor residue slurry for being obtained after concentrate
Agent is preferably one or more in methyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate
Mixture, the mass ratio of the mother liquor residue slurry, water and extractant is preferably 1 during extraction:0.5-2.0:1.5-4.0, extraction
Temperature is preferably 40-90 DEG C.
A kind of low energy consumption material consumption, the PTA production systems of few waste discharge, including oxidation subsystem, refined subsystem and oxygen
Change vent gas treatment subsystem, top gas phase outlet one steam generator of connection of the oxidation reactor of the oxidation subsystem, institute
The thermal medium outlet for stating steam generator connects the bottom gas phase import of an Acetic Acid Recovering Column, the top gas of the Acetic Acid Recovering Column
Mutually outlet connects the thermal medium inlet of the steam generator group being composed in series by multiple steam generators, the heat of steam generator group
Media outlet connects the import of Acetic Acid Recovering Column return tank, and the top gas phase outlet connection of the Acetic Acid Recovering Column return tank is described
Oxidized tail gas processing subsystem, the bottom of towe liquid phase primary outlet of the Acetic Acid Recovering Column（For going out for outer row major part bottom of towe liquid phase
Mouthful）Connect the tower top dewatering period import of the oxidation reactor, the refinement mother liquor outlet connection vinegar of the refined subsystem
The fluid inlet of tower top first of acid recovery tower, first fluid inlet is located at one piece of the top tower tray of the Acetic Acid Recovering Column
Top.
The solvent recovery subsystem can include extraction dehydrating tower, extractant recovery tower and extractant rectifying column, described
The bottom of towe liquid phase sub-outlet of Acetic Acid Recovering Column（For the outlet of outer row's fraction bottom of towe liquid phase）The extraction is connected through cooler
The tower top import of dehydrating tower, the charging in the middle part of the tower top oil phase outlet connection extractant rectifying column of the extraction dehydrating tower
Mouthful, the bottom of towe water of the extraction dehydrating tower mutually exports the import of tower top first for connecting the extractant recovery tower, the extractant
The top gaseous phase outlet of recovery tower is dehydrated the extractant import of tower bottom through the cooler connection extraction, and the extractant is reclaimed
The bottom of towe water of tower mutually exports connection Sewage Disposal, and the top gas phase outlet of the extractant rectifying column is connected through cooler and is decanted
The import of device, the extractant import of the oil phase outlet connection extraction dehydration tower bottom of the decanter, the decantation
First water of device mutually exports the import of tower top second for connecting the extractant recovery tower, the second water of the decanter mutually company of outlet
The refluxing opening of the extractant rectifier is connect, the extractant rectifying column is provided with some bottom of towe acetic acid discharging openings, extraction used
Take any one or a few any ratio in agent preferably methyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate
The mixture of example.
Multiple oxidizing and crystallizing devices of the bottom discharge mouthful of the oxidation reactor through being sequentially connected connect a rotational pressure mistake
The charging aperture of filter, the rotary pressure filter is sequentially provided with filtering, three areas of blow dried and Washing of Filter Cake, filtering area
Export and be connected with the mother liquor reflux mouthful of the oxidation reactor bottom, the gas import that dries in blow dried area connects dried oxygen
Change one or more in the air duct of tail gas, fresh nitrogen or water vapour, Washing of Filter Cake area is provided with multistage washing subregion, most
The cleaning solution import of rear stage washing subregion connects the first bottom liquid phases outlet of the acetic acid reflux column return tank, and remaining is at different levels
In washing subregion, the outlet of the washing filtrate of the cleaning solution import connection rear stage washing subregion of previous stage washing subregion is described
The filtered solid outlet in Washing of Filter Cake area connects the solid material import of the slurry preparation tank of the refined subsystem, the slurry preparation
The water inlet of tank connects the first bottom liquid phases outlet of the acetic acid reflux column return tank.
The low energy consumption material consumption, the PTA production systems of few waste discharge are also preferably equipped with methyl acetate stripper, the vinegar
The first bottom liquid phases outlet of acid recovery tower return tank is through the methyl acetate stripper and afterbody washing subregion
The water inlet of cleaning solution import and the slurry preparation tank is connected, and specific connected mode is：The Acetic Acid Recovering Column return tank
The outlet of first bottom liquid phases is connected to the top inlet of the methyl acetate stripper, and the bottom of the methyl acetate stripper goes out
The cleaning solution import of the mouth connection afterbody washing subregion and the water inlet of the slurry preparation tank, the methyl acetate vapour
The top gaseous phase outlet connection one of stripper is used for the bottom of towe import of the ordinary-pressure absorption tower of recovery of acetic acid methyl esters.
The low energy consumption material consumption, the PTA production systems of few waste discharge also include oxidation mother liquor processing subsystem, the oxygen
Changing mother liquid disposal subsystem can include acetic acid stripper, residue extractor, residue filter machine, residue drying machine, decanter, residual
Slag extractant recovery tower and benzoic acid rectifying column, the bottom inlet of the acetic acid stripper process subsystem as the oxidation mother liquor
The pending liquid import of system, the outlet at bottom of the acetic acid stripper connects the bottom inlet of the residue extractor, described residual
Slag extractor is provided with top water inlet and top extractant import, and the top water inlet connects the Acetic Acid Recovering Column return tank
The outlet of the second bottom liquid phases, the outlet at bottom of the residue extractor connects the import of the residue filter machine, the residue
The filtered solid outlet of filter connects the import of the residue drying machine, and the filtrate (liquid of the residue filter machine connects the decantation
The import of device, the water of the decanter mutually exports the mother liquor reflux mouthful for connecting the oxidation reactor bottom, the decanter
The bottom inlet of the oil phase outlet connection residue extractant recovery tower, the top extractant of the residue extractant recovery tower goes out
Mouth connects the top extractant import of the residue extractor through cooler, and the outlet at bottom of the residue extractant recovery tower connects
Connect the import of the benzoic acid rectifying column.
Enter acetate concentration in the mother liquor residue slurry of the residue extractor from the acetic acid stripper and be preferably 60-
85wt%, the extractant into the residue extractor is preferably the positive fourth of methyl acetate, n-propyl acetate, isopropyl acetate, acetic acid
The mixture of any one or a few the arbitrary proportion in ester, isobutyl acetate, mother liquor is residual described in the residue extractor
The mass ratio of slurry material, water and extractant is preferably 1:0.5-2.0:1.5-4.0, extraction temperature is preferably 40-90 DEG C.
Further, the crude terephthalic acid moisture percentage 5-20% in oxidation section after filtration drying, liquid phase is 85-95%'s
Acetum；The crude terephthalic acid moisture percentage of the filter outlet is 25-35%, acetic acid content is 1-5%, afterbody
The acetic acid content for washing filtrate is 25-45%.
Further, the steam generator（1st grade of steam generator 21）Byproduct steam grade is pressure 0.3-
0.6MPaG, steam generator outlet liquid phase temperature is 155-185 DEG C.
Further, the Acetic Acid Recovering Column column bottom temperature is 155-185 DEG C, water content is 45- in bottom of towe spirit of vinegar
75wt%, return tank of top of the tower go out the temperature of saliva in 30-50 DEG C, water acetic acid content be 0.5-2wt%, in return tank outlet liquid phase
97~99% go methyl acetate stripper, the residue extractor of 3-1% deoxidation mother liquid disposal subsystems, remainder to be back to vinegar
Acid recovery tower.
Further, the methyl acetate stripping（Carried out in methyl acetate stripper）Operating pressure is 0-0.3MPaG,
Tower top outlet gas phase temperature is 90-130 DEG C, and bottom of towe drop temperature is 102-145 DEG C, and methyl acetate content is 0-0.1wt%, is gone
The mass fraction of methyl acetate recovery tower afterbody crystallizer top flash-off steam is 20-60%.20-35% goes in bottom of towe discharging
Oxidation filter, 15-25% goes refining filtering machine, 45-65% to remove refined slurry preparation.
Further, the extractant used by dehydrating tower is extracted described in solvent recovery and is preferably methyl acetate, isopropyl acetate
The mixture of any one or a few the arbitrary proportion in ester, n-butyl acetate, isobutyl acetate, extraction dehydrating tower operation is excellent
It is 30~50 DEG C to select temperature, and the mass ratio of the agent of bottom of towe feeding extraction and tower top charging spirit of vinegar is preferably 1.5-4:1；The extraction
Acetate concentration in the bottom water outlet of agent recovery tower is 0-0.2wt%, extractant concentration is 0-1.5wt%；The extractant rectifying tower
Extractant concentration is that 0-0.1wt%, water concentration are 5-15wt% in bottom discharging acetic acid, and acetate concentration in decanter water phase is 0-
0.1wt%。
Beneficial effects of the present invention are：
（1）By setting Acetic Acid Recovering Column 22 and refinement mother liquor being back into Acetic Acid Recovering Column, traditional PTA techniques are eliminated
To refinement mother liquor cooling filtering processing system, not only simple flow but also can effectively reclaim the water in refinement mother liquor, cobalt manganese and acetic acid,
The organic matter such as PT acid, 4-CBA, TA, reduces PX unit consumption 2.5kg, acetic acid unit consumption 1.0kg, the demineralized water unit consumption of PTA products per ton
The respective 0.01kg of 2.0t, catalyst cobalt and manganese unit consumption, also reduces sewage discharge 2.0t/tPTA, while refined subsystem mother liquor
Heat is also recycled；It can be seen that setting the consumption that Acetic Acid Recovering Column reduces raw material PX, acetic acid, catalyst, substantially reduce
Desalination water consumption and quantity of wastewater effluent, effectively promote energy-conserving and environment-protective and clean manufacturing；Particular, it is important that being returned by acetic acid
The operation of tower is received, oxidation section and refinement is become from independent control and is jointly controlled, refined mother liquor is saved cooling
Process, remain temperature water higher and enter oxidation subsystem, waste heat is not consumed not only, essence has effectively been reclaimed on the contrary
Heat in mother liquor processed；The reuse of refinement mother liquor, eliminates the scale formation of former refinement mother liquor processing unit, transports whole device
Row is more steady；
（2）First order steam generator 21 is set between oxidation reactor top gas phase and Acetic Acid Recovering Column, by this
The outlet temperature of steam generator adjusts the water gone out from Acetic Acid Recovering Column top row, with meet refined subsystem water consumption and
The water consume of oxidation mother liquor processing subsystem；
（3）Set by foregoing first order steam generator and Acetic Acid Recovering Column so that oxidation reaction produces meaning
Outer benefit：In the oxidation reaction, the not only oxidation reaction of PX, while with the oxidation reaction of acetic acid, because water is in oxidation
Subsystem and refined subsystem are recycled so that the water content in oxidation reactor increases, but when the content of water increases, energy
Enough oxidations for substantially suppressing acetic acid so that the consumption reduction of acetic acid, and the increased water of institute can be by flashing from oxidation reaction
Device top discharge, on follow-up crystallization, hydrofinishing without generation influence；
（4）The water that the water and washing tail gas of oxidation reaction generation are added, extraction dehydration are removed using extraction dehydrating tower 32
The charging of tower is produced from acetic acid recovery tower bottom, then draining, draining vinegar after extracting dehydrating tower and extractant recovery tower 33
Acid content is 0-0.2wt%；Compared with traditional handicraft is dehydrated using azeotropic distillation, the steam of extraction dehydration of the present invention disappears
Consumption only has half of azeotropic distillation or so；
（5）Oxidation subsystem eliminates oxidizing and drying machine, the gas of traditional PTA techniques using the filter-press of water washing
Body is conveyed and intermediate bunker, is significantly simplified and is shortened technological process, significantly reduces one-time investment expense；Filter is used
First filtering, the technological process that gas is dried, finally washed again, can greatly improve the clean result of filter cake and reduce washings use
Amount；Cancelling drying machine then reduces the steam consumption of device；
（6）In multistage washing afterbody washing with cleaning solution using Acetic Acid Recovering Column overhead reflux containing a small amount of acetic acid
Water, makes the water of the backflow sufficiently be recycled, while significantly reducing the consumption of the outer water of system；
（7）The water of Acetic Acid Recovering Column overhead reflux is first stripped off methyl acetate and sends to work again through methyl acetate stripper 29
It is the Washing of Filter Cake liquid of oxidation section, the mashing liquid of refinement and Washing of Filter Cake liquid, methyl acetate pair can be prevented effectively from and be added
The influence of palladium carbon catalyst in hydrogen reaction（The presence of organic matter methyl acetate can cause expensive hydrogenation palladium carbon catalyst to lose
Living, blocking catalyst active site influences hydrogenation reaction, causes final products PTA unqualified）；The acetic acid that stripper is reclaimed simultaneously
Methyl esters is all back to oxidation subsystem, the discharge of methyl acetate is reduced, so as to reduce the consumption of acetic acid；
（8）Oxidation mother liquor removal of impurities treatment uses extraction, eliminates thin film evaporator, has both reclaimed the benzene in oxidation residua
Formic acid, terephthalic acid (TPA), M-phthalic acid and catalyst cobalt manganese, eliminate the high steam consumption of former thin film evaporator again, can
High steam consumption 0.03t/tPTA is reduced, PX unit consumption 3.0kg/tPTA are reduced, oxidation residua discharge is eliminated；In place of particularly
It is, though significantly reduced through the acetate concentration of the slurry after acetic acid stripper 50, but still up to 60-85wt%, and work as water in vinegar
Content in acid can not all be separated when higher and relatively low by the way of extraction, therefore not will recognize that generally under prior art
Using extraction.The present invention is will to carry out one by a part of water from acetic acid recovery top of tower of addition in the relatively low acetic acid of water content
Determine the dilution of degree, the solution that using extraction cannot separate originally is become suitable for the solution of extract and separate, and thus take
Obtained above-mentioned good result；
After comprehensively using items innovative technology as described above, PTA technological innovations are generated and is greatly acted on, with tradition
PTA techniques are compared, and present invention process flow is simple, material consumption energy consumption is low, waste water and dregs are few, change PTA devices for a long time by
Be considered as energy consumption rich and influential family, water consumption rich and influential family, sewage discharge rich and influential family, the features such as waste residue is not disposable, then become resource-conserving,
Environmentally friendly PTA new technologies, consumption electric power is not needed not only, can also send electric power, while meeting own device and use,
Can also be to being transmitted electric power outside PTA devices, the part as extra earning is the typical case of energy-conservation, with good environmental benefit,
Economic benefit and operability.The technology of the present invention is applicable not only to newly-built PTA devices, is applied equally to existing PTA devices
Transformation and upgrade, make the more energy-saving operation of device.
Brief description of the drawings
Fig. 1 is the process chart of PTA production methods of the invention；
Fig. 2 is the process chart of traditional PTA production methods.
Reference is：
1st, oxidation reactor, 2, the first crystallizer of oxidation, 3, the second crystallizer of oxidation, 4, the 3rd crystallizer of oxidation, 5, oxygen
Change filter-press, 6, refined slurry blend tank, 7~12, refined paste heater, 13, hydrogenation reactor, 14~18, first
~level V refining crystallization device, 19, refined filter-press, 20, the dry machines of PTA, 21, first order steam generator, 22, acetic acid returns
Receive tower, 23, second level steam generator, 24, third level steam generator, 25, fourth stage steam generator, 26, demineralized water adds
Hot device, 27, water recirculator, 28, Acetic Acid Recovering Column return tank, 29, methyl acetate stripper, 30, ordinary-pressure absorption tower, 31,
Cooler, 32, extraction dehydrating tower, 33, extractant recovery tower, 34, extractant reclaim overhead condenser, 35, extractant rectifying column,
36th, acetic acid cooler is washed, 37, extractant rectifying column tower top condenser, 38, decanter, 39, Sewage Disposal, 40, high pressure inhales
Receive tower, 41, tail gas CIU, 42, off-gas expander, 43, tail gas washing tower, 50, acetic acid stripper, 51, residue extractor,
52nd, residue filter machine, 53, residue drying machine, 54, decanter, 55, residue extractant recovery tower, 56, the condensation of residue extractant
Device, 57, benzoic acid rectifying column, 58, benzoic acid cooler, 100, raw material paraxylene, 101, air, 102, catalyst, 103,
Hydrogen, 104, PTA products, 105, water, 106, rinse acetic acid, 107, mixed phthalic acid, 108, benzoic acid；
201st, oxidation reactor, 202, oxidation the first crystallizer, 203, oxidation the second crystallizer, 204, oxidation the 3rd crystallize
Device, 205, oxidation filter, 206, oxidizing and drying machine, 207, intermediate bunker, 208, refined slurry blend tank, 209~214, essence
Paste heater processed, 215, hydrogenation reactor, 216~220, first~level V refining crystallization device, 221, refined pressure filtration
Machine, 222, the dry machines of PTA, 231, first order steam generator, 232, second level steam generator, 233, third level steam generation
Device, 234, fourth stage steam generator, 235, cooler, 236, reactor return tank, 237, cooler, 238, high pressure absorbs
Tower, 239, tail gas CIU, 240, off-gas expander, 241, tail gas washing tower, 251, dehydrating tower, 252, washing acetic acid cooling
Device, 253, dehydration overhead condenser, 254, decanter, 255, entrainer recovery tower, 256, entrainer reclaim overhead condenser,
257th, Sewage Disposal, 261, acetic acid stripper, 262, thin film evaporator, 263, catalyst water extractor, 264, residue centrifugation
Machine, 265, concentrate heater, 266, catalyst recycling can, 300, raw material paraxylene, 301, air, 302, catalyst,
303rd, hydrogen, 304, PTA products, 305, demineralized water, 306, rinse acetic acid, 307, water, 308, oxidation residua.
Specific embodiment
Fig. 1 gives implementation technological process of the invention, including following five parts：
（1）P xylene oxidation subsystem：In oxidation reactor 1, with acetic acid as solvent, with cobalt acetate, manganese acetate, hydrogen
Bromic acid is catalyst, and raw material paraxylene 100 reacts generation CTA with air 101 under the effect of catalyst 102.Reactor is band
The non-stirring reactor of dewatering period, or any type of reactor applied in other existing PTA devices, operation temperature
It is 180-200 DEG C to spend, and operating pressure is 1-1.5MPa（Absolute pressure）, herein by patent ZL03142246.2 and
ZL200910076703.1 refers to this.The dewatering period of tower top plays a part of acetic acid and water separates and reduce solid phase entrainment,
The height of dewatering period can be adjusted according to water content, device quantity of steam and acid balance in oxidation reactor, heat of reaction quilt
Acetic acid, water and the tail gas for evaporating are taken away from tower top.Due to product TA, solubility is not high in solvent acetic acid, and more than 90%
TA crystallize precipitation in the reactor and form slurry, slurry is sequentially sent to follow-up the first crystallizer of oxidation 2, oxidation second and crystallizes
Device 3, the 3rd crystallizer 4 of oxidation are flashed and crystallized with decrease temperature and pressure step by step, and the oxidation temperature control of the 3rd crystallizer 4 is in 90-140
DEG C, its bottom slurry delivers to oxidative pressure filter 5, and filter-press 5 is rotary pressure filter, slurry in filter according to
It is secondary to complete filtering, blow dried, Washing of Filter Cake totally three processes：Filtered first, will most of liquid phase and TA crystal point
From in 15-35%, filtrated stock is the acetic acid of 85-95%, except small part delivers to mother liquid disposal subsystem for rate of cake moisture content control
（Enter mother liquid disposal processing subsystem from acetic acid stripper 50）Outward, most of mother liquor is back to oxidation reactor；Then carry out
Blow dried, dry gas can be dried oxidized tail gas, fresh nitrogen or water vapour, and rate of cake moisture content can be from after drying
15-35% is reduced to 10~12% or even less than 8%；Finally filter cake is washed, washing process is washed using 2~4 grades, finally
The cleaning solution of one-level is the bottom discharge of methyl acetate stripper 29, other grades with cleaning solution be washing after next stage is washed
Filtrate, acetic acid content is less than 10wt%, acetic acid in the washing filtrate after the 1st grade of washing in the washing filtrate after afterbody washing
Content is 25-45%, and the washing filtrate send Acetic Acid Recovering Column 22, and gained filter cake is crude terephthalic acid wet feed after washing, and this is wet
The moisture percentage of material is 20-40wt%, acetic acid content is 1-5%, and wet feed removes refinement of crude terephthalic acid subsystem（Enter refined slurry to adjust
Distribution tank 6）.
（2）Refinement of crude terephthalic acid subsystem：From the crude terephthalic acid wet feed out of oxidative pressure filter 5 with come
It is beaten in refined slurry blend tank 6 from the water of methyl acetate stripper 29, the control of slurry solid content is in 25-35wt%, temperature
At 95-140 DEG C, Stress control is in 0-0.5MPaG for degree control；It is refined by six grades from refined slurry blend tank 6 slurry out
Paste heater 7-12 stepped heatings to 280-290 DEG C, the 1st~5 grade of heater and the 1st~5 grade of refining crystallization device one above
One correspondence, is heated using the flash steam of correspondence crystallizer, and afterbody uses high pressure steam heating；Exist by the slurry for heating
Hydrogenation reaction is carried out in hydrogenation reactor 13 with hydrogen 103, hydrogenation reactor is fixed bed reactors, and catalyst is palladium charcoal solid
Particle, the impurity 4-CBA that the purpose of hydrogenation process is so that in crude terephthalic acid is reacted with hydrogen so that 4-CBA is reduced
It is PT acid more soluble in water；The discharging of hydrogenation reactor 13 carries out decrease temperature and pressure into the 1st~5 grade of refining crystallization device 14~18
Flash crystallization, the 5th grade of temperature of crystallizer 18 is 140-150 DEG C；The flash steam of crystallizers at different levels is used to heat slurry above
To reclaim heat, refined filter-press 19 is delivered in the 5th grade of crystalliser feet discharging carries out separation of solid and liquid to heater.Feed slurry
Filtered successively in refined filter-press 19, dry totally three processes of the gentle soma of Washing of Filter Cake：Filtered first, institute
It is 25-30wt% to obtain rate of cake moisture content；Then washed, washing process is washed using multistage, and the cleaning solution of every grade of washing is
Washing filtrate after next stage washing, the washings of afterbody come from methyl acetate stripper 29, wash sum of series washings
Consumption reaches product requirement to control according to impurity content in filter cake, and filter liquor and washing filtrate constitute refinement mother liquor, refine
Mother liquor enters Acetic Acid Recovering Column 22 from top, so that the organic matter such as PT acid, 4-CBA and TA in having reclaimed refinement mother liquor；Finally
Gas drying is carried out, desiccant gas is dried oxidized tail gas, nitrogen, water vapour.From the wet of refined filter press blanking
Moisture percentage is 5-15wt% in filter cake（It is preferred that 8-12wt%）, the wet cake finally enter PTA drying machines 20 dry after obtain PTA product
Product 104.
（3）Solvent recovery cycle subsystem：From the top of oxidation reactor 1, oxidized tail gas out are sent out by first order steam
Steam needed for the raw by-product device of device 21, the grade of byproduct steam is adjusted according to device balance of steam in 0.3-0.6MPaG；Steam
The outlet temperature of vapour generator is controlled at 150-180 DEG C, and the liquid phase condensed out in tail gas is back to oxidation reactor, and gas phase is sent
To Acetic Acid Recovering Column 22；The row of Acetic Acid Recovering Column return tank 28 is adjusted by adjusting the outlet temperature of first order steam generator 21
The water for going out, to meet the demand of Purified Water；Enter vinegar from bottom of towe from the oxidized tail gas out of first order steam generator 21
Acid recovery tower 22, the washing filtrate from oxidative pressure filter 5 enters the bottom of Acetic Acid Recovering Column 22, carrys out autofining pressure mistake
, from tower top is into Acetic Acid Recovering Column 22 and is back to first piece of tower tray, each feed stream is in acetic acid recovery for the refinement mother liquor of filter 19
Realize that acetic acid is separated with water in tower, tower reactor is acetic acid-aqueous solution（Water containing a small amount of acetic acid）, dissolved in solution from refined
The organic matters such as PT acid, the 4-CBA and TA of disposing mother liquor, tower reactor discharging is extracted fraction out and is dehydrated to dehydrating tower 31 is extracted, its
It is remaining to be back to oxidation reactor 1；The bottom of towe operation temperature of Acetic Acid Recovering Column 22 is 155-185 DEG C, preferably 160-180 DEG C, vinegar
The rate of recovery of acid is more than 98.5%, and the water content of tower reactor is 45-75wt%；Acetic Acid Recovering Column ejection gas is mainly containing acetic acid and water
Oxidized tail gas, the oxidized tail gas sequentially pass through 2-4 grades of steam generator 23-25 condensation and by-product water vapour, then pass through again
Desalination water heater 26 and water recirculator 27 go the Acetic Acid Recovering Column return tank 28 to carry out gas-liquid after continuing cool to 30-50 DEG C
Separate, return tank outlet gas phase truncates gas disposal subsystem（Into high pressure absorber 40）, return tank outlet liquid phase is water, the water
The 97-99% of amount removes methyl acetate stripper 29 to remove the residue extraction of methyl acetate, 1-3% deoxidation mother liquid disposal subsystems
Tank 51, remainder is back to Acetic Acid Recovering Column 22（Into first piece of tower of the top of tower tray positioned at the Acetic Acid Recovering Column
Top second liquid phase import）；The methyl acetate being stripped off of methyl acetate stripper 29 is into being back to oxygen after ordinary-pressure absorption tower 30
Chemical industry section（Not shown in figure）, being flowed out from tower reactor by the water after stripping, 20-35% deoxidation filters, 15-25% goes to refine
Filter, 45-65% feedings refine slurry blend tank 6 as mashing water, it is achieved thereby that the recycling of water, methyl acetate stripping
Tower operating pressure is 0-0.3MPaG, and tower top outlet gas phase temperature is 90-130 DEG C, and bottom of towe leaving water temperature is 102-140 DEG C, acetic acid
Methyl ester content is 0-0.1wt%；Bottom of towe liquid phase from Acetic Acid Recovering Column 22 enters extraction dehydrating tower 32 from tower top after cooling,
From bottom of towe into extraction dehydrating tower 32, extraction dehydrating tower bottom discharge is aqueous phase extracted to extractant, and the water enters extraction from tower top
Agent recovery tower 33 is taken, extractant recovery tower bottom discharge is water, and the water is emitted into Sewage Disposal 39, extractant recovery tower top
Outlet gas phase is gaseous state extractant, is recycled by being back to extraction dehydrating tower 32 after condensation, extraction dehydrating tower top discharge
It is extraction oil phase, oil phase removes extractant rectifying column 35, and the discharging of extractant rectifying column bottom is dense acetic acid, the dense acetic acid part is through cold
But high pressure absorber 40 is removed after the cooling of device 36, and as washing, acetic acid is used, a part makes as the flushing acetic acid 106 of whole device
Oxidation reactor 1 is back to, remainder, the condensed device 37 of tower top outlet gas phase of extractant rectifying 35 removes decantation after condensing
38 points of device is water-oil phase, and oil phase returns to extraction dehydrating tower 32 and recycles, and aqueous portion enters extractant rectifying from tower top
Tower 35 enters extractant recovery tower 33 as backflow, remainder from tower top；The extractant that extraction dehydrating tower 32 is used is acetic acid
The mixture of one or more in methyl esters, isopropyl acetate, n-butyl acetate, isobutyl acetate, the operation temperature of tower is 30-
50 DEG C, the agent of bottom of towe feeding extraction and tower top charging spirit of vinegar mass ratio be 1.5-4：1, the bottom of towe water outlet of extractant recovery tower 33
In acetate concentration for 0-0.2wt%, extractant concentration be 0-0.2wt%, extractant rectifying column 35 bottom of towe discharging acetic acid in extract
Agent concentration is taken for 0-0.2wt%, water concentration are 5-15wt%.
（4）Vent gas treatment subsystem：Oxidized tail gas from Acetic Acid Recovering Column return tank 28 are inhaled from bottom of towe into high pressure
Receive tower 40, high pressure absorber middle part using from extractant rectifier bottoms cooler 36 come dense acetic acid spray, top use remove
Salt solution 105 is sprayed, and high pressure absorber top exit gas phase goes tail gas catalytic burning system 41 to purify, and the tail gas after purification removes tail gas
The decompression acting of expanding machine 42, the tail gas after decompression acting goes tail gas washing tower 43 to be finally exhausted in air after alkali cleaning.
（5）Mother liquid disposal：The oxidation mother liquor for extracting 5-30% out from oxidative pressure filter 5 carries out mother liquid disposal, first passes through vinegar
The concentrate of sour stripper 50 is while recovery of acetic acid, the discharging of acetic acid stripping tower bottom is mother liquor residue slurry, and mother liquor residue slurry enters residual
Slag extractor 51, while to adding extractant and water to be stirred, extract in residue extractor 51, water is returned from Acetic Acid Recovering Column
The stream outlet liquid phase of tank 28, residue extractor discharging goes residue filter machine 52 to obtain filter cake and filtrate after filtering, and filter cake is by drying machine
53 dried recovered acetic acid, extractant simultaneously obtain mixed phthalic acid coarse fodder 107, and 54 points of filtrate lease making decanter is water-oil phase, oil
Residue extractant recovery tower 55 is first mutually sent to reclaim extractant, and entering back into benzoic acid rectifying column 57 carries out rectification and purification and through cold
Condenser 58 obtains benzoic acid product 108 after condensing, and the condensed device 56 of the extractant for being reclaimed returns to residue extractor 51 after condensing,
Water is mutually back to oxidation reactor 1；Acetate concentration in mother liquor residue slurry is 60-85wt%, is added in residue extractor 51
Extractant is one or more in methyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate
Mixture, mother liquor residue slurry：Water：The mass ratio of extractant is 1：0.5-2.0：1.5-4.0, the extraction temperature of residue extractor
It is 40-90 DEG C.
It is below one of the invention specific PTA production technology operating process embodiment, designed annual production capacity is 1,200,000 tons
PTA process units, PTA yield is 150t/h, including following five subsystems.
（1）P xylene oxidation subsystem：In oxidation reactor 1, with acetic acid as solvent, with cobalt acetate, manganese acetate, hydrogen
Bromic acid is catalyst, and the raw material paraxylene 100 of 98.25t/h reacts with the air 101 of 470t/h under the effect of catalyst 102
Generation crude terephthalic acid CTA.Reactor is the non-stirring reactor with dewatering period, and operation temperature is 187 DEG C, and operating pressure is
1.1MPaG, catalyst concn is cobalt 400ppm, manganese 400, bromine 950pppm in reactor liquid phase, and the residence time is 65min.Tower top
Dewatering period play a part of acetic acid and water and separate and reduce solid phase entrainment, dewatering period is 500mm, heat of reaction quilt for height
Acetic acid, water and the tail gas for evaporating are taken away from tower top.Reactor discharging slurry be sequentially sent to follow-up the first crystallizer of oxidation 2,
Aoxidize the second crystallizer 3, the 3rd crystallizer 4 of oxidation to flash and crystallize with decrease temperature and pressure step by step, aoxidize the temperature control of the 3rd crystallizer 4
At 90 DEG C, its bottom slurry delivers to oxidative pressure filter 5 to system, and filter-press 5 is rotary pressure filter, and slurry is in filtering
Filtering, blow dried, Washing of Filter Cake totally three processes are sequentially completed in machine：Filtered first, will most of liquid phase and TA
Crystal is separated, and rate of cake moisture content is controlled in 28wt%, and filtrated stock is 91% acetic acid, except small part delivers to mother liquid disposal subsystem
（Enter mother liquid disposal processing subsystem from acetic acid stripper 50）Outward, most of mother liquor is back to oxidation reactor；Then carry out
Blow dried, dry gas are dried oxidized tail gas, and rate of cake moisture content can be reduced to less than 15% from 28% after drying；Finally
Filter cake is washed, using 2 grades of washings, the cleaning solution of afterbody is refined methyl acetate stripper bottom to washing process
Discharging 100t/h, other grades with cleaning solution be washing filtrate after next stage wash, afterbody wash after washing filtrate
Middle acetic acid content is less than 10wt%, and acetic acid content is 40% in the washing filtrate after the 1st grade of washing, and the washing filtrate send acetic acid recovery
Tower 22, gained filter cake is crude terephthalic acid wet feed after washing, and the moisture percentage of the wet feed is 35wt%, acetic acid content is 3%, wet
Material removes refinement of crude terephthalic acid subsystem（Enter refined slurry blend tank 6）.
（2）Refinement of crude terephthalic acid subsystem：From the crude terephthalic acid wet feed out of oxidative pressure filter 5 with come
It is beaten in refined slurry blend tank 6 from the water of methyl acetate stripper 29, slurry solid content is controlled in 31wt%, temperature
At 135 DEG C, Stress control is in 0.2MPaG for control；Heated by seven grades of refined slurries from refined slurry blend tank 6 slurry out
To 286 DEG C, 1-5 grades of heater and 1-5 grades of refining crystallization device above are corresponded device 7-12 stepped heatings, use correspondence
The flash steam of crystallizer is heated, and last two-stage uses high pressure steam heating；By the slurry of heating in hydrogenation reactor 13
Hydrogenation reaction is carried out with hydrogen 103, hydrogenation reactor is fixed bed reactors, and catalyst is palladium charcoal solid particle, hydrogenation process
The impurity 4-CBA that is so that in crude terephthalic acid of purpose reacted with hydrogen so that 4-CBA be reduced to it is more soluble in water
PT acid；The discharging of hydrogenation reactor 13 carries out decrease temperature and pressure flash crystallization, the 5th grade into 1-5 grades of refining crystallization device 14-18
The temperature of crystallizer 18 is 148 DEG C；The flash steam of crystallizers at different levels is used for heating paste heater above to reclaim heat, the
Refined filter-press 19 is delivered in 5 grades of crystalliser feet dischargings carries out separation of solid and liquid, and feed slurry is in refined filter-press 19
In filtered successively, dry totally three processes of the gentle soma of Washing of Filter Cake：Filtered first, gained rate of cake moisture content is
28wt%；Then washed, washing process is washed using two-stage, the cleaning solution of one-level washing is the washing after two grades of washings
Filtrate, two grades of washings come from Acetic Acid Recovering Column return tank 28（Consumption 70t/h）, filter liquor and washing filtrate composition are refined
Mother liquor, a refinement mother liquor part delivers to cleaning solution of the oxidative pressure filter 5 as its afterbody, and remaining refinement mother liquor is from top
Portion enters Acetic Acid Recovering Column 22, so that the organic matter such as PT acid, 4-CBA and TA in having reclaimed refinement mother liquor；Finally carry out gas
Dry, desiccant gas is dried oxidized tail gas, nitrogen, water vapour.Contain from the wet cake of refined filter press blanking
Wet rate is 12wt%, and the wet cake finally enters the PTA products 104 that 150t/h is obtained after PTA drying machines 20 are dried.
（3）Solvent recovery cycle subsystem：From the top of oxidation reactor 1, oxidized tail gas out are sent out by first order steam
Steam needed for the raw by-product device of device 21, the grade of byproduct steam is 0.35MPaG；The outlet temperature of steam generator is controlled 176
DEG C, the liquid phase condensed out in tail gas is back to oxidation reactor, and gas phase delivers to Acetic Acid Recovering Column 22；Steamed by adjusting the first order
The outlet temperature of vapour generator 21 come adjust Acetic Acid Recovering Column return tank 28 discharge water, to meet the demand of water；From
The oxidized tail gas out of one-level steam generator 21 enter Acetic Acid Recovering Column 22 from bottom of towe, from washing for oxidative pressure filter 5
Filtrate into the bottom of Acetic Acid Recovering Column 22 is washed, the refinement mother liquor for carrying out autofining filter-press 19 enters acetic acid recovery from tower top
Tower 22 is simultaneously back to first piece of tower tray, and each feed stream realizes that acetic acid is separated with water in Acetic Acid Recovering Column, and tower reactor is vinegar
Acid-the aqueous solution, has dissolved the organic matter such as PT acid, 4-CBA and TA reclaimed from refinement mother liquor, tower reactor discharging extraction in solution
110t/h is dehydrated to dehydrating tower 31 is extracted, and remaining is back to oxidation reactor 1；The bottom of towe operation temperature of Acetic Acid Recovering Column 22
It it is 160 DEG C, up to 99.0%, the water content of tower reactor is 55wt% to the rate of recovery of acetic acid；Acetic Acid Recovering Column ejection gas is mainly containing acetic acid
With the oxidized tail gas of water, the oxidized tail gas sequentially pass through 2-4 grades of steam generator 23-26 condensation and by-product water vapour, then
Removing Acetic Acid Recovering Column return tank 28 after desalination water heater 27 and water recirculator 28 continue cool to 40 DEG C again is carried out
Gas-liquid separation, return tank outlet gas phase truncates gas disposal subsystem（Into high pressure absorber 40）, return tank outlet liquid phase is water,
The 300t/h of the water removes methyl acetate stripper 29 to remove the residue of methyl acetate, 5t/h deoxidation mother liquid disposal subsystems
Extractor 51, remaining 70t/h are back to Acetic Acid Recovering Column 22；The methyl acetate being stripped off of methyl acetate stripper 29 enters normal
Pressure is back to oxidation section behind absorption tower 30, and by the water after stripping, 100t/h deoxidations filter press 5 is used as cleaning solution, 70t/h
Go refined filter press 19 to be flowed out from tower reactor as cleaning solution, 130t/h and send into refined slurry blend tank 6 as mashing water, so that
The recycling of water is realized, methyl acetate stripper operating pressure is 0.2MPaG, and tower top outlet gas phase temperature is 90 DEG C, tower
Bottom leaving water temperature is 140 DEG C, methyl acetate content is 0.05wt%；Bottom of towe liquid phase from Acetic Acid Recovering Column 22 is sent after cooling
Enter tower top and enter extraction dehydrating tower 32, extractant enters extraction dehydrating tower 32 from bottom of towe, and extraction dehydrating tower bottom discharge is extraction
Water phase, the water enters extractant recovery tower 33 from tower top, and extractant recovery tower bottom discharge is water, and the water is emitted at sewage
Reason station 39, extractant recovery tower top exit gas phase is gaseous state extractant, is circulated by being back to extraction dehydrating tower 32 after condensation
Use, the top discharge of extraction dehydrating tower is extraction oil phase, oil phase removes extractant rectifying column 35, and the discharging of extractant rectifying column bottom is dense
Acetic acid, the dense acetic acid part goes high pressure absorber 40 to be used as washing acetic acid after being cooled down through cooler 36, a part of conduct
The flushing acetic acid 106 of whole device is used, remainder is back to oxidation reactor 1, the tower top outlet gas of extractant rectifying 35
Mutually condensed device 37 removes 38 points of decanter after condensing be water-oil phase, and oil phase returns to extraction dehydrating tower 32 and recycles, water phase portion
Divide from tower top and enter extractant recovery tower 33 from tower top as backflow, remainder into extractant rectifying column 35；Extraction is de-
The extractant that water tower 32 is used is n-butyl acetate, and the operation temperature of tower is 40 DEG C, and the agent of bottom of towe feeding extraction and tower top charging are dilute
The mass ratio of acetic acid is 2：1, the acetate concentration in the bottom of towe water outlet of extractant recovery tower 33 is 0.05wt%, extractant concentration is
0.02wt%, extractant rectifying column 35 bottom of towe discharging acetic acid in extractant concentration be 0.05wt%, water concentration be 5wt%.
（4）Vent gas treatment subsystem：Oxidized tail gas from Acetic Acid Recovering Column return tank 28 are inhaled from bottom of towe into high pressure
Receive tower 40, high pressure absorber middle part using from extractant rectifier bottoms cooler 36 come dense acetic acid spray, top use remove
Salt solution 105 is sprayed, and high pressure absorber top exit gas phase goes tail gas catalytic burning system 41 to purify, and the tail gas after purification removes tail gas
The decompression acting of expanding machine 42, the tail gas after decompression acting goes tail gas washing tower 43 to be finally exhausted in air after alkali cleaning.
（5）Mother liquid disposal：The oxidation mother liquor for extracting 10% out from oxidative pressure filter 5 carries out mother liquid disposal, first passes through acetic acid
The concentrate of stripper 50 is while recovery of acetic acid, the discharging of acetic acid stripping tower bottom is mother liquor residue slurry, and mother liquor residue slurry enters residue
Extractor 51, while to adding extractant and water to be stirred, extract in residue extractor 51, water flows back from Acetic Acid Recovering Column
Tank 28 exports liquid phase, and the discharging of residue extractor goes residue filter machine 52 to obtain filter cake and filtrate after filtering, and filter cake is by drying machine 53
Dried recovered acetic acid, extractant simultaneously obtain mixed phthalic acid coarse fodder 107, and 54 points of filtrate lease making decanter is water-oil phase, oil phase
Residue extractant recovery tower 55 is first sent to reclaim extractant, the condensed device 56 of extractant of recovery returns to residue extraction after condensing
Then tank 51 enters back into after benzoic acid rectifying column 57 carries out rectification and purification and the condensation of condensed device 58 and obtains benzoic acid product 108,
Water is mutually back to oxidation reactor 1；Acetate concentration in mother liquor residue slurry is 72wt%, the extraction added in residue extractor 51
Take agent mixing for one or more in methyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate
Compound, mother liquor residue slurry：Water：The mass ratio of extractant is 1：1：2, the extraction temperature of residue extractor is 52 DEG C.
The result of implementation of the present embodiment is：The PX unit consumption of the PTA products per ton of PTA full devices is 650kg, acetic acid unit consumption
35kg, demineralized water unit consumption 0.2t, catalyst cobalt unit consumption 0.01kg, steam mono-consumption 0.5t, generating 70KW.
And use the traditional PTA techniques shown in Fig. 2（Identical Operating parameters are used at same apparatus）When, PTA is complete
The PX unit consumption of the PTA products per ton of device is 655kg, acetic acid unit consumption 38kg, demineralized water unit consumption 2.2t, catalyst cobalt unit consumption
0.04kg, steam mono-consumption 0.70t, generating -15KW.
It can be seen that, 5kg, acetic acid unit consumption reduction 3kg are reduced than the PX unit consumption of traditional PTA techniques using the method for the present invention, is removed
Salt solution unit consumption reduction 2.0t, catalyst cobalt unit consumption reduction 0.03kg, steam mono-consumption reduction 0.2t, generating increase 55KW.
Wherein, due to the presence of dewatering system of the invention, the water and the fresh water whole into system of generation will be reacted
Out of system, thus the steam that can decline to a great extent usage amount.PTA devices with 1,200,000 tons/year of the annual output of the present embodiment are
Example, the quantity of steam for using present invention consumption 0.35MPaG is 20t/h, 0.13t/tPTA is converted into, than using traditional handicraft（Consumption
The quantity of steam of 0.35MPaG is 50t/h, converts into 0.33t/tPTA）When quantity of steam consumption the range of decrease up to 60%, steamed with 180 yuan/t
Vapour meter, saves expense and be about ten thousand yuan of 30*8000*180/10000=4320 in year.
The present invention uses new oxidation mother liquor processing method, not only reduces the consumption of steam, acetic acid and catalyst, keeps away
Exempt from the hazardous waste processing cost to oxidation residua, also reclaim other materials, energy conservation and consumption reduction effects highly significant.Still with this
As a example by the PTA devices of 1,200,000 tons/year of the annual output of embodiment, using oxidation mother liquor processing method of the invention, 9.5MPaG is consumed
Quantity of steam be 1.3t/h, low-pressure steam consumption be 1t/h, catalyst cobalt consumption be 1.5kg/h, acetic acid all reclaim, while can
Recovery of benzoic acid 300kg/h, mixes phthalic acid 300kg/h.And it is 2.5t/ to use the quantity of steam that traditional handicraft consumes 9.5MPaG
H, low-pressure steam consumption is 5t/h, acetic acid consumption 300kg/h；Catalyst cobalt consumption is 4.5kg/h, and 1000kg/h oxidation residuas send
Hazardous waste processing center.It can be seen that, oxidation mother liquor treatment is carried out using the present invention, the usage amount of high steam can be reduced
1.2t/h, the usage amount 4t/h of low-pressure steam, acetic acid consumption amount 300kg/h, catalyst cobalt consumption 3kg/h, while reclaiming benzene
Formic acid 300kg/h, saves expense and be about 40,500,000 yuan in year.
Claims (8)
1. a kind of low energy consumption material consumption, the PTA production methods of few waste discharge, including oxidation section and refinement, its feature exist
In the oxidation reactor top of the oxidation section, oxidized tail gas out are introduced into first order steam generator byproduct steam, the
The thermal medium outlet gas phase of one-level steam generator enters Acetic Acid Recovering Column, the Acetic Acid Recovering Column top gaseous phase discharging from bottom of towe
Sequentially passing through the steam generator group that multiple steam generators are composed in series carries out multi-stage condensing and byproduct steam, and the acetic acid is returned
The most of bottom of towe liquid phase for receiving tower is back to the tower top dewatering period of the oxidation reactor, the refinement mother liquor of the refinement from
Enter the Acetic Acid Recovering Column on one piece of the top tower tray of the Acetic Acid Recovering Column.
2. low energy consumption material consumption as described in claim 1, the PTA production methods of few waste discharge, it is characterised in that also include
To the solvent recovery of the fraction bottom of towe liquid phase of the Acetic Acid Recovering Column, the solvent recovery include extraction, extractant reclaim and
Extractant rectification step, the extraction step is the pending liquid through cooling down to be carried out extraction oil phase and extraction water is obtained by extraction
Phase, extractant is preferably using any one or a few in methyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate
Arbitrary proportion mixture, the extractant recycling step be to the aqueous phase extracted further isolated gaseous state extractant
And water, the extraction step wherein is back to use after the cooling of gaseous state extractant, the extractant rectification step is to the extraction oil
Phase rectifying obtains gas phase mixture and dense acetic acid, and wherein gas phase mixture carries out water-oil separating after cooling, obtains oil phase extraction
Agent is back to use the extraction step, obtains aqueous phase substance and is back to the extractant recycling step, and the dense acetic acid is back to use oxygen
Change in reacting and/or the flushing acetic acid as whole system.
3. low energy consumption material consumption as described in claim 2, the PTA production methods of few waste discharge, it is characterised in that the oxygen
The terephthalic acid crystals of oxidation reaction generation separate out to form slurry described in chemical industry section, and the slurry sequentially passes through some crystallizations
Feeding filter-press is filtered successively after device crystallization, filtration cakes torrefaction and the multistage washing of filter cake obtain the wet filter of crude terephthalic acid
Cake, oxidation mother liquor and washing filtrate, the crude terephthalic acid wet cake are directly sent to refinement as primary raw material and are carried out
Slurry preparation, the oxidation reaction is back to by most of oxidation mother liquor, and oxidation mother liquor described in remainder sends to oxidation
Mother liquid disposal, dries with gas preferably using one or more in dried oxidized tail gas, fresh nitrogen or water vapour, described
Washing filtrate is back to the Acetic Acid Recovering Column and carries out acetic acid recovery, and afterbody is washed and described in the multistage washing of the filter cake
Obtained by slurry preparation liquid uses water, the water preferably to use the gas phase that the steam generator group is exported through gas-liquid separation
Liquid phase.
4. low energy consumption material consumption as described in claim 3, the PTA production methods of few waste discharge, it is characterised in that the oxygen
Change mother liquid disposal the step of be：Oxidation mother liquor first passes through acetic acid stripper concentrate recovery of acetic acid, the mother liquor residue obtained after concentrate
Slurry is diluted with water and puts into extractant and extracted, and the bottom slurry after extraction is filtrated to get filter cake and filtrate, filter cake
Mixed phthalic acid coarse fodder is obtained through dried recovered acetic acid and extractant, filtrate obtains oil phase and water phase through water-oil separating, to oil phase
First reclaim extractant carries out rectification and purification and cools down to obtain benzoic acid product again, and it is female to return to oxidation after the extractant cooling reclaimed
The extraction of liquid, water is mutually back to the oxidation reaction；Acetate concentration preferably reaches 60- in the mother liquor residue slurry obtained after concentrate
85wt%, extractant used is preferably in methyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate
The mixture of one or more, the mass ratio of the mother liquor residue slurry, water and extractant is preferably 1 during extraction:0.5-
2.0:1.5-4.0, extraction temperature is preferably 40-90 DEG C.
5. a kind of low energy consumption material consumption, the PTA production systems of few waste discharge, including oxidation subsystem, refined subsystem and oxidation
Vent gas treatment subsystem, it is characterised in that the top gas phase outlet connection one steam hair of the oxidation reactor of the oxidation subsystem
Raw device, the thermal medium outlet of the steam generator connects the bottom gas phase import of an Acetic Acid Recovering Column, the Acetic Acid Recovering Column
The thermal medium inlet of steam generator group that is composed in series by multiple steam generators of top gas phase outlet connection, steam generation
The thermal medium outlet of device group connects the import of Acetic Acid Recovering Column return tank, the top gas phase outlet of the Acetic Acid Recovering Column return tank
The oxidized tail gas processing subsystem is connected, the bottom of towe liquid phase primary outlet of the Acetic Acid Recovering Column connects the oxidation reactor
Tower top dewatering period import, the liquid phase of tower top first of the refinement mother liquor outlet connection Acetic Acid Recovering Column of the refined subsystem is entered
Mouthful, first fluid inlet is located at one piece of the top top of tower tray of the Acetic Acid Recovering Column.
6. low energy consumption material consumption as described in claim 5, the PTA production systems of few waste discharge, it is characterised in that also include
Solvent recovery subsystem, the solvent recovery subsystem includes extraction dehydrating tower, extractant recovery tower and extractant rectifying column, institute
The bottom of towe liquid phase sub-outlet of Acetic Acid Recovering Column is stated through the tower top import of the cooler connection extraction dehydrating tower, the extraction dehydration
Charging aperture in the middle part of the tower top oil phase outlet connection extractant rectifying column of tower, the bottom of towe water of the extraction dehydrating tower is mutually exported
The import of tower top first of the extractant recovery tower is connected, the top gaseous phase outlet of the extractant recovery tower is connected through cooler
The extractant import of the extraction dehydration tower bottom, the bottom of towe water of the extractant recovery tower mutually exports connection Sewage Disposal,
The top gas phase outlet of the extractant rectifying column connects the import of decanter through cooler, and the oil phase outlet of the decanter connects
The extractant import of the extraction dehydration tower bottom is connect, the first water of the decanter mutually exports the connection extractant and returns
The import of tower top second of tower is received, the second water of the decanter mutually exports the refluxing opening for connecting the extractant rectifier,
The extractant rectifying column is provided with some bottom of towe acetic acid discharging openings, and extractant used is preferably methyl acetate, isopropyl acetate, second
The mixture of any one or a few the arbitrary proportion in sour N-butyl, isobutyl acetate.
7. low energy consumption material consumption as described in claim 6, the PTA production systems of few waste discharge, it is characterised in that the oxygen
Change the charging aperture that multiple oxidizing and crystallizing devices of the bottom discharge mouthful of reactor through being sequentially connected connect a rotary pressure filter, institute
State rotary pressure filter and be sequentially provided with filtering, three areas of blow dried and Washing of Filter Cake, the outlet of filtering area and the oxidation
The mother liquor reflux mouthful connection of reactor bottom, the gas import that dries in blow dried area connects dried oxidized tail gas, fresh nitrogen
One or more in the air duct of gas or water vapour, Washing of Filter Cake area is provided with multistage washing subregion, afterbody washing point
The cleaning solution import in area connects the first bottom liquid phases outlet of the acetic acid reflux column return tank, in remaining washing subregion at different levels,
The outlet of the washing filtrate of the cleaning solution import connection rear stage washing subregion of previous stage washing subregion, the Washing of Filter Cake area
Filtered solid outlet connects the solid material import of the slurry preparation tank of the refined subsystem, and the water inlet of the slurry preparation tank connects
Connect the first bottom liquid phases outlet of the acetic acid reflux column return tank.
8. low energy consumption material consumption as described in claim 7, the PTA production systems of few waste discharge, it is characterised in that also include
Oxidation mother liquor processing subsystem, the oxidation mother liquor processing subsystem includes acetic acid stripper, residue extractor, residue filter
Machine, residue drying machine, decanter, residue extractant recovery tower and benzoic acid rectifying column, the bottom inlet of the acetic acid stripper
Used as the pending liquid import of the oxidation mother liquor processing subsystem, the outlet at bottom of the acetic acid stripper connects the residue
The bottom inlet of extractor, the residue extractor is provided with top water inlet and top extractant import, the top water inlet
The second bottom liquid phases outlet of the Acetic Acid Recovering Column return tank is connected, the outlet at bottom connection of the residue extractor is described residual
The import of slag filter, the filtered solid outlet of the residue filter machine connects the import of the residue drying machine, the residue filter
The filtrate (liquid of machine connects the import of the decanter, and the water of the decanter mutually exports the connection oxidation reactor bottom
Mother liquor reflux mouthful, the bottom inlet of the oil phase outlet connection residue extractant recovery tower of the decanter, the residue extraction
The top extractant outlet for taking agent recovery tower connects the top extractant import of the residue extractor, the residue through cooler
The outlet at bottom of extractant recovery tower connects the import of the benzoic acid rectifying column, and the residue is entered from the acetic acid stripper
Acetate concentration is preferably 60-85wt% in the mother liquor residue slurry of extractor, and the extractant into the residue extractor is preferably
Any one or a few any in methyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate
The mixture of ratio, the mass ratio of mother liquor residue slurry, water and extractant is preferably 1 described in the residue extractor:0.5-
2.0:1.5-4.0, extraction temperature is preferably 40-90 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510380472.9A CN105001073B (en) | 2015-07-02 | 2015-07-02 | Low energy consumption material consumption, the PTA production methods and system of few waste discharge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510380472.9A CN105001073B (en) | 2015-07-02 | 2015-07-02 | Low energy consumption material consumption, the PTA production methods and system of few waste discharge |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105001073A CN105001073A (en) | 2015-10-28 |
| CN105001073B true CN105001073B (en) | 2017-06-20 |
Family
ID=54373988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510380472.9A Active CN105001073B (en) | 2015-07-02 | 2015-07-02 | Low energy consumption material consumption, the PTA production methods and system of few waste discharge |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105001073B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108623065B (en) * | 2017-03-22 | 2020-08-25 | 天华化工机械及自动化研究设计院有限公司 | Method for recycling mother liquor of PTA refining unit |
| CN108359081A (en) * | 2018-01-19 | 2018-08-03 | 浙江省现代纺织工业研究院 | A kind of preparation method of doping vario-property PTA |
| CN108484390A (en) * | 2018-06-04 | 2018-09-04 | 浙江逸盛新材料有限公司 | A kind of aromatic carboxylic acid production process method and apparatus of energy-saving and environmental protection |
| CN109096089A (en) * | 2018-08-28 | 2018-12-28 | 天津市昊永化工工程有限公司 | The preparation method and its device of terephthalic acid (TPA) |
| CN109251139B (en) * | 2018-11-02 | 2021-06-25 | 中国石油天然气集团有限公司 | PIA production method and production system adopting deep oxidation |
| CN110078284B (en) * | 2019-04-25 | 2021-08-24 | 杭州多向流化学科技有限公司 | Water-rich solvent grading utilization emission reduction system for preparing terephthalic acid |
| CN110092715A (en) * | 2019-06-06 | 2019-08-06 | 恒力石化（大连）有限公司 | A kind of system of the BA recycled in PTA residue and catalyst |
| CN110128265A (en) * | 2019-06-21 | 2019-08-16 | 恒力石化（大连）有限公司 | A kind of system and method that BA and catalyst in PTA residue are recycled in optimization |
| CN110864308B (en) * | 2019-11-29 | 2021-11-23 | 沈福昌 | Harmless recovery and incineration treatment method for residue of purified terephthalic acid |
| CN110836378B (en) * | 2019-11-29 | 2021-11-23 | 沈福昌 | Resource recovery incineration treatment method for fine terephthalic acid residue |
| WO2021103338A1 (en) * | 2019-11-29 | 2021-06-03 | 沈福昌 | Purified terephthalic acid residue recylcing recovery incineration treatment method |
| CN111018925A (en) * | 2019-12-18 | 2020-04-17 | 广西浦北制药厂 | Steam system working process in trinosin production |
| CN111646892A (en) * | 2020-06-01 | 2020-09-11 | 佰仕邦水处理环保科技(大连)有限公司 | Process for separating and recovering materials from slurry of solvent recovery unit in oxidation process of terephthalic acid production device |
| CN113697830A (en) * | 2021-09-27 | 2021-11-26 | 深圳新宸华科技有限公司 | Device and process for producing high-purity nano lithium carbonate |
| CN114057252B (en) * | 2021-12-07 | 2024-05-03 | 天华化工机械及自动化研究设计院有限公司 | System and method for improving water quality of dehydration tower of purified terephthalic acid device |
| CN114181065B (en) * | 2021-12-24 | 2022-12-20 | 福州大学 | A kind of energy-saving and consumption-reducing purified terephthalic acid production method |
| CN117924075B (en) * | 2024-03-20 | 2024-06-21 | 泰兴市福昌环保科技有限公司 | PTA oxidation residue recovery and separation TA material process and filtering separation device thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63156744A (en) * | 1986-12-22 | 1988-06-29 | Toray Ind Inc | Recovery of acetic acid |
| CN1257146C (en) * | 2004-10-19 | 2006-05-24 | 浙江大学 | Process for producing terephthalic acid and device therefor |
| CN1307109C (en) * | 2005-07-22 | 2007-03-28 | 中国石化仪征化纤股份有限公司 | Method for recovering aromatic carboxylic acid in waste water |
| CN102786412B (en) * | 2012-09-03 | 2014-09-03 | 绍兴汉青环保科技有限公司 | Extraction method for extracting benzoic acid, p-toluic acid, terephthalic acid and isophthalic acid from pure terephthalic acid (PTA) oxidation residues |
| CN102910761B (en) * | 2012-11-06 | 2015-03-11 | 绍兴汉青环保科技有限公司 | Extraction method for reducing emission of chemical oxygen demand (COD) in pure terephthalic acid (PTA) wastewater |
| CN104418720B (en) * | 2013-09-10 | 2016-06-08 | 中国石油化工股份有限公司 | A kind of method of the recycling of PTA oxidation residua |
-
2015
- 2015-07-02 CN CN201510380472.9A patent/CN105001073B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105001073A (en) | 2015-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105001073B (en) | Low energy consumption material consumption, the PTA production methods and system of few waste discharge | |
| US5705682A (en) | Process for producing highly pure terephthalic acid | |
| MXPA02003036A (en) | Process for producing pure terephthalic acid with improved recovery of precursors, solvent and methyl acetate. | |
| US20060014979A1 (en) | Process for producing terephthalic acid | |
| CN204874349U (en) | PTA production system that low energy consumption material consumption, few wastes material discharged | |
| CN103025700B (en) | The preparation of aromatic carboxylic acid | |
| JP2014221791A (en) | Improved method for recovering terephthalic acid | |
| CN100402482C (en) | The preparation method of aromatic carboxylic acid | |
| CN109251139B (en) | PIA production method and production system adopting deep oxidation | |
| TWI742248B (en) | Energy and environmentally integrated method for production of aromatic dicarboxylic acids by oxidation | |
| JP2002522519A (en) | Method for recovering methyl acetate and residual acetic acid in the production of pure terephthalic acid | |
| CN101244999B (en) | Process for producing terephthalic acid | |
| JPH0127054B2 (en) | ||
| JPH0717901A (en) | Production of high-purity isophthalic acid | |
| TW201802064A (en) | Pure plant mother liquor solvent extraction method | |
| CN108484390A (en) | A kind of aromatic carboxylic acid production process method and apparatus of energy-saving and environmental protection | |
| CN208471943U (en) | A kind of aromatic carboxylic acid's process units of energy-saving and environmental protection | |
| KR100881166B1 (en) | Method of preparing terephthalic acid | |
| JP2004175797A (en) | Method for producing terephthalic acid | |
| JPH10306059A (en) | Production of high purity 2,6-naphthalenedicarboxylic acid dimethyl | |
| CN1960961B (en) | Method for producing high-purity terephthalic acid | |
| JPH01121238A (en) | Treatment of filtrate containing aromatic carboxylic acid | |
| WO2015100089A2 (en) | Methods and apparatus for isolating dicarboxylic acid | |
| KR100527416B1 (en) | Method for producing high purity isophthalic acid | |
| JP2004269521A (en) | Method for producing aromatic carboxylic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 100007 Beijing, Dongzhimen, North Street, No. 9, No. Applicant after: China National Petroleum Corporation Applicant after: China Kunlun Engineering Co., Ltd. Address before: 100007 Beijing, Dongzhimen, North Street, No. 9, No. Applicant before: China National Petroleum Corporation Applicant before: China Kunlun Contracting & Engineering Corporation |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |