CN105668891A - Supercritical water oxidation waste water preheating and purifying system - Google Patents
Supercritical water oxidation waste water preheating and purifying system Download PDFInfo
- Publication number
- CN105668891A CN105668891A CN201610040723.3A CN201610040723A CN105668891A CN 105668891 A CN105668891 A CN 105668891A CN 201610040723 A CN201610040723 A CN 201610040723A CN 105668891 A CN105668891 A CN 105668891A
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- waste water
- preheating
- supercritical
- temperature
- preheating device
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
Abstract
The invention relates to a supercritical water oxidation waste water preheating and purifying system.The supercritical water oxidation waste water preheating and purifying system comprises a sewage pump, a preheating device and purifying device.Within 400 DEG C, different substances are separated by utilizing the supercritical state under different temperature and pressure, the chlorine and sodium in waste water are separated, equipment corrosion of a waste water treating system is avoided greatly, material selectivity is increased, manufacturing cost is lowered, the high-purity separated substances can be recycled, and waste water treatment cost is lowered.
Description
Technical field:
The present invention relates to the process equipment of a kind of waste water, particularly to a kind of supercritical water oxidation waste water preheating purification system.
Background technology
Supercritical refers to a kind of special state of flowing material. When being in the fluid increasing temperature and pressure of VLE, thermal expansion causes fluid density to reduce, and the boundary that the rising of pressure makes vehicle repair major disappears, and becomes homogeneous system, here it is critical point. When the temperature of fluid, pressure are known as being in supercriticality when being respectively higher than critical temperature and critical pressure. Supercritical fluid has the good fluidity of similar gas, but density is again much larger than gas, therefore has the physicochemical property of many uniquenesses.
The critical point of water is temperature 374.3 DEG C, pressure 22.064MPa, if the temperature of water, pressure are increased to more than critical point, it is supercritical water, the key propertys such as its density, viscosity, electrical conductivity, dielectric constant all have very big-difference with light water, show the character being similar to nonpolar organic compound. Therefore, supercritical water can dissolve each other completely with apolar substance (such as hydro carbons) and other Organic substances, and inorganic matter particularly salt, ionization constant and dissolubility in supercritical water are but very low. Meanwhile, supercritical water can dissolve each other completely with gases such as air, oxygen, nitrogen and carbon dioxide.
Due to the solvent that Organic substance and oxygen are all fabulous by supercritical water, therefore organic oxidation can carry out in the homogeneous phase of oxygen enrichment, and reaction is absent from the restriction produced because needing alternate transfer. Meanwhile, the high reaction temperature of 400～600 DEG C also makes response speed accelerate, it is possible within the response time of several seconds, can reach the destructive rate of more than 99%.
Supercritical water oxidation is fully and completely: organic carbon is converted into CO2, and hydrogen is converted into H20, and halogen atom is converted into halogen ion, sulfur and phosphorus and is separately converted to sulfate and phosphate, and nitrogen transformation is nitrate anion and nitrite ion or nitrogen. And supercritical water oxidation to a certain extent with simple combustion process similarity, oxidizing process discharges substantial amounts of heat. Owing to supercritical water oxidation is the homogeneous reaction carried out at high temperature under high pressure, reaction rate is fast, and the time of staying short (being smaller than 1min), so structure of reactor is succinct, volume is little; Applied widely, it is possible to suitable in the process of various noxious substances, wastewater and waste materials; Being formed without secondary pollution, product cleaning need not process further, and inorganic salt can be separated from water, and the waste water after process can be recycled completely; When content of organics is more than 2%, it is possible to rely on autoxidation heat release in course of reaction to maintain the temperature that reaction is required, it is not necessary to additionally supplying heat, if concentration is higher, then release the more heat of oxidation, this partial heat energy can reclaim.
At present, supercritical water oxidation method processes waste water and still suffers from shortcoming, and equipment material is proposed strict requirement by the operating condition of its High Temperature High Pressure undoubtedly; On the other hand, although having carried out some researchs in the reaction kinetics and mechanism of the character of supercritical water and material dissolubility wherein and supercritical water chemical reaction, but these are compared with exploitation, design and controlling the required knowledge of supercritical water oxidation process and data, also far from meeting requirement; Actual carry out engineering design time, except consider system reacting dynamics characteristic except, it is necessary to note the factor of some engineering aspects, for instance the precipitation of burn into salt, the use of catalyst, heat transmission etc.
Supercritical water oxidation environment is more easily caused corrosion of metal than under usual conditions. The dissolved oxygen of high concentration, the condition of High Temperature High Pressure, extreme pH value and some kinds of inorganic ions all can make corrosion accelerate. Corrosion can produce the problem of two aspects, and one is containing some metal ion (such as chromium etc.) in effluent after completion of the reaction, can affect the quality of process; The corrosion that two is excessive can affect pressure system normal operation. 300～500 DEG C, pH value 2～9, chloride concentration be 400mg/L when, the corrosion of 13 kinds of alloys has been carried out experimentation. It is shown that pH is little on the impact of corrosion in given temperature range. Under the subcritical state of 300 DEG C, owing to the dielectric constant of water and the dissolubility of inorganic salt are all relatively big, mainly based on electrochemical corrosion. When temperature rises to more than 400 DEG C, the dielectric constant of water and the dissolubility of salt decline rapidly, at this moment based on chemical attack.
In supercritical water oxidation, in charging, often add the salt of acid and the generation produced in alkali N-process, because under super critical condition, the dissolubility of inorganic matter is only small, process has the precipitation of salt. The viscosity of some salt is bigger, it is possible to can cause the blocking of reactor or pipeline. Can partly be improved with suitable mode of operation by optimizing of reactor types. Some high salt-containing system is likely to need pretreatment.
So, supercritical water oxidation increasingly comes into one's own in processing debirs, and the defect of the prior art of its existence is urgently to be resolved hurrily.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, preheating purification system in a kind of supercritical water oxidation wastewater treatment system is provided, equipment is avoided to bear the comprehensive corrosion of multiple acid, alkali and inorganic salt, solution processes the limitation that the material of system selects, equipment can the transformation temperature of basis, corrosive medium situation select certain to adapt to separate material, the soda acid removed according to point temperature section is chosen corresponding material and can greatly be reduced manufacturing cost; The material extracted can recycling, decrease the cost of operation.
The preheating purification system of this supercritical water oxidation waste water, containing sewage pump, 1～6 preheating device, purification devices composition;
The preheating purification system of this supercritical water oxidation, is be composed in series by two and above preheating device, and the temperature of this pre-hot system presents stepped intensification by water inlet end, and temperature range is≤400 DEG C, pressure > 8.26Mpa;
Further, the pre-hot system of this supercritical water oxidation, it is made up of sewage pump, 1～6 preheating device, purification devices, the temperature of this preheating device rises to 100～250 DEG C of stages, the chloride ion-containing material in supercritical separation waste water; Preheating device rises to 250～400 DEG C of stages, in supercritical separation waste water containing sodium ion material;
Further, the temperature of preheating device rises to 150～250 DEG C of stages, supercritical water oxidation separation chloride ion-containing material; Described chloride ion material is hydrogen chloride.
Further, pre-hot system is further characterized in that preheating device have employed different nickel-based metallic materials along with the rising of temperature, goes out sodium and chlorine element adapting to this system separation and Extraction;
Further, preheating device is connected with purification devices and further supercritical water oxidized organic wastewater device, the high-purity hydrogen sodium oxide separated that purification devices main purification reclaims.
Due to traditional supercritical water oxidation technique product all of in waste water all along with water enters container and the reactor of warm-up phase, thus causing a great problem that metal material selects, currently available technology does not have simultaneously same metal to be adopted to solve under high temperature, high pressure, hyperoxia, chloride ion-containing, complex situations containing sodium.
Above, the pre-hot system of the present invention extracts some to the disadvantageous chloride ion of metal material and salt (mainly some chloride ion and sodium ion composition), waste water after extraction is significantly high with purity, the organic principle of not chloride and salt enters reactor, thus whole technologic all metal materials is obtained tremendous change; Also making supercritical water oxidation plants be produced on material and select there is very big leeway, the cost of making also has substantial degradation.
Complicated component in waste water, but the acids of the corrosion of material there are hydrochloric acid, nitric acid, phosphoric acid, sulphuric acid, organic acid etc. by common waste water. Bases has sodium hydroxide, sodium hypochlorite, sodium nitrate, sodium chloride etc. Owing in different sodium salts common in sodium salt, all chloride this means that in this water acid, 300～500 DEG C, pH value 2～9, chloride concentration be 400mg/L when, the corrosion of multiple alloy has been carried out experimentation. It is shown that pH is little on the impact of corrosion in given temperature range. Under the subcritical state of 300 DEG C, owing to the dielectric constant of water and the dissolubility of inorganic salt are all relatively big, mainly based on electrochemical corrosion. When temperature rises to more than 400 DEG C, the dielectric constant of water and the dissolubility of salt decline rapidly, at this moment based on chemical attack, owing to this patent of this characteristic mainly gets off to complete to separate at 400 DEG C one. Due to temperature on inorganic salt impact very big, so the temperature near critical point or Near The Critical Point can complete to separate, but depend on temperature, the change of temperature affects the purity of inorganic salt, if temperature difference very conference forms very big change, not being single component containing electrodeless salt composition in waste water, the one-tenth of such isolated inorganic salt will produce composite parts. But after improving temperature a little, the composition of inorganic salt just has a very large change and is become single component namely from composite parts: sodium hydroxide. After waste water extracts sodium hydroxide, it is effective saving to supercritical water oxidation plants overall operation cost. Thus form the recycling economy of waste reclaimation, also promote commercial production and the enthusiasm processing waste water.
Above, this invention can be applied not only to remove the corrosive substance to equipment in Waste Water Treatment, it is also possible to is applied in desalination treatment system and removes sodium chloride, to industry extensive application prospect.
Above, the present invention having the prominent advantages that relative to prior art: the chlorine of supercritical separation purified wastewater and sodium in the pre-hot system within 400 DEG C, greatly reduce the waste water corrosion to supercritical water oxidation system device;Pre-hot system separation purification reclaims highly purified hydrogen chloride and sodium hydroxide, it is to avoid secondary pollution, reduces the cost of sewage disposal, reduces operating cost; Meanwhile, the material selectivity of supercritical water oxidation system device and manufacturing cost are added.
Accompanying drawing explanation
Fig. 1 is the structural representation of the pre-hot system of supercritical water oxidized organic wastewater treating system.
Detailed description of the invention
Embodiment 1
Referring to accompanying drawing 1, in figure, the pre-hot system in supercritical water oxygen organic wastewater treating system is 7 waste water pumps, 1～6 preheating device, purification devices 8, as schemed series connection, waste water enters from waste water pump 7, pass sequentially through preheating device 1～6, temperature is risen to 50 DEG C by preheating device successively, 100 DEG C, 150 DEG C, 250 DEG C, 300 DEG C, 400 DEG C, bulk temperature and pressure respectively temperature range is≤400 DEG C, pressure > 8.26Mpa, each device to prepare material that material removes according to temperature section different and different, for nickel-base material, to realize the separation purifying substance requirement to material under different temperatures different pressures, when device is warming up to 100～250 DEG C, realize the separation to chlorine, isolate hydrogen chloride, 250～400 DEG C make sodium be separated, the outlet of last preheating device 6 connects purification devices 8 and further supercritical organic wastewater treating system respectively, supercritical separating chlorine and sodium under implementation above different temperatures and pressure, purification devices 8 reclaims high-purity hydrogen sodium oxide, to reach to recycle the cost of the minimizing such as high-purity hydrogen chloride and sodium hydroxide process waste water.
Embodiment 2
The present embodiment is substantially the same manner as Example 1, and something in common does not repeat, and is different in that: preheating device can be arranged as required to the pre-heating device of varying number, can also be separated as other inorganic salts are issued to finite concentration in uniform temperature and pressure.
The above, it it is only the preferred embodiment of the present invention, the present invention not does any pro forma restriction, and every technical spirit according to the present invention, to any simple modification made for any of the above embodiments, equivalent variations and modification, all still falls within the scope of technical solution of the present invention.
Claims (6)
1. a supercritical water oxidation waste water preheating purification system, containing sewage pump, 1～6 preheating device, purification devices composition, it is characterized in that: described preheating device is in series, preheating temperature is stepped, temperature range is≤400 DEG C, pressure > 8.26Mpa, the temperature of this preheating device rises to 100～250 DEG C of stages, the chloride ion-containing material in supercritical separation waste water; Preheating device rises to 250～400 DEG C of stages, in supercritical separation waste water containing sodium ion material.
2. preheating device described in claim 1, it is characterised in that 1～3 preheating device temperature rises to 100 DEG C, 150 DEG C, 250 DEG C respectively, temperature when 150～250 DEG C, separating chlorine ionic species.
3. pre-heating system described in claim 2, it is characterised in that described chloride ion material is hydrogen chloride.
4. preheating device described in claim 1, it is characterised in that selected materials is the nickel based metal of unlike material.
5. supercritical preheating purification system described in claim 1, it is characterised in that it is high-purity hydrogen sodium oxide that purification devices purification reclaims material.
6. described in claim 1, preheat purification system, the application in sewage disposal system, desalination treatment system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610040723.3A CN105668891A (en) | 2016-01-20 | 2016-01-20 | Supercritical water oxidation waste water preheating and purifying system |
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| CN201610040723.3A CN105668891A (en) | 2016-01-20 | 2016-01-20 | Supercritical water oxidation waste water preheating and purifying system |
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Cited By (2)
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| CN108217785A (en) * | 2018-03-27 | 2018-06-29 | 楼龙春 | A kind of method and device of overcritical sea water desalination |
| CN111748834A (en) * | 2020-06-23 | 2020-10-09 | 东莞东阳光科研发有限公司 | Preparation method of electrode foil for aluminum electrolytic capacitor and electrode foil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111748834A (en) * | 2020-06-23 | 2020-10-09 | 东莞东阳光科研发有限公司 | Preparation method of electrode foil for aluminum electrolytic capacitor and electrode foil |
| CN111748834B (en) * | 2020-06-23 | 2022-03-04 | 东莞东阳光科研发有限公司 | Preparation method of electrode foil for aluminum electrolytic capacitor and electrode foil |
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Effective date of registration: 20180411 Address after: 224500 coastal industrial park of Yancheng City Binhai Economic Development Zone, Jiangsu (North District) Applicant after: Emperor Sheng Technology Co., Ltd. Address before: 310003 room 506, Jianguo North Road, Xiacheng District, Hangzhou, Zhejiang, China, 707 Applicant before: ZHEJIANG DISHENG TECHNOLOGY CO., LTD. |
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