CN109053376A - The recovery method of methanol in a kind of diclofenac salt waste water - Google Patents
The recovery method of methanol in a kind of diclofenac salt waste water Download PDFInfo
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- CN109053376A CN109053376A CN201811090523.4A CN201811090523A CN109053376A CN 109053376 A CN109053376 A CN 109053376A CN 201811090523 A CN201811090523 A CN 201811090523A CN 109053376 A CN109053376 A CN 109053376A
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- Prior art keywords
- methanol
- rectifying
- azeotropic mixture
- waste water
- diclofenac salt
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 177
- DCOPUUMXTXDBNB-UHFFFAOYSA-N diclofenac Chemical class OC(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCOPUUMXTXDBNB-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002351 wastewater Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000011084 recovery Methods 0.000 title claims abstract description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims description 74
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical compound OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 claims description 71
- 238000010992 reflux Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 abstract description 10
- 238000004064 recycling Methods 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 230000003110 anti-inflammatory effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229940021182 non-steroidal anti-inflammatory drug Drugs 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229960001259 diclofenac Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000041 non-steroidal anti-inflammatory agent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
- C07C29/82—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by azeotropic distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The present invention provides a kind of recovery methods of methanol in diclofenac salt waste water, belong to the recovery technology field of solvent in pharmaceuticals industry.The present invention is, according to the azeotropic nature between each component in system, diclofenac salt waste water to be carried out azeotropic-decompression rectifying twice from entrainer, effective recycling of methanol in diclofenac salt is realized, wherein can be recycled in process from entrainer with methanol or toluene.It can reach 99.95% or more using the methanol purity that the present invention recycles, reached methanol and recycled purity requirement in diclofenac salt preparation；Meanwhile the concentration of discharge Organic substance in water is reduced, mitigate discharge of wastewater and take a step forward the load of processing, and technical process is simple, equipment investment is few, low energy consumption, easy to operate, is easy to industrializing implementation.
Description
Technical field
The present invention relates to first in the recovery technology field of solvent in pharmaceuticals industry more particularly to a kind of diclofenac salt waste water
The recovery method of alcohol.
Background technique
Diclofenac salt be a kind of nonsteroidal anti-inflammatory analgetic compared with other non-steroidal anti-inflammatory drugs have it is relatively strong
Anti-inflammatory effect and higher safety, be one of current most widely used non-steroidal anti-inflammatory drug, and synthesis vinegar chlorine
The key intermediate of the other drugs such as fragrant acid.In its preparation process, toluene and methanol are important organic solvent, these solvents
After processing, usually exist as an aqueous solution.It is diclofenac salt system for the wastewater treatment containing high levels of organic solvents
The significant process of standby process not only wastes resource if waste water treatment system will be directly discharged into containing methanol-toluene aqueous solution, but also
Increase the load of wastewater treatment.Further, since in the waste liquid in diclofenac salt preparation process, water-toluene, toluene-methanol
Azeotropic system is belonged to, the solvent methanol of high-purity is recycled and reduces the concentration of Organic substance in water, is difficult to reach using conventional method
To expected treatment effect.
Separation for toluene-methanol azeotropic system, in extraction and distillation technology reported in the literature, recycling methanol purity is only
99.4%, the rate of recovery 97.4%.And solvent for use methanol purity requires to reach 99.8% in diclofenac salt preparation process
More than, therefore, it cannot be recycled in diclofenac salt preparation process using the methanol that existing isolation technics recycles.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of recovery methods of methanol in diclofenac salt waste water.Using
It is high that recovery method of the invention obtains methanol purity, can cycle applications in the preparation process of diclofenac salt.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of recovery methods of methanol in diclofenac salt waste water, comprising the following steps:
(1) after mixing diclofenac salt waste water with from entrainer, a rectifying is carried out through the first rectifying device, obtains one
Secondary methanol-toluene azeotropic mixture and high concentration water；
(2) a methanol-toluene azeotropic mixture for obtaining the step (1) is partly refluxed to the first of the step (1)
Rectifying device carries out a rectifying；A remaining methanol-toluene azeotropic mixture carries out secondary fine after depressurizing, through the second rectifying device
It evaporates, obtains secondary rectifying methanol-toluene azeotropic mixture and high concentration methanol；
(3) the secondary methanol-toluene azeotropic mixture for obtaining the step (2) is partly refluxed in the step (2)
Two rectifying devices carry out secondary rectifying；Diclofenac salt waste water in remaining secondary methanol-toluene azeotropic mixture and the step (1)
With from entrainer mix after through the first rectifying device carry out a rectifying, formed circulation distillation process；
It from entrainer include toluene or methanol in the step (1).
Preferably, the diclofenac salt waste water mainly includes the component of following weight percentage: methanol 5~35%,
Toluene 2~10%, water 55~93%.
Preferably, the charging rate of the diclofenac salt waste water is 500~2000kg/h.
Preferably, the charging rate from entrainer is 20~100kg/h.
Preferably, it is 1~2.5atm that the parameter of a rectifying, which includes: pressure, and number of theoretical plate is 30~50 pieces, charging
Position is the 16th~28 block of column plate, and tower top temperature is 62.5~64.1 DEG C, and column bottom temperature is 101.2~103.5 DEG C.
Preferably, reflux ratio is 3.5~5.0 in the step (2).
Preferably, the parameter of the secondary rectifying include: pressure be 0.25~0.45atm, 40~60 pieces of number of theoretical plate, into
Material position is set to the 22nd~32 block of column plate, and 38.5~39.8 DEG C of tower top temperature, 41.5~43.2 DEG C of column bottom temperature.
Preferably, reflux ratio is 2.5~4.0 in the step (3).
The present invention provides a kind of recovery methods of methanol in diclofenac salt waste water, comprising the following steps: (1) by double chlorine
After fragrant hydrochlorate waste water is mixed with from entrainer, a rectifying is carried out through the first rectifying device, obtains a methanol-toluene azeotropic mixture
And high concentration water；(2) a methanol-toluene azeotropic mixture for obtaining the step (1) is partly refluxed to the of the step (1)
One rectifying device carries out a rectifying；A remaining methanol-toluene azeotropic mixture carries out secondary after depressurizing through the second rectifying device
Rectifying obtains secondary rectifying methanol-toluene azeotropic mixture and high concentration methanol；(3) the secondary methanol-for obtaining the step (2)
Toluene azeotropic mixture is partly refluxed to the second rectifying device in the step (2) and carries out secondary rectifying；Remaining secondary methanol-toluene
Azeotropic mixture through the first rectifying device carries out primary essence after mixing with the diclofenac salt waste water in the step (1) and from entrainer
It evaporates, forms circulation distillation process；It from entrainer include toluene or methanol in the step (1).The present invention is with toluene or methanol
From entrainer, other impurity are not introduced, secondary rectifying is carried out in conjunction with to diclofenac salt waste water, has obtained high-purity first
Alcohol, high purity methanol can be applied to the preparation process of diclofenac salt.From embodiment as can be seen that using method of the invention
The methanol purity of acquisition is up to 99.97~99.98%, can be applied to the preparation process of diclofenac salt.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of two-tower rectification device of the present invention.
Specific embodiment
The present invention provides a kind of recovery methods of methanol in diclofenac salt waste water, comprising the following steps:
(1) after mixing diclofenac salt waste water with from entrainer, a rectifying is carried out through the first rectifying device, obtains one
Secondary methanol-toluene azeotropic mixture and high concentration water；
(2) a methanol-toluene azeotropic mixture for obtaining the step (1) is partly refluxed to the first of the step (1)
Rectifying device carries out a rectifying；A remaining methanol-toluene azeotropic mixture carries out secondary fine after depressurizing, through the second rectifying device
It evaporates, obtains secondary rectifying methanol-toluene azeotropic mixture and high concentration methanol；
(3) the secondary methanol-toluene azeotropic mixture for obtaining the step (2) is partly refluxed in the step (2)
Two rectifying devices carry out secondary rectifying；Diclofenac salt waste water in remaining secondary methanol-toluene azeotropic mixture and the step (1)
With from entrainer mix after through the first rectifying device carry out a rectifying, formed circulation distillation process；
It from entrainer include toluene or methanol in the step (1).
After the present invention mixes diclofenac salt waste water with from entrainer, a rectifying is carried out through the first rectifying device, is obtained
To a methanol-toluene azeotropic mixture and high concentration water.In the present invention, it is described from entrainer include toluene or methanol.In this hair
In bright, the diclofenac salt waste water preferably mainly comprise the component of following weight percentage: methanol 5~35%, and toluene 2~
10%, water 55~93%.The present invention does not have special restriction to the source of diclofenac salt waste water, using those skilled in the art
The diclofenac salt waste water that well knownization production. art generates.In the present invention, the charging speed of the diclofenac salt waste water
Degree is preferably 500~2000kg/h, more preferably 1000~1800kg/h, most preferably 1300~1600kg/h.In the present invention
In, it is described from the charging rate of entrainer be preferably 20~100kg/h, more preferably 40~80kg/h, most preferably 50~
60kg/h.The present invention does not have special restriction to the mixed mode, using hybrid mode well known to those skilled in the art
, specifically, as stirred.In the present invention, the revolving speed of the stirring is preferably 60~120r/min, more preferably 70~
100r/min, most preferably 80~90r/min；The time of the stirring is preferably 10~40min, more preferably 20~35min,
Most preferably 25~30min.
After mixing, the present invention preferably pressurizes mixed system, carries out a rectifying through the first rectifying device.In the present invention
In, the pressure of a rectifying is preferably 1~2.5atm, more preferably 1.25~2.25atm, most preferably 1.5~2atm.
In the present invention, the number of theoretical plate of first rectifying device is preferably 30~50 pieces, and more preferably 35~45 pieces, most preferably
38~42 pieces.In the present invention, the feed entrance point of a rectifying is preferably the 16th~28 block of column plate, the more preferably the 19th~
27 blocks of column plates, most preferably the 22nd~25 block of column plate.In the present invention, the tower top temperature of first rectifying device is preferably
62.5~64.1 DEG C.In the present invention, the column bottom temperature of the first rectifying column is preferably 101.2~103.5 DEG C.In the present invention
In, after a rectifying, a methanol-toluene azeotropic mixture steam is obtained in the tower top of the first rectifying device, is set in the first rectifying
Standby tower bottom is obtained containing high concentration water；An obtained methanol-toluene azeotropic mixture steam obtains a methanol-toluene through condensation
Azeotropic mixture.In the present invention, the reflux ratio is preferably 4.0~4.8.In the present invention, the high concentration Organic substance in water of recycling
Content is 5~20ppm.
After obtaining a methanol-toluene azeotropic mixture, a methanol-toluene azeotropic mixture is partly refluxed to the first essence by the present invention
It evaporates equipment and carries out a rectifying；A remaining methanol-toluene azeotropic mixture carries out secondary fine after depressurizing, through the second rectifying device
It evaporates, obtains secondary rectifying methanol-toluene azeotropic mixture and high concentration methanol.In the present invention, the reflux ratio be preferably 3.5~
5.0, more preferably 3.8~4.5, most preferably 4.0~4.2.In the present invention, the pressure of the secondary rectifying is preferably 0.25
~0.45atm, more preferably 0.28~0.40atm, most preferably 0.30~0.35atm.In the present invention, second rectifying
The number of theoretical plate of equipment is preferably 40~60 pieces, more preferably 45~55 pieces, most preferably 46~50 pieces.In the present invention, institute
The feed entrance point for stating secondary rectifying is preferably the 22nd~32 block of column plate, more preferably the 24th~30 block of column plate, and the most preferably the 26th
~28 blocks of column plates.In the present invention, the tower top temperature of second rectifying device is preferably 38.5~39.8 DEG C.In the present invention
In, 41.5~43.2 DEG C of the column bottom temperature of second rectifying device.In the present invention, after secondary rectifying, secondary first is obtained
Alcohol-toluene azeotropic mixture steam and high concentration methanol；Obtained secondary methanol-toluene azeotropic mixture steam obtains secondary first through condensation
Alcohol-toluene azeotropic mixture.In the present invention, the reflux ratio is preferably 3.0~3.8.In the present invention, the high purity methanol of recycling
Purity is 99.95~99.99%, and moisture content is 50~100ppm, and the rate of recovery is 99.95~99.98%；The first that the present invention obtains
Alcohol purity is high, can be applied to the preparation process of diclofenac salt.
After obtaining secondary methanol-toluene azeotropic mixture, secondary methanol-toluene azeotropic mixture is partly refluxed to the second essence by the present invention
It evaporates equipment and carries out secondary rectifying；Remaining secondary methanol-toluene azeotropic mixture and diclofenac salt waste water and after mixing from entrainer, pass through
First rectifying device carries out a rectifying, forms circulation distillation process.
In the present invention, the reflux ratio is preferably 2.5~4.0, and more preferable 2.8~3.5, most preferably 3.0~3.2.
In the present invention, again with diclofenac salt waste water and from entrainer after the secondary methanol-toluene azeotropic mixture of the residue preferably pressurizes
After mixing, a rectifying is carried out through the first rectifying device.
The present invention does not have special restriction to the device of rectifying twice, using two-tower rectification well known to those skilled in the art
Device.In an embodiment of the present invention preferably using two-tower rectification device described in Fig. 1.F represents diclofenac salt in Fig. 1
Waste water, T are represented from entrainer, and X represents remaining secondary methanol-toluene azeotropic mixture, and W1 represents high concentration water, and W2 represents high concentration first
Alcohol；R1 represents mixer, and P1 and P2 respectively represent force (forcing) pump, and T1 represents the first rectifying device, and T2 represents the second rectifying device,
E1, E2 respectively represent condenser, and E3, E4 respectively represent reboiler；V1 represents pressure reducing valve.In the present invention, diclofenac salt is useless
Water F, it is mixed in mixer R1 from entrainer T and remaining secondary methanol-toluene azeotropic mixture X, pressurized pump P1 pressurizes, into the
One rectifying device T1 carries out a rectifying；The tower bottom of first rectifying device obtains high concentration water W1, the tower of the first rectifying device T1
Top obtains a methanol-toluene azeotropic mixture steam, condenses to obtain a methanol-toluene azeotropic mixture through condenser E1；Part is primary
Methanol-toluene azeotropic mixture is back to the first rectifying device T1；A remaining methanol-toluene azeotropic mixture is depressurized through pressure reducing valve V1, into
Enter the second rectifying device T2；Second rectifying device tower bottom obtains high concentration methanol W2；The tower top of second rectifying device T2 obtains two
Secondary methanol-toluene azeotropic mixture steam condenses to obtain secondary methanol-toluene azeotropic mixture through condenser E2；The secondary methanol-toluene in part
Azeotropic mixture is back to the second rectifying device T2, and mixer R1 is squeezed into the remaining secondary pressurized pump P2 pressurization of methanol-toluene azeotropic mixture X
With diclofenac salt waste water F and from from entrainer T after evenly mixing, the first rectifying device is squeezed into through first rectifying column charge pump P1
T1 carries out a rectifying, forms circulation distillation process.
It is carried out below with reference to recovery method of the embodiment to methanol in diclofenac salt waste water provided by the invention detailed
Illustrate, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The recovery method of methanol in a kind of diclofenac salt waste water, comprising the following steps:
(1) by flow velocity be 1000kg/h diclofenac salt waste water and flow velocity be 20kg/h from entrainer toluene, mixed
It is mixed in clutch, carries out a rectifying in the first rectifying device under conditions of pressure 1atm, obtain a methanol-toluene azeotropic
Object and high concentration water；Wherein the number of theoretical plate of the first rectifying device is 30 pieces, and the feed entrance point of a rectifying is the 16th block of column plate；
(2) a methanol-toluene azeotropic mixture for obtaining the step (1) is back to the first rectifying by reflux ratio 5.0 and sets
It is standby to carry out a rectifying；A remaining methanol-toluene azeotropic mixture is through depressurizing, in the second rectifying device under conditions of 0.35atm
Secondary rectifying is carried out, secondary rectifying methanol-toluene azeotropic mixture and high concentration methanol are respectively obtained；The wherein reason of the second rectifying device
It is 50 pieces by plate number, the feed entrance point of secondary rectifying is the 30th piece；
(3) the secondary methanol-toluene azeotropic mixture for obtaining the step (2) is back to the second rectifying by reflux ratio 3.0 and sets
It is standby to carry out secondary rectifying；Remaining secondary methanol-toluene azeotropic mixture and diclofenac salt waste water and entrainment certainly in the step (1)
After the mixing of agent toluene, a rectifying is carried out into the first rectifying device, forms circulation distillation process；
Wherein, diclofenac salt waste water mainly includes the component of following weight percentage: water 55%, methanol 35%, first
Benzene 10%.
First rectifying device T1 tower bottom recycles the mass fraction 99.98% of high concentration water, content of organics 15ppm, and water returns
Yield 99.95%；The mass fraction 99.98% of second rectifying device T2 tower bottom recycling high concentration methanol, the content 59ppm of water,
Methanol Recovery rate 99.95%.
Embodiment 2
The recovery method of methanol in a kind of diclofenac salt waste water, comprising the following steps:
(1) by flow velocity be 2000kg/h diclofenac salt waste water and flow velocity be 100kg/h from entrainer toluene mixed
It is mixed in clutch, carries out a rectifying in the first rectifying device under conditions of pressure 1.5atm, respectively obtain a methanol-first
Benzene azeotropic object and high concentration water；Wherein the number of theoretical plate of the first rectifying device is 50 pieces, and the feed entrance point of a rectifying is the 24th
Block column plate；
(2) a methanol-toluene azeotropic mixture for obtaining the step (1) is back to the first rectifying by reflux ratio 3.5 and sets
It is standby to carry out a rectifying；A remaining methanol-toluene azeotropic mixture is through depressurizing, in the second rectifying device under conditions of 0.45atm
Secondary rectifying is carried out, secondary rectifying methanol-toluene azeotropic mixture and high concentration methanol are respectively obtained；The wherein reason of the second rectifying device
It is 40 pieces by plate number, the feed entrance point of secondary rectifying is the 18th piece；
(3) the secondary methanol-toluene azeotropic mixture for obtaining the step (2) is back to the second rectifying by reflux ratio 4.0 and sets
It is standby to carry out secondary rectifying；Remaining secondary methanol-toluene azeotropic mixture and diclofenac salt waste water and entrainment certainly in the step (1)
After agent mixing, a rectifying is carried out into the first rectifying device, forms circulation distillation process.
Wherein, diclofenac salt waste water mainly includes the component of following weight percentage: water 55%, methanol 35%, first
Benzene 10%；
First rectifying device T1 tower bottom recycles the mass fraction 99.99% of high concentration water, content of organics 10ppm, and water returns
Yield 99.98%；The mass fraction 99.97% of second rectifying device T2 tower bottom recycling high concentration methanol, the content 85ppm of water,
Methanol Recovery rate 99.98%.
Embodiment 3
The recovery method of methanol in a kind of diclofenac salt waste water, comprising the following steps:
(1) by diclofenac salt waste water and flow velocity that flow velocity is 500kg/h be 30kg/h from entrainer toluene in mixing
It is mixed in device, carries out a rectifying in the first rectifying device under conditions of pressure 2.5atm, respectively obtain a methanol-toluene
Azeotropic mixture and high concentration water；Wherein the number of theoretical plate of the first rectifying device is 40 pieces, and the feed entrance point of a rectifying is the 22nd piece
Column plate；
(2) a methanol-toluene azeotropic mixture for obtaining the step (1) is back to the first rectifying by reflux ratio 4.5 and sets
It is standby to carry out a rectifying；A remaining methanol-toluene azeotropic mixture is through depressurizing, in the second rectifying device under conditions of 0.25atm
Secondary rectifying is carried out, secondary rectifying methanol-toluene azeotropic mixture and high concentration methanol are respectively obtained；The wherein reason of the second rectifying device
It is 60 pieces by plate number, the feed entrance point of secondary rectifying is the 30th block of column plate；
(3) the secondary methanol-toluene azeotropic mixture for obtaining the step (2) is back to the second rectifying by reflux ratio 2.5 and sets
It is standby to carry out secondary rectifying；Remaining secondary methanol-toluene azeotropic mixture and diclofenac salt waste water and entrainment certainly in the step (1)
After agent mixing, a rectifying is carried out into the first rectifying device, forms circulation distillation process.
Wherein, diclofenac salt waste water mainly includes the component of following weight percentage: water 70%, methanol 28%, first
Benzene 2%；
First rectifying device T1 tower bottom recycles the mass fraction 99.99% of high concentration water, content of organics 8ppm, water recycling
Rate 99.95%；Second rectifying device T2 tower bottom recycles the mass fraction 99.98% of high concentration methanol, the content 72ppm of water, first
The alcohol rate of recovery 99.95%.
Embodiment 4.
The recovery method of methanol in a kind of diclofenac salt waste water, comprising the following steps:
(1) by diclofenac salt waste water and flow velocity that flow velocity is 1000kg/h be 80kg/h from entrainer methanol in mixing
It is mixed in device, carries out a rectifying in the first rectifying device under conditions of pressure 1.5atm, respectively obtain a methanol-toluene
Azeotropic mixture and high concentration water；Wherein the number of theoretical plate of the first rectifying device is 40 pieces, and the feed entrance point of a rectifying is the 18th piece
Column plate；
(2) a methanol-toluene azeotropic mixture for obtaining the step (1) is back to the first rectifying by reflux ratio 2.5 and sets
It is standby to carry out a rectifying；A remaining methanol-toluene azeotropic mixture is through depressurizing, in the second rectifying device under conditions of 0.25atm
Secondary rectifying is carried out, secondary rectifying methanol-toluene azeotropic mixture and high concentration methanol are respectively obtained；The wherein reason of the second rectifying device
It is 48 pieces by plate number, the feed entrance point of secondary rectifying is the 25th block of column plate；
(3) the secondary methanol-toluene azeotropic mixture for obtaining the step (2) is back to the second rectifying by reflux ratio 3.2 and sets
It is standby to carry out secondary rectifying；Remaining secondary methanol-toluene azeotropic mixture and diclofenac salt waste water and entrainment certainly in the step (1)
After agent mixing, a rectifying is carried out into the first rectifying device, forms circulation distillation process.
Wherein, diclofenac salt waste water mainly includes the component of following weight percentage: water 90%, methanol 5%, toluene
5%.
First rectifying device T1 tower bottom recycles the mass fraction 99.99% of high concentration water, content of organics 16ppm, and water returns
Yield 99.98%；The mass fraction 99.98% of second rectifying device T2 tower bottom recycling high concentration methanol, the content 65ppm of water,
Methanol Recovery rate 99.95%.
From embodiment as can be seen that the methanol purity for using recovery method of the invention to obtain is 99.97~99.98%,
It can be applied to the preparation process of Diclofenac.Meanwhile the concentration of discharge Organic substance in water is reduced, mitigate discharge of wastewater and advances
The load of one step processing.Due to the solvent-free reclaimer operation process of this method, technical process is simple, equipment investment is few, low energy consumption, easily
In operation, it is suitable for industrialized implementation.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
1. the recovery method of methanol in a kind of diclofenac salt waste water, comprising the following steps:
(1) after mixing diclofenac salt waste water with from entrainer, a rectifying is carried out through the first rectifying device, obtains a first
Alcohol-toluene azeotropic mixture and high concentration water；
(2) a methanol-toluene azeotropic mixture for obtaining the step (1) is partly refluxed to the first rectifying of the step (1)
Equipment carries out a rectifying；A remaining methanol-toluene azeotropic mixture carries out secondary rectifying after depressurizing, through the second rectifying device,
Obtain secondary rectifying methanol-toluene azeotropic mixture and high concentration methanol；
(3) the secondary methanol-toluene azeotropic mixture for obtaining the step (2) is partly refluxed to the second essence in the step (2)
It evaporates equipment and carries out secondary rectifying；Remaining secondary methanol-toluene azeotropic mixture is with the diclofenac salt waste water in the step (1) and certainly
A rectifying is carried out through the first rectifying device after entrainer mixing, forms circulation distillation process；
It from entrainer include toluene or methanol in the step (1).
2. recovery method according to claim 1, which is characterized in that the diclofenac salt waste water mainly includes following heavy
Measure the component of percentage composition: methanol 5~35%, toluene 2~10%, water 55~93%.
3. recovery method according to claim 1, which is characterized in that the charging rate of the diclofenac salt waste water is
500~2000kg/h.
4. recovery method according to claim 1 or 3, which is characterized in that the charging rate from entrainer be 20~
100kg/h。
5. recovery method according to claim 1, which is characterized in that the parameter of a rectifying include: pressure be 1~
2.5atm, number of theoretical plate are 30~50 pieces, and feed entrance point is the 16th~28 block of column plate, and tower top temperature is 62.5~64.1 DEG C, tower
Bottom temperature is 101.2~103.5 DEG C.
6. recovery method according to claim 1, which is characterized in that reflux ratio is 3.5~5.0 in the step (2).
7. recovery method according to claim 1, which is characterized in that the parameter of the secondary rectifying includes: that pressure is
0.25~0.45atm, 40~60 pieces of number of theoretical plate, feed entrance point be the 22nd~32 block of column plate, 38.5~39.8 DEG C of tower top temperature,
41.5~43.2 DEG C of column bottom temperature.
8. recovery method according to claim 1, which is characterized in that reflux ratio is 2.5~4.0 in the step (3).
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| CN201811090523.4A CN109053376B (en) | 2018-09-19 | 2018-09-19 | Method for recovering methanol in diclofenac salt wastewater |
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| CN201811090523.4A CN109053376B (en) | 2018-09-19 | 2018-09-19 | Method for recovering methanol in diclofenac salt wastewater |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63205101A (en) * | 1987-02-20 | 1988-08-24 | Daicel Chem Ind Ltd | Separation of dimethyl carbonate |
| CN103214345A (en) * | 2013-04-22 | 2013-07-24 | 河北工业大学 | Technological method for separating methanol, acetonitrile and benzene tertiary mixture |
| CN106431812A (en) * | 2016-09-21 | 2017-02-22 | 青岛科技大学 | Method and device for separating methylbenzene-methanol-water azeotrope using extractive distillation |
-
2018
- 2018-09-19 CN CN201811090523.4A patent/CN109053376B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63205101A (en) * | 1987-02-20 | 1988-08-24 | Daicel Chem Ind Ltd | Separation of dimethyl carbonate |
| CN103214345A (en) * | 2013-04-22 | 2013-07-24 | 河北工业大学 | Technological method for separating methanol, acetonitrile and benzene tertiary mixture |
| CN106431812A (en) * | 2016-09-21 | 2017-02-22 | 青岛科技大学 | Method and device for separating methylbenzene-methanol-water azeotrope using extractive distillation |
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