CN109516918A - The separation of paranitrobenzoic acid and o-nitrobenzoic acid and recovery method in m-Nitrobenzoic Acid technique waste water - Google Patents
The separation of paranitrobenzoic acid and o-nitrobenzoic acid and recovery method in m-Nitrobenzoic Acid technique waste water Download PDFInfo
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- CN109516918A CN109516918A CN201811599204.6A CN201811599204A CN109516918A CN 109516918 A CN109516918 A CN 109516918A CN 201811599204 A CN201811599204 A CN 201811599204A CN 109516918 A CN109516918 A CN 109516918A
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- acid
- paranitrobenzoic
- nitrobenzoic acid
- waste water
- nitrobenzoic
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- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000002351 wastewater Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 44
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000011084 recovery Methods 0.000 title claims abstract description 29
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000926 separation method Methods 0.000 title claims abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 61
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 28
- 239000012043 crude product Substances 0.000 claims abstract description 26
- 239000000047 product Substances 0.000 claims abstract description 23
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000012046 mixed solvent Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000004128 high performance liquid chromatography Methods 0.000 abstract description 2
- 238000003916 acid precipitation Methods 0.000 abstract 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 abstract 1
- 239000012071 phase Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 11
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 9
- 238000004064 recycling Methods 0.000 description 8
- 238000007670 refining Methods 0.000 description 5
- 239000005711 Benzoic acid Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 150000005338 nitrobenzoic acids Chemical class 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 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 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention discloses the separation of paranitrobenzoic acid and o-nitrobenzoic acid in a kind of m-Nitrobenzoic Acid technique waste water and recovery methods, m-Nitrobenzoic Acid technique waste water is mixed with concentrated nitric acid, adjusts its pH, is stirred, filtering, obtains paranitrobenzoic acid crude product and filtrate；Gained paranitrobenzoic acid crude product is washed with clear water, paranitrobenzoic acid product is further purified to obtain；Filtrate pH value is adjusted to a certain range, toluene/n-octyl alcohol mixed solvent is added, extraction separates after standing, and obtains raffinate water phase, adjusts the pH acid precipitation of raffinate water phase, and o-nitrobenzoic acid crude product is recycled in filtering.This method has the advantages that simple process, equipment are simple to operation, the organic matter rate of recovery is high, processing cost is low etc..The technique is greater than 97% to the removal rate of m-Nitrobenzoic Acid refined wastewater CODcr, and waste liquid coloration is substantially reduced；It is detected through HPLC, the rate of recovery of paranitrobenzoic acid is greater than 80%, and content is greater than 95%；The rate of recovery of o-nitrobenzoic acid is greater than 80%, and content is greater than 99%.
Description
Technical field
The present invention relates to the separation of paranitrobenzoic acid and o-nitrobenzoic acid in a kind of m-Nitrobenzoic Acid technique waste water
With recovery method, belong to wastewater treatment and resource reclaim field.
Background technique
Nitrobenzoic acid is important Organic Chemicals, is widely used in dyestuff, medicine and other Fine Chemicals.Between
Nitrobenzoic acid is made mainly using benzoic acid as raw material by the concentrated sulfuric acid and nitric acid nitrating.M-Nitrobenzoic Acid production and
A large amount of strong basicity waste water is generated in subtractive process, color is deep, organic concentration is high, toxicity is big；In waste water in addition to it is o-, m-,
Outside paranitrobenzoic acid, there are also nitrobenzenes and a large amount of inorganic salts, it is considered to be one of intractable waste water.Utilize combination technique
Separate and recover waste water in o-nitrobenzoic acid and paranitrobenzoic acid, the recycling treatment waste water to reduce production cost, disappear
Except the environment influence of waste water is significant.
The processing of nitrobenzene-containing formic acid wastewater generally uses active carbon/coke or ion exchange resin absorption, catalysis oxidation
Deng.Contain a certain amount of o-, m-, paranitrobenzoic acid in the technique waste water for producing and refining due to m-Nitrobenzoic Acid, especially
It is that o-nitrobenzoic acid reaches 100g/L or more, the COD of waste waterCrTen thousand mgO/L up to more than 20.If directly to the wastewater oxidation or
Adsorption treatment, processing cost is higher, and enterprise can not receive.It will also result in o-nitrobenzoic acid and paranitrobenzoic acid resource simultaneously
Waste.Currently, the separation of nitrobenzoic acid isomer mainly utilizes dissolubility difference, complexing abstraction or UF membrane skill
Art.But since the property of three kinds of nitrobenzoic acid isomers is close, content difference is big in waste water, dissolubility difference is small,
Individual Crystallization Separation difficulty is big, effect is poor, and complexing abstraction is generally applicable in the waste water system containing a small amount of organic matter.Existing work
Containing organic acid similar in a large amount of properties, individual complexometric extraction, at high cost, complex process in the waste water that skill generates.
Summary of the invention
Technical problem: it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of m-Nitrobenzoic Acid techniques
The separation of paranitrobenzoic acid and o-nitrobenzoic acid and recovery method in waste water, this method are directed to the property and feature of waste water,
Using crystallization-extraction-crystallization group technology, the paranitrobenzoic acid and o-nitrobenzoic acid in waste water can be efficiently separated,
To achieve the purpose that recycling o-nitrobenzoic acid therein, paranitrobenzoic acid；Meanwhile substantially reducing the chemical oxygen demand of waste water
Amount has the advantages that the rate of recovery is high, processing cost is low etc. in order to the further advanced treating of waste water.
Technical solution: in a kind of m-Nitrobenzoic Acid technique waste water the separation of paranitrobenzoic acid and o-nitrobenzoic acid with
Recovery method mixes the organic wastewater that m-Nitrobenzoic Acid technique generates with concentrated nitric acid, and the pH for adjusting mixed solution is 4.0-
4.5, concentrated nitric acid acidification is then slowly added to the speed of 1.0 ~ 2.0mL/min, the pH of mixed solution is adjusted in 3.0-3.3, stirs
After mixing 2-4h, filtering obtains paranitrobenzoic acid crude product and filtrate；Gained paranitrobenzoic acid crude product is washed with clear water, into
One step purifies to obtain paranitrobenzoic acid product；It is 3.0-3.3 that concentrated nitric acid, which is added, and adjusts the pH of filtrate, adds toluene/n-octyl alcohol
Mixed extractant solvent 5min is separated after then standing 1h, obtains raffinate oil mutually with raffinate water phase, wherein toluene/n-octyl alcohol mixes
Toluene and n-octyl alcohol volume ratio are 1 ~ 5:10 in solvent, and toluene/n-octyl alcohol mixed solvent and filtrate volume ratio are 3 ~ 5:10, are added
The pH that concentrated nitric acid adjusts raffinate water phase is 1.0-2.0, and filtering recycles and obtains o-nitrobenzoic acid product.
The concentration of the concentrated nitric acid is 50% ~ 65%.
The paranitrobenzoic acid crude product is washed in the ratio of 2 ~ 5mL/g of solid-to-liquid ratio with clear water.
Lye back extraction is added in the raffinate oil phase, settle and separate obtains toluene/n-octyl alcohol mixed solvent.
The concentration of the lye is 1 ~ 3mol/L.
Working principle: one is the acidity of aromatic acid changes because of the influence of the type of benzene ring substituents and position.It is adjacent
Nitrobenzoic acid is acid most strong due to conjugation, vucubak effectl alpha effect, inductive effect collective effect；Paranitrobenzoic acid is to be conjugated
Based on effect, acidity is taken second place；M-Nitrobenzoic Acid only has faint inductive effect, acid most weak.Therefore, the acid of waste water solution
Basicity variation will make o-, m-, paranitrobenzoic acid dissociation degree and existence form change.Secondly due to the sky of substituent group
Between steric hindrance, there are larger differences for solubility of the o-, m-, paranitrobenzoic acid in water and in organic solvent.Utilize waste water
The difference of influence and they in different solvents solubility of the solution acid alkalinity to o-, m-, paranitrobenzoic acid existing forms
It is different, group technology is constructed, purifies and recycles the o-nitrobenzoic acid in waste water and paranitrobenzoic acid.
The utility model has the advantages that the present invention provides paranitrobenzoic acid and ortho-nitrophenyls in a kind of m-Nitrobenzoic Acid technique waste water
The separation of formic acid and recovery method, according to o-, m-, paranitrobenzoic acid in water and organic solvent deliquescent difference, in conjunction with
The difference for the benzoic acid acidity that different nitros replace, using group technology step by step by the paranitrobenzoic acid and adjacent nitro in waste water
Benzoic acid separation obtains the higher o-nitrobenzoic acid of purity, paranitrobenzoic acid product.This method has simple process, sets
The advantages such as the standby rate of recovery simple to operation, organic matter is high, processing cost is low.The group technology refines m-Nitrobenzoic Acid useless
The removal rate of water CODcr is greater than 97%, and waste liquid coloration is substantially reduced；It is detected through HPLC, the rate of recovery of paranitrobenzoic acid is greater than
80%, content is greater than 95%；The rate of recovery of o-nitrobenzoic acid is greater than 80%, and content is greater than 99%.
Detailed description of the invention
Fig. 1 is the paranitrobenzoic acid (A) and o-nitrobenzoic acid (B) sample chromatogram figure recycled for the embodiment of the present invention 1,
Wherein (1) o-NBA； (2) m-NBA； (3) p-NBA.
Fig. 2 is the paranitrobenzoic acid (A) and o-nitrobenzoic acid (B) sample chromatogram figure recycled for the embodiment of the present invention 2,
Wherein (1) o-NBA； (2) m-NBA； (3) p-NBA.
Fig. 3 is the paranitrobenzoic acid (A) and o-nitrobenzoic acid (B) sample chromatogram figure recycled for the embodiment of the present invention 3,
Wherein (1) o-NBA； (2) m-NBA； (3) p-NBA.
Fig. 4 is the paranitrobenzoic acid (A) and o-nitrobenzoic acid (B) sample chromatogram figure recycled for the embodiment of the present invention 4,
Wherein (1) o-NBA； (2) m-NBA； (3) p-NBA.
Fig. 5 is separation, recycling paranitrobenzoic acid and adjacent nitro in the m-Nitrobenzoic Acid technique waste water of the invention implemented
The process flow chart of benzoic acid.
Specific embodiment
It elaborates, but does not want in this, as to the application right to the present invention below with reference to embodiment and its attached drawing
Ask the restriction of protection scope.
Embodiment 1
The concentrated nitric acid that concentration is 50% is added in the waste water of 100mL, the pH for adjusting waste water solution is 4.1, then with 1.0mL/min
Speed be slowly added to concentrated nitric acid, control solution pH be 3.0, stir 2h after, filtering, recycle paranitrobenzoic acid crude product；Again
Gained crude product is washed in the ratio of solid-to-liquid ratio (2mL/g) with clear water, paranitrobenzoic acid product is further purified to obtain.It will be dense
Nitric acid is added in filtrate, and the pH for adjusting filtrate is 3.0, and extractant-toluene/n-octyl alcohol solvent (toluene is added by oil-water ratio 0.3
With the volume ratio 0.1 of n-octyl alcohol) extraction 5min, it is separated after standing 1h, obtains raffinate oil phase and raffinate water phase；Into raffinate water phase
It is 1.2 that concentrated nitric acid, which is added, and adjusts the pH of raffinate water phase, and filtering is recycled o-nitrobenzoic acid product, is added into raffinate oil phase dense
The lye of 1 ~ 3mol/L of degree is stripped, and settle and separate obtains toluene/n-octyl alcohol mixed solvent (extractant), recyclable to make
With.
According to above-mentioned process m-Nitrobenzoic Acid waste water 1L(strong basicity), wherein the initial COD value of waste water is
The initial concentration of 269300mg/L, paranitrobenzoic acid and o-nitrobenzoic acid is respectively 17.86g/L and 129.50g/L, warp
The COD value for crossing processed waste water is 5925mg/L, and the COD removal rate of waste water is 97.8%；The paranitrobenzoic acid crude product being collected into
Middle paranitrobenzoic acid quality is 15.2g, and the rate of recovery is 85.11% in crude product, is further refining to obtain paranitrobenzoic acid product,
Its content is 95.43%, the rate of recovery 81.3%；The quality for recycling o-nitrobenzoic acid is 108.6g, and content is greater than 99%, is returned
Yield is 83.8%, the test chart for recycling product is shown in attached drawing 1.
Embodiment 2
The nitric acid that concentration is 55% is added in the waste water of 100mL, controls the pH of solution 4.2, then with the speed of 1.2mL/min
Concentrated nitric acid is slowly added dropwise, the pH for controlling solution is 3.1, and after stirring 2h, paranitrobenzoic acid crude product is recycled in filtering；Again by institute
It obtains crude product to be washed in the ratio of solid-to-liquid ratio (3mL/g) with clear water, paranitrobenzoic acid product is further purified to obtain；Separately by nitric acid
It is added in filtrate, the pH for adjusting filtrate is 3.1, and extractant-toluene/n-octyl alcohol (toluene and n-octyl alcohol is added by oil-water ratio 0.3
Volume ratio 0.2) solvent extraction 5min, then separated after standing 1h, obtain raffinate oil mutually and raffinate water phase；Add into raffinate water phase
Entering nitric acid to adjust the pH range of aqueous phase extracted is 1.3, and filtering is recycled o-nitrobenzoic acid crude product, is added into raffinate oil phase dense
The lye of 1 ~ 3mol/L of degree is stripped, and settle and separate obtains toluene/n-octyl alcohol mixed solvent (extractant), recyclable to make
With.
According to above-mentioned process m-Nitrobenzoic Acid waste water 1L(strong basicity), the former initial COD value of strong basicity waste water is
The initial concentration of 242600mg/L, paranitrobenzoic acid and o-nitrobenzoic acid is respectively 17.46g/L, 129.13g/L, is passed through
The COD value of processed waste water is 6065mg/L, and the COD removal rate of waste water is 97.5%；And the paranitrobenzoic acid being collected into is thick
Paranitrobenzoic acid quality is 14.8g in product, and the crude product rate of recovery is 84.77%, is further refining to obtain paranitrobenzoic acid product,
Its content is 95.81%, the rate of recovery 80.7%；O-nitrobenzoic acid quality is 107.1g, its content of o-nitrobenzoic acid is greater than
99%, the rate of recovery 82.9%, the test chart for recycling product is shown in attached drawing 2.
Embodiment 3
The nitric acid that concentration is 60% is added in the waste water of 100mL, controls the pH of solution 4.3, then with the speed of 1.5mL/min
Concentrated nitric acid is slowly added dropwise, the pH for controlling solution is 3.2, and after stirring 2h, paranitrobenzoic acid crude product is recycled in filtering；Again by gained
Crude product is washed in the ratio of solid-to-liquid ratio (4mL/g) with clear water, and paranitrobenzoic acid product is further purified to obtain；Separately nitric acid is added
Enter into filtrate, the pH for adjusting filtrate is 3.2, by the addition of oil-water ratio 0.4 extractant-toluene/n-octyl alcohol (toluene and n-octyl alcohol
Volume ratio 0.3) solvent extraction 2min, then separated after standing 1h, obtain raffinate oil phase and raffinate water phase；It is added into raffinate water phase
The pH range that nitric acid adjusts aqueous phase extracted is 1.5, and o-nitrobenzoic acid crude product is recycled in filtering, and concentration 1 is added into raffinate oil phase
The lye of ~ 3mol/L is stripped, and settle and separate obtains toluene/n-octyl alcohol mixed solvent (extractant), can be recycled.
According to above-mentioned process m-Nitrobenzoic Acid waste water 1L(strong basicity), the former initial COD value of strong basicity waste water is
The initial concentration of 260333mg/L, paranitrobenzoic acid and o-nitrobenzoic acid is respectively 17.56g/L, 128.74g/L, is passed through
The COD value of processed waste water is 6248mg/L, and the COD removal rate of waste water is greater than 97.6%；And the paranitrobenzoic acid being collected into
Paranitrobenzoic acid quality is 14.6g in crude product, and the crude product rate of recovery is 83.14%, is further refining to obtain paranitrobenzoic acid production
Product, content 96.31%, the rate of recovery 81.1%；The quality of o-nitrobenzoic acid product is 108.4g, and content is greater than 99%,
The rate of recovery is 84.2%, and the test chart for recycling product is shown in attached drawing 3.
Embodiment 4
The nitric acid that concentration is 65% is added in the waste water of 100mL, controls the pH of solution 4.4, then with the speed of 2.0mL/min
Concentrated nitric acid is slowly added dropwise, controls the pH of solution 3.3, after stirring 2h, paranitrobenzoic acid crude product is recycled in filtering；Again by gained
Crude product is washed in the ratio of solid-to-liquid ratio (5mL/g) with clear water, and paranitrobenzoic acid product is further purified to obtain；Separately nitric acid is added
Enter into filtrate, the pH for adjusting filtrate is 3.2, by the addition of oil-water ratio 0.4 extractant-toluene/n-octyl alcohol (toluene and n-octyl alcohol
Volume ratio 0.4) solvent extraction 5min, then separated after standing 1h, obtain raffinate oil phase and raffinate water phase；It is added into raffinate water phase
The pH range that nitric acid adjusts aqueous phase extracted is 1.4, and o-nitrobenzoic acid crude product is recycled in filtering, and concentration 1 is added into raffinate oil phase
The lye of ~ 3mol/L is stripped, and settle and separate obtains toluene/n-octyl alcohol mixed solvent (extractant), can be recycled.
According to above-mentioned process m-Nitrobenzoic Acid waste water 1L(strong basicity), the former initial COD value of strong basicity waste water is
The initial concentration of 252520mg/L, paranitrobenzoic acid and o-nitrobenzoic acid is respectively 17.73g/L, 130.24g/L, is passed through
The COD value of processed waste water is 6313mg/L, and the COD removal rate of waste water is greater than 97.5%；And the paranitrobenzoic acid being collected into is thick
Paranitrobenzoic acid quality is 15.2g in product, and the crude product rate of recovery is 85.73%, is further refining to obtain paranitrobenzoic acid product,
Its content is 96.30%, the rate of recovery 81.8%；The quality of o-nitrobenzoic acid product is 107.5g, and content is greater than 99%, is returned
Yield is 82.5%, and the test chart for recycling product is shown in attached drawing 4.
Claims (5)
1. the separation of paranitrobenzoic acid and o-nitrobenzoic acid and recovery method in a kind of m-Nitrobenzoic Acid technique waste water,
It is characterized in that: the organic wastewater that m-Nitrobenzoic Acid technique generates is mixed with concentrated nitric acid, the pH for adjusting mixed solution is 4.0-
4.5, concentrated nitric acid acidification is then slowly added to the speed of 1.0 ~ 2.0mL/min, the pH of mixed solution is adjusted in 3.0-3.3, stirs
After mixing 2-4h, filtering obtains paranitrobenzoic acid crude product and filtrate；Gained paranitrobenzoic acid crude product is washed with clear water, into
One step purifies to obtain paranitrobenzoic acid product；It is 3.0-3.3 that concentrated nitric acid, which is added, and adjusts the pH of filtrate, adds toluene/n-octyl alcohol
Mixed extractant solvent 5min is separated after then standing 1h, obtains raffinate oil mutually with raffinate water phase, wherein toluene/n-octyl alcohol mixes
Toluene and n-octyl alcohol volume ratio are 1 ~ 5:10 in solvent, and toluene/n-octyl alcohol mixed solvent and filtrate volume ratio are 3 ~ 5:10, are added
The pH that concentrated nitric acid adjusts raffinate water phase is 1.0-2.0, and filtering recycles and obtains o-nitrobenzoic acid product.
2. point of paranitrobenzoic acid and o-nitrobenzoic acid in m-Nitrobenzoic Acid technique waste water according to claim 1
From with recovery method, it is characterised in that: the concentration of the concentrated nitric acid be 50% ~ 65%.
3. point of paranitrobenzoic acid and o-nitrobenzoic acid in m-Nitrobenzoic Acid technique waste water according to claim 1
From with recovery method, it is characterised in that: the paranitrobenzoic acid crude product is washed in the ratio of 2 ~ 5mL/g of solid-to-liquid ratio with clear water.
4. point of paranitrobenzoic acid and o-nitrobenzoic acid in m-Nitrobenzoic Acid technique waste water according to claim 1
From with recovery method, it is characterised in that: lye back extraction is added in the raffinate oil phase, settle and separate obtains toluene/n-octyl alcohol
Mixed solvent.
5. point of paranitrobenzoic acid and o-nitrobenzoic acid in m-Nitrobenzoic Acid technique waste water according to claim 4
From with recovery method, it is characterised in that: the concentration of the lye be 1 ~ 3mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811599204.6A CN109516918B (en) | 2018-12-26 | 2018-12-26 | Method for separating and recovering p-nitrobenzoic acid and o-nitrobenzoic acid from m-nitrobenzoic acid process wastewater |
Applications Claiming Priority (1)
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| 王琛 等: "活性焦吸附处理对硝基苯甲酸废水", 《环境工程学报》 * |
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| CN111792631A (en) * | 2020-06-24 | 2020-10-20 | 山东友道化学有限公司 | Device and method for treating nitric acid containing high-boiling-point organic matters |
| CN111792631B (en) * | 2020-06-24 | 2023-08-18 | 山东友道化学有限公司 | Device and method for treating nitric acid containing high-boiling-point organic matters |
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