CN101260031B - Method for preparing low-grade aliphatic acid from benzene and its homologues waste water - Google Patents
Method for preparing low-grade aliphatic acid from benzene and its homologues waste water Download PDFInfo
- Publication number
- CN101260031B CN101260031B CN2008100363160A CN200810036316A CN101260031B CN 101260031 B CN101260031 B CN 101260031B CN 2008100363160 A CN2008100363160 A CN 2008100363160A CN 200810036316 A CN200810036316 A CN 200810036316A CN 101260031 B CN101260031 B CN 101260031B
- Authority
- CN
- China
- Prior art keywords
- waste water
- benzene
- formic acid
- oxygen
- benzene series
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to a method of using benzene series wastewater to prepare low-class fatty acid, in particular to a method of transforming benzene series wastewater into formic acid and acetic acid. The benzene series material of the invention is the organic matter with the molecular structure containing benzene rings. Benzene series wastewater and oxygen (oxygen gas, air or hydrogen peroxide) are first input into a hydrothermal oxidation reactor; then reaction is carried out under the conditions that: the temperature is 200-450 DEG C; the pressure is 5-20 Mpa; the pH value is 7-14; the addition amount of oxygen is 10-200 percent of the needed oxygen content to oxidize all carbon contained in the benzene series material of wastewater into CO2; reaction time is from 30 s to 30 min. The benzene series material is first oxidized to crack benzene rings, generate muconic acid and other unsaturated diacid; a great amount of formic acid and acetic acid is generated further by controlling the hydrothermal oxidation reaction of unsaturated diacid; finally mixed solution containing a great amount of formic acid and acetic acid is separated to prepare formic acid and acetic acid. Differing from the prior method of realizing mineralization through the thermal oxidative decomposition of wastewater, the invention aims to transform wastewater containing benzene series material into formic acid and acetic acid products which can be utilized, so as to realize the resource utilization of wastes.
Description
Technical field
The present invention relates to a kind of benzene series thing waste water is transformed and produce formic acid and acetate, as the method that industrial raw material uses, specifically is to adopt hydrothermal oxidization technology to transform, and belongs to the changing waste into resources technical field.
Background technology
At present, some benzene series thing wastewater discharges are big, concentration is high, difficult degradation, are the primary pollution source of contaminate environment.Benzene series thing (benzene series) typically refers to the compound fragrant hydrocarbon that benzene, phenol, toluene etc. contain phenyl ring.HUMAN HEALTH and ecology are all had more serious harm, and the benzene series thing clearly has been a strong carcinogen by the World Health Organization.Be mainly derived from production processes such as petrochemical complex, Coal Chemical Industry, paint, agricultural chemicals, medicine, contain the material that xylogen etc. comprises phenyl ring in a large number as the paper mill black liquor, coking chemical waste water contains a large amount of aldehydes matters, benzene series things such as the benzene of one of bulk drug commonly used, phenol or the like in the pharmaceutical industry.For these pollutents, traditional technology is to adopt physico-chemical process or biological process to handle.Need to add coagulating agent etc. because the existence of a large amount of hardly degraded organic substances in the waste water, physico-chemical process are handled, the coagulate sludge of generation can cause secondary pollution, and the expense of coagulating agent is higher, and is uneconomical economically.The characteristics that biological process is handled are that investment is big, the working cost height, and conventional biological treatment is difficult to prove effective (Persistent organic pollutants can not effectively be degraded), and the draining after the processing is difficult to directly reach the emission standard of regulation, also needs aftertreatment technology usually.
Hydrothermal oxidization is a kind of high-level oxidation technology that developed recently gets up, and has speed of response and soon, easily decomposes chemical substance, non-secondary pollution, the energy consumption of difficult degradation low (even recyclable heat etc.) characteristics.In academic research and application, all shown great attention to.At present, the hydrothermal oxidization technology mainly is limited to handle in the research in Industrial Wastewater Treatment field and discharges after waste water reaches emission standard.The Zimmermann of the pioneer-U.S. of hydrothermal oxidization (being referred to as wet oxidation at first) technology makes it reach emission standard for disaggregating treatment paper mill black liquor.What the hydrothermal oxidization technology adopted is overcritical catalytic wet oxidation technology, and reaction conditions is 400 ℃～500 ℃, 20MPa～30MPa, and need to add the catalyzer of type such as heavy metal, all benzene series things are oxidized to CO
2And H
2O, reaction conditions is higher, to the seriously corroded of reaction vessel, and need the extra expensive catalyzer that adds, catalyzer also exists the possibility of inactivation simultaneously, and reacting phase is higher to the required energy consumption of higher temperature and pressure, although the discharged wastewater met the national standard after handling does not have any economic benefit.Therefore, from as a whole, the hydrothermal oxidization technology is directly handled the trade effluent qualified discharge does not have any economy advantage.
Summary of the invention
The objective of the invention is to disclose and a kind of benzene series thing waste water is converted into formic acid and acetate, the method for using as industrial raw material.
For reaching above-mentioned purpose, the present invention is by the discovery that studies for a long period of time to benzene series thing waste water, irrelevant with the kind of benzene series thing, no matter be which kind of benzene series thing, all the phenyl ring ring-opening reaction can at first take place under hydrothermal condition, the post-rift first step product of open loop is unsaturated bisgallic acid (as a muconic acid), then by control reaction conditions optionally generate formic acid and acetate, reaction mechanism as shown in the formula:
Acetate is quite stable, and the acetate of generation is difficult for being decomposed, and is expected to obtain with high yield.But the formic acid instability will obtain the formic acid of high yield, and the oxygenolysis that prevents formic acid is crucial.The existing promotion of alkali has the effect that stops the organism hydrothermal oxidization to decompose again.This patent is to utilize original salkali waste in industrial soda or the waste water to stop the decomposition of formic acid, and the yield of its formic acid is improved.When the benzene series substrate concentration is higher than the carrying out that heat that 5% reaction produces just can be kept reaction, this method operation energy consumption is low, and technology is simple, and is easy to operate, and non-secondary pollution has valuable economic and social benefit.
The present invention is different with the method that traditional wastewater oxidation is decomposed realization mineralising purpose, its objective is that the waste water that will contain the benzene series thing changes into utilizable Industrial products formic acid and acetate, realizes the resource utilization of refuse.
Formic acid and acetate belong to lower fatty acid, are important chemical material.Wherein, (formic acid, formic acid are one of organic chemical industry's basic materials HCOOH) to formic acid, are widely used in industries such as agricultural chemicals, leather, medicine, rubber, printing and dyeing and industrial chemicals.On medicine industry, it can do local excitants, astringent matter and bubble cream, also is to produce important source material such as Sulpyrine, metronidazole, caffeine, pyramidon, borneol, VITMAIN B1.In pesticide industry, formic acid can be produced higher effective and lower toxic pesticide desinsection ether, triadimefon, paclobutrazol, leather industry can be made tanning agents, deliming agent and the neutralizing agent of leather, and chemical industry is used to produce formic acid ammonia, dimethylbenzoyl ammonia, various formate, anti-aging agent etc.The more important thing is that the formic acid of discovering that the U.S. is up-to-date can directly be used for making aminic acid fuel battery.Acetate (acetic acid, aceticacid, CH
3COOH) be a kind of important chemical reagent.In chemical industry, it is used to make polyethylene terephthalate, and the latter is the major portion of beverage bottle.Acetate also is used to make the needed cellulose acetate of cinefilm and timber and sticks with glue polyvinyl acetate in the agent and a lot of synthon and fabric.In the family, dilute solution of acetic acid is often used as scale remover.Acetate is a kind of acidity regulator of regulation in foodstuffs industry.In addition, acetate also can be used to make the calcium-magnesium acetic environment friendly type snow melt agent.
Concrete technology of the present invention is: at first will contain in the waste water and oxygen (oxygen can be oxygen and/or air and/or hydrogen peroxide) input hydrothermal oxidization reactor of benzene series thing, then at 200 ℃～450 ℃, 5Mpa～20Mpa, pH=7～14, the addition of oxygen are that the contained carbon of benzene series thing all is oxidized to CO in the waste water
210%～200% of requisite oxygen amount, the reaction times is to react under the condition of 30s～30min.Need not catalyzer such as other heavy metals, oxidizing reaction at first takes place the benzene series thing in the waste water makes the phenyl ring fracture, generates unsaturated bisgallic acids such as muconic acid, and the further hydrothermal oxidization of unsaturated bisgallic acid generates the mixed solution that contains a large amount of formic acid and acetate.The mixed solution separation and purification that will contain a large amount of formic acid, acetate at last makes product formic acid and acetate.Because the hydrothermal oxidization reaction is a thermopositive reaction, therefore react the heat that self produces and not only can keep the required temperature condition of hydrothermal oxidization reaction of self, can also adopt heat exchanger, the chuck that is suitable for or enters reaction vessel behind the residual heat collection that produces after the hydrothermal oxidization reaction for bathing is regulated and maintenance hydrothermal oxidization temperature.
Described benzene series thing waste water has the waste water of paper waste, coking chemical waste water, pharmacy waste water, producer gas generator waste water, dyeing waste water and organic chemical industry's production process etc.Benzene series thing among the present invention comprises the organism that contains phenyl ring, as phenol, hydroxyanisole, dihydroxy-benzene, 2-methoxyl group-1,4-Resorcinol, 2,6-syringol etc.
Described pH=7～14th, the potential of hydrogen of regulating waste water is to add industrial soda or utilize that original salkali waste carries out in the waste water, the hydrothermal oxidization reaction process plays catalyst action, makes the output of formic acid and acetate improve.
The addition of described oxygen is to become CO according to the contained whole oxidation of coals of benzene series thing in the waste water (as phenol, hydroxyanisole, dihydroxy-benzene, 2-methoxyl group-1,4-Resorcinol, 2,6-syringol etc.)
210%～200% of requisite oxygen amount is determined.
The present invention is applied to the resource utilization process of benzene series thing waste water with the hydrothermal oxidization technology, and concrete advantageous effect is embodied in the following aspects;
1. because the present invention is converted into formic acid and acetate with the benzene series thing in the waste water, so treatment effect is that the high more effect of concentration is good more with containing benzene series substrate concentration relation, and traditional biological process is handled the technology of benzene series thing waste water, just in time opposite, it is good more to contain the low more effect of benzene series substrate concentration.
2. compare with acetic acid process with traditional production formic acid, raw material of the present invention is a refuse, therefore cost is extremely low, has valuable economic benefit, and is raw material with benzene series thing waste water, also carried out simultaneously polluting and handled obtaining product, can save the required expense of wastewater treatment, simultaneously with waste water as a kind of energy that produces product, be a kind of changing waste into resources technology, utilization of waste material is reentered industrial chain later on develop, also embodied a kind of theory of recycling economy Sustainable development.
3. because the present invention directly handles the back qualified discharge with benzene series thing waste water, and the required condition of required reaction conditions and overcritical wet oxidation reaction is compared milder, and entire reaction course is thermopositive reaction, the benzene series substrate concentration is higher than at 5% o'clock in waste water, the carrying out that can also keep reaction by the heat that reaction process self produces, therefore operation energy consumption of the present invention is lower.
4. technology of the present invention need not to add catalyzer such as other heavy metals, and the hydrothermal oxidization reaction can take place the benzene series thing in the waste water, so technical process is simple, need not equipment such as pre-treatment, the main reactor simple structure, and technological operation is convenient.
5. non-secondary pollution of the present invention because of the oxidized decomposition of organic pollutant, after the formic acid and separated from acetic acid that produces, only contains micromolecular organic acid in a small amount of waste water of generation, can be by conventional sewage disposal back up to standard discharging.
6. the present invention has valuable economic benefit and social benefit.
Description of drawings
Fig. 1 utilizes the technical process of preparing low-grade aliphatic acid from benzene and its homologues waste water for the present invention.
The present invention has carried out some model things of benzene series thing and (has compared with the benzene series thing molecule of complexity, similar, the better simply representational material of molecular structure, as phenol, 2,6-syringol, 1,2-pyrocatechol, 1,4-Resorcinol, hydroxyanisole, Eugenol etc.) experimental study, its result is shown in following each figure.
The test that the small-sized batch reactor (filling ratio 30%) that Fig. 2 adopts for the present invention carries out, content is 2 of 0.041g/mL, and 6-syringol waste water is at 280 ℃, reaction times 60S, the addition of oxygen is in the waste water 2, and the contained carbon of 6-syringol all is oxidized to CO
2120% of requisite oxygen amount, NaOH concentration are the HPLC spectrogram that hydro-thermal reaction is produced formic acid and acetate under the 0.5mol/L condition, and the result shows that the yield of formic acid can reach 59.59%, and the yield of acetate can reach 7.10%.
The test that the small-sized batch reactor (filling ratio 30%) that Fig. 3 adopts for the present invention carries out, content is 2 of 0.041g/mL, and 6-syringol waste water is at 280 ℃, reaction times 60S, the addition of oxygen is in the waste water 2, and the contained carbon of 6-syringol all is oxidized to CO
2100% of requisite oxygen amount, NaOH concentration are the HPLC spectrogram that hydro-thermal reaction is produced formic acid and acetate under the 0.8mol/L condition, and the result shows that the yield of formic acid can reach 42.91%, and the yield of acetate can reach 14.98%.
The test that the small-sized batch reactor (filling ratio 30%) that Fig. 4 adopts for the present invention carries out, content is 2 of 0.041g/mL, and 6-syringol waste water is at 280 ℃, reaction times 60S, the addition of oxygen is in the waste water 2, and the contained carbon of 6-syringol all is oxidized to CO
2100% of requisite oxygen amount does not add the HPLC spectrogram that hydro-thermal reaction under the alkali condition is produced formic acid and acetate, and the result shows that the yield of formic acid can reach 15.20%, and the yield of acetate can reach 8.75%.
The test that the small-sized batch reactor (filling ratio 30%) that Fig. 5 adopts for the present invention carries out, content is 2 of 0.041g/mL, and 6-syringol waste water is at 300 ℃, reaction times 60S, the addition of oxygen is in the waste water 2, and the contained carbon of 6-syringol all is oxidized to CO
2100% of requisite oxygen amount does not add the HPLC spectrogram that hydro-thermal reaction under the alkali condition is produced formic acid and acetate, and the result shows that the yield of formic acid can reach 11.69%, and the yield of acetate can reach 5.69%.
The test that the small-sized batch reactor (filling ratio 30%) that Fig. 6 adopts for the present invention carries out, content is 2 of 0.041g/mL, and 6-syringol waste water is at 300 ℃, reaction times 60S, the addition of oxygen is in the waste water 2, and the contained carbon of 6-syringol all is oxidized to CO
250% of requisite oxygen amount does not add the HPLC spectrogram that hydro-thermal reaction under the alkali condition is produced formic acid and acetate, and the result shows that the yield of formic acid can reach 8.66%, and the yield of acetate can reach 3.67%.
The test that the small-sized batch reactor (filling ratio 30%) that Fig. 7 adopts for the present invention carries out, content is 2 of 0.041g/mL, and 6-syringol waste water is at 300 ℃, reaction times 90S, the addition of oxygen is in the waste water 2, and the contained carbon of 6-syringol all is oxidized to CO
2100% of requisite oxygen amount does not add the HPLC spectrogram that hydro-thermal reaction under the alkali condition is produced formic acid and acetate, and the result shows that the yield of formic acid can reach 9.36%, and the yield of acetate can reach 5.88%.
The test that the small-sized batch reactor (filling ratio 60%) that Fig. 8 adopts for the present invention carries out, content is the phenol, 1 of 0.042g/mL, 2-pyrocatechol, 1,4-Resorcinol waste water is at 300 ℃, reaction times 30S, the addition of oxygen is a phenol in wastewater, 1,2-pyrocatechol, 1, and the contained carbon of 4-Resorcinol all is oxidized to CO
2Hydro-thermal reaction is produced the GC/MS spectrogram of formic acid and acetate under 10% condition of requisite oxygen amount.
The test that the small-sized batch reactor (filling ratio 60%) that Fig. 9 adopts for the present invention carries out, content is the phenol, 1 of 0.042g/mL, 2-pyrocatechol, 1,4-Resorcinol waste water is at 300 ℃, reaction times 30S, the addition of oxygen is a phenol in wastewater, 1,2-pyrocatechol, 1, and the contained carbon of 4-Resorcinol all is oxidized to CO
2Hydro-thermal reaction is produced the GC/MS spectrogram of formic acid and acetate under 100% the condition of requisite oxygen amount.
The test that the small-sized batch reactor (filling ratio 60%) that Figure 10 adopts for the present invention carries out, content is that the waste water of 0.042g/mL is at 300 ℃, reaction times 30S, the addition of oxygen is a hydroxyanisole, 1 in the waste water, 2-pyrocatechol, 2-methoxyl group-1, the contained carbon of 4-Resorcinol all is oxidized to CO
2Hydro-thermal reaction is produced the GC/MS spectrogram of formic acid and acetate under 10% condition of requisite oxygen amount.
The test that the small-sized batch reactor (filling ratio 60%) that Figure 11 adopts for the present invention carries out, content is the hydroxyanisole, 1 of 0.042g/mL, 2-pyrocatechol, 2-methoxyl group-1,4-Resorcinol waste water is at 300 ℃, reaction times 30S, the addition of oxygen is a hydroxyanisole, 1 in the waste water, 2-pyrocatechol, 2-methoxyl group-1, and the contained carbon of 4-Resorcinol all is oxidized to CO
2Hydro-thermal reaction is produced the GC/MS spectrogram of formic acid and acetate under 100% the condition of requisite oxygen amount.
The test that the small-sized batch reactor (filling ratio 60%) that Figure 12 adopts for the present invention carries out, content be the hydroxyanisole waste water of 0.042g/mL at 300 ℃, reaction times 10S, the addition of oxygen are that the contained carbon of hydroxyanisole all is oxidized to CO in the waste water
2Hydro-thermal reaction is produced the HPLC spectrogram of formic acid and acetate under 100% condition of requisite oxygen amount.
The test that the small-sized batch reactor (filling ratio 60%) that Figure 13 adopts for the present invention carries out, content be the Eugenol waste water of 0.042g/mL at 300 ℃, reaction times 10S, the addition of oxygen are that the contained carbon of Eugenol all is oxidized to CO in the waste water
2Hydro-thermal reaction is produced the HPLC spectrogram of formic acid and acetate under 100% condition of requisite oxygen amount.
The test that the small-sized batch reactor (filling ratio 60%) that Figure 14 adopts for the present invention carries out, content be the phenolic waste water of 0.042g/mL at 300 ℃, reaction times 10S, the addition of oxygen are that the contained carbon of phenol in wastewater all is oxidized to CO
2Hydro-thermal reaction is produced the HPLC spectrogram of formic acid and acetate under 100% condition of requisite oxygen amount.
Embodiment
The present invention is converted into the technology of lower fatty acid, the industrial enterprise field that can be widely used in producing high concentration hard-degraded organic waste water with benzene series thing waste water:
Embodiment 1, paper waste.
Paper-making industrial waste water is the difficult organic waste water that a kind of water yield is big, colourity is high, suspension content is big, organic concentration is high, component is complicated.The source of paper waste mainly contains pulping waste liquor, middle section water, paper machine white water.Pulping waste liquor pollutes the most seriously, is chocolate, is called Heisui River, and Pollutant levels are very high in the Heisui River, contain a large amount of fibers and pigment.The middle section water water yield is maximum, and pollution substance has xylogen, Mierocrystalline cellulose and the VFA etc. of the higher concentration composition than difficult for biological degradation, and colourity is dark, frowziness, and contaminative is very strong, COD
Cr400～700mg/L, BOD
5200～400mg/L, pH 7～14.The paper machine white water main component is Mierocrystalline cellulose, hemicellulose, lignin, extractum etc., generally adopts closed circulation, but a small amount of easily the loss.
The principal constituent of paper-making industrial waste water is an xylogen.Xylogen is a kind of phenol polymer of complexity, and structure is closely similar with polyphenol.Paper waste is added the hydrothermal oxidization reactor, is 200 ℃～450 ℃ in temperature, and pressure is 5Mpa～20Mpa, pH=7～14, and the addition of oxygen is that the contained carbon of benzene series thing all is oxidized to CO in the waste water
210%～200% of requisite oxygen amount, the reaction times is that 30s reacts to tens of minutes condition.The addition of oxygen becomes CO by the oxidation of coal of contained benzene series thing in the waste water
2The conversion of required amount of oxygen, the hydrothermal oxidization reaction can take place in the benzene series thing that need not in the containing wastewater from catalyst such as other heavy metals.The time that hydrothermal oxidization reacts is that 30s arrived about tens of minutes, and the phenyl ring open loop generates unsaturated bisgallic acids such as muconic acid, because mostly paper waste is alkalescence at present, so need not add industrial soda again to change pH.Further generate the mixed solution that contains a large amount of formic acid and acetate and a spot of small molecules acid behind the control reaction conditions hydrothermal oxidization.At last, the mixed solution separation and purification that will contain a large amount of formic acid, acetate can make formic acid and acetate.The remaining small molecular organic acid waste water that contains on a small quantity discharges sewage disposal back up to standard routinely, also can enter the supplementary carbon source of the sewage work of traditional biological method processing as microbial growth.The part of waste heat of reaction process is used for bathing after can adopting waste-heat recovery device to reclaim.
The model thing of pollutent is a phenol, 1 in the paper waste, 2-pyrocatechol, 1, and 4-Resorcinol etc., the spectrogram by HPLC, GC/MS sees also accompanying drawing as can be seen, and the hydrothermal oxidization paper waste produces formic acid and acetate is fully feasible.
Embodiment 2, coking chemical waste water.
Coking chemical waste water is by producing in the high temperature carbonization of raw coal, gas purification and the product purification process.The waste water complicated component, seriously polluted, be outstanding environmental problem in the industrial wastewater discharge, its water quality changes with raw coal composition and coke making process.Organic compound in the coking chemical waste water also has the heterogeneous ring compound of monocycle and polycyclic aromatics, nitrogenous, sulphur, oxygen etc. except that phenols, comprise hydroxyanisole, 1,2-pyrocatechol, 2-methoxyl group-1,4-Resorcinol etc.
Coking chemical waste water is added the hydrothermal oxidization reactor, is 240 ℃～450 ℃ in temperature, and pressure is 5Mpa～20Mpa, pH=7～14, and the addition of oxygen is that the contained carbon of benzene series thing all is oxidized to CO in the waste water
210%～200% of requisite oxygen amount, the reaction times is that 30s reacts to tens of minutes condition, the addition of oxygen becomes CO by the oxidation of coal of contained benzene series thing in the waste water
2The conversion of required amount of oxygen, the hydrothermal oxidization reaction can take place in the benzene series thing that need not in the containing wastewater from catalyst such as other heavy metals.The time that hydrothermal oxidization reacts is that 30s arrived about tens of minutes, the phenyl ring open loop generates unsaturated bisgallic acids such as muconic acid, further generate the mixed solution that contains a large amount of formic acid and acetate and a spot of small molecules acid behind the control reaction conditions hydrothermal oxidization, at last, the mixed solution separation and purification that will contain a large amount of formic acid, acetate can make formic acid and acetate.The remaining small molecular organic acid waste water that contains on a small quantity discharges sewage disposal back up to standard routinely, also can enter the supplementary carbon source of the sewage work of traditional biological method processing as microbial growth.The part of waste heat of reaction process is used for bathing after can adopting waste-heat recovery device to reclaim.
When oxygen supply rate is that oxidation of coal becomes CO in the contained benzene series thing
2100% o'clock of required amount of oxygen, target compound formic acid and acetate productive rate are higher, see also accompanying drawing, the spectrogram by HPLC, GC/MS as can be seen, the hydrothermal oxidization coking chemical waste water produces formic acid and acetate is fully feasible.
Embodiment 3. contains the organic chemical waste water of benzo pollutants
The organic chemical waste water complicated component.Because product category is many and technological process has nothing in common with each other, the waste water composition is very complicated.Total characteristics are that suspended substance is few, and solvability or milkiness organic matter are many, mainly are at the organic chemical waste water that contains benzo pollutants here, and pollutent mainly comprises benzo pollutants such as phenol, dihydroxy-benzene.
Organic chemical waste water is added the hydrothermal oxidization reactor, is 250 ℃～430 ℃ in temperature, and pressure is 8Mpa～20Mpa, pH=7～14, and the addition of oxygen is that the contained carbon of benzene series thing all is oxidized to CO in the waste water
210%～200% of requisite oxygen amount, the reaction times is that 30s reacts to tens of minutes condition, the addition of oxygen becomes CO by the oxidation of coal of contained benzene series thing in the waste water
2The conversion of required amount of oxygen, the hydrothermal oxidization reaction can take place in the benzene series thing that need not in the containing wastewater from catalyst such as other heavy metals.The time that hydrothermal oxidization reacts is that 30s arrived about tens of minutes, and the phenyl ring open loop generates unsaturated bisgallic acids such as muconic acid.Further generate the mixed solution that contains a large amount of formic acid and acetate behind the control reaction conditions control reaction conditions hydrothermal oxidization.At last, the mixed solution that will contain a large amount of formic acid, acetate carries out separation and purification and can make formic acid and acetate.The remaining small molecular organic acid waste water that contains on a small quantity discharges sewage disposal back up to standard routinely, also can enter the supplementary carbon source of the sewage work of traditional biological method processing as microbial growth.The part of waste heat of reaction process is used for bathing after can adopting waste-heat recovery device to reclaim.
The HPLC, the GC/MS spectrogram that produce formic acid and acetate by the hydrothermal oxidization that contains benzo pollutants waste water such as phenol, dihydroxy-benzene (see also accompanying drawing) as can be seen, and the hydrothermal oxidization organic chemical waste water produces formic acid and acetate is fully feasible.
Embodiment 4. pharmacy waste waters
Pharmaceutical industry to the pollution of environment mainly from production of raw medicine, it is one of bulk drug commonly used in the pharmaceutical industry that benzene, phenol etc. contain benzene ring compound, and these contain the pharmacy waste water steady chemical structure of benzo pollutants such as phenol, dihydroxy-benzene, and traditional biological treatment is difficult to remove objectionable impurities wherein.
Pharmacy waste water is added the hydrothermal oxidization reactor, is 280 ℃～400 ℃ in temperature, and pressure is 7Mpa～20Mpa, pH=7～14, and the addition of oxygen is that the contained carbon of benzene series thing all is oxidized to CO in the waste water
210%～200% of requisite oxygen amount, the reaction times is that 30s reacts to tens of minutes condition, the addition of oxygen becomes CO by the oxidation of coal of contained benzene series thing in the waste water
2The conversion of required amount of oxygen, the hydrothermal oxidization reaction can take place in the benzene series thing that need not in the containing wastewater from catalyst such as other heavy metals, and the time that hydrothermal oxidization reacts is that 30s arrived about tens of minutes, and the phenyl ring open loop generates unsaturated bisgallic acids such as muconic acid.Further generate the mixed solution that contains a large amount of formic acid and acetate and a spot of small molecules acid behind the hydrothermal oxidization.At last, the mixed solution that will contain a large amount of formic acid, acetate carries out separation and purification and can make formic acid and acetate.The remaining small molecular organic acid waste water that contains on a small quantity discharges sewage disposal back up to standard routinely, also can enter the supplementary carbon source of the sewage work of traditional biological method processing as microbial growth.The part of waste heat of reaction process is used for bathing after can adopting waste-heat recovery device to reclaim.
The HPLC, the GC/MS spectrogram that produce formic acid and acetate by the hydrothermal oxidization that contains benzo pollutants waste water such as phenol, dihydroxy-benzene (see also accompanying drawing) as can be seen, and the hydrothermal oxidization pharmacy waste water produces formic acid and acetate is fully feasible.
Producer gas generator is can generation in washing and refrigerative process a large amount of to contain the waste water of noxious pollutant such as phenols.The content of phenol in waster concentration best result of producer gas plant can not reach 3000mg/L and 2000mg/L.If the gas washing wastewater of producer gas generator middle and high concentration does not take effectively to improve the measure of water quality, will influence the circulating water system works better, cause the line clogging of equipment, the corrosion and the wearing and tearing of equipment, finally destroy the closed cycle of gas washing, and can cause the severe contamination of water body environment.
Producer gas generator waste water is added the hydrothermal oxidization reactor, is 250 ℃～380 ℃ in temperature, and pressure is 6Mpa～20Mpa, pH=7～14, and the addition of oxygen is that the contained carbon of benzene series thing all is oxidized to CO in the waste water
210%～200% of requisite oxygen amount, the reaction times is that 30s reacts to tens of minutes condition, the addition of oxygen becomes CO by the oxidation of coal of contained benzene series thing in the waste water
2The conversion of required amount of oxygen, the hydrothermal oxidization reaction can take place in the benzene series thing that need not in the containing wastewater from catalyst such as other heavy metals.The time that hydrothermal oxidization reacts is that 30s arrived about tens of minutes, and the phenyl ring open loop generates unsaturated bisgallic acids such as muconic acid.Further generate the mixed solution that contains a large amount of formic acid and acetate and a spot of small molecules acid behind the control reaction conditions hydrothermal oxidization, last, the mixed solution that will contain a large amount of formic acid, acetate carries out separation and purification and can make formic acid and acetate.The remaining small molecular organic acid waste water that contains on a small quantity discharges sewage disposal back up to standard routinely, also can enter the supplementary carbon source of the sewage work of traditional biological method processing as microbial growth.The part of waste heat of reaction process is used for bathing after can adopting waste-heat recovery device to reclaim.
The HPLC, the GC/MS spectrogram that produce formic acid and acetate by the hydrothermal oxidization that contains benzo pollutants waste water such as phenol, dihydroxy-benzene (see also accompanying drawing) as can be seen, and hydrothermal oxidization producer gas generator waste water produces formic acid and acetate is fully feasible.
Claims (4)
1. use the method for preparing low-grade aliphatic acid from benzene and its homologues waste water, it is characterized in that: at first will contain in the waste water and oxygen input hydrothermal oxidization reactor of benzene series thing, then at 200 ℃～450 ℃, 5Mpa～20Mpa, pH=7～14, the addition of oxygen are that the carbon of contained benzene series thing in the waste water all is oxidized to CO
210%～200% of requisite oxygen, the reaction times is to react under the condition of 30s～30min; Oxidizing reaction at first takes place benzene series thing in the waste water makes the phenyl ring fracture, generates the unsaturated bisgallic acid of muconic acid, and the further hydrothermal oxidization of unsaturated bisgallic acid generates the mixed solution that contains formic acid and acetate; The mixed solution separation and purification that will contain formic acid, acetate at last makes product formic acid and acetate;
Described benzene series thing comprises phenol, hydroxyanisole, dihydroxy-benzene, the 2-methoxyl group-1 that contains phenyl ring, 4-Resorcinol and 2,6-syringol.
2. the method with preparing low-grade aliphatic acid from benzene and its homologues waste water according to claim 1, it is characterized in that: described benzene series thing waste water has paper waste, coking chemical waste water, pharmacy waste water, producer gas generator waste water, the waste water of dyeing waste water and organic chemical industry's production process.
3. the method with preparing low-grade aliphatic acid from benzene and its homologues waste water according to claim 1, it is characterized in that: described pH=7～14th, utilize in the waste water original alkali or industrial soda added in the waste water and carry out, be used as catalyzer in the hydrothermal oxidization reaction process, make the output of formic acid and acetate improve.
4. the method with preparing low-grade aliphatic acid from benzene and its homologues waste water according to claim 1 is characterized in that: in the described oxygen input hydrothermal oxidization reactor, be oxygen supply in reactor, oxygen is oxygen and/or air and/or hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100363160A CN101260031B (en) | 2008-04-21 | 2008-04-21 | Method for preparing low-grade aliphatic acid from benzene and its homologues waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100363160A CN101260031B (en) | 2008-04-21 | 2008-04-21 | Method for preparing low-grade aliphatic acid from benzene and its homologues waste water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101260031A CN101260031A (en) | 2008-09-10 |
| CN101260031B true CN101260031B (en) | 2010-08-18 |
Family
ID=39960767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100363160A Expired - Fee Related CN101260031B (en) | 2008-04-21 | 2008-04-21 | Method for preparing low-grade aliphatic acid from benzene and its homologues waste water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101260031B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212336B (en) * | 2011-05-30 | 2014-05-28 | 广东慧信环保有限公司 | Method for preparing calcium magnesium carboxylate snow-melting agent by utilizing municipal sludge |
| CN107746375B (en) * | 2017-09-15 | 2021-03-30 | 上海交通大学 | Method for producing formic acid by selective hydrothermal oxidative conversion of household garbage |
-
2008
- 2008-04-21 CN CN2008100363160A patent/CN101260031B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 万家峰,冯玉杰,杨少霞,蔡伟民.Ru/CeO2/A1203湿式氧化催化剂处理苯酚配水的研究.《黑龙江大学自然科学学报》.2003,第20卷(第4期),101-103. * |
| 姜洪泉,徐贵潭,李瑞波.高铁酸钾氧化处理水中苯酚的机理.《牡丹江师范学院学报》.2003,第2卷36-37. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101260031A (en) | 2008-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Prabakar et al. | Pretreatment technologies for industrial effluents: Critical review on bioenergy production and environmental concerns | |
| CN105417869A (en) | Fenton oxidation-biological combination treatment technology capable of achieving ozone-anaerobic iron reduction and sludge reduction | |
| CN105254150A (en) | Pretreatment method for increasing yield of excess sludge anaerobic digestion methane | |
| CN207375999U (en) | A kind of organic refuse treatment appts for coupling hydrothermal carbonization and biochemical reaction principle | |
| SE540137C2 (en) | Method for oxidation of a liquid phase in a hydrothermal carbonization process | |
| CN115286091A (en) | Controllable wet catalytic oxidation plug flow type tubular reaction system for treating organic waste | |
| CN108675587B (en) | Method for deep dehydration of sludge through hydrothermal catalytic oxidation | |
| Wagh et al. | Biogas generation from distillery spent wash by using an OPUR western biotechnology process: a case study | |
| CN101260031B (en) | Method for preparing low-grade aliphatic acid from benzene and its homologues waste water | |
| CN109912150B (en) | Process method for treating residual activated sludge by anaerobic drying | |
| CN101805092A (en) | New process for treatment of APMP pulp-making wastewater | |
| KR101003482B1 (en) | Disposal method of high concentration organic matter waste water | |
| RU2646621C2 (en) | Method for processing organic components of solid residential waste and waste of mechanobiological cleaning of residential waste water and a device for its implementation | |
| CN107603644A (en) | It is a kind of to couple hydrothermal carbonization and the organic refuse treatment appts and handling process of biochemical reaction principle | |
| Mavrodin et al. | Energy recovering from tanneries by biogas production | |
| Hii et al. | Hydrothermal processing of Sludge–A review | |
| CN102249487B (en) | Comprehensive processing device for wastewater and waste liquid | |
| CN112607982B (en) | Sludge pyrohydrolysis system and sludge anaerobic digestion system | |
| Liu et al. | Thermal hydrolysis prior to hydrothermal carbonization resulted in high quality sludge hydrochar with low nitrogen and sulfur content | |
| KR102153490B1 (en) | High-efficiency biogasfication Process through denitrification of digested waste leachate using digestion gas and CHAR production using digested sludge | |
| CN114410349A (en) | Waste pretreatment process matched with coal water slurry gasification | |
| CN110015803A (en) | A kind of carbonization waste water treatment process technology | |
| Singh et al. | A review on hydrothermal pretreatment of sewage sludge: Energy recovery options and major challenges | |
| CN113045160A (en) | Sludge treatment method for improving residual sludge methane yield through reflux of digestive fluid | |
| CN103663826B (en) | A kind of pretreatment process of HTS factory effluent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100818 Termination date: 20130421 |