CN1611481A - Terephthalic acid and water scrubbing residue recovery and utilization method - Google Patents
Terephthalic acid and water scrubbing residue recovery and utilization method Download PDFInfo
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- CN1611481A CN1611481A CNA2003101034327A CN200310103432A CN1611481A CN 1611481 A CN1611481 A CN 1611481A CN A2003101034327 A CNA2003101034327 A CN A2003101034327A CN 200310103432 A CN200310103432 A CN 200310103432A CN 1611481 A CN1611481 A CN 1611481A
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- terephthalic acid
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- dmt
- rinsing residue
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 25
- 238000011084 recovery Methods 0.000 title description 2
- 238000005201 scrubbing Methods 0.000 title 1
- 230000008569 process Effects 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000007670 refining Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001953 recrystallisation Methods 0.000 claims abstract description 6
- 238000004064 recycling Methods 0.000 claims abstract 18
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 196
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 129
- 238000005886 esterification reaction Methods 0.000 claims description 42
- 239000000047 product Substances 0.000 claims description 39
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 claims description 25
- 238000004821 distillation Methods 0.000 claims description 25
- 150000007524 organic acids Chemical class 0.000 claims description 24
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims description 24
- 230000035484 reaction time Effects 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- QSSJZLPUHJDYKF-UHFFFAOYSA-N methyl 4-methylbenzoate Chemical compound COC(=O)C1=CC=C(C)C=C1 QSSJZLPUHJDYKF-UHFFFAOYSA-N 0.000 claims description 16
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 15
- 238000005809 transesterification reaction Methods 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- 239000013067 intermediate product Substances 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical group 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000004508 fractional distillation Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000003208 petroleum Substances 0.000 abstract description 3
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 abstract 2
- 238000009884 interesterification Methods 0.000 abstract 1
- 150000004702 methyl esters Chemical class 0.000 abstract 1
- 230000032050 esterification Effects 0.000 description 18
- 239000002253 acid Substances 0.000 description 7
- REIDAMBAPLIATC-UHFFFAOYSA-N 4-methoxycarbonylbenzoic acid Chemical compound COC(=O)C1=CC=C(C(O)=O)C=C1 REIDAMBAPLIATC-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000004902 Softening Agent Substances 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 3
- -1 toluic acid methyl esters Chemical class 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a kind of recycling method of tere phthalic acid (TPA) water-washing residue. The invention uses the processes such as twice methyl ester reaction, rectification for separating, recrystallization for refining, interesterification reaction, and so on, to recycle tere phthalic acid (TPA) and tere methyl benzoic acid in petroleum chemical industry production residue. The invention solves problems such as low recycling ratio and more impurity of the product and so on in existing technique. The method is mainly used in recycling of tere phthalic acid (TPA) water-washing residue.
Description
Technical field
The present invention relates to a kind of petrochemical complex and produce the method that the recoverying and utilizing method of residue, particularly terephthalic acid rinsing residue are recycled.
Background technology
Terephthalic acid is a kind of important petrochemicals, and it is a main raw material of producing polyester.Industrial production method of terephthalic acid has multiple, and wherein the p-Xylol high-temperature oxidation is topmost production method.This method is a raw material with the p-Xylol, is solvent with acetic acid, is Cobaltous diacetate, manganese acetate and tetrabromoethane catalyzer, and oxidation at high temperature generates crude terephthalic acid, and then is refined into the pure terephthalic acid.
Have a large amount of side reactions in the process of p xylene oxidation generation terephthalic acid, the by product of generation and unreacted raw material enter in the mother liquor, and mother liquor reclaims the solid impurity that produces behind the acetic acid through pervaporation and is called the terephthalic acid oxidation residua.
Isolated residue is called the purification of terephthalic acid residue in the crude terephthalic acid treating process; A large amount of waste materials of discharging when cleaning production unit enter effluent settling chamber, are called the pond material by the waste material that picks up in the effluent settling chamber; Purification of terephthalic acid residue and pond material are collectively referred to as the terephthalic acid rinsing residue.
Contain a large amount of valuable constituents in terephthalic acid oxidation residua and the terephthalic acid rinsing residue: in the terephthalic acid oxidation residua, contain terephthalic acid, m-phthalic acid and phenylformic acid, in the terephthalic acid rinsing residue, contain terephthalic acid and p-methylbenzoic acid.
In order to recycle terephthalic acid and the p-methylbenzoic acid in the terephthalic acid rinsing residue, document " terephthaldehyde's acid residue production dimethyl terephthalate (DMT) " (Shu Xinhua. Jiangsu chemical industry .1997.25 (6) .-29-31) to disclose a kind of be raw material with terephthaldehyde's acid residue, adopt sulfuric acid catalysis esterification process production dimethyl terephthalate (DMT), and reclaim the method for methyl p-methyl benzoate.This method comprise the terephthalic acid rinsing residue pre-treatment, esterification, Methanol Recovery and to the toluic acid methyl esters reclaim, the process such as refining of dimethyl terephthalate (DMT).The subject matter that this method exists is: the utilization ratio of terephthalic acid and p-methylbenzoic acid is lower in the terephthalic acid rinsing residue, and the purity of products obtained therefrom is low.The major cause that produces the problems referred to above is: the esterification reaction of organic acid of this method is insufficient; Terephthaldehyde's acid residue complicated component, wherein a lot of impurity and by product enter product, influence the purity of product.
Summary of the invention
In order to solve problems such as the terephthalic acid that exists in the prior art and p-methylbenzoic acid utilization ratio purity lower, products obtained therefrom are low, the invention provides the method that a kind of terephthalic acid rinsing residue is recycled.The present invention adopts the technological process of secondary esterification reaction of organic acid and rectifying, makes full use of the valuable material in the terephthalic acid rinsing residue, has improved the purity of utilization ratio and product.
The method that terephthalic acid rinsing residue of the present invention is recycled is achieved in that
Contain terephthalic acid 60～93% (weight), p-methylbenzoic acid 5～37% (weight) in the terephthalic acid rinsing residue of the present invention, this recoverying and utilizing method may further comprise the steps successively:
A. will pulverize after the described terephthalic acid rinsing residue drying;
B. rinsing residue and methyl alcohol after pulverizing carry out the esterification reaction of organic acid first time, and the weight ratio of rinsing residue and methyl alcohol is 1: 0.5～1: 5, and temperature of reaction is 150～250 ℃, and the reaction times is 1～5 hour;
C. with water and methyl alcohol in the distillation method removal esterification reaction of organic acid resultant first time;
D. remove water and methyl alcohol intermediate product and methyl alcohol afterwards and carry out the esterification reaction of organic acid second time, the weight ratio of intermediate product and methyl alcohol is 1: 0.5～1: 4, and temperature of reaction is 150～230 ℃, and the reaction times is 0.5～4 hour;
E. with rectification method by isolating dimethyl terephthalate (DMT) and methyl p-methyl benzoate the second time in the esterification reaction of organic acid resultant, the reflux ratio of rectifying is 0～5, theoretical plate number is 10～50.
Concrete implement the inventive method in, optimum condition is: in step b, the weight ratio of rinsing residue and methyl alcohol is 1: 0.8～1: 2.0, temperature of reaction is that 180～220 ℃, reaction times are 2.5～3.5 hours.In steps d, removing the intermediate product after water and the methyl alcohol and the weight ratio of methyl alcohol is 1: 0.8～1: 1.6, and temperature of reaction is that 170～210 ℃, reaction times are 1.5～2.5 hours.
With the methyl p-methyl benzoate that fractional distillation refining is obtained by step e, the reflux ratio of rectifying is 0～5, and theoretical plate number is 10～50.
With the refining dimethyl terephthalate (DMT) that is obtained by step e of recrystallization method, this process for purification may further comprise the steps successively:
(a) dimethyl terephthalate (DMT) and methyl alcohol is mixed by weight 1: 1～1: 10;
(b) with the said mixture heated and stirred, temperature is 50～65 ℃, and the time is 1～3 hour;
(c) then mixture is cooled to room temperature, carries out solid-liquid separation;
Above-mentioned steps (a)～(c) can be carried out 1～3 time, with till obtaining the purified dimethyl terephthalate (DMT).
In concrete enforcement the inventive method, optimum condition is: in step (a), the weight ratio of dimethyl terephthalate (DMT) and methyl alcohol is 1: 2～1: 5; In step (b), the mixture heating up churning time is 2～3 hours.
Utilize the purified dimethyl terephthalate (DMT) can prepare dioctyl terephthalate.The dioctyl terephthalate product is a kind of softening agent.This process may further comprise the steps successively:
A. dimethyl terephthalate (DMT) is mixed with isooctyl alcohol, add catalyzer, transesterification reaction is carried out in heating; The mol ratio of dimethyl terephthalate (DMT) and isooctyl alcohol is 1: 1～1: 10, temperature of reaction is 140～240 ℃, reaction times is 1～5 hour, catalyst for ester exchange reaction is one of tetrabutyl titanate, p-methyl benzenesulfonic acid, zinc acetate, sulfuric acid, and catalyst levels is 0.1～0.5% of a reactant gross weight;
B. with isooctyl alcohol and low-boiling-point substance in the distillation method removal product of transesterification reaction, distillation temperature is 100～200 ℃, and distillation time is 1～5 hour, obtains dioctyl terephthalate.
In concrete enforcement the inventive method, optimum condition is: in steps A, the mol ratio of dimethyl terephthalate (DMT) and isooctyl alcohol is 1: 2～1: 4, temperature of reaction is 180～220 ℃, reaction times is 2～3 hours, catalyzer is a tetrabutyl titanate, and catalyst levels is 0.2～0.4% of a reactant gross weight; In step B, underpressure distillation is adopted in distillation, and vacuum tightness is lower than gauge pressure-0.09MPa, and distillation temperature is 160～200 ℃, and distillation time is 2～3 hours.
Can adopt alkali cleaning to add the method purified terephthalic dioctyl ester of washing.This purified method is: be 5～15% 1: 5 by volume～5: 1 mixed of sodium carbonate solution with dioctyl terephthalate and concentration, under 60～90 ℃ temperature, stirred 0.5～2 hour, carry out oily water separation afterwards, with oil phase 1: 5～5: 1 water washing of volume ratio 1～5 time, afterwards with the moisture in the method for evaporation removal oil phase, solid impurity with in the suction method removal oil phase obtains the purified dioctyl terephthalate.
In concrete enforcement the inventive method, optimum condition is: be 8～10% 1: 2 by volume～2: 1 mixed of sodium carbonate solution with dioctyl terephthalate and concentration, under 70～80 ℃ temperature, stirred 1～1.5 hour, carry out oily water separation afterwards, oil phase is washed 2～3 times with 1: 2～2: 1 water of volume ratio, with the moisture in the method for evaporation removal oil phase, the solid impurity with in the suction method removal oil phase obtains the purified dioctyl terephthalate afterwards.
Adopt above treating processes: rinsing residue can reach more than 98% through the esterification yield of respective acids behind twice esterification reaction of organic acid, the content of methyl p-methyl benzoate product can reach more than 99.5%, and obtained purified dimethyl terephthalate (DMT) product and dioctyl terephthalate softening agent product, its product reaches the quality standard of petroleum chemical industry standard SH1543-93 first grade and the quality standard of chemical industry standard HG/T2423-93 top grade product respectively.
Embodiment
State technical scheme of the present invention below in conjunction with embodiment is further auspicious, protection scope of the present invention is not limited to following embodiment.
Method of the present invention can be implemented according to following process:
Esterification reaction of organic acid:
In the terephthalic acid rinsing residue, contain terephthalic acid and p-methylbenzoic acid.Terephthalic acid carries out esterification with methyl alcohol under high-temperature and high-pressure conditions, generate dimethyl terephthalate (DMT).Reaction is carried out in two steps, and at first, terephthalic acid and methanol esterification obtain the terephthalic acid monomethyl ester, follows the terephthalic acid monomethyl ester and continues esterification and obtain dimethyl terephthalate (DMT).Simultaneously, the p-methylbenzoic acid in the residue also generates methyl p-methyl benzoate with methyl alcohol generation esterification.
Terephthalic acid rinsing residue after will drying, pulverizing is put into autoclave, adds methyl alcohol, mixes, and heating begins reaction.After reaction is finished, cool.Reacted product is distilled, remove water in products and divide and excessive methyl alcohol, obtain the esterification product one time.
Because the esterification yield of respective acids is not high in esterification reaction of organic acid, has more mono-methyl in the product, therefore need carry out the secondary esterification reaction of organic acid, making mono-methyl continue esterification becomes dimethyl ester.The raw material of secondary esterification reaction of organic acid is an esterification product having removed moisture and excessive methanol, and the secondary esterification reaction of organic acid is identical with the process of an esterification.
The main component that the secondary esterification reaction of organic acid obtains thick ester is dimethyl terephthalate (DMT) and methyl p-methyl benzoate, and next contains a spot of terephthalic acid monomethyl ester, unreacted acids and some high boiling material etc.Utilize the difference of each boiling point substance, adopt the thick ester of method separated secondary esterification reaction of organic acid gained of rectifying, isolate two products of dimethyl terephthalate (DMT) and methyl p-methyl benzoate.
Making with extra care of esterification product:
Adopt the fractional distillation refining methyl p-methyl benzoate, obtain highly purified methyl p-methyl benzoate product.
In the dimethyl terephthalate (DMT) crude product, contain the terephthalaldehydic acid methyl esters of trace, influenced quality product.Because the variation difference of terephthalaldehydic acid methyl esters, the solubility with temperature of dimethyl terephthalate (DMT) in methyl alcohol can adopt recrystallization method to make with extra care this product.
Add methyl alcohol in the dimethyl terephthalate (DMT) crude product, heating is cooled to room temperature then, carries out solid-liquid separation with suction method, obtains the purified dimethyl terephthalate (DMT).For guaranteeing the quality of product, said process can carry out repeatedly.
Transesterification reaction:
Utilize the purified dimethyl terephthalate (DMT) to prepare the softening agent product by transesterification reaction.Under certain temperature and catalyst action, dimethyl terephthalate (DMT) and isooctyl alcohol carry out transesterification reaction, can produce corresponding monooctyl ester.
Add isooctyl alcohol and catalyzer in dimethyl terephthalate (DMT), transesterification reaction is carried out in heating, stirring.Adopt isooctyl alcohol and low-boiling-point substance in the vacuum distillation method removal product then, obtain the dioctyl terephthalate product.
Making with extra care of ester interchanged prod:
The employing alkali cleaning adds the method purified terephthalic dioctyl ester of washing, removes the by product of transesterification reaction.
At first the product with transesterification reaction mixes, stirs with sodium carbonate solution, carries out oily water separation then, the washing of oil reservoir process, and evaporative removal moisture, suction filtration is removed solid impurity, obtains purified dioctyl terephthalate product.
Embodiment 1
Contain terephthalic acid 76% (weight), p-methylbenzoic acid 21% (weight) in the terephthalic acid rinsing residue.
To pulverize after the above-mentioned residue drying; Residue and methyl alcohol after pulverizing carry out the esterification reaction of organic acid first time, and the weight ratio of residue and methyl alcohol is 1: 1.2, and temperature of reaction is 210 ℃, and the reaction times is 3 hours; Again with water and methyl alcohol in the distillation method removal esterification reaction of organic acid resultant first time; Carry out the esterification reaction of organic acid second time afterwards, removing the water and the intermediate product of methyl alcohol and the weight ratio of methyl alcohol is 1: 1, and temperature of reaction is 200 ℃, and the reaction times is 2 hours; Again with rectification method by isolating dimethyl terephthalate (DMT) and methyl p-methyl benzoate in the esterification reaction of organic acid resultant second time, the overhead fraction reflux ratio is 1 in the rectifying, theoretical plate number is 30.
The methyl p-methyl benzoate that adopts the fractional distillation refining said process to obtain, the overhead fraction reflux ratio of rectifying is 1, theoretical plate number is 30.
The dimethyl terephthalate (DMT) that adopts the refining said process of recrystallization method to obtain.Earlier that dimethyl terephthalate (DMT) and methyl alcohol is mixed, the weight ratio of dimethyl terephthalate (DMT) and methyl alcohol is 1: 3; With the said mixture heated and stirred, temperature is 65 ℃ again, and the time is 2 hours; Afterwards mixture is cooled to room temperature, carries out solid-liquid separation, obtain dimethyl terephthalate (DMT); Above recrystallizing and refining process is carried out 2 times altogether.
Through said process, in the terephthalic acid rinsing residue p phthalic acid esterification lead be 99.3%, p-methylbenzoic acid 98.2%, methyl p-methyl benzoate content is 99.6%, and the dimethyl terephthalate (DMT) product reaches the quality standard of petroleum chemical industry standard SH1543-93 first grade.
Embodiment 2～5
The process of embodiment 2～5 is identical with embodiment 1, the material composition of embodiment 1～5, the parameter for the treatment of processes and the results are shown in Table 1.
Table 1
| Process | Parameter | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Raw material | Terephthalic acid % (weight) | ????76 | ????60 | ????93 | ????75 | ????80 | |
| P-methylbenzoic acid % (weight) | ????21 | ????37 | ????5 | ????23 | ????17 | ||
| Processing parameter | Esterification for the first time | The weight ratio of residue and methyl alcohol | ????1∶1.2 | ????1∶0.5 | ????1∶0.8 | ????1∶2.0 | ????1∶4.5 |
| Temperature of reaction ℃ | ????210 | ????150 | ????180 | ????220 | ????250 | ||
| Reaction times (hour) | ????3.0 | ????1.0 | ????2.5 | ????3.5 | ????5.0 | ||
| Esterification for the second time | The weight ratio of intermediate product and methyl alcohol | ????1∶1.0 | ????1∶0.5 | ????1∶0.8 | ????1∶1.6 | ????1∶4.0 | |
| Temperature of reaction ℃ | ????200 | ????150 | ????170 | ????210 | ????230 | ||
| Reaction times (hour) | ????2.0 | ????0.5 | ????1.5 | ????2.5 | ????4.0 | ||
| Rectifying after the esterification | Reflux ratio | ????1.0 | ????0 | ????0.5 | ????2 | ????5.0 | |
| Number of theoretical plate | ????30 | ????50 | ????40 | ????20 | ????10 | ||
| Methyl p-methyl benzoate is refining | Reflux ratio | ????1.0 | ????5 | ????2 | ????0.5 | ????0 | |
| Number of theoretical plate | ????30 | ????10 | ????40 | ????20 | ????50 | ||
| Dimethyl terephthalate (DMT) is refining | The weight ratio of dimethyl terephthalate (DMT) and methyl alcohol | ????1∶3 | ????1∶10 | ????1∶5 | ????1∶2 | ????1∶1 | |
| Heating temperature ℃ | ????65 | ????60 | ????65 | ????60 | ????50 | ||
| The recrystallization number of times | ????2.0 | ????3.0 | ????2.5 | ????1.5 | ????1.0 | ||
| Heat-up time (hour) | ????2 | ????3 | ????3 | ????2 | ????1 | ||
| The result | Esterification yield % | Terephthalic acid | ????99.3 | ????89.6 | ????92.5 | ????99.1 | ????99.0 |
| P-methylbenzoic acid | ????98.2 | ????87.4 | ????92.3 | ????98.6 | ????98.1 | ||
| Quality product | The dimethyl terephthalate (DMT) grade | First grade | First grade | First grade | First grade | First grade | |
| Methyl p-methyl benzoate content % | ????99.6 | ????99.5 | ????99.5 | ????99.6 | ????99.5 |
Embodiment 6
The dimethyl terephthalate (DMT) of utilizing embodiment 1 to obtain prepares dioctyl terephthalate.
Dimethyl terephthalate (DMT) with after isooctyl alcohol mixes, is added catalyzer metatitanic acid four butyl esters, and transesterification reaction is carried out in heating.The mol ratio of dimethyl terephthalate (DMT) and isooctyl alcohol is 1: 3, and temperature of reaction is 200 ℃, and the reaction times is 3 hours, and catalyst levels is 0.2% of a reactant gross weight.
With isooctyl alcohol and low-boiling-point substance in the underpressure distillation removal product of transesterification reaction, distillation temperature is 180 ℃ then, and distillation time is 3 hours, and vacuum tightness-0.095MPa (gauge pressure) obtains the dioctyl terephthalate crude product.
Be 10% 1: 1 by volume mixed of sodium carbonate solution then with dioctyl terephthalate crude product and concentration, under 75 ℃ temperature, stirred 1.2 hours, carry out oily water separation afterwards, oil phase is washed 3 times with 1: 1 water of volume ratio, afterwards with the moisture in the method for evaporation removal oil phase, solid impurity with in the suction method removal oil phase obtains the purified dioctyl terephthalate.
Obtain the dioctyl terephthalate softening agent by above process, product yield is 95%, and product content is 99.5%, and quality product reaches the requirement of national chemical industry standard HG/T2423-93 top grade product standard.
Embodiment 7～13
The process of embodiment 7～13 is identical with embodiment 6, wherein embodiment 7 utilizes the dimethyl terephthalate (DMT) that embodiment 3 obtains, the dimethyl terephthalate (DMT) that embodiment 8,9 utilizes embodiment 4 to obtain, the dimethyl terephthalate (DMT) that embodiment 10,11,12,13 utilizes embodiment 1 to obtain.The parameter of embodiment 6～13 treating processess and the results are shown in Table 2.
Table 2
| Process | Parameter | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | |
| Processing parameter | Transesterification reaction | The mol ratio of dimethyl terephthalate (DMT) and isooctyl alcohol | ???1∶3 | ???1∶1 | ???1∶2 | ???1∶4 | ???1∶10 | ???1∶3 | ???1∶3 | ???1∶3 |
| Temperature of reaction ℃ | ???200 | ???140 | ???180 | ???220 | ???240 | ???200 | ???200 | ???200 | ||
| Reaction times (hour) | ???3.0 | ???1.0 | ???2.0 | ???4.0 | ???5.0 | ???2.0 | ???2.0 | ???2.0 | ||
| Catalyzer | Tetrabutyl titanate | Tetrabutyl titanate | Tetrabutyl titanate | Tetrabutyl titanate | Tetrabutyl titanate | P-methyl benzenesulfonic acid | Zinc acetate | Sulfuric acid | ||
| Catalyst levels % | ???0.2 | ???0.1 | ???0.2 | ???0.4 | ???0.5 | ???0.2 | ???0.2 | ???0.2 | ||
| Distillation | System pressure (gauge pressure MPa) | ???-0.095 | ???-0.095 | ???-0.095 | ???-0.090 | Normal pressure | ???-0.095 | ???-0.095 | ???-0.095 | |
| Distillation temperature ℃ | ???180 | ???100 | ???160 | ???190 | ???200 | ???180 | ???180 | ???180 | ||
| Distillation time (hour) | ???3.0 | ???2.0 | ???1.0 | ???4.0 | ???5.0 | ???3.0 | ???3.0 | ???3.0 | ||
| Refining | Sodium carbonate solution concentration % | ???10 | ???15 | ???12 | ???8 | ???5 | ???10 | ???10 | ???10 | |
| The sodium carbonate solution volume ratio | ???1∶1 | ???1∶5 | ???1∶2 | ???2∶1 | ???5∶1 | ???1∶1 | ???1∶1 | ???1∶1 | ||
| Wash temperature ℃ | ???75 | ???90 | ???80 | ???70 | ???60 | ???75 | ???75 | ???75 | ||
| Time (hour) | ???1.2 | ???2.0 | ???1.5 | ???1.0 | ???0.5 | ???1.2 | ???1.2 | ???1.2 | ||
| Water and oil phase volume ratio | ???1∶1 | ???1∶5 | ???1∶2 | ???2∶1 | ???5∶1 | ???1∶1 | ???1∶1 | ???1∶1 | ||
| Washing times | ???3 | ???5 | ???3 | ???2 | ???1 | ???3 | ???3 | ???3 | ||
| The result | Quality product | Product content % | ???99.5 | ???99.0 | ???99.2 | ???99.3 | ???99.5 | ???99.4 | ???99.4 | ???99.4 |
| Product yield % | ???95 | ???80 | ???88 | ???94 | ???93 | ???91 | ???90 | ???90 |
Claims (15)
1, a kind of method of terephthalic acid rinsing residue recycling contains terephthalic acid 60～93% (weight), p-methylbenzoic acid 5～37% (weight) in the described terephthalic acid rinsing residue, and this recoverying and utilizing method may further comprise the steps successively:
A. will pulverize after the described terephthalic acid rinsing residue drying;
B. rinsing residue and methyl alcohol after pulverizing carry out the esterification reaction of organic acid first time, and the weight ratio of rinsing residue and methyl alcohol is 1: 0.5～1: 5, and temperature of reaction is 150～250 ℃, and the reaction times is 1～5 hour;
C. with water and methyl alcohol in the distillation method removal esterification reaction of organic acid resultant first time;
D. remove water and methyl alcohol intermediate product and methyl alcohol afterwards and carry out the esterification reaction of organic acid second time, the weight ratio of intermediate product and methyl alcohol is 1: 0.5～1: 4, and temperature of reaction is 150～230 ℃, and the reaction times is 0.5～4 hour;
E. with rectification method by isolating dimethyl terephthalate (DMT) and methyl p-methyl benzoate the second time in the esterification reaction of organic acid resultant, the reflux ratio of rectifying is 0～5, theoretical plate number is 10～50.
2, the method for a kind of terephthalic acid rinsing residue recycling according to claim 1 is characterized in that:
In step b, the weight ratio of rinsing residue and methyl alcohol is 1: 0.8～1: 2.0, and temperature of reaction is that 180～220 ℃, reaction times are 2.5～3.5 hours.
3, the method for a kind of terephthalic acid rinsing residue recycling according to claim 1 is characterized in that:
In steps d, removing the intermediate product after water and the methyl alcohol and the weight ratio of methyl alcohol is 1: 0.8～1: 1.6, and the esterification reaction of organic acid temperature is that 170～210 ℃, reaction times are 1.5～2.5 hours.
4, the method for a kind of terephthalic acid rinsing residue recycling according to claim 2 is characterized in that:
In steps d, removing the intermediate product after water and the methyl alcohol and the weight ratio of methyl alcohol is 1: 0.8～1: 1.6, and the esterification reaction of organic acid temperature is that 170～210 ℃, reaction times are 1.5～2.5 hours;
5, the method for recycling according to the described a kind of terephthalic acid rinsing residue of one of claim 1～4 is characterized in that:
With the methyl p-methyl benzoate that fractional distillation refining is obtained by step e, the reflux ratio of rectifying is 0～5, and theoretical plate number is 10～50.
6, the method for recycling according to the described a kind of terephthalic acid rinsing residue of one of claim 1～4 is characterized in that:
With the refining dimethyl terephthalate (DMT) that is obtained by step e of recrystallization method, this process for purification may further comprise the steps successively:
(a) dimethyl terephthalate (DMT) and methyl alcohol is mixed by weight 1: 1～1: 10;
(b) with the said mixture heated and stirred, temperature is 50～65 ℃, and the time is 1～3 hour;
(c) then mixture is cooled to room temperature, carries out solid-liquid separation;
Above-mentioned steps (a)～(c) can be carried out 1～3 time, obtains the purified dimethyl terephthalate (DMT).
7, the method for a kind of terephthalic acid rinsing residue recycling according to claim 6 is characterized in that:
In step (a), the weight ratio of dimethyl terephthalate (DMT) and methyl alcohol is 1: 2～1: 5.
8, the method for a kind of terephthalic acid rinsing residue recycling according to claim 6 is characterized in that:
In step (b), the time that mixture heating up stirs is 2～3 hours.
9, the method for a kind of terephthalic acid rinsing residue recycling according to claim 7 is characterized in that:
In step (b), the time that mixture heating up stirs is 2～3 hours.
10, the method for a kind of terephthalic acid rinsing residue recycling according to claim 6 is characterized in that:
Utilize the purified dimethyl terephthalate (DMT) to prepare dioctyl terephthalate, this process may further comprise the steps successively:
A. dimethyl terephthalate (DMT) is mixed with isooctyl alcohol, add catalyzer, transesterification reaction is carried out in heating; The mol ratio of dimethyl terephthalate (DMT) and isooctyl alcohol is 1: 1～1: 10, temperature of reaction is 140～240 ℃, reaction times is 1～5 hour, catalyst for ester exchange reaction is one of tetrabutyl titanate, p-methyl benzenesulfonic acid, zinc acetate, sulfuric acid, and catalyst levels is 0.1～0.5% of a reactant gross weight;
B. with isooctyl alcohol and low-boiling-point substance in the distillation method removal product of transesterification reaction, distillation temperature is 100～200 ℃, and distillation time is 1～5 hour, obtains dioctyl terephthalate.
11, the method for a kind of terephthalic acid rinsing residue recycling according to claim 10 is characterized in that:
In steps A, the mol ratio of dimethyl terephthalate (DMT) and isooctyl alcohol is 1: 2～1: 4, and temperature of reaction is 180～220 ℃, and the reaction times is 2～3 hours, and catalyzer is a tetrabutyl titanate, and consumption is 0.2～0.4% of a reactant gross weight.
12, the method for a kind of terephthalic acid rinsing residue recycling according to claim 10 is characterized in that:
In step B, adopt underpressure distillation, vacuum tightness is lower than gauge pressure-0.09Mpa, and distillation temperature is 160～200 ℃, and distillation time is 2～3 hours.
13, the method for a kind of terephthalic acid rinsing residue recycling according to claim 10 is characterized in that:
It with dioctyl terephthalate and concentration 5～15% 1: 5 by volume～5: 1 mixed of sodium carbonate solution, under 60～90 ℃ temperature, stirred 0.5～2 hour, carry out oily water separation afterwards, with oil phase 1: 5～5: 1 water washing of volume ratio 1～5 time, afterwards with the moisture in the method for evaporation removal oil phase, solid impurity with in the suction method removal oil phase obtains the purified dioctyl terephthalate.
14, the method for a kind of terephthalic acid rinsing residue recycling according to claim 13 is characterized in that:
It with dioctyl terephthalate and concentration 8～10% 1: 2 by volume～2: 1 mixed of sodium carbonate solution, under 70～80 ℃ temperature, stirred 1～1.5 hour, carry out oily water separation afterwards, oil phase is washed 2～3 times with 1: 2～2: 1 water of volume ratio, afterwards with the moisture in the method for evaporation removal oil phase, solid impurity with in the suction method removal oil phase obtains the purified dioctyl terephthalate.
15, the method for a kind of terephthalic acid rinsing residue recycling according to claim 11 is characterized in that:
In step B, adopt underpressure distillation, vacuum tightness is lower than gauge pressure-0.09Mpa, and distillation temperature is 160～200 ℃, and distillation time is 2～3 hours;
It with dioctyl terephthalate and concentration 8～10% 1: 2 by volume～2: 1 mixed of sodium carbonate solution, under 70～80 ℃ temperature, stirred 1～1.5 hour, carry out oily water separation afterwards, oil phase is washed 2～3 times with 1: 2～2: 1 water of volume ratio, afterwards with the moisture in the method for evaporation removal oil phase, solid impurity with in the suction method removal oil phase obtains the purified dioctyl terephthalate.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102206156A (en) * | 2011-03-08 | 2011-10-05 | 福建天大化工有限公司 | Method for comprehensive recycling of crude terephthalic acid (CTA) residue |
| CN102617351A (en) * | 2012-03-09 | 2012-08-01 | 无锡百川化工股份有限公司 | Method for recovering trioctyl trimellitate |
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| CN1073549C (en) * | 1998-03-10 | 2001-10-24 | 辽阳市石油化工研究所 | Method for preparing mixed ester terephthalate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206156A (en) * | 2011-03-08 | 2011-10-05 | 福建天大化工有限公司 | Method for comprehensive recycling of crude terephthalic acid (CTA) residue |
| CN102206156B (en) * | 2011-03-08 | 2013-04-03 | 福建天大化工有限公司 | Method for comprehensive recycling of crude terephthalic acid (CTA) residue |
| CN102617351A (en) * | 2012-03-09 | 2012-08-01 | 无锡百川化工股份有限公司 | Method for recovering trioctyl trimellitate |
| CN102617351B (en) * | 2012-03-09 | 2013-03-27 | 无锡百川化工股份有限公司 | Method for recovering trioctyl trimellitate |
| CN102660075A (en) * | 2012-04-18 | 2012-09-12 | 山东大学 | Comprehensive utilization method for aromatic carboxylic acid residues |
| CN102660075B (en) * | 2012-04-18 | 2013-10-23 | 山东大学 | Comprehensive utilization method for aromatic carboxylic acid residues |
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| CN106187778B (en) * | 2015-05-06 | 2019-04-23 | 中国科学院大连化学物理研究所 | A method of processing o-Xylene Oxidation in Liquid Phase residue |
| CN107129433A (en) * | 2017-06-09 | 2017-09-05 | 常州大学 | A kind of method that pure mixed phthalic acid methyl esters is prepared by PTA secondary residuals |
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