CN102241802A - Comprehensive utilization of phenol-containing wastewater - Google Patents

Comprehensive utilization of phenol-containing wastewater Download PDF

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Publication number
CN102241802A
CN102241802A CN 201110107244 CN201110107244A CN102241802A CN 102241802 A CN102241802 A CN 102241802A CN 201110107244 CN201110107244 CN 201110107244 CN 201110107244 A CN201110107244 A CN 201110107244A CN 102241802 A CN102241802 A CN 102241802A
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China
Prior art keywords
resol
phenol
phenolic
phenolic wastewater
liquid
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Pending
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CN 201110107244
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Chinese (zh)
Inventor
苏志强
姚亚琳
于征
张安阳
陈晓农
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Application filed by Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CN 201110107244 priority Critical patent/CN102241802A/en
Publication of CN102241802A publication Critical patent/CN102241802A/en
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Abstract

The invention relates to a method for treating phenol-containing wastewater by regulating the pH value of the phenol-containing wastewater generated in phenolic resin (comprising thermoplastic and thermoset phenolic aldehyde) production and synthesizing into thermoset liquid phenolic resin having different purposes. The thermoset liquid phenolic resin can be applied to producing rockwool glue, wood glue, expandable phenolic resin, grinding materials, coatings and the like; the wastewater is comprehensively utilized; and the zero emission of the phenol-containing wastewater generated in the phenolic resin production is realized. The thermoset liquid phenolic resin is prepared from the following raw materials in part by mass: 100 parts of phenol, 38 to 90 parts of paraformaldehyde, 0.5 to 5 parts of catalyst, 20 to 180 parts of phenol-containing wastewater and 0.5 to 20 parts of modification aid.

Description

The comprehensive utilization of phenolic wastewater
Technical field
The present invention relates to a kind of method of utilizing the liquid thermoset resol of the synthetic various uses of phenolic wastewater that produces in the resol production, its application comprises rock wool glue, carpenter's glue, expandable phenolic resin, removing material and coating etc., thereby has realized the comprehensive utilization of phenolic wastewater.
Technical background
Resol is as the existing synthetic resins of century-old industrialization history, compare with other thermosetting resins, solidification value is higher, the mechanical property of cured resin, chemical resistance can be suitable with unsaturated polyester, but its cost of material is low, technology is simple, stable and heat-resisting, the anti-combustion of product size, corrosion-resistant, low-smoke low-toxicity, electrical insulating property are good, thereby be widely used in fields such as space flight and aircraft, military equipment, transportation, building, articles for daily use, at present, the annual production of resol has reached tons up to a million.In the production process of resol, can produce a large amount of phenolic wastewater, not get rid of, pollute the environment, endanger animals and plants and human beings'health if these waste water do not add to handle directly.Along with the deep enforcement of national energy-saving and emission-reduction policy, more and more higher for the processing requirements of phenolic wastewater.The phenolic wastewater treatment process has chemical oxidization method, biological process, physical method, physical chemistry method four big classes at present.Wherein commonly used is preceding two kinds, and chemical oxidization method is effective, but the oxygenant of usefulness costs an arm and a leg, and should not be used to handle waste water; A lot of large-lot producer adopt biological process to handle, and its advantage is to remove phenol rate height, and treatment capacity is big, and unit cost expends low, and shortcoming is that investment is big, and floor space is big, is not suitable for medium and small sized enterprises and uses.
Utilizing Paraformaldehyde 96 is solid and aqueous hardly characteristics, is used for substituting liquid Formaldehyde Production resol, has realized that dehydration is dewatered less or not in the resol production process, has greatly reduced the generation of phenolic wastewater.The application of this respect has very big progress.China's patent 200810124388.0 usefulness Paraformaldehyde 96s replace 37% liquid formaldehyde to produce novolac resin, but have waste water to produce, and do not accomplish the zero release of waste water.China's patent 201010208432.3 provides a kind of Paraformaldehyde 96,37% liquid formaldehyde and phenolic wastewater of utilizing to be used for preparing the resol that does not dewater by certain ratio, this resol can be used to make fixed mould, but in preparation process, used liquid formaldehyde, thereby do not utilized phenolic wastewater efficiently.
The phenolic wastewater that the present invention produces in resol (comprising thermoplasticity and heat-reactive phenolic resin) can being produced, after the pH value is adjusted to neutrality, add Paraformaldehyde 96 and dissolving, be made into the formaldehyde solution of desired concn, can synthesize the liquid thermoset resol of different purposes, realize the comprehensive utilization of waste water.
The present invention has following advantage:
1. the present invention can effectively utilize the phenolic wastewater that produces in resol (comprising thermosetting phenolic and the novolac resin) production.
2. the present invention regulates the pH value for after the neutrality with phenolic wastewater, add Paraformaldehyde 96 and dissolving, the formaldehyde solution of preparation different concns is used for synthesizing the liquid thermoset resol of different purposes, and its application comprises rock wool glue, carpenter's glue, expandable phenolic resin, removing material and coating etc.
3. the present invention has replaced liquid formaldehyde fully with Paraformaldehyde 96, can the most effectively utilize all kinds of phenolic wastewater, is used for the liquid thermoset resol of synthetic different purposes.
4. the present invention does not have discharge of wastewater in producing, and when realizing energy-saving and emission-reduction, reducing cost, also produces various liquid thermoset resol, has created economic worth.
Summary of the invention
The objective of the invention is to phenolic wastewater with generation in resol (comprising thermoplasticity and the heat-reactive phenolic resin) production, after the pH value is adjusted to neutrality, be used to produce the liquid thermoset resol of different purposes, comprehensive utilization waste water is realized the phenolic wastewater zero release that resol is produced.
For achieving the above object, the present invention reacts by following component (mass fraction):
The catalyst type that the present invention uses comprises basic catalyst (as sodium hydroxide, potassium hydroxide, ammoniacal liquor, hydrated barta), bivalent metal oxide or salt (as zinc oxide, magnesium oxide, magnesium acetate, zinc acetate, cadmium acetate, Cobaltous diacetate) and composite catalyst (multiple catalyst mix use).
The Paraformaldehyde 96 that uses among the present invention is technical grade, and purity is 95~96%, has substituted traditional liquid formaldehyde.
The Paraformaldehyde 96 that the present invention uses has two kinds of adding modes: a kind of is directly to join in the reactor together with solid form and other raw materials to synthesize; Another kind is earlier it to be dissolved in the phenolic wastewater, is made into the formaldehyde solution of different concns, is used for building-up reactions.
The paraformaldehyde solution that the present invention uses, the ratio that determine Paraformaldehyde 96 and phenolic wastewater according to the purposes and the performance of institute's synthetic resins, otherwise resin can't satisfy qualified performance under the condition of not dewatering.
The phenolic wastewater that the present invention uses derives from the phenolic wastewater that produces in the resol production, and after its proximate analysis was measured, after adjusting pH value was neutrality, the liquid thermoset resol that is used for different purposes was synthetic.
The modified additive that the present invention uses, comprise the formaldehyde-trapping agent (for example urea, trimeric cyanamide, quadrol, N,N-DIMETHYLACETAMIDE etc.) that reduces free aldehyde, plasticized modifier (for example carboxylic styrene butadiene latex, carboxylic acrylonitrile butadiene rubber latex, liquid butadiene-styrene rubber, liquid nbr, polyvinyl acetal, polymeric amide etc.), and heat-proof combustion-resistant properties-correcting agent (for example flame retardant polyether polyol, organosilicon etc.).
Embodiment
Further describe the present invention by the following examples.But these examples do not constitute limitation of the scope of the invention.
Table 1 is the every index that produces phenolic wastewater during certain factory phenolic aldehyde is produced, below equal this phenolic wastewater that adopts of synthesis technique of all kinds of phenolic aldehyde:
Every index of certain phenolic wastewater of table 1
COD/ppm Free phenol/ppm Free aldehyde/ppm pH
(1.5~3)×10 5 56600 9300 6~7
Its pH value is adjusted to neutral standby with massfraction 30% hydrochloric acid soln.
Embodiment 1
Synthetic phenolic aldehyde rock wool glue
1) in the four-hole boiling flask that mechanical stirring, condenser and thermometer are housed, adds 80g Paraformaldehyde 96,160g phenolic wastewater at 90 ℃ of constant temperature 40min postcooling;
2) will going up formaldehyde solution, to pour out 120g standby, adds 100g phenol in four-hole bottle, is warming up to 75 ℃ of reaction 30min;
3) 120g formaldehyde solution is poured in the four-hole bottle, and is warming up to 90 ℃ of isothermal reaction 35min, be cooled to 75 ℃, add 3g urea, stir 10min after, be cooled to 35 ℃ of dischargings after regulating the pH value and be 7~8.
The product that obtains is a reddish-brown transparent liquid shape resol, and viscosity is 15~20mpa.s (25 ℃), and solid content is 41~45%, free phenol≤7.5%, and free aldehyde<0.5% can be used as rock wool glue, is used for the manufacturing of rock cotton board.
Embodiment 2
Synthetic phenolic aldehyde carpenter's glue
1) in the four-hole boiling flask that mechanical stirring, condenser and thermometer are housed, adds 60g Paraformaldehyde 96,100g phenolic wastewater, at 90 ℃ of constant temperature 40min postcooling;
2) will going up formaldehyde solution, to pour out 80g standby, adds 100g phenol in four-hole bottle, is warming up to 80 ℃ of reaction 20min;
3) 80g formaldehyde solution is poured in the four-hole bottle, and adds 4g sodium hydroxide, and be warming up to 92 ℃ of isothermal reaction 45min, after be cooled to 35 ℃ of dischargings.
The product that obtains is the liquid phenolic carpenter's glue, and viscosity is 400~500mpa.s (25 ℃), and solid content is 55~60%, can be applicable to bonding wood glue.
Embodiment 3
Synthetic expandable phenolic resin
1) adding 100g phenol, 25g Paraformaldehyde 96,20g phenolic wastewater, 3g magnesium oxide are being warming up to 82 ℃ of constant temperature 40min in the four-hole boiling flask that mechanical stirring, condenser and thermometer are housed;
2) in four-hole boiling flask, add the 30g Paraformaldehyde 96, after slowly be warming up to 95 ℃ the reaction 90min;
3) add the 3g trimeric cyanamide after, continue reaction 15min and be cooled to 35 ℃ of dischargings;
Obtaining product is the reddish-brown liquid phenolic resin, and viscosity is 2000~3000mpa.s (25 ℃), and solid content is 78~82%, can be used to prepare phenolic foam board, is applied to the material of construction of fire-retardant heat insulation.
Embodiment 4
Epoxy-phenol resin paint is synthetic
1) ammoniacal liquor of adding 100g phenol and 10g massfraction 25% is mixed and heated to 40 ℃ in the four-hole boiling flask that mechanical stirring, condenser and thermometer are housed;
2) add 45g Paraformaldehyde 96,50g phenolic wastewater, be warming up to 65 ℃ of constant temperature 140min;
3) add a certain amount of solvent or diluent, be heated to 120 ℃ of backflow 50min;
4) with itself and a certain proportion of Resins, epoxy mixing for standby use;
The product that obtains is an epoxy-phenol resin paint, and solid content is 34~36%, has good sticking power, holds and impact and erosion resistance, can be used as environment-friendly type food cans package coating.

Claims (7)

1. the phenolic wastewater that produces in resol (comprising thermoplasticity and heat-reactive phenolic resin) being produced, after the pH value is adjusted to neutrality, be used to produce the liquid thermoset resol of different purposes, comprehensive utilization waste water has been realized the phenolic wastewater zero release that resol is produced.
For achieving the above object, the present invention reacts by following component (mass fraction):
2. the liquid thermoset resol with the synthetic different purposes of phenolic wastewater according to claim 1 comes the method for Phenol-Containing Wastewater Treatment, it is characterized in that, described catalyzer comprises basic catalyst (as sodium hydroxide, potassium hydroxide, ammoniacal liquor, hydrated barta), bivalent metal oxide or salt (as zinc oxide, magnesium oxide, magnesium acetate, zinc acetate, cadmium acetate, Cobaltous diacetate) and composite catalyst (multiple catalyst mix use).
3. the liquid thermoset resol with the synthetic different purposes of phenolic wastewater according to claim 1 comes the method for Phenol-Containing Wastewater Treatment, it is characterized in that, described Paraformaldehyde 96 is for being technical grade, purity is 95%~96%, replace traditional liquid formaldehyde by certain proportion Paraformaldehyde 96 and phenolic wastewater, needing no vacuum dehydration in the production.
4. the liquid thermoset resol with the synthetic different purposes of phenolic wastewater according to claim 3 comes the method for Phenol-Containing Wastewater Treatment, it is characterized in that Paraformaldehyde 96 has two kinds of adding modes: a kind of is directly to join in the reactor together with solid form and other raw materials to synthesize; Another kind is earlier it to be dissolved in the phenolic wastewater, is made into the formaldehyde solution of different concns, is used for building-up reactions.
5. the liquid thermoset resol with the synthetic different purposes of phenolic wastewater according to claim 4 comes the method for Phenol-Containing Wastewater Treatment, it is characterized in that, the ratio that paraformaldehyde solution will be determined Paraformaldehyde 96 and phenolic wastewater according to the purposes and the performance of institute's synthetic resins, otherwise resin can't satisfy qualified performance under the condition of not dewatering.
6. the liquid thermoset resol with the synthetic different purposes of phenolic wastewater according to claim 1 comes the method for Phenol-Containing Wastewater Treatment, it is characterized in that, described phenolic wastewater, derive from the waste water that produces in resol (comprising thermoset and the novolac resin) production, after its proximate analysis mensuration, after adjusting pH value is neutrality, can be used for the synthetic of different purposes liquid thermoset resol.
7. the liquid thermoset resol with the synthetic different purposes of phenolic wastewater according to claim 1 comes the method for Phenol-Containing Wastewater Treatment, it is characterized in that, described modified additive comprises the formaldehyde-trapping agent (for example urea, trimeric cyanamide, quadrol, N,N-DIMETHYLACETAMIDE etc.) that reduces free aldehyde, plasticized modifier (for example carboxylic styrene butadiene latex, carboxylic acrylonitrile butadiene rubber latex, liquid butadiene-styrene rubber, liquid nbr, polyvinyl acetal, polymeric amide etc.) and heat-proof combustion-resistant properties-correcting agent (for example flame retardant polyether polyol, organosilicon etc.).For satisfying the different performance of various resol, can realize by adding modified additive.
CN 201110107244 2011-04-28 2011-04-28 Comprehensive utilization of phenol-containing wastewater Pending CN102241802A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102757618A (en) * 2012-07-11 2012-10-31 黄石金朝阳粉末材料有限责任公司 Modified phenol formaldehyde resin and preparation method thereof
CN103087280A (en) * 2013-01-25 2013-05-08 河北龙港工贸有限公司 Method for synthesizing phenolic resins by using paraformaldehyde
CN103214641A (en) * 2013-05-09 2013-07-24 沙县宏盛塑料有限公司 Production method of melamine-formaldehyde resin
CN104072941A (en) * 2014-07-18 2014-10-01 锦州市好为尔保温材料有限公司 Nano modified phenolic aldehyde foam insulation board and preparation method thereof
CN105315610A (en) * 2014-08-04 2016-02-10 南京集美新型材料研发有限公司 Modified phenolic resin and preparation method therefor
CN106186165A (en) * 2016-08-24 2016-12-07 何晓东 A kind of material for water treatment of heavy metal wastewater thereby and preparation method thereof
CN108727547A (en) * 2018-07-03 2018-11-02 山西新元太生物科技股份有限公司 The method of thiram distilled water is utilized when a kind of thermosetting phenolic resin production
CN109306043A (en) * 2018-09-20 2019-02-05 吉林大学 A kind of method that biomass power generation Sewage treatment containing phenolic tar utilizes

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CN101307124A (en) * 2008-07-14 2008-11-19 江苏九鼎新材料股份有限公司 Thermoplastic phenolic resin and production process thereof
CN101348548A (en) * 2007-10-18 2009-01-21 李绍通 Environment-protective process for synthesizing phenolic resin
CN101899137A (en) * 2010-04-15 2010-12-01 河南许绝电工绝缘材料有限公司 Method for producing phenolic insulating resin

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CN101348548A (en) * 2007-10-18 2009-01-21 李绍通 Environment-protective process for synthesizing phenolic resin
CN101307124A (en) * 2008-07-14 2008-11-19 江苏九鼎新材料股份有限公司 Thermoplastic phenolic resin and production process thereof
CN101899137A (en) * 2010-04-15 2010-12-01 河南许绝电工绝缘材料有限公司 Method for producing phenolic insulating resin

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102757618A (en) * 2012-07-11 2012-10-31 黄石金朝阳粉末材料有限责任公司 Modified phenol formaldehyde resin and preparation method thereof
CN102757618B (en) * 2012-07-11 2014-10-08 黄石金朝阳粉末材料有限责任公司 Modified phenol formaldehyde resin and preparation method thereof
CN103087280A (en) * 2013-01-25 2013-05-08 河北龙港工贸有限公司 Method for synthesizing phenolic resins by using paraformaldehyde
CN103214641A (en) * 2013-05-09 2013-07-24 沙县宏盛塑料有限公司 Production method of melamine-formaldehyde resin
CN103214641B (en) * 2013-05-09 2015-02-18 沙县宏盛塑料有限公司 Production method of melamine-formaldehyde resin
CN104072941A (en) * 2014-07-18 2014-10-01 锦州市好为尔保温材料有限公司 Nano modified phenolic aldehyde foam insulation board and preparation method thereof
CN105315610A (en) * 2014-08-04 2016-02-10 南京集美新型材料研发有限公司 Modified phenolic resin and preparation method therefor
CN106186165A (en) * 2016-08-24 2016-12-07 何晓东 A kind of material for water treatment of heavy metal wastewater thereby and preparation method thereof
CN108727547A (en) * 2018-07-03 2018-11-02 山西新元太生物科技股份有限公司 The method of thiram distilled water is utilized when a kind of thermosetting phenolic resin production
CN108727547B (en) * 2018-07-03 2019-05-03 山西新元太生物科技股份有限公司 The method of thiram distilled water is utilized when a kind of thermosetting phenolic resin produces
CN109306043A (en) * 2018-09-20 2019-02-05 吉林大学 A kind of method that biomass power generation Sewage treatment containing phenolic tar utilizes
CN109306043B (en) * 2018-09-20 2021-01-12 吉林大学 Method for recycling phenol-containing tar wastewater generated in biomass power generation

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Application publication date: 20111116