CN101037283B - Treatment method of hydroxybenzene-containing wastewater - Google Patents
Treatment method of hydroxybenzene-containing wastewater Download PDFInfo
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- CN101037283B CN101037283B CN2007100672954A CN200710067295A CN101037283B CN 101037283 B CN101037283 B CN 101037283B CN 2007100672954 A CN2007100672954 A CN 2007100672954A CN 200710067295 A CN200710067295 A CN 200710067295A CN 101037283 B CN101037283 B CN 101037283B
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Abstract
The invention discloses a method of treating waste water including hydroxybenzene, including following steps: (1) synchronously adopting three segments target control method, a control method of mol ratio of hydroxybenzene to aldehyde and a timely separating method of resin and waste water, and processing a condensation polymerization of waste water in an acid condition with acid catalyst to produce resin with low molecular weight; (2) removing aldehyde of the waste water after the first treatment in an alkaline condition with alkaline catalyst and then processing an neutralization and deposition treatment; (3) adopting anaerobic and aerobic treatment to process a biochemical treatment of the waste water after the second treatment to meet emission requirements. The method meets the prescribed emission requirements of the hydroxybenzene-aldehyde resin waste water or waste water containing hydroxybenzen and has a simple art, a reliable operation, a low investment and a low operation fees and adequately utilizes the hydroxybenzene-aldehyde in the waste water.
Description
Technical field
The present invention relates to a kind of treatment process of phenolic wastewater, the method for especially phenolic resin wastewater being handled and the raw material in the waste water being used.
Background technology
In the production process of resol and modified phenolic resins, need a certain amount of processing wastewater of discharging, this phenol in wastewater content is up to 30,000～80, and 000mg/L, formaldehyde are up to 10,000～30,000mg/L, COD (chemical oxygen demand (COD)) is up to 100,000～250,000mg/L belongs to unmanageable organic chemical waste water.The treatment process of existing phenolic wastewater has polycondensation method, vaporizing extract process, extraction process, liquid membrane separation method, chemical oxidization method, catalytic oxidation, complexing abstraction, photocatalytic method, biochemical process etc. multiple, but, still lack simple, low cost method at present to the processing of industrial phenolic resin wastewater.At present, the polycondensation method is generally adopted in domestic processing to industrial phenolic resin wastewater, promptly adopts to add acid or alkaline purification, and recovery part low-molecular-weight resin from waste water is used to produce coating or low molecular binder.But the phenol in wastewater content after handling is still up to 2,000～5, and 000mg/l, formaldehyde are up to 1,000～3, and 000mg/l, COD, need to further process with above-mentioned other method more than the 000mg/l up to 25 again.A kind of more feasible way is, with above-mentioned wastewater dilution several times, makes it have biodegradability, carry out biochemical treatment again, but amount of dilution is excessive, makes the investment of biochemical treatment and processing cost too high, also makes the absolute magnitude of COD discharging higher simultaneously.He Qihuan proposes the treatment process of following condensation, oxidation, SBR biochemistry: by the condensation of 9h, COD and volatile phenol clearance are respectively 75% and 66% under 100 ℃; 95～100 ℃ of following secondary condensation 4h, COD and volatile phenol clearance are respectively 81% and 99%; Add dioxide peroxide under the normal temperature and pressure, catalyzed oxidation 4h, COD and volatile phenol clearance are respectively 41% and 78%; Behind the dechlorination coagulation, waste water is pressed the 1:4 dilution, but handles qualified discharge (chemical industry environmental protection Vol.23, No.4,2003) through the PAC.SBR biochemical process.The shortcoming of aforesaid method is that the water amount of dilution is still excessive.Wang Qiong and He Qihuan propose new treatment process again, and the first step adopts interpolation formaldehyde and hydrochloric acid to carry out condensation, removes the phenol in the waste water; Second step adopted interpolation urea to carry out condensation, removed the formaldehyde in the waste water; After twice polycondensation, the COD clearance reaches more than 79%, volatile phenol and formaldehyde clearance reach more than 99%, and by after the coagulating treatment, COD can reach 15 again, 000mg/L, substantially do not contain biological harmful toxic matter, after dilution, can carry out biochemical treatment (pollution prevention technique Vol.17, No.1,2004).The shortcoming of this method is that though interpolation urea can be removed the formaldehyde in the waste water, the COD value and the ammonia nitrogen of urea enter in the water, and the cost of processing is increased.In addition, aforesaid method is condensation under the excessive acidic conditions of formaldehyde, as not taking the particular processing technology, the resin that forms under this condition very easily takes place excessively crosslinked in the further polycondensation of waste water, forming insoluble infusible resin sticks on the reactor wall, often need clear wall, and the recyclable amount of resin of utilizing is significantly reduced, cause the waste of phenol and aldehyde resource in the waste water.
Summary of the invention
Technical problem to be solved by this invention is to propose that a kind of technology is simple, reliable, the treatment process of less investment, phenolic wastewater that working cost is low, it can make the waste water after the processing satisfy the qualified discharge requirement, in treating processes, do not need waste water is diluted, and phenol and aldehyde in the waste water are utilized fully, prepare qualified resol effectively.
For solving the problems of the technologies described above, the treatment process of phenolic wastewater of the present invention comprises the steps: that (1) adopt three sections control indexes methods, phenol and aldehyde mol ratio control method and resin and the timely partition method of waste water simultaneously, and use an acidic catalyst to make waste water under acidic conditions, carry out polycondensation, produce the lower molecular weight tree and refer to; (2) adopt basic catalyst to make the waste water after the 1st step handled under alkaline condition, remove aldehyde reaction, neutralize again and precipitation process; (3) adopt the anaerobic-aerobic method, the waste water of handling through the 2nd step is carried out biochemical treatment again, reach emission request.
The treatment process of above-mentioned phenolic wastewater, low-molecular-weight resin and formaldehyde that its 1st step is generated react in reactor, are prepared into novolac resin.
The treatment process of above-mentioned phenolic wastewater, when adopting described three sections control indexes methods under acidic conditions, to carry out polycondensation, the fs controlling index of reaction is: phenol content is less than 1000mg/l, the controlling index of subordinate phase reaction is: phenol content is 50～200mg/l, and aldehyde is less than 2000mg/l; The controlling index of phase III reaction: making COD content is 4000～8000mg/l.
The treatment process of above-mentioned phenolic wastewater during with three sections control indexes methods, adopts phenol and aldehyde mol ratio control method to regulate phenol, the formaldehyde mole ratio of waste water simultaneously, and the phenol of fs waste water, aldehyde mol ratio are 0.85～1.1; The phenol content of subordinate phase waste water and aldehyde meet following relational expression: Y=0.32X+ (800～1800), and X is a phenol content, and Y is a formaldehyde content, and unit is mg/l; In the reaction process of waste water, the phenol and the aldehyde of waste water is detected, and in waste water, add formaldehyde or phenol in time.
The treatment process of above-mentioned phenolic wastewater, the phenol of fs waste water, aldehyde mol ratio are 0.95～1.05; The phenol content and the aldehyde of subordinate phase waste water meet following relational expression: Y=0.32 μ X+ (800～1200), X are phenol content, and Y is a formaldehyde content, and unit is mg/l, and μ is the ratio between the molecular weight of the molecular weight of phenol and other phenol; In the reaction process of waste water, need the phenol and the aldehyde of waste water be detected, and in waste water, add formaldehyde or phenol in time.
The treatment process of above-mentioned phenolic wastewater, the temperature of described polycondensation are 85 ℃～100 ℃; The pH value of waste water is 0.5～2.0.
The treatment process of above-mentioned phenolic wastewater, the temperature of described polycondensation are 95 ℃～100 ℃; The pH value 0.8～1.5 of fs waste water; The pH value of subordinate phase waste water is 0.7～1.0; The pH value of phase III waste water is than being 0.5～0.8.
The treatment process of above-mentioned phenolic wastewater, the timely partition method of described resin and waste water is will react the low-molecular-weight resin that forms in time to discharge from reactor, promptly,, the resin that is deposited on the reactor bottom is emitted from still every 30～90 minutes in the reaction of fs; In the reaction of subordinate phase,, resin is emitted from reactor every 1～4 hour.
The treatment process of above-mentioned phenolic wastewater adopts the pH value of waste water after the polycondensation of described basic catalyst adjustment of acidity, and making its value is 10～12, reacts 2～5 hours under 75 ℃～100 ℃ temperature and stirring condition, and the aldehyde contenting amount that makes waste water is less than 20mg/l; Adopting the pH value of sulfuric acid or hydrochloric acid readjustment waste water again is 7～8, puts into settling tank and carries out precipitation process.
The treatment process of above-mentioned phenolic wastewater, in the biochemical process of described anaerobic-aerobic method, anaerobism partly adopts the anaerobism moving-bed, and aerobic part adopts contact oxidation method.
The treatment process of above-mentioned phenolic wastewater, the water content of described low-molecular-weight resin be less than 20%, resin 25 ℃ viscosity less than 1.5Pas.
The treatment process of above-mentioned phenolic wastewater, with described low-molecular-weight resin and formaldehyde reaction, the formalin that adds 6～25 part of 37% concentration in 100 parts of described low-molecular-weight resins, hydrochloric acid or 0.3～1.5% part of oxalic acid of adding 0.05～0.2% part of 30% concentration, under 100 ℃ of conditions, reacted 2～4 hours, after reaching needed terminal point, stopped reaction is also washed, water with vacuum sucking-off washing, reheat carries out normal pressure dehydration and vacuum hydro-extraction, heating makes the temperature of resin be higher than 120 ℃, the qualified resin that has the specific technology index for it is become.
The treatment process of above-mentioned phenolic wastewater, described an acidic catalyst refers to the catalyzer of one or more compositions in hydrochloric acid, sulfuric acid, hypochlorous acid, aluminum chloride, the phosphoric acid.
The treatment process of above-mentioned phenolic wastewater, described basic catalyst refers to the catalyzer of one or more compositions of sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, hydrated barta, magnesium hydroxide.
The treatment process of above-mentioned phenolic wastewater, described phenol refer to phenol, technical phenol, cresols, xylenol, alkylphenol or aralkyl phenol.
The method of this patent can reduce chemical treating process and biochemical treatment process, and technology is simple.The method of this patent is in industrial operational process, operating parameters (mol ratio of the temperature of waste water, pH value, phenol and aldehyde, contain phenol amount, aldehyde contenting amount and COD value) is convenient to control, make the waste water index of each operational phase stable, the process operation that can guarantee wastewater treatment is reliable, can reach the emission request of regulation.This patent method devices needed is reactor and biochemical treatment tank, and other treatment process, need complicated treatment facility as vaporizing extract process, extraction process, liquid membrane separation method, chemical oxidization method, photocatalytic method etc., therefore, this patent method have that equipment is simple, less investment, characteristics that running cost is low.The low-molecular-weight resin that adopts timely partition method in time reaction to be formed in reaction process is isolated from waste water, promptly from reactor, take out, excessive with the molecular resin amount of avoiding forming, even form insoluble infusible resin, be bonded on the wall of reactor.In addition, low-molecular-weight resin is isolated from waste water, helps that a spot of phenol and aldehyde react in the waste water, and phenol content and aldehyde in the waste water are significantly reduced.With the control indexes of low-molecular-weight resin in water content less than 20%, resin 25 ℃ viscosity less than 1.5Pas, can be convenient to resin emits in reactor, reduce resin-bonded amount significantly, also be convenient to low-molecular-weight resin is processed into qualified solid thermoplastics resin simultaneously at the reactor wall.Waste water through the 1st step of this patent method and the processing of the 2nd step contains phenol amount and aldehyde contenting amount and has reached lower value, has good biodegradability, does not need waste water is diluted, and waste water can directly enter biochemistry pool.Through the biochemical process step process of anaerobic-aerobic method, the residence time of design waste water in corresponding Aerobic Pond and anaerobic pond, can make phenolic resin wastewater or phenolic wastewater satisfy the emission request of regulation.
Embodiment
Below in conjunction with embodiment the present invention is described in further details.
The processing of embodiment 1 novolac resin waste water:
1, be 68 with phenol content, 000mg/L, formaldehyde content are 13,000mg/L, COD is 210, the novolac resin waste water waste water of 000mg/L pumps into 10 for 8.5 tons, 000 liter waste water reaction still is controlled at 1.03 with phenol, the aldehyde mol ratio of waste water, so add 190 kilograms in 37% concentration formaldehyde in the waste water reaction still.The mixed acid as catalyst that adopts the hydrochloric acid of the sulfuric acid of 90% concentration and 30% concentration to form, the weight ratio between the two is 1:2.Add catalyzer in waste water, the pH value that makes waste water is 1.01～1.05.Start the stirring rake of reactor, and adopt steam that reactor is heated, make temperature in the kettle reach 95～100 ℃, waste water reached above-mentioned temperature of reaction after 1 hour, low-molecular-weight resin begins to form in the bottom of reactor, resin is emitted from the reactor bottom, subsequently, will react the resin that forms every 1 hour and emit (said process is and adopts the instant partition method of resin that low-molecular-weight resin is isolated) from the reactor bottom from waste water.After 4 hours, add catalyzer again, the pH value that makes waste water is 0.85～0.90, continues reaction 2～6 hours under 85～100 ℃ temperature.The phenol content of measuring waste water is 4, and 600mg/L, formaldehyde content are 680mg/L, adds 22 kilograms in 37% concentration formaldehyde in the waste water reaction still, and the phenol of waste water, aldehyde mol ratio are maintained about 0.91, continues reaction 2～6 hours under 95～100 ℃ temperature.The phenol content of measuring waste water is that 870mg/L, formaldehyde content are 1,080mg/L, calculate by following relational expression: Y=0.32X+ (800～1800), in the waste water reaction still, add 9 kilograms in 37% concentration formaldehyde, add catalyzer, the pH value that makes waste water is 0.78～0.82, continues reaction 2～6 hours under 95～100 ℃ temperature.The phenol content of measuring waste water is that 185mg/L, formaldehyde content are 1,380mg/L.Add catalyzer again, the pH value that makes waste water is 0.70～0.75, under 95～100 ℃ temperature, continue reaction 4～20 hours, measure the COD content of waste water, when COD less than 5, during 000mg/L, waste water can be pumped into another waste water reaction still of 10000 liters, carry out the processing of next step technology again.
2, the pH value that adopts sodium hydroxide to regulate waste water is 7～8, and the pH value that adopts calcium oxide to regulate waste water again is 10～12, and reaction is 3 hours under 95 ℃ temperature and stirring condition.Measure the aldehyde of waste water, when the aldehyde of waste water during less than 20mg/l, stopped reaction, adopting sulfuric acid to return adjust pH is 7～8, and the waste water after handling is put into settling tank, precipitates.In this stage, the phenol content of waste water is 93mg/l, and aldehyde contenting amount is 11
Mg/l, COD are 3,300mg/l.
3, above-mentioned waste water enters biochemical treatment tank.Behind one-level anaerobism moving-bed and secondary anaerobic moving-bed, the COD of waste water is 1400mg/l; Behind one-level catalytic oxidation and two-stage biological contact oxidation, the COD of waste water is 170mg/l, and phenol content is 0.3mg/l, and aldehyde contenting amount is 0.2mg/l.
Embodiment 2 Cresol Formaldehyde Resin waste water are handled:
1, be 18 with cresols content, 000mg/L, formaldehyde content are 8,000mg/L, COD is 98,8.5 tons of waste water reaction stills that pump into 10000 liters of the Cresol Formaldehyde Resin waste water of 000mg/L are controlled at 1.03 with phenol, the aldehyde mol ratio of waste water, so add 99 kilograms in cresols in the waste water reaction still.The mixed acid as catalyst that adopts sulfuric acid, phosphoric acid and hydrochloric acid to form, in the mixing acid, the weight ratio between the hydrochloric acid of the sulfuric acid of 90% concentration, 30% concentration and the phosphoric acid three of 90% concentration is 3:1:1.Add catalyzer, the pH value that makes waste water is 1.10～1.15.Start the stirring rake of reactor, and adopt steam that reactor is heated, and make temperature in the kettle reach 95～100 ℃, waste water reached above-mentioned temperature of reaction after 0.5～3 hour, low-molecular-weight resin begins to form in the bottom of reactor, resin is emitted from the reactor bottom, subsequently, will react the resin that forms every 30～90 minutes and from reactor, take out, after 4 hours, add catalyzer again, the pH value that makes waste water is 0.95～0.99, continues reaction 2～6 hours under 95～100 ℃ temperature.The cresols content of measuring waste water is 2, and 900mg/L, formaldehyde content are 350mg/L, adds 12 kilograms in 37% concentration formaldehyde in the waste water reaction still, and the phenol of waste water, aldehyde mol ratio are maintained about 0.95, continues reaction 2～6 hours under 95～100 ℃ temperature.The phenol content of measuring waste water is that 770mg/L, formaldehyde content are 580mg/L, calculate by following relational expression: Y=0.32 μ X+ (800～1200), going the μ value is 0.87, in the waste water reaction still, add 16 kilograms in 37% concentration formaldehyde, add catalyzer, the pH value that makes waste water is 0.85～0.88, continues reaction 2～6 hours under 95～100 ℃ temperature.The phenol content of measuring waste water is that 136mg/L, formaldehyde content are 1980mg/L.Add catalyzer again, the pH value that makes waste water is 0.75～0.78, continues reaction 4～20 hours under 95～100 ℃ temperature, measure the COD content of waste water, when COD less than 4, during 500mg/L, waste water can be pumped into another waste water reaction still, carry out next step art breading again.
2, the pH value that adopts hydrated barta to regulate waste water is 6～8, and the pH value that adopts calcium oxide to regulate waste water again is 10～12, and reaction is 5 hours under 75 ℃ temperature and stirring condition.Measure the aldehyde of waste water, when the aldehyde of waste water during less than 20mg/l, stopped reaction, adopting sulfuric acid to return adjust pH is 7～8, and the waste water after handling is put into settling tank, precipitates.In this stage, the phenol content of waste water is 63mg/l, and aldehyde contenting amount is 9mg/l, and COD is 2900mg/l.
3, above-mentioned waste water enters biochemical treatment tank.Behind one-level anaerobism moving-bed and secondary anaerobic moving-bed, the COD of waste water is 1260mg/l; Behind one-level catalytic oxidation and two-stage biological contact oxidation, the COD of waste water is 85mg/l, and cresols content is 0.2mg/l, and aldehyde is 0.4mg/l.
Embodiment 3
The low-molecular-weight resin that obtains among the embodiment 1 is added in 2000 liters of enamel reaction stills for 1300 kilograms, type of heating adopts steam to feed the chuck of reactor, be heated to 80 ℃, stirred 30 minutes, the viscosity of sampling and measuring low-molecular-weight resin, recording 25 ℃ of viscosity is 1.33Pas, the water content that records resin is 11.5%, and 105 kg 37% formaldehyde is added in the reactor, adds 2Kg concentration again and be 30% hydrochloric acid, at 100 ℃, reaction times is 2～3 hours, and reaction end is determined in sampling, and resin is washed two times, water with vacuum sucking-off washing, normal pressure dehydration and vacuum hydro-extraction are carried out in heating, and making the top temperature of resin in the still is 150 ℃, and the ultimate pressure in the still is less than 3000Pa, under this temperature and pressure, kept 1 hour, and got final product discharging.The technical indicator that records resin is as follows:
Softening temperature: 102 ℃, polymerization velocity: 95 seconds, free phenol: 2.7%.
Embodiment 4
The low-molecular-weight resin that obtains among the embodiment 2 is added in 2000 liters of stainless steel cauldrons for 1300 kilograms, type of heating adopts steam to feed the outer dish semicanal of reactor, be heated to 80 ℃, stirred 30 minutes, the viscosity of sampling and measuring low-molecular-weight resin, recording 25 ℃ of viscosity is 0.15Pas, the water content that records resin is 17.8%, and 210 kilogram of 37% formaldehyde is added in the reactor, adds 7.8Kg oxalic acid again, at 100 ℃, reaction times is 2～3 hours, and reaction end is determined in sampling, and resin is washed two times, water with vacuum sucking-off washing, normal pressure dehydration and vacuum hydro-extraction are carried out in heating, and making the top temperature of resin in the still is 170 ℃, and the ultimate pressure in the still is less than 3000Pa, under this temperature and pressure, kept 1 hour, and got final product discharging.The technical indicator that records resin is as follows:
Softening temperature: 100 ℃, polymerization velocity: 130 seconds, free phenol: 1.5%.
In the inventive method, the selection of an acidic catalyst and basic catalyst is not subjected to the restriction of above-mentioned embodiment.An acidic catalyst can adopt the one or more combination in hydrochloric acid, sulfuric acid, hypochlorous acid, aluminum chloride, the phosphoric acid to form, and basic catalyst can adopt the one or more combination of sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, hydrated barta, magnesium hydroxide to form.
Claims (13)
1. the treatment process of phenolic wastewater, it is characterized in that, it comprises the steps: that (1) adopt three sections control indexes methods, phenol and aldehyde mol ratio control method and resin and the timely partition method of waste water simultaneously, and use an acidic catalyst to make waste water under acidic conditions, carry out polycondensation, produce low-molecular-weight resin; When adopting described three sections control indexes methods under acidic conditions, to carry out polycondensation, the fs controlling index of reaction is: phenol content is less than 1000mg/L, and the controlling index of subordinate phase reaction is: phenol content is that 50～200mg/L, aldehyde are less than 2000mg/L; The controlling index of phase III reaction: making COD content is 4000～8000mg/L; (2) adopt basic catalyst to make the waste water after the 1st step handled under alkaline condition, remove aldehyde reaction, neutralize again and precipitation process; (3) adopt the anaerobic-aerobic method, the waste water of handling through the 2nd step is carried out biochemical treatment again, reach emission request.
2. the treatment process of phenolic wastewater as claimed in claim 1 is characterized in that, low-molecular-weight resin and formaldehyde that its 1st step is generated react in reactor, are prepared into novolac resin.
3. the treatment process of phenolic wastewater as claimed in claim 1 or 2, it is characterized in that, during with three sections control indexes methods, adopt phenol and aldehyde mol ratio control method to regulate phenol, the formaldehyde mole ratio of waste water simultaneously, the phenol of fs waste water, aldehyde mol ratio are 0.85～1.1; The phenol content of subordinate phase waste water and aldehyde meet following relational expression: Y=0.32X+ (800～1800), and X is a phenol content, and Y is a formaldehyde content, and unit is mg/L; In the reaction process of waste water, the phenol and the aldehyde of waste water is detected, and in waste water, add formaldehyde or phenol in time.
4. the treatment process of phenolic wastewater as claimed in claim 1 or 2 is characterized in that, the phenol of fs waste water, aldehyde mol ratio are 0.95～1.05; The phenol content and the aldehyde of subordinate phase waste water meet following relational expression: Y=0.32 μ X+ (800～1200), X are phenol content, and Y is a formaldehyde content, and unit is mg/L, and μ is the ratio between the molecular weight of the molecular weight of phenol and other phenol; In the reaction process of waste water, need the phenol and the aldehyde of waste water be detected, and in waste water, add formaldehyde or phenol in time.
5. the treatment process of phenolic wastewater as claimed in claim 1 or 2 is characterized in that, the temperature of described polycondensation is 95 ℃～100 ℃; The pH value 0.8～1.5 of fs waste water; The pH value of subordinate phase waste water is 0.7～1.0; The pH value of phase III waste water is 0.5～0.8.
6. the treatment process of phenolic wastewater as claimed in claim 1 or 2, it is characterized in that, the timely partition method of described resin and waste water is will react the low-molecular-weight resin that forms in time to discharge from reactor, promptly in the reaction of fs, every 30～90 minutes, the resin that is deposited on the reactor bottom is emitted from still; In the reaction of subordinate phase,, resin is emitted from reactor every 1～4 hour.
7. the treatment process of phenolic wastewater as claimed in claim 1 or 2, it is characterized in that, adopt the pH value of waste water after the polycondensation of described basic catalyst adjustment of acidity, making its value is 10～12, reacted 2～5 hours under 75 ℃～100 ℃ temperature and stirring condition, the aldehyde contenting amount that makes waste water is less than 20mg/L; Adopting the pH value of sulfuric acid or hydrochloric acid readjustment waste water again is 7～8, puts into settling tank and carries out precipitation process.
8. the treatment process of phenolic wastewater as claimed in claim 1 or 2 is characterized in that, in the biochemical process of described anaerobism one aerobic method, anaerobism partly adopts the anaerobism moving-bed, and aerobic part adopts contact oxidation method.
9. the treatment process of phenolic wastewater as claimed in claim 1 or 2 is characterized in that, the water content of described low-molecular-weight resin is less than 20%, resin 25 ℃ viscosity less than 1.5Pas.
10. the treatment process of phenolic wastewater as claimed in claim 1 or 2, it is characterized in that, with described low-molecular-weight resin and formaldehyde reaction, the formalin that adds 6～25 part of 37% concentration in 100 parts of described low-molecular-weight resins, hydrochloric acid or 0.3～1.5% part of oxalic acid of adding 0.05～0.2% part of 30% concentration, under 100 ℃ of conditions, reacted 2～4 hours, after reaching needed terminal point, stopped reaction is also washed, water with vacuum sucking-off washing, reheat carries out normal pressure dehydration and vacuum hydro-extraction, and heating makes the temperature of resin be higher than 120 ℃, the qualified resin that has the specific technology index for it is become.
11. the treatment process of phenolic wastewater as claimed in claim 1 or 2 is characterized in that, described an acidic catalyst refers to the catalyzer of one or more compositions in hydrochloric acid, sulfuric acid, hypochlorous acid, aluminum chloride, the phosphoric acid.
12. the treatment process of phenolic wastewater as claimed in claim 1 or 2 is characterized in that, described basic catalyst refers to the catalyzer of one or more compositions of sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, hydrated barta, magnesium hydroxide.
13. the treatment process of phenolic wastewater as claimed in claim 1 or 2 is characterized in that, described phenol refers to phenol, technical phenol, cresols, xylenol, alkylphenol or aralkyl phenol.
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| CN111115940A (en) * | 2019-12-31 | 2020-05-08 | 江苏远畅环保科技有限公司 | Industrial wastewater treatment system |
| CN113816563A (en) * | 2021-09-30 | 2021-12-21 | 天津正达科技有限责任公司 | Treatment method of phenol-containing wastewater in coal chemical industry |
| CN115044001A (en) * | 2022-06-20 | 2022-09-13 | 安徽进化硅纳米材料科技有限公司 | Method for producing water-soluble phenolic resin and co-producing aqueous calcium carbonate suspension by using white carbon black wastewater |
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