CN102336659A - Method for separating diphenic acid from tower bottom waste for preparing benzoic acid - Google Patents
Method for separating diphenic acid from tower bottom waste for preparing benzoic acid Download PDFInfo
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Abstract
The invention provides a method for separating diphenic acid from tower bottom waste for preparing benzoic acid, and in particular relates to a method for extracting mixed diphenic acid from tower bottom waste for preparing benzoic acid by direct liquid phase oxidation of toluene and separating and purifying 3-phenyl benzoic acid and 4-phenyl benzoic acid. Any high-toxicity organic solvent and any catalyst are not used in the reaction process; the purification process is simple in operation; and the toluene serving as an organic solvent in the reaction process and the purification process can be recycled in a rectifying mode, and ethanol serving as an organic solvent can be recycled by rectification after simple treatment. The method further expands the utilization range of the tower bottom waste for preparing the benzoic acid by direct liquid phase oxidation of the toluene, and has the advantages of simplicity and convenience in operation, easiness in separation and purification of the product, low environmental pollution, low cost, high economic value and the like.
Description
Technical field
The present invention relates to aromatic organic compounds, specifically is that a kind of from waste material at the bottom of the direct liquid phase oxidation of toluene prepares benzoic tower, the extraction mixed the method that diphenic acid and separation of pure dissolve 3-Phenylbenzoic acid and 4-Phenylbenzoic acid.
Background technology
Phenylformic acid is important Organic Chemicals; Be widely used in the industrial production such as foodstuff additive, medicine intermediate, makeup and macromolecular material; Especially as the starting material of producing hexanolactam and phenol, the consumption in whole world every year is just more than 1,000,000 tons.At present, phenylformic acid YO in the whole world is more than 2,000,000 tons.Phenylformic acid is to be made by loban destructive distillation or buck hydrolysis at first, also can make with the urobenzoic acid hydrolysis or by the Tetra hydro Phthalic anhydride hydrolysis decarboxylation.The benzoic method of suitability for industrialized production is in the presence of catalyzer such as cobalt, manganese, to make with atmospheric oxidation toluene mostly now.This production technique can produce a large amount of waste residues, buries or burns not only environment is caused huge pollution, and cause the wasting of resources.In decades; Various countries scientist para Toluic Acid produces the recycling of waste liquid and has done a large amount of work; Through the cyclic oxidation method; Repeatedly method such as distillation is brought up to the overall yield of phenylic acid more than 80%, some company even brought up to more than 85%, and successfully be recovered to benzylalcohol, by product such as peruscabin.Proposed a kind ofly to produce purifying phenylformic acid method the benzoic process like U.S. Pat 4578511 from toluene oxidation.U.S. Pat 20010020579 has been reported and has a kind ofly been prepared the method for extraction separation high-purity benzene benzyl formate the benzoic still raffinate from the direct liquid phase oxidation of toluene.4296245 of U.S. Pat have reported that a kind of is the method for raw material production purified petroleum benzin formate and benzylalcohol to prepare the crude benzol benzyl formate of separating the benzoic still raffinate from the direct liquid phase oxidation of toluene.In China; Shijiangzhuang Oil-Refining Chemical Co., Ltd. and University Of Tianjin have developed the method that the method for utilizing flash distillation and rectification under vacuum to combine reclaims compounds such as phenylformic acid, peruscabin and Fluorenone in the still raffinate cooperatively; And set up production line, but waste material at the bottom of the tower after the rectification under vacuum is not done further recycling.
Summary of the invention
The object of the present invention is to provide a kind of method of separating diphenic acid at the bottom of prepare benzoic tower the waste material, reclaim with rectifying at the bottom of the tower behind the compounds such as phenylformic acid, peruscabin and Fluorenone in the waste material that separation and Extraction goes out the diphenic acid mixture and purifying obtains 3-Phenylbenzoic acid and the pure article of 4-Phenylbenzoic acid.
A kind of method of separating diphenic acid at the bottom of prepare benzoic tower the waste material provided by the invention comprises the steps:
(1) the direct liquid phase oxidation of toluene is prepared waste material and ethanol join in the reactor drum heating, 60～80 ℃ of following stir about 1～3h by weight 1:3～6 at the bottom of the benzoic tower; Stop heating, be cooled to room temperature, then toward the water that wherein adds ethanol volume 5～20%, after stirring mixed it, suction filtration got thick solid of black and brownish black filtrating;
(2) get the water that brownish black filtrating adds 1.0～2.0 times of ethanol volumes, stir, leave standstill 0.5～2.0h, suction filtration gets khaki color solid and faint yellow waste liquid;
(3) yellow solid that fetches earth adds the water of 2.0～4.0 times of ethanol volumes, and the yellow soda ash of waste material quality 25～45% at the bottom of the tower stirs 0.5～2.0h under the room temperature, suction filtration, khaki color solid and pale brown look transparent filtrating;
(4) get pale brown look transparent filtrating, and dripping hydrochloric acid to regulate pH value be 1～3, leave standstill, treat that filtrating is cooled to suction filtration after the room temperature, obtain khaki color and mix diphenic acid solid and filtrating, mixing diphenic acid solid productive rate is 25.0～28.5%;
(5) khaki color is mixed the diphenic acid solid and toluene joins in the reactor drum by weight 1:12～18, heating, stir about 0.5～2.0h under the 60 ℃～reflux temperature; Stop heating, be cooled to room temperature, suction filtration obtains purity and is 95～98% 4-Phenylbenzoic acid white solid and toluene filtrating, and 4-Phenylbenzoic acid white solid productive rate is 35.0%～40.0%;
(6) be that 95～98% 4-Phenylbenzoic acid white solid and toluene join in the reactor drum by weight 1:12～18 with massfraction, heating, stir about 0.5～2.0h under the 60 ℃～reflux temperature; Stop heating, be cooled to 35～45 ℃, 35～45 ℃ of following suction filtrations obtain purity and filtrate for >=98% 4-Phenylbenzoic acid white solid and toluene, and 4-Phenylbenzoic acid white solid productive rate is 92.0～98.0%;
(7) the toluene filtrating that step (5) is obtained, the water that the toluene filtrate volume is 1.0～1.5 times, and the yellow soda ash of the toluene filtrating mass ratio 3.5～4.0% that obtains of step (5) joins in the reactor drum; Stir 0.5～2.0h under the room temperature; Suction filtration is removed insoluble solids, obtains colourless filtrating, and colourless filtrating is poured in the liquid liquid separating apparatus; Leave standstill after obvious layering is arranged, separatory obtains water and toluene mutually; Adding the salt acid for adjusting pH value toward aqueous phase is 1～3, leaves standstill to room temperature, and suction filtration obtains light yellow mixing diphenic acid solid and filtrating;
(8) get light yellow mixing diphenic acid solid and join in the reactor drum, according to light yellow mixing diphenic acid solid/g: the ratio of water/mL: ethanol/mL=1.0:8.0～12.0:8.0～12.0 joins ethanol and water in the reactor drum; Stir 0.5～2.0h down in 50～80 ℃; Stop heating then, be cooled to room temperature, suction filtration; Obtain purity and be 65～80% 3-Phenylbenzoic acid solid and filtrating, purity is that 65～80% 3-Phenylbenzoic acid solid productive rate is 35.0～40.0%;
(9) getting 3-Phenylbenzoic acid solid joins in the reactor drum; According to 3-Phenylbenzoic acid solid/g: the ratio of water/mL: ethanol/mL=1.0:27.0～32.0:22.0～27.0; Ethanol and water are joined in the reactor drum, and 60～80 ℃ are stirred 0.5～2.0h down, leave standstill 2.0～6.0h; Suction filtration obtains the 3-Phenylbenzoic acid and the filtrating of purity >=98%, and the 3-Phenylbenzoic acid productive rate of purity >=98% is 55.0～65.0%.
Step (1) preferred reaction conditions: waste material and ethanol are by weight 1:3.5～4.5 at the bottom of the tower; Hierarchy of control temperature is 65～75 ℃; Reaction times is 1.5～2.0h; The amount that adds entry is 8～10% of an ethanol volume.
Step (2) preferred reaction conditions: the amount that adds entry is 1.2～1.5 times of ethanol volume, and time of repose is 1.0～1.5h.
Step (3) preferred reaction conditions: the amount that adds entry is 2.8～3.2 times of ethanol volume, the consumption of yellow soda ash be at the bottom of the tower waste material quality 32～36%; Reaction times is 1.0～1.5h.
Step (4) preferred reaction conditions: adding the salt acid for adjusting pH value is 1～2.
Step (5) preferred reaction conditions: mix diphenic acid solid (4) and toluene by weight 1:13～15; Hierarchy of control temperature is 80～100 ℃; Reaction times is 1.0～1.5h.
Step (6) preferred reaction conditions: mix diphenic acid solid (4) and toluene by weight 1:12～15; Hierarchy of control temperature is 80～100 ℃; Reaction times is 1.0～1.5h; The suction filtration temperature is 38～42 ℃.
Step (7) preferred reaction conditions: toluene filtrating and water is 1:1.0～1.2 by volume, and the consumption of yellow soda ash is 3.6～4.0% of a toluene quality (density of toluene is multiply by in the calculating of toluene quality according to the volume of toluene filtrating); Reaction times is 1.2～1.5h; Adding the salt acid for adjusting pH value is 1～2.
Step (8) preferred reaction conditions: according to the ratio of mixing diphenic acid/g: water/mL: ethanol/mL=1.0:9.0～10.0:9.0～10.0; Hierarchy of control temperature is 60～80 ℃; Reaction times is 0.5～1.5h.
Step (9) preferred reaction conditions: according to the ratio of mixing diphenic acid/g: water/mL: ethanol/mL=1.0:27.0～32.0:22.0～26.0; Hierarchy of control temperature is 60～80 ℃; Reaction times is 0.5～1.0h; Time of repose is 4.0～5.0h.
Compared with prior art, do not relate in the reaction process of the present invention and use any high toxicity organic solvent, need not to add any catalyzer; Purge process is simple to operate, and involved organic solvent toluene (operation steps 5,6 and 7) can be through the mode recycle of rectifying in reaction process and the purge process; Organic solvent ethanol (operation steps 2; 4,8 and 9) through after the simple process, can be recycled through rectifying again.The present invention has further expanded the scope of utilizing that waste material at the bottom of the benzoic tower is produced in the toluene liquid phase air oxidation, have easy and simple to handle, the product easy separation and easy purification, environmental pollution is little, cost is low, the economic worth advantages of higher.
Embodiment
Embodiment 1
Raw material and reagent: waste material at the bottom of the tower, waste material at the bottom of the tower behind Shijiangzhuang Oil-Refining Chemical Co., Ltd.'s rectifying phenylformic acid; Yellow soda ash, CP; Ethanol, CP; Toluene, CP; Hydrochloric acid; CP.
Operation steps:
Waste material 100g at the bottom of the tower and ethanol 500mL are joined in three mouthfuls of glass flask of 1000mL heating, 65～70 ℃ of following stir about 1.5h; Stop heating, be cooled to room temperature, toward wherein adding 50mL water, after stirring mixed it, suction filtration got thick solid of black (1) and brownish black filtrating (1) then.In brownish black filtrating (1), add 700mL water, mix, leave standstill 1.0h, suction filtration gets khaki color solid (2) and faint yellow waste liquid (2).In khaki color solid (2), add 1500mL water, 35g yellow soda ash stirs 1.0h under the room temperature, and suction filtration gets khaki color solid (3) and pale brown look transparent filtrating (3).To regulate pH value is 1～2 to dripping hydrochloric acid in the pale brown look transparent filtrating (3), leaves standstill, and treats that filtrating is cooled to suction filtration after the room temperature, obtains the 26.5g khaki color and mixes diphenic acid solid (4) and filtrate (4), and productive rate is 26.5%.
26.5g khaki color mixing diphenic acid solid (4) and 400mL toluene are joined in three mouthfuls of glass flask of 1000mL, heating, 80～90 ℃ are stirred 1.2h down; Stop heating, be cooled to room temperature, suction filtration obtains massfraction and is 96% 4-Phenylbenzoic acid solid (5) 10.1g and toluene filtrating (5), and productive rate is 38.1%.Thick 4-Phenylbenzoic acid white solid (5) 10.1g and 150mL toluene are joined in three mouthfuls of glass flask reactor drums of 250mL, heating, 80～90 ℃ are stirred 1.2h down; Stop heating, be cooled to 38～41 ℃, suction filtration obtains massfraction and is 99.0% 4-Phenylbenzoic acid white solid (6) 9.7g and toluene filtrating (6), and productive rate is 96.1%;
With toluene filtrating (5), 400mL water and 13g yellow soda ash join in three mouthfuls of glass flask of 2000mL; Stir 1.2h under the room temperature, suction filtration is removed insoluble solids (7), obtains colourless filtrating (7); Colourless filtrating (7) is poured in the liquid liquid separating apparatus; Leave standstill about 0.5h, treated after the obvious layering, separatory obtains water and toluene mutually; Adding the salt acid for adjusting pH value toward aqueous phase is 1～2, leaves standstill about 0.5h, and suction filtration obtains mixing diphenic acid solid (8) 15.6g and waste liquid (8);
With 15.6g mixing diphenic acid solid (8), 150mL ethanol and 150mL water join in three mouthfuls of glass flask of 500mL, and 65～70 ℃ are stirred 1h down; Be cooled to room temperature; Suction filtration obtains massfraction and is 75.5% 3-Phenylbenzoic acid solid (9) 6.1g and filtrating (9), and productive rate is 39.1%; With the thick 3-Phenylbenzoic acid of 6.1g solid (9); 170mL ethanol and 140mL water join in three mouthfuls of glass flask of 500mL, and 65～70 ℃ are stirred 1h down, are cooled to room temperature; Leave standstill 5.0h; Suction filtration obtains massfraction and is 98.0% 3-Phenylbenzoic acid solid (10) 3.9g and filtrating (10), and productive rate is 63.9%.
The content that mixes diphenic acid at the bottom of the tower among this embodiment behind Shijiangzhuang Oil-Refining Chemical Co., Ltd.'s rectifying phenylformic acid in the waste material is 33.1%, and the present invention's mixing diphenic acid solid isolated yield is 26.5%, separation efficiency 80.1%; 3-Phenylbenzoic acid and 4-Phenylbenzoic acid mass ratio are 1:1.3 in the mixing diphenic acid solid, and wherein the isolated yield of 4-Phenylbenzoic acid is 36.6%, and separation efficiency is 64.8%; The isolated yield of 3-Phenylbenzoic acid is 25.0%; Separation efficiency is 57.5%.
Embodiment 2
Raw material and reagent: with embodiment 1.
Operation steps:
Waste material 100kg at the bottom of the tower and ethanol 500L are joined in the 1000L reaction kettle heating, 65～70 ℃ of following stir about 1.5h; Stop heating, be cooled to room temperature, toward wherein adding 50L water, after stirring mixed it, suction filtration got thick solid of black (1) and brownish black filtrating (1) then.In brownish black filtrating (1), add 700L water, mix, leave standstill 1h, suction filtration gets khaki color solid (2) and faint yellow waste liquid (2).In khaki color solid (2), add 1500L water, 35kg yellow soda ash stirs 1.0h under the room temperature, and suction filtration gets khaki color solid (3) and pale brown look transparent filtrating (3).To regulate pH value is 1～2 to dripping hydrochloric acid in the pale brown look transparent filtrating (3), leaves standstill, and treats that filtrating is cooled to suction filtration after the room temperature, obtains the 28.0kg khaki color and mixes diphenic acid solid (4) and filtrate (4), and productive rate is 28.0%.
The 28.0kg khaki color is mixed diphenic acid solid (4) join in the 1000L reaction kettle with 450L toluene, heating, under 80～90 ℃, stirring 1.2h; Stop heating, be cooled to room temperature, suction filtration obtains massfraction and is 97% 4-Phenylbenzoic acid solid (5) 11.2kg and toluene filtrating (5), and productive rate is 40.0%.Thick 4-Phenylbenzoic acid white solid (5) 11.2kg and 180L toluene are joined in the 500L reaction kettle, and heating under 80～90 ℃, is stirred 1.2h; Stop heating, be cooled to 38～41 ℃, suction filtration obtains massfraction and is 99.0% 4-Phenylbenzoic acid white solid (6) 10.9kg and toluene filtrating (6), and productive rate is 97.3%;
With toluene filtrating (5), 450L water and 15kg yellow soda ash join in the 2000L reaction kettle; Stir 1.2h under the room temperature, suction filtration is removed insoluble solids (7), obtains colourless filtrating (7); Colourless filtrating (7) is poured in the liquid liquid separating apparatus; Leave standstill about 0.5h, treated after the obvious layering, separatory obtains water and toluene mutually; Adding the salt acid for adjusting pH value toward aqueous phase is 1～2, leaves standstill about 0.5～1h, and suction filtration obtains mixing diphenic acid solid (8) 16.3kg and waste liquid (8);
With 16.3kg mixing diphenic acid solid (8), 160L ethanol and 160L water join in the 500L reaction kettle, under 65～70 ℃; Stir 1h, be cooled to room temperature, suction filtration; Obtain massfraction and be 76.5% 3-Phenylbenzoic acid solid (9) 6.5kg and filtrating (9), productive rate is 39.9%; With the thick 3-Phenylbenzoic acid of 6.5kg solid (9), 180L ethanol and 150L water join in the 500L reaction kettle, under 65～70 ℃; Stir 1h, leave standstill 5.0h, suction filtration; Obtain massfraction and be 98.0% 3-Phenylbenzoic acid solid (10) 4.2kg and filtrating (10), productive rate is 64.6%.
The content that mixes diphenic acid at the bottom of the tower in this embodiment behind Shijiangzhuang Oil-Refining Chemical Co., Ltd.'s rectifying phenylformic acid in the waste material is 32.0%, and the present invention's mixing diphenic acid solid isolated yield is 28.0%, separation efficiency 87.5%; 3-Phenylbenzoic acid and 4-Phenylbenzoic acid mass ratio are 1:1.31 in the mixing diphenic acid solid, and wherein the isolated yield of 4-Phenylbenzoic acid is 38.9%, and separation efficiency is 68.6%; The isolated yield of 3-Phenylbenzoic acid is 25.8%; Separation efficiency is 59.6%.
Organic solvent toluene involved in the foregoing description 1 and 2 reaction process and the purge process can be through the mode recycle of rectifying, and organic solvent ethanol is through after the simple process, and the mode through rectifying recycles again.
The physical constant of product and spectral data:
The 4-Phenylbenzoic acid
Product appearance: the cotton-shaped solid of white cotton; Fusing point: 226-228 ℃;
- 1H NMR (400 MHz, (CD
3)
2CO-d
6): 8.13 (d, J=8.4 Hz, 2H), 7.81 (d, J=8.4 Hz, 2H), 7.75 (d, J=7.2 Hz, 2H), 7.52 (d, J=7.2Hz, 2H), 7.45-7.42 (m, 1H);
- 13C NMR (100 MHz, (CD
3)
2CO-d
6): 167.01,145.21,139.74,130.18,129.59,129.16,128.40,127.07,126.87.
The 3-Phenylbenzoic acid
Product appearance: white, needle-shaped crystals solid, fusing point: 165-167 ℃.
- 1H?NMR(400?MHz,?(CD
3)
2CO-d
6):?8.30(s,?1H),?8.04(d,?J?=?7.6?Hz,?1H),?7.92(d,?J?=?7.6?Hz,?1H),?7.72(d,?J?=?7.6?Hz,?2H),?7.63(t,?J?=?7.6?Hz,?1H),?7.52(t,?J=?7.6?Hz,?2H),?7.42(t,?J=?7.4Hz,?1H);?
13C?NMR(100?MHz,?(CD
3)
2CO-d
6):?167.08,?141.24,?139.94,?131.46,?131.24,?129.60,?129.04,?128.19,?127.81,?127.08,?126.91.
Claims (10)
1. a method of separating diphenic acid at the bottom of prepare benzoic tower the waste material is characterized in that, comprises the steps:
(1) the direct liquid phase oxidation of toluene is prepared waste material and ethanol join in the reactor drum by weight 1:3～6 at the bottom of the benzoic tower, heating, 60～80 ℃ are stirred 1～3h down; Stop heating, be cooled to room temperature, then toward the water that wherein adds ethanol volume 5～20%, after stirring mixed it, suction filtration got brownish black filtrating;
(2) get the water that brownish black filtrating adds 1.0～2.0 times of ethanol volumes, stir, leave standstill 0.5～2.0h, suction filtration gets the khaki color solid;
(3) yellow solid that fetches earth adds the water of 2.0～4.0 times of ethanol volumes, and the yellow soda ash of waste material quality 25～45% at the bottom of the tower stirs 0.5～2.0h under the room temperature, suction filtration, pale brown look transparent filtrating;
(4) get pale brown look transparent filtrating, and dripping hydrochloric acid to regulate pH value be 1～3, leave standstill, treat that filtrating is cooled to suction filtration after the room temperature, obtains khaki color mixing diphenic acid solid;
(5) khaki color is mixed the diphenic acid solid and toluene joins in the reactor drum by weight 1:12～18, heating, 60 ℃～reflux temperature stirs 0.5～2.0h down; Stop heating, be cooled to room temperature, suction filtration obtains purity and is 95～98% 4-Phenylbenzoic acid white solid and toluene filtrating;
(6) be that 95～98% 4-Phenylbenzoic acid white solid and toluene join in the reactor drum by weight 1:12～18 with purity, heating, 60 ℃～reflux temperature stirs 0.5～2.0h down; Stop heating, be cooled to 35～45 ℃, 35～45 ℃ of following suction filtrations obtain purity and are >=98% 4-Phenylbenzoic acid white solid;
(7) the toluene filtrating that step (5) is obtained, the water that the toluene filtrate volume is 1.0～1.5 times, and the yellow soda ash of the toluene filtrating mass ratio 3.5～4.0% that obtains of step (5) joins in the reactor drum; Stir 0.5～2.0h under the room temperature; Suction filtration is removed insoluble solids, obtains colourless filtrating, and colourless filtrating is poured in the liquid liquid separating apparatus; Leave standstill after obvious layering is arranged, separatory obtains water and toluene mutually; Adding the salt acid for adjusting pH value toward aqueous phase is 1～3, leaves standstill to room temperature, and suction filtration obtains light yellow mixing diphenic acid solid;
(8) getting light yellow mixing diphenic acid solid joins in the reactor drum; According to light yellow mixing diphenic acid solid/g: the ratio of water/mL: ethanol/mL=1.0:8.0～12.0:8.0～12.0, ethanol and water are joined in the reactor drum, 50～80 ℃ are stirred 0.5～2.0h down; Stop heating then; Be cooled to room temperature, suction filtration obtains purity and is 65～80% 3-Phenylbenzoic acid solid;
(9) getting 3-Phenylbenzoic acid solid joins in the reactor drum; According to 3-Phenylbenzoic acid solid/g: the ratio of water/mL: ethanol/mL=1.0:27.0～32.0:22.0～27.0; Ethanol and water are joined in the reactor drum; 60～80 ℃ are stirred 0.5～2.0h down, leave standstill 2.0～6.0h, and suction filtration obtains the 3-Phenylbenzoic acid of purity >=98%.
2. a kind of method of separating diphenic acid at the bottom of prepare benzoic tower the waste material as claimed in claim 1 is characterized in that, in the step (1) at the bottom of the tower waste material and ethanol weight ratio be 1:3.5～4.5; 65～75 ℃ are stirred 1.5～2.0h down; The amount that adds entry is 8～10% of an ethanol volume.
3. a kind of method of separating diphenic acid at the bottom of prepare benzoic tower the waste material as claimed in claim 1 is characterized in that the amount that adds entry in the step (2) is 1.2～1.5 times of ethanol volume, and time of repose is 1.0～1.5h.
4. a kind of method of separating diphenic acid at the bottom of prepare benzoic tower the waste material as claimed in claim 1 is characterized in that the amount that adds entry in the step (3) is 2.8～3.2 times of ethanol volume, the consumption of yellow soda ash be at the bottom of the tower waste material quality 32～36%; Churning time 1.0～1.5h.
5. a kind of method of separating diphenic acid at the bottom of prepare benzoic tower the waste material as claimed in claim 1 is characterized in that, adds salt acid for adjusting pH value 1～2 in the step (4).
6. a kind of method of separating diphenic acid at the bottom of prepare benzoic tower the waste material as claimed in claim 1 is characterized in that, mixes diphenic acid solid and toluene in the step (5) by weight 1:13～15; 80～100 ℃ are stirred 1.0～1.5h down.
7. a kind of method of separating diphenic acid at the bottom of prepare benzoic tower the waste material as claimed in claim 1 is characterized in that, mixes diphenic acid solid and toluene in the step (6) by weight 1:12～15; 80～100 ℃ are stirred 1.0～1.5h down; The suction filtration temperature is 38～42 ℃.
8. a kind of method of separating diphenic acid at the bottom of prepare benzoic tower the waste material as claimed in claim 1 is characterized in that, toluene filtrating and water 1:1.0～1.2 by volume in the step (7), and the consumption of yellow soda ash is 3.6～4.0% of a toluene quality; Stir 1.2～1.5h; Add salt acid for adjusting pH value 1～2.
9. a kind of method of separating diphenic acid at the bottom of prepare benzoic tower the waste material as claimed in claim 1 is characterized in that, mixes diphenic acid/g: water/mL: ethanol/mL=1.0:9.0～10.0:9.0～10.0 in the step (8); 60～80 ℃ are stirred 0.5～1.5h down.
10. a kind of method of separating diphenic acid at the bottom of prepare benzoic tower the waste material as claimed in claim 1 is characterized in that, mixes diphenic acid/g: water/mL: ethanol/mL=1.0:27.0～32.0:22.0～26.0 in the step (9); 60～80 ℃ are stirred 0.5～1.0h down; Leave standstill 4.0～5.0h.
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