TW503223B - Treatment of waste water - Google Patents

Abstract

This invention provides a method to efficiently purify waste water containing an ammonia component and/or a low boiling organonitrogen compound component and a metal component capable of forming a hardly soluble substance such as calcium while effectively preventing the formation of scale. Waste water is purified through two processes, that is, a diffusion treatment process of an ammonia component and/or a low boiling organonitrogen compound component and a decomposition treatment process of the diffused ammonia component and/or the low boiling-organonitrogen compound component and the diffusion treatment process is performed in the presence of a polymeric scale dispersant with an acid group concentration of 1-20 meq/g, a mol.wt. of 600-100,000 and a mol.wt. distribution of 1.2-7. The scale dispersant is added in an adequate timing.

Description

503223 V. Description of the invention 0) [Technical field to which the invention belongs] The present invention relates to a waste water treatment process that is discharged by chemical industry, electronic parts manufacturing, metal plating equipment, printing platemaking equipment, and power generation plants. Wastewater containing ammonia. More specifically, tw Q I is far from a wastewater treatment method that uses ammonia and organic gas compounds to decompose and purify low-boiling organic gas compounds, and decomposes and purifies organic nitrogen compounds. Specifically, the ammonia component and the low-boiling-point organic nitrogen compound are attached to the waste water in the heat exchanger subjected to the heat treatment, and the low-boiling-point organic nitrogen compound is removed and attached, so that the long-term stability and the rate can be further improved. When decomposing waste water containing organic compounds such as (dimethyl amide) and organic nitrogen compounds, the scale components in the removal tower and other places such as in the removal tower when the organic nitrogen compounds are boiled are removed. Efficient operation processing. [Conventional Technology] The method of removing ammonia from wastewater containing ammonia (ammonia stripping) is the best known. After the removal of ammonia, the waste gas is produced through the use of solid catalysts. The preparation, food equipment, and ingredients are related to the removal treatment during chemical treatment. The operating place of dimethylformamide is as low as that with which it can be prevented. Therefore, the system can be used to clean the processing equipment, and the photo processing is equipped with an organic nitriding device. The law system is a method that can prevent and remove ammonia to form scale components at the right time. Limeamine Boiling point organic nitrogen Decomposes ammonia and decomposes it for long-term safety. It is decomposed by ammonia stripping method and degassing treatment device by ammonia stripping method.

Page 5 503223 ϊ

V. Description of the invention (2) Purification with nitrogen. The ammonia stripping method and the steam stripping method and steaming ammonia-containing wastewater will increase the pH of the wastewater (even if the gas-liquid ratio effect is achieved. In addition, the steamed water will have a gas-liquid ratio as large as ammonia removal, and the decomposed compounds will be decomposed. Wastewater-based amines that decompose and apply amidoamine (the dimethyl method is the most commonly used in two methods, the gas stripping method. The ammonia is removed to make ammonia larger and the wastewater from Tinan is larger). By this method, although it is still good, ammonia can be generated or alkali can be added in low-line removal treatment, and it is known that amine). ^ With the & physical aspect, the well-known air extraction method is by blowing air Λ t method. In this air stripping method, the removal rate of ammonia between ίf and increasing the amount of blowing air is very large. The steam is blown into the temple containing ammonia by the steam. This method does not have the efficiency to remove ammonia as the air stripping method. For the organic image method of organic nitrogen compounds of Buddha, it is processed by transferring the air containing dioxin to decompose it into dioxin gas phase. However, the wastewater contains scale components such as calcium or magnesium. At this time, the above-mentioned components of water may adhere to heat exchangers, heaters, etc., and cause problems such as an increase in pressure loss and clogging. At this time, not only the degree of purification of waste water is reduced, but also the situation that it cannot be treated may be formed. The above phenomenon is particularly significant when the wastewater contains many carbonate ions.

[Problems to be Solved by the Invention] The object of the present invention is to provide a solution that can solve the above problems. That is, 'the waste water containing low boiling point organic nitrogen compound components and the waste water containing ammonia components are removed to improve the purification degree of the waste water. In addition, in the shape of 3 m, a heat that can prevent waste water from being subjected to heat treatment is also provided. 503223 Five 'Description of invention (3) Inside the exchanger, piping, and inside the removal tower of ammonia components and low-boiling organic nitrogen compounds A novel wastewater treatment method where scale components adhere to each other, and thus can perform long-term stable treatment. In addition, the invention also provides a long-term stabilization even when the organic nitrogen compound that decomposes ammonia and / or low-boiling organic nitrogen compound after decomposition is decomposed and the gas such as ambient air or steam is removed. Novel wastewater treatment method. Furthermore, it provides a novel wastewater treatment method which is convenient in terms of equipment cost and wastewater treatment operation cost. In addition, the present invention also seeks to decompose and purify the ammonia component and the low-boiling organic nitrogen compound component removed from the gas with high efficiency, so as to reduce the harmful substances discharged to the environment. In this case, harmful substances other than the ammonia component and the low-knot point organic nitrogen compound component removed from the gas can also be easily purified with high efficiency. 'In the process consisting of the 1st process (ammonia and low-boiling organic nitrogen compounds removal tower i and Ϊ2 process (catalyst reactor) ° Reli ί Τ ί tower has scale attached to it "may It can cause clogging of the removal tower, increase of droplets from the removal tower, etc., and if 0K > / Narita wounds on the catalyst, it will cause poisoning and other effects. Also, the burden will be on the catalyst. ^ ^ ^ That is to say, there will be a decrease in the treatment of the second project, and the gas pipeline or life. The clogging of the removal tower will be prone to flooding. ) The trouble caused by the phenomenon of two bows 丨 generally occurred, had to respond by washing the removal tower or = to prevent the above problems. The present invention is to solve the above: 503223 V. Description of the invention (4) Problem [Method to solve the problem] In order to solve the above problem, the inventor found a treatment method for treating wastewater containing ammonia-containing substances. In this method, the components are stably removed into the gas, and the gas is decomposed. Wastewater treatment The present invention is to add ammonia component and low boiling point organic nitride to the machine, so the ammonia component and other harmful substances removed from the waste gas can improve the purification degree of the waste water. As a result of intensive research on the above-mentioned problems, the waste water or novel waste water containing low-boiling organic nitridation and high purification degree of the waste water and ammonia components and low-boiling organic nitrogen compounds are further purified by using an exhaust gas treatment device. The present invention is therefore The complete scale inhibitor prevents the scale from becoming stable for wastewater treatment when the components are removed. This low-boiling organic nitrogen compound component is processed by the peripheral waste gas treatment device.

That is, the method of the present invention is a wastewater treatment method, which contains ammonia and / or low boiling point right after decomposition # Organic nitrogen compound component 50 ~ 200,000mg / l, and / or ammonia component ^ 500 ~ 200,000mg / l, and / or low-boiling organic f knives are used to purify wastewater containing 50 to 200,000 mg / l of compound and gold, 0.02 to 30 0 mg / 1, which will form insoluble substances. The injury _ X is characterized by: This method is composed of the first worker, M, and the second project to perform decomposition and decontamination; the first project is to make acid * r Mn ΠM octadecyl θ ^ base reduction degree is 20meq / g and the molecule is set to 600 ~ 100, and the molecular weight is 1 MW / MN = 1 2 ~ 7 Liter waste water Tim knows Λ · person 0.5 · 50 ~ 50 0mg ratio Tim

503223 V. Description of the invention (5) Add to wastewater to remove ammonia and / or low-level organic nitrogen compounds at pH 10 ~ 14; this second project will The ammonia component and / or low-boiling organic nitrogen compound component contained in the gas after the removal treatment is decomposed and purified by using a solid catalyst; and in the above-mentioned first project, the ammonia component and / or low-boiling organic nitrogen component are carried out. Before removing the chemical components, adjust the pH value of the wastewater, and add the polymer scale inhibitor before adjusting the pH of the wastewater and / or adjusting the pH. [Inventive Example] The method of the present invention is a novel method for treating wastewater, which involves heating and evaporating waste water containing ammonia and / or waste water containing low-boiling organic nitrogen compounds, and using air or steam to discharge waste water into the waste water. When the ammonia component and / or low boiling point organic nitrogen compound component is removed, and then the f water purification treatment is performed by decomposing the ammonia component and / or low boiling point organic nitrogen compound component of the gas ^ ^ Scale inhibitor is added to the wastewater to achieve long-term stability and continuous management. Rear protection lever I ί ΐ 51 ammonia and / or low-boiling organic nitrogen compounds into the " " " ^ treatment method is not particularly limited, for example, using a sleeve heater, multi-tube type Reboiler of heat exchanger, etc. Heating #. For example, in the W2 system, steam, hot kerosene, and hot water can be used directly. The ammonia gas and / or low-boiling organic nitrogen compound components can be used as a heat source after the material is divided into materials. Nitrogen-containing wastewater: Body: containing ammonia and / or low-boiling organic solvents. Regarding the gas used: a heater is required to bury it '503223 V. Description of the invention (6) = Air, steam, nitrogen, oxygen, argon and other gases or a mixture of the above can be used. The above contents also include the ammonia component and / or low sea point organic nitrogen component using solid catalyst to decompose and purify the processing gas and the gas released by other enemy equipment. 、 Ammonia in wastewater containing ammonia and / or low-boiling organic nitrogen components ^ Injury and / or low-boiling organic nitrogen components and purification treatment of wastewater% 'The ammonia-containing component and / or low boiling point Waste water of organic nitrogen ingredients $ heat. During the heating process, a heat exchanger or heater is usually mentioned. The higher the heating temperature is, the more purified the wastewater will be. 3 m ΐ L. If the heating temperature rises to a certain level, it will be significantly better, 50 ~ 9 (Γ. The problem of soil inspection is attached. Therefore, the heating temperature is 40 ~ 95 °. It is better to add it to the unit-it is better to add 0 °. The use of the liquid after removal and purification treatment and heat exchange in this case 32: = can effectively use the heat emitted It is better. However, the difference between the right and the bottom of the shape is 1. If the stress is less than 40 C, the heat recovery will be better than the metal in the square stove of the present invention ...! The metal components of iron, chromium, zinc, titanium, and two contained in the hardened armor: 2: !!!: Calcium, Zhen Erm The type of water is not special ... find. Names of the above-mentioned metal components

Concentration of metal components I (with two: limit f 'can be a compound or ion. 1

In terms of calcium, the concentration of calcium (i.e., i) is 0.02 to 3 mg / l. More J element for nose replacement) is 300 mg / 1, and manganese, iron, chromium, Ciyi, 3 ~ 50 mg / 1 is more preferred; while magnesium, chain, copper, each is 0.02 ~ SOmg / i, / fan and the concentration of nickel (in terms of element), preferably 0.3 ~ 30mg / 1,

503223 V. Description of the invention (7) • 05 ~ 20mg / l is better. In the case where there are many metal components that will form insoluble substances, the amount of scale inhibitor added can be increased to excess, so the wastewater treatment method of the present invention can be used to effectively remove the metal before treatment. Injury. On the other hand, if the metal component is small, the wastewater treatment method of the present invention can be maintained stably for a long period of time even if the wastewater treatment method of the present invention is not particularly used. The wastewater to be the subject of the method of the present invention may contain at least one kind of carbonate ion, phosphate ion component, and silicic acid ion in addition to the above-mentioned metal component. The carbonic acid ion component contained in the wastewater may be contained in the incoming wastewater, and in the present invention, a gas such as wastewater toilet air is mixed to dissolve and contain the carbonic acid gas in the gas. At least one of the above-mentioned carbonic acid ion component, phosphate ion component, and silicon, and the amount of the ion component is 2 to 100,000 mg / 1, and preferably 5 to 50, 000 mg / i, '1 〇 to 1 〇〇〇mgmg / 1 is more preferable. In the case where there are many carbonate ion components, by using the wastewater treatment method of the present invention, scale components can be effectively removed in advance before treatment. 1 Ming is particularly effective for wastewater containing carbonate ions, even in the case of a low ionic component. 'If the wastewater treatment method of the present invention is used, the long-term stable treatment can be further maintained. Saponin will react with osmium, sulphur, etc. to form insoluble obstructing salts, phosphorus ions will react with osmium and other reactions to form insoluble dish salts, and oxalic acid ions will react with magnesium, aluminum, calcium, etc. to form insoluble Silicate. In addition, when the concentration of lice oxide ions is also high, calcium, magnesium, aluminum, copper, fibrous, iron, chromium, zinc, nickel, titanium and other insoluble chlorine oxides and / or 503223% will be formed. Description of the Invention (8) Soluble oxide. The ammonia component contained in the wastewater which is the object of the method of the present invention is ammonia and / or ammonia ions. The amount of the above-mentioned ammonia component is 500 to 200,000 mg / l, and more preferably 1,000 to 100, 000 mg / i, and more preferably 2,000 to 50,000 mg / l. When the ammonia content is high, the amount of heat generated when the ammonia is treated by the exhaust gas treatment device becomes too large, thereby reducing the ammonia treatment performance. In addition, in this case, in order to suppress the temperature rise of the exhaust gas treatment device due to a large amount of heat generation, two large amounts of dilution gas must be made, and the device size becomes excessively large because of 1. On the other hand, when the ammonia content is small, even if the wastewater treatment method of the present invention is not used, the wastewater can be easily purified by biological treatment. In the compound method of the invention, even when the waste water contains low-boiling organic nitridation. Diamine a can be used to remove amines and organic nitrogen compounds after elaboration using 11-catalyst catalyst described below. For example, ′ may include amines such as tris (methyl butyl) methyl and dimethylamine. The amount of μ compound added and the amount of organic nitrogen compound is 50 ~ 200 οο〇ϋ-"It is better to have 〇〇 / 1, 500 ~ 50,000mg / 1 ', and 乂 100 ~ 100. In the case of exhaust gas treatment, shock treatment = 7. Nitriding, the amount of heat generated during the composition will become too large, thus reducing the processing performance of low-boiling and lice compounds. In addition, in this case; Eph = organic nitriding, resulting in The temperature of the exhaust gas treatment device is up: down = due to the large dilution gas, it is necessary to use a large amount of too much U, so the size of the device becomes too large. Ingredients ::: In the method 'even in wastewater Organic 4 containing low boiling point can be added after removal by using the solid catalyst described later; dagger combination 050323 Fifth invention description (9)

Examples of the low-boiling organic compounds include alcohols such as methanol, ethanol, and propanol; aldehydes such as acetaldehyde and formaldehyde; and solvents such as benzene, toluene, and dimethylbenzyl.

In the method of the present invention, the components of organic nitrogen compounds that generate ammonia and / or low-boiling organic compounds after decomposition are not particularly limited, and can be decomposed by hydration, such as hydrolyzing the base of a compound having an amidine bond. And amines (low-boiling organic nitrogen compounds) or amine compounds such as difluorenylamine, monomethylamine, and trimethylamine are formed. Specifically, for example, it can be decomposed into monomethylamine by adding alkali in wastewater containing monomethylformamide, and it can be decomposed into Dimethylamine and others. In addition, compounds such as hydrazine or urea which can be decomposed to generate amines and / or ammonium ions also belong to the object of the present invention that contains organic nitrogen compounds. In the present invention, when treating an organic nitrogen compound component containing ammonia and / or a low-boiling point organic compound after decomposition and a wastewater compounded with an ammonia component and a low stagnation point organic nitrogen compound component, the total amount of the component is expressed as It is preferably 50 to 200,000 mg / i, and more preferably 100 to 100, ⑽⑽g / 1, more preferably = 0 to 50,000 mg / i. When the above components are reported for a long time, they are treated with exhaust gas

f The amount of heat generated when this component is processed becomes too large, thereby deteriorating the processing performance of the component. In addition, in this case, in order to suppress the increase in the temperature of the exhaust gas treatment device due to a large amount of heat generation, & a large amount of diluting milk must be used: because the size of the decoration will become too large. _Therefore, 'the specific example of the wastewater that can be purified and treated in the present invention' can be exemplified as follows:

503223 V. Description of the invention (10) ① Wastewater containing 500 mg / 1 or more of ammonia and 0.02 mg / 1 or more of metal components that will form insoluble substances. ② A group consisting of 500 mg / l or more of ammonia, 0.02 mg / l or more of a metal component that forms a poorly soluble substance, and 2 mg / 1 or more of a free carbonate ion component, a phosphate ion component, and a silicic acid ion component Wastewater with less than one ionic component in mash. ③ Contains organic nitrogen compound components that generate ammonia and / or low-boiling organic compounds when decomposed at 50 mg / 1 or more, metal components that are difficult to form at a concentration of 0.002 mg / l or more, and metal components at 2fflg / 1 or more Wastewater containing at least one ion component selected from the group consisting of carbonate ion component, phosphate ion component and silicic acid ion component. ④ Waste water containing low boiling point organic nitrogen compounds of 50 mg / l or more, ammonia content of 500 mg / l or more, and metal components of Q 02 mg / i or more that form insoluble substances. The above-mentioned metal components that form insoluble substances refer to those that form insoluble solid-shaped substances (scale) in waste water. Representative examples include calcium, magnesium, aluminum, copper, manganese, iron, chromium, However, the above description is not intended to limit the present invention. The method of the present invention is a person who can purify waste water containing one or two or more kinds of metal-finding components. '' Except for ammonia and / or low-boiling organic nitrogen compounds and metal components that form insoluble substances, the wastewater containing carbonate ions, phosphate ions, and silicic acid ions is more effective than bismuth when purifying wastewater. Purification of wastewater without carbonate, phosphate and silicic acid ions

Page 14

503223

V. Description of the invention (11) Scale is more likely to be formed during treatment, but if the method according to the present invention is used, the wastewater that easily forms scale as described above can also be efficiently treated for purification. Therefore, the method of the present invention can also be applied to wastewater purification treatment like the above-mentioned ②③. x, In addition, if the concentration of the soluble silica is between 0.02 and 300 mg / l and the pH of the liquid supplied to the removal tower is 105 or more, scale will hardly be generated. · '

In the wastewater treatment method of the present invention, a heat exchanger or a heater is used when heating the wastewater to 3000 t. In addition, this heating process is particularly prone to scale adhesion. The total heat transfer coefficient of the heat exchanger or heater in this case is 10 to 3,000 kcal / m2h ° C, and it is assumed to be 50 to 2,000 kcai / m2h t: preferably, 100 to i, 500 kcal / m2h It's better. If the total thermal conductivity is less than 10kcal / ffi2h ° c, the size of the device becomes larger and worse. In addition, if it exceeds 3,000 kcal / m2h < 3C, the pressure loss will increase, and the increase of the pressure loss will increase with the increase of scale adhesion, so it is easy to cause difficult operation. A. In the method of the present invention, the polymer scale is based on a polymer scale with an acid group concentration of 20 ineq / g, a molecular weight of 600 to 100,000, and a molecular weight distribution of MW / MN = 12 to 7. Preventive agent in the presence of ammonia and / or low-boiling organic nitriding

The reason why the above-mentioned scale prevention agent is specified in the present invention is as follows for the removal treatment of chemical components. The amount of scale inhibitor is 0.5 ~ 500mg (0.5 ~ SOOmg / i) per liter of wastewater, and the effect of adding 200mg / 1 is better, and the effect of adding 2 ~ 100mg / i Better. When this amount is too small

Page 15 503223 # V. Explanation of the invention (12) Under the scale component, it will become easy to adhere and the effect of the present invention will not be exerted. On the other hand, if the amount of the scale inhibitor is added too much, the running cost will increase, and at the same time, too much scale inhibitor will remain in the liquid after the treatment of the present invention, which is not good.

The polymer-type scale inhibitor used in the present invention can reduce the running cost with a low addition amount. The polymer scale inhibitors include, for example, polymaleic acid and its salts, polyacrylic acid and its salts, polyacrylic acid and its salts, and copolymerization of acrylic acid and maleic acid. Compounds and their salts, copolymers of methacrylic acid and maleic acid and their salts, copolymers of acrylic acid and changmaric acid and their salts, copolymers of methacrylic acid and fumaric acid and their salts, Copolymers of (meth) acrylic acid and 2-hydroxy ethyl aery late and their salts, (fluorenyl) acrylic acid and 2-hydroxyethylated methacrylate (2-hydroxyethy 1 methacrylate) ) Copolymers and their salts, copolymers of (fluorenyl) acrylic acid and 3-allyloxy-2-acrylic acid sodium and their salts. Among the above, a (poly) acrylic acid sodium base, a copolymer of (fluorenyl) acrylic acid and a sulfonic acid group-containing monomer, and a copolymer of (meth) acrylic acid and a hydroxyl group-containing monomer are particularly preferred. In the case where the wastewater contains iron and aluminum, the copolymer of (meth) acrylic acid and a monomer containing a sulfonic acid group also has the same effect as a homopolymer of homopolyacrylic acid (homopoymer). In addition, when the wastewater contains calcium, magnesium, iron, copper, aluminum, etc., it is more effective to use a sodium polyacrylate-base homopolymer. The molecular weight of the polymer scale preventive agent must be 60 ~ 1 0 0, 0 0, and it is thought that 5,000 ~ 80,000 is more preferably 1 000 0 ~ 50, ⑽〇. If the molecule 1 503223 V. Description of the invention (13) The quantity is less than 600 or more than inn nnn, it must be increased, so it is not good. … The added amount of this scale preventive agent is 2 ～ 7. The molecular weight distribution of poly-type scale preventive agent has a MW / M ratio of 糸 is better than 2 ~ 4. The MW / MN ratio in the super fast 7 is too high. In the case of the scale preventive agent, the heart is over 7. In the case of full 1.2, due to silicon people, ^ ^ Wen Ji 乂 is not good. However, the production of A5 products will become more complicated, which makes the cost of the polymer higher and worse. U teeth are more complicated. The acid group 5 of the scale preventive agent used by Gome in the second example can be anionic groups such as sulphur clay, carboxymethyl and phosphate groups. The degree of the base of the preventive agent is expressed as 2 t li = Emole), and the acid group of the scale preventive agent of the present invention is 20 nieq / g, and preferably 5 to 18 ineq / g. When the acid group concentration is less than 1 meQ / g, the amount of the scale inhibitor must be increased, which is not preferable. In the case of more than 20 meq / g, the 'polymer is not good because the cost becomes high. In the process of removing gaseous wounds and / or low-level organic nitrogen compounds, the Qiu system of the wastewater sent to the removal tower is 10 ~ 14, and the ratio is 10.5 · 1 ~ 2 · 5. Good, 11 ~ 1 2 is better. When the pii of the wastewater is less than i 0, the gas-injury and / or low-removal-point organic nitrogen compound component removal performance will be reduced ', so it is not good. In addition, when the pH of the wastewater exceeds 4, the scale component is likely to become hydroxide and adhere to the machine, so it is not good. In particular, if the removal of ammonia and / or low-boiling organic nitrogen compounds is performed under the conditions of pH 10.5 ~ 12 · 5, the scale can be effectively prevented on the one hand, and at the same time it can be high. Efficient removal of ammonia and /

Page 17 503223 5. Description of the invention (14) or low boiling point organic nitrogen compounds. Therefore, in a preferred embodiment of the present invention, the above-mentioned ①④, especially 疋 ② or ③ is used to perform the ammonia component and / or the low-boiling organic nitrogen compound component under the conditions of ρΗ10 · 5 ~ 12 · 5. Remove treatment. In addition, in the case where iron is contained in the waste water, the removal of the ammonia component and / or the low-boiling organic nitrogen compound component can be performed efficiently by setting the waste water to a range of 10 to 12. Therefore, when the removal treatment of wastewater containing 0. 02 to 20 mg / l of iron is carried out, it is preferable to carry out within the range of "~ to ~, especially in the range of 10.5 to 12." Because it contains ammonia and / Or the low-boiling point organic nitrogen compound wastewater usually has a pH of less than 11, so adding alkali can effectively adjust the wastewater to the above pH range. When adjusting the p | j of the wastewater, sodium hydroxide and hydrogen can be added Caustic alkali such as potassium oxide or alkali such as slaked lime and magnesium hydroxide is used for treatment. However, when using calcium or magnesium-containing compounds such as slaked lime or magnesium hydroxide, it is not good because the amount of scale inhibitor must be increased. It is better to use caustic, and it is better to use sodium hydroxide in terms of cost. The addition of alkali during the pH adjustment can be directly added to the raw water tank of the wastewater. The pump is supplied to the pipeline used to supply wastewater to the removal unit. In addition, a pH adjustment tank can also be set up before the ammonia and / or low-boiling organic nitrogen compound removal treatment process, and additional information can be added there. PH of wastewater 4. In the whole 1〇~ Shu for the purposes in terms of easiness of pH adjustment 'to the alkali-based solution into the use state to the preferred, but of course also of use into a solid way to use.

503223 V. Description of the invention (15) ^ ----— The method and position of adding the scale preventive agent are not particularly limited, but it is more effective to add the scale preventive agent in the form of an aqueous solution. In addition, the scale can be added to the waste water ^ ^ raw water tank 'can also be added to the alkali for pH adjustment' can also be directly supplied to the removal treatment place by a supply pump Of the pipeline. However, when alkali is added to the wastewater to adjust the pH of the wastewater, the addition of the scale inhibitor is effective before the alkali is added (before the pH is adjusted). That is to say, by adding a scale preventive agent before adding alkali, the scale preventer can be reduced. 3t: 5 steps-adding the scale preventive agent directly to the pH adjustment test can also reduce the addition of scale preventive agent. the amount. Alternatively, Π Li can be split into multiple positions. As mentioned above, the polymer-type scale inhibitor is particularly effective in the treatment of wastewater that is added with the added magnesium powder before adjusting the pH of the wastewater ρΗβ ^ / or adjusting the pH.仃 3 Wei Tiehe

According to the present invention, the exhausted hemp P is organically treated with a gas such as air or water vapor; In addition, in this case, it can also be used to purify the waste water in the heat exchanger, the piping, and the removal tower boiling point where the waste water is subjected to heat treatment. The organic nitridation can be stabilized for a long time. The internal 3 is generated = part of the adhesion 'After the operation, there will be a small amount of scale adhesion G' also = the scale is washed when the long-term regular maintenance is observed, etc. = obstacle shape. In this case, it can also be more stable in maintaining long-term stable operation. Further, this move has water washing for washing at this time, washing with steam, and high utilization.

50322J V. Description of the invention (16) Examination > Grain solution for washing, using acid inflammation, spring: golden method, but using acid for washing with organic solvent, etc. B, 4 F1 surname Yin Zheng Another 4. In addition, when washing with acetic acid, the washing effect can be further enhanced by heating the two or two. The cleaning solution can be large and quantity; it is better than V can be recycled. The flow rate of the cleaning solution is based on the green + ^ ^ g used in the cleaning. For example, hydrochloric acid, sulfuric acid, nitric acid, and citric acid, oxalic acid, / sa 1j are preferred. The above is based on; it is better to select the appropriate one as "cleaning solution"). ; = Or sulfuric acid aqueous solution (hereinafter referred to as above Ug / i ==: 3 degrees of acid or salt, Mang nq Quan Jiaya is better k / 1, 10g / l is the best. The following Ξ t = XT When ', the washing effect will be lower; if it is between W. In addition,', the effect will be lower, and it takes a long time to wash and oxidize, etc.! Below, you must spend iron oxide or Short-term door ~ Zhiwei ^ scale component time. In this case, if you want to use two soils: first clean, you must wash under higher temperature washing conditions. It can also be based on the washed plants, sulphuric acid Aqueous solution and nitric acid solution, ―Dan and the type of scale, etc. will be used to slow down the solution. For the non-recorded steel, the sulfuric acid concentration of the sulfuric acid aqueous solution is very strong, and it can effectively make the device resistant to corrosion. But there will be two problems. There is also a method of heating with organic acids. The problem is that the treatment of C0D (the component that directly affects the COD value) is left.

> 03223 V. Description of the invention (17) '----- In the present invention, the material of the device to be cleaned is not particularly limited, but may include: ^ sus, titanium, Hastelloy (registered trademark), inc〇nei ( Registration * ΐίρ), such as vinyl chloride, polyethylene, polypropylene, Teflón (registered trademark). In the method of the present invention, after the removal treatment, the gas containing ammonia and / or low-budget organic nitrogen compounds ( The following only "gas") can be used to purify the waste gas treatment device m: gas generated from waste water tanks or other processes, such as alcohols such as methanol and ethanol, carbon monoxide, hydrogen and aldehydes such as acetaldehyde and acetaldehyde, etc. , Can also be processed using this exhaust gas treatment device. As for the exhaust gas treatment device, various kinds of exhaust gas treatment devices can be used. In addition, if a catalyst is used in this exhaust gas treatment device, it will be very effective. The above catalysts are not particularly limited. Any group containing oxides of at least one element from the group consisting of aluminum, titanium, silicon and thorium, and / or groups consisting of vanadium, tungsten, thorium, and iron The oxides of at least one of the elements and / or the catalysts of the metals and / or oxides of at least one element in the group consisting of free radicals, palladium, germanium, ruthenium, iridium, manganese and copper are all very suitable. In addition, the exhaust gas can be heated by various types of heat exchangers before the exhaust gas treatment is performed. Its treatment temperature can reach a good effect within the range of 200 ~ 500, and if it is 250 ~ 450 ° c Time is better. In addition, the space velocity of the gas is not particularly limited, and can be appropriately selected and used, but the effect is preferably below SOOh-1 and above 10,000h-1, and if it is above 1,000lr1 and above 50,000 0 Ir1 is better. Also, in this exhaust

V. Description of the invention (18) The oxygen-containing gas (preferably air) can be appropriately supplied during the treatment, and the supplier thereof is not particularly limited. '' When there is only one reactor in the second project, the catalyst in the reactor contains at least one 7L element oxide, which is selected from the group consisting of aluminum, titanium, silicon, and gadolinium. An oxide of at least one element in a group consisting of free vanadium, tungsten, rhenium, and iron, and / or a metal of at least one element in a group consisting of platinum, palladium, rhodium, ruthenium, t, manganese, and copper And / or oxidation 2 ::: Turbid medium can also be laminated with other catalysts and used in combination. In the case of a plurality of reactors, it is only necessary to fill the above-mentioned catalyst in the final reactor (that is, the closest to the hemp t anti-theft). Special restrictions. In addition, there is also a second-generation reactor. If used in the final reactor: 述 ii 灰 灰 t t t reduce the formation of NOx, and can decompose ammonia to purify and water with high efficiency. Person B, ΐΐ ΐΐ, introduced into the reactor and prepared to be treated with the above catalyst ^ 2 π The amount of oxygen at the Γ state inlet (the reactor closest to the outlet side) must be equal to or greater than the theoretical amount of oxygen at the inlet ammonia In terms of the theoretical term II, the amount of milk gas required in the following reaction formula relative to the amount of ammonia at the reactor inlet. When 2NH3 + (3/2) 02 N2 + 3Η20 # A H π contains low-boiling organic nitrogen compounds other than ammonia, or in the presence of oxygen, the above substances must be added for combustion. In this i, the amount of oxygen must take into account the decomposition of nitrogen-containing components into molecular nitrogen (chemical)

Page 22 503223 V. Description of the invention (19) ^ In the present invention, the treatment liquid after removal treatment can be used after performing any post-treatment such as pH adjustment or COD component treatment or can be directly put k is not particularly limited. "The waste water to be treated in the present invention includes, for example, factories in various industries such as chemical equipment, manufacturing equipment, food processing equipment, metal plating equipment, printing and printing equipment, power generation equipment, and photo processing equipment. The discharged wastewater and daily wastewater such as urine and dirty water, etc., but the treatment object of the present invention is not limited to the above. [Examples] Hereinafter, examples and comparative examples of the present invention will be described in detail. The present invention is not limited to the following. Example 1 Figure 1 shows an outline of a device configuration example for carrying out the method of the present invention, and it is illustrated in the figure. In the figure, it is a waste tank, and 2 is a waste water tank. Alkali tank (alkali tank), 4 is inspection supply pump, 5 is 1 η 6 preventive agent tank, 6 is scale preventive agent supply pump, 7, 2 = device, 8 is removal tower, 9 is air supply line , 12 are cold: ,,, and treatment liquid discharge pumps, 4 are treatment body discharge lines, 16 are air supply lines, "Yan Pi Yizha,", ", and & lines, and 18 are exhaust gas treatment devices. 1 〇〇〇 丨 Η As shown in Figure 1 above The device shown below is to be processed under the following conditions. The waste water supplied for treatment at this time is the waste water discharged from power generation. The waste water contains 5000mg / 1 of ammonia, and the first mg of touch mg. / 1 and wastewater with a carbonate ion of 40 mg / 1 and a pH of 9.5. F First, the wastewater will be supplied from the wastewater supply tank!

503223 5. Description of the invention (20) Pump 2 feeds (fee ^) at a flow rate of 1 1 / h (liters / hour), and ρ the heater with a total thermal conductivity of 3 0 0 kca 1 / m2 h ° C 7 After heating up to $ q ', it is supplied to the upper part of the removal tower 8. In this wastewater, a 25% by weight aqueous solution of sodium lice from alkaloid 3 was first used in a test pump 4 to be mixed with the wastewater before heating up by heating 7 to make the pH of the wastewater 2. In addition, the Taijiyu wastewater is also firstly supplied with 10% by weight of scale-preventing / stopping agent solution from the scale-preventing agent tank 5 to the pump 6 using the scale-preventing agent before the temperature is raised by the heater 7 and the pH is not adjusted Mix with wastewater first. In addition, after the scale inhibitor was added, the concentration of the scale inhibitor in the wastewater at this time was 25 mg / l. In addition, the added scale inhibitor is composed of a copolymer of acrylic sodium and 3-allyloxy-2-hydroxypropane sulfonate (copolymerization molar ratio: 85/15). The copolymer The molecular weight of the polymer was 20,000 ΛΛ, the molecular weight distribution was MW / MN = 2.5, and the acid group concentration was 8.9 meq / g. In the removal tower 8, the air sent from the air supply line 9 is heated to 20 ° C by the heater 10, and then supplied from the bottom of the removal tower 8 at 2 Mm3 / h. In addition, the inside of the removal tower 8 is filled in order to perform ammonia removal treatment with better efficiency! Liters of MacMahon type fill brothers. At the bottom of the removal tower 8, a liquid level controller (lic) is used to detect the liquid level, and a certain liquid level is maintained by the operation of the processing liquid discharge pump i 3, and cooled to 40 ° by a cooler 12 The treatment liquid below C is discharged through the liquid discharge line 14. In addition, the ammonia-containing gas system subjected to the removal treatment in the removal tower 8 is discharged from the gas discharge line 15 at the upper portion of the removal tower 8. The ammonia-containing gas is mixed with the air introduced from the air supply line 16 before the gas discharge line 15 and then heated by the heater 1. Pick up

Page 24

503223 5. Description of the invention (21) The mixed gas is sent to the exhaust gas treatment device 18, the inlet temperature of the device is 380 ° C, and the ammonia decomposition is performed with SV = 10,000lr1. The exhaust gas treatment device 18 is filled with the following catalysts. -<Catalyst> ~ A composite oxide composed of titanium dioxide and silicon dioxide is prepared by the method shown below. To 700 liters of 10% by weight ammonia water was added 20% by weight of si 1 ica sol 35.5 kg, and after stirring and mixing, an aqueous sulfuric acid solution of titanium dioxide (12.5 g of Ti02 / liter, 5 50 g H2S04 / liter) 300 liters dripping slowly while stirring. The obtained gel (gel_) was aged, filtered, and washed with water, and then dried at 150 ° C for 10 hours, and then baked at 50 ° C for 6 hours. The powder composition obtained is Ti02:

Si02 = 4: 1 (Molar ratio), and the BET specific surface area is 200 m2 / g (square meter / gram). Add 20 kg of this powder containing ammoniuin metavanadate 2. 00 kg and ammonium paratungstate 〇. 77 kg of 15% monoethanolamine aqueous solution 12 kg ', and then add starch as a forming aid And after kneading with a kneader (knea (jer)), a honeycomb shaped article having an outer size of 100 mm, an opening of 2 ^ 8 mm, a thickness of 0.5 mm, and a length of 45 mm was formed by an extruder. _ After the shape is dried at 80 ° C, it is baked at 45 ° t for 5 hours with air. The composition of this honeycomb shaped body is Ti—Si composite oxide: ^ Q = Q Π · 7 · Π ✓ Non ^ ζ ϊ) 3, Moribbi). The formed article was immersed in a solution of lithokic acid in water solution and dried at 150 C for 3 hours, and then placed under a temperature of 45 ° C.

503223 V. Description of the invention (22) _ J gas to bake for 3 hours. The composite of the obtained catalyst: ^^ 3 ^ = 89.1: 6.9: 3: 1 (weight ratio), and the fold reduction ratio table back product is 120m &quot; g, and the pore volume is 0.45cc / g. The gas processed by the exhaust gas treatment device 18 ^. Sampling of 4 and analysis using cation chromatography]] 80 hours, the treatment liquid discharged from the treatment liquid discharge line 14; into the second. At this time, analysis was performed using a cation chromatography analysis device. "Shigou" detected the presence of ammonia in both the mess and the treatment solution (the gas was not 1 ppm, and the physical solution was not full. /!). Then, at 10 〇〇Hours later: Fruit container 5 and removal tower? 'Pay special attention to whether water is attached: As a result, there is a scale adhering to Yawei's burnt offering. Comparative Example 1 = Device shown in Figure 1' Adding scale to prevent the weather; 2 conditions are the same as in the example &quot; treatment is the same. As a result, scale C made of horn and magnesium is attached to the C heater 7 and it is difficult to handle. In addition, check the removal tower Scale adhesion was also observed after 8. Example 2

The device 5 shown in Figure Λ 'of Figure 9 and the air supply line in Figure 1 was selected to be steamed, and subjected to continuous, ..., and shell treatment for 25 hours under the following conditions. The wastewater supplied for treatment at this time was the sample uOdei) wastewater. The wastewater was ammonia containing 1,000 mg / 1, calcium 15 mg / 1, magnesium 5 mg / ^, iron 2 mg / l, and carbonate ion 100 mg / 1. Wastewater with a pH of 4. First 'will use the waste water supplied from the waste water supply tank 1

503223 V. Description of the invention (23) The pump 2 is fed at a flow rate of 5 1 / h. The heater 7 with a total thermal conductivity of 300 kcal / m 2 h ° C is heated to 85 cC, and then supplied to the &amp; removal tower. 8 上部。 8 upper part. In the wastewater, 25 weights from the alkali tank 3 are firstly used. /. Aqueous sodium oxide aqueous solution is mixed with mill water by alkali supply pump 4 before heating up by heater 7 'to adjust the pH of the wastewater to 11 · 8. In addition, in this grinding, the scale preventive agent solution from the scale preventive agent tank 5 10% by weight of the aqueous solution of the scale preventive agent is pumped to the pump 6 before the temperature is raised by the heater 7 and the pH is not adjusted. Wastewater mixing. -In addition, after the scale inhibitor is added, the concentration of the scale inhibitor in the wastewater is 100 mg / 1 at this time. In addition, the added scale inhibitor is composed of a homopolymer of sodium propionate base, the molecular weight of the homopolymer is 5000 ′, the molecular weight distribution is MW / MN = 3, and the acid group concentration is 104me (j In the removal tower 8, the air in the air supply line 9 is changed to steam and sent out, and the temperature is maintained at 1 Q by a heater 10, and then from the bottom of the removal tower 8 to Supply is 2.5 kg / h. In addition, in order to perform ammonia removal treatment in the inside of the removal tower 8 with better efficiency, a 1-liter McMa type packing material is filled. The bottom of the removal tower 8 is The liquid level controller (LIC) is used to detect the liquid level, and the fixed liquid level is maintained by the operation of the processing liquid discharge pump 13, and the cooling liquid 12 is cooled to 4 (the processing liquid below rc is discharged through the liquid It is discharged through line 14. In addition, the ammonia-containing gas system subjected to the removal treatment in the removal tower 8 is discharged from the gas discharge line 丨 5 in the upper part of the removal tower 8. The ammonia-containing gas precedes the gas discharge line 15 It is mixed with the air supplied through the air supply line 16 and then heated by a heater 丨 7.

503223 5. Description of the invention (24) The mixed gas is sent to the exhaust gas treatment device 18, the inlet temperature of the device is 350 ° C, and the ammonia is decomposed by SVrSJOOlr1. The exhaust gas &amp; management device is filled with a touch &amp; medium of the same material as that used in the embodiment. The gas processed by the exhaust gas treatment device is sampled at intervals of 24 hours, and the analysis is performed by using a cation chromatography analysis device. In addition, the processing liquid discharged from the processing liquid discharge line was also sampled 24 hours apart 'and analyzed by a cation chromatography analysis device. As a result, the presence of ammonia could not be detected in either the gas or the treatment liquid (the gas was not full, and the treatment liquid was less than 1 mg / i). Then, the shaking installation was stopped after 250 hours, and the heater 5 and the removal tower 6 were inspected. As a result, no scale adhesion was observed. Comparative Example 2 &amp; The device shown in FIG. 1 was used, and in addition to changing the air in the air supply line 9 in FIG. 1 to steam, and the addition position and position of the scale inhibitor was changed to borrow The treatment was performed under the same conditions as in Example 2 except that the temperature was adjusted by the heater 7 and mixed with the wastewater after the pH was adjusted. The gas treated by the exhaust gas treatment device was sampled 24 hours apart 'and analyzed by a cation chromatography analysis device. In addition, the processing liquid discharged from the processing liquid discharge line 14 was also sampled at intervals of 24 hours, and analyzed by a cation chromatography analysis device. As a result, the presence of ammonia could not be detected in both the gas and the treatment liquid (the gas was less than 1 ρρπι, and the treatment liquid was less than 1 mg / 1). Then, the apparatus was stopped after 25 hours, and the heater 5 and the removal tower 6 were inspected. As a result, no scale adhesion was observed. Example 3

Page 28 503223 V. Description of the invention (25) Use the device as shown in Figure 1, and change the air in the air supply line 9 in Figure 1 to steam, and perform it for 2 500 hours under the following conditions. Continuous processing. The waste water supplied for treatment at this time is sample wastewater, which is 50 mg / l of ammonia and 500 mg of diamidoxamine; [, 15 mg / i of calcium, 1 mg / 1 of magnesium, and Carbonate ion 100 ％ / 丨 And what is Qiu? In the same way as in the wastewater, a 10% by weight aqueous solution of a scale inhibitor has been previously mixed with the wastewater as a scale inhibitor. In addition, after the scale inhibitor was added, the concentration of the scale inhibitor in the wastewater was 1 Q Q jjj g / 1. In addition, the added scale preventing agent is composed of a homopolymer of sodium acrylate and alkali, and the fraction of the homopolymer is 5000 ′ molecular weight distribution foot / ^ = 3, and the acid group is specifically 10.4meq / g. The above-mentioned liquid was sent into the waste water supply tank 1, and a 25% by weight sodium hydroxide aqueous solution was further added to the waste water supply tank 1 to adjust the waste water to 13. The waste water supplied from the waste water supply tank 1 was fed by the waste water supply pump 2 at a flow rate of 5 1 / h, and heated to a temperature of 8 (rc after the heater 7 with a total thermal conductivity of 300 kcal / m2hQC, and then supplied to the Remove the upper part of the tower 8. At this time, the alkali supply pump 4 and the scale preventive agent supply pump are not used. In the removal tower 8, the air in the air supply line 9 is changed to steam and sent out by a heater. The temperature was maintained at 1000 ° C, and then supplied from the bottom of the removal tower 8 at 2.5 kg / h. In addition, an ammonia removal treatment was performed in the inside of the removal tower 8 to achieve better efficiency. Therefore, it is filled with a liter of McMa-type filling material. At the bottom of the removal tower 8, a liquid level controller (LIC) is used to detect the liquid level, and the operation of the processing liquid discharge pump 丨 3 is maintained to ensure

Page 29

Chuan 3223 V. Description of the invention (26) Maintain a certain liquid level, and the processing liquid cooled by the cooler 12 to below 40 ° C is discharged through the liquid discharge line 14. In addition, the gas system containing male ammonia and dimethylamine in the removal section 8 passing through the removal section is discharged from the gas discharge line 15 at the upper part of the removal column 8.

The ammonia and difluorenylamine-containing gas are mixed with the air introduced into the tritium air supply line 丨 6 in the gas exhaust line 15 before being heated by the heater 17. The mixed gas is then sent to the exhaust gas treatment device 18, the inlet temperature of the device is 350 ° C, and the decomposition treatment of ammonia and dimethylamine is performed at SV ^ JOOh-1. The exhaust gas treatment device is filled with a catalyst of the same material as that used in the first embodiment. The gas treated by the exhaust gas treatment device was sampled 24 hours apart 'and analyzed by a cation chromatography analysis device. In addition, the treatment liquid discharged from the treatment liquid discharge line 14 was also sampled 24 hours apart 'and analyzed by a cation chromatography analysis device. As a result, the presence of ammonia could not be detected in the gas or in the treatment liquid (the gas was not full, ρριη, the treatment liquid was less than 1 mg / 1), and the fluorenyl ammonia in the gas was also not detected (the gas was not

Full lppm); the total nitrogen content in the treatment solution was 20 mg / i (in terms of nitrogen); while dimethylamine was detected in the treatment solution, but dimethylformamide was not detected. Then, the device was stopped after 250 hours, and the heater 5 and the removal tower 6 were inspected. As a result, no scale adhesion was observed.

Example A An effect confirmation test of a scale inhibitor was performed under the following conditions. At this time, the waste water supplied in the test was sample (mode 1) waste water. The waste water contained 2000 mg / l of ammonia, # 525 mg / l, 5 mg / l of tritium carbonate, and carbonate ion.

503223 V. Description of the invention (27) 200 mg / 1 wastewater with pH 7 °

In the test, the waste water was first placed in a container, and a 30% by weight aqueous solution of a scale inhibitor was added to the container in advance on the premise that the concentration of the scale inhibitor in the wastewater reached 7 mg / l, and then mixed and stirred. The added scale preventing agent is composed of a copolymer of sodium acrylate alkali and sodium 3-allyloxy-2-hydroxypropane sulfonate (copolymerization Morr ratio · 85/15). The molecular weight is 5000 'molecular weight distribution MW / MN = 2.5, and the acid group concentration is 8.9 meq / g. Further, a 25% by weight aqueous sodium hydroxide solution was then mixed with the waste water to adjust the pH of the waste water to il5. Furthermore, the container is hermetically sealed, and the closed container containing the wastewater is kept at 105 ° C on the premise that the temperature of the wastewater can reach ≧ 100 ° C or higher. 〇In a constant temperature heater, steam was used for 3 hours. Observing the waste water in the container before heating, no scale was found. When inspecting the waste water in the heated container, no scale was found. After the wastewater in Gu Er was filtered through a 0.2 micron membrane filter (membrane), the filtrate was analyzed by ICCP. As a result, 25 mg / 1 of calcium and ^ mg / i of magnesium were obtained, that is, the content of the original wastewater did not change. Therefore, it is impossible to confirm that no scale has been generated due to the precipitation of solid components through analysis and analysis. Example B

Except that the order of adding the scale inhibitor is changed, the other conditions are the same as those in Example 2 and the same steps as in Example A are performed to perform the effect confirmation test of the scale inhibitor. In the test system, the waste water was placed in a container, and 25% by weight of the hydroxide cold liquid was mixed with the waste water to adjust the water content of the waste water to 5.1.5. After that

503223 V. Description of the invention (28) Add the 30% by weight aqueous solution of scale inhibitor on the premise that the concentration of the scale inhibitor in the wastewater reaches 7mg / l and mix and stir it. In addition, the container is hermetically sealed, and before the temperature of the wastewater can reach 100 ° C or higher, the closed container containing the wastewater is statically placed in a constant temperature heater at 105 ° C and heated by steam. 3 hours. Observing the waste water in the container before heating, no scale was found. However, when inspecting the waste water in the heated container, you can see that there is some scale. The combined wastewater was filtered through a 0.2-micron membrane filter, and the filtrate was analyzed using cp. As a result, it was found that calcium was 15 mg / 1 and magnesium was lmg / 1, that is, the content of 1 in the original wastewater was changed. Therefore, it was confirmed from the analysis results that part of the scale was formed due to the precipitation of solid components.

Comparative Example A Except that no scale inhibitor was added, the other conditions were the same as those in Example 8. The same procedure as in Example A was performed at a pH of 15 of the wastewater to perform a confirmation test. innv · One hundred, first, the container should be sealed tightly, so as to make the temperature of the wastewater reach the level of imitation &amp; so that the closed container containing the wastewater should be placed at 105 °: mouth 2 | § use of radon gas Heat for 3 hours. Observe '7 in the container before heating, head: No scale is seen. Observe that the wastewater in the container after heating is wailing, and there is scale in the flood. The effluent in the container was passed through a 0.2-micron film, and then, the analysis was carried out using ICP. As a result, the obtained angle is changed, and squeezed below \ 01mg / 1. That is, the content of the original waste water has been reported. The result of multi-scale scaling analysis can confirm that it was formed due to the precipitation of solid components.

Page 32 503223 V. Description of the invention (29) Example C1 has the same procedures as in Example A. The effect confirmation test of scale inhibitor is performed under the following conditions. At this time, the waste water supplied in the test was sample waste water. The waste water was ammonia containing 2000 mg / l, -1 mg / 1, magnesium 1 mg /; l, iron 7 mg / 1, copper 2 mg / l, and carbonate ion 50 mg / 1. And? 11 is wastewater of 3. In this test, the waste water is first placed in a container, and a 30% by weight aqueous solution of the scale inhibitor is added in advance on the premise that the concentration of the scale inhibitor in the wastewater can reach 20 mg / l, and then mixed and stirred. The added scale inhibitor is a homopolymer of sodium acrylate and alkali. The molecular weight of the homopolymer is 5000, the molecular weight distribution is MW / MN = 3, and the acid group concentration is 〇e6meq / g. In addition, a 25% by weight aqueous sodium hydroxide solution was then mixed with the wastewater to adjust the wastewater to = 11. Furthermore, the container was surely sealed, and the closed container containing the wastewater was statically placed in a constant temperature heater at 105 C for 3 hours under the premise that the degree of wastewater could reach 100 ° C or more. . Observing the waste water in the container before heating, no scale was found. However, when inspecting the wastewater in the heated container, no scale was found. After the wastewater in the device was filtered through a 0.2 micron membrane filter, lcp was used to separate the filtrate. As a result, the calcium content was 1 mg / l, magnesium was 1 mg / 1, iron was 7 mg / i, and ^ was 2 mg / 1. That is, the content of the original wastewater has not changed. Therefore, it can be confirmed from the analysis results that it is not due to solid shape. The precipitation of the ingredients produces scale. In Example C2, the effect of the scale inhibitor was confirmed in the same manner as in Example C1 except that the amount of the scale inhibitor and the adjusted pH were the same. In this test, the same waste as that used in Example 01 was first used.

503223 V. Description of the invention (30) --- Put water in the container and add 10% by weight of the same scale preventive agent as in Example ^ in advance on the premise that the concentration of the scale preventive agent in the wastewater can reach 50 ing / l. The aqueous solution was mixed and stirred. Furthermore, a 25% by weight aqueous sodium hydroxide solution was mixed with the waste water to adjust the waste water to 12. Next, the same operations as those in Example C1 are performed. 2. Observe the content of heating Θ | § Wastewater, no scale is found. However, when the waste water in the container after heating, there is a little scale present. The internal wastewater was filtered through a 0.2-micron membrane filter, and the filtrate was analyzed using cp. As a result, it was found that calcium was 1 mg / 1, magnesium was 0.5 mg / 1, iron was 2 mg / 1, and copper was 1 mg / 1, that is, the content of the original wastewater was changed. Therefore, it can be confirmed from the analysis results that the Precipitation formed scale. Example C3 The conditions were the same as in Example C2, except for the amount of the scale inhibitor added, and an effect confirmation test of the scale inhibitor was performed. In this test, the same wastewater as the user used in Example ^ was first placed in a container, and added in advance under the premise that the concentration of scale inhibitor in the wastewater could reach 100 mg / l. 10% by weight of the same water-preventing solution as in Example 0 was mixed with the water solution. Then proceed with the same steps as the implementation. Observing the waste water in the container before heating, no scale was found. When the waste water in the heated container was observed, no scale deposits were also observed. After the heated waste water in each container was filtered through a 0.2-micron membrane, the filtrate was analyzed using 1 cp. As a result, calcium was 1 mg / 1, osmium was 1 mg / 1, iron was 7 mg / 1, and copper was 2 mg / l.

Page 34 503223 V. Description of the invention (31) 1. There is no change. Therefore, it can be confirmed from the analysis results that no scale is formed due to the precipitation of solid components. Example C4 Except for the addition amount of the scale inhibitor and the adjusted pH, the other conditions were the same as those of Example C1, and an effect confirmation test of the scale inhibitor was performed. In this test, the same wastewater as that used in Example ^ was first placed in a container, and the concentration of scale inhibitor in the wastewater was increased to 500 mg / 1 in advance. The same scale inhibitor aqueous solution as in Example C1 was mixed and stirred. Furthermore, a 25% by weight aqueous sodium hydroxide solution was mixed with the wastewater to adjust the pH of the wastewater to 12.5. Next, the same steps as those in Embodiment C1 are performed. # ^ Observe the waste water in the container before heating. No scale was found. When observing the wastewater in the heated container, no scale was found in the same way. The heated waste water in the container was filtered through a 2 micron membrane filter, and the filtrate was analyzed by icp. As a result, calcium * lfflg / 1, magnesium was 1 mg / 1, iron was 7 mg / 1, and copper was 2 mg / 1, that is, the content of the original wastewater did not change. Therefore, it can be confirmed from the analysis results that it is not due to solid components. Scale out. Example C5 Except for the addition amount of the scale inhibitor and the concentration of the iron component contained in the waste water, the conditions were the same as in the example, and the effect confirmation test of the scale inhibitor was performed. The wastewater used for the test was sample wastewater. The wastewater was different from the C · water in Example C4, and only the iron component concentration was changed. The iron component content was

Page 35 503223 V. Description of the invention (32) The adjustment becomes 2mg / l. In the test, the waste water was placed in a container, and 10% by weight of the same scale prevention agent aqueous solution as in Example C1 was added in advance under the premise that the concentration of the scale prevention agent in the wastewater reached 50 mg / i. . Then, the same steps as those in Example C4 are performed. No scale was found in the wastewater in the container before and after heating. After filtering the internally heated waste water through a 0.2-micron membrane filter ', the filtrate was analyzed by ICP. As a result, the feed was 1 mg / 1, magnesium was ImgU, iron was 2 mg / 1, and copper was 2 mg / l. That is, the content of the original wastewater did not change. Therefore, it can be recognized from the analysis results that it is not due to solid components. It precipitates to form scale. 1

Comparative Example B A confirmation test was performed under the same conditions as in the implementation except that no scale inhibitor was added. In the test, the same wastewater f as the user used in Example C1 was first placed in a container, and a 25% by weight aqueous sodium hydroxide solution was mixed with the wastewater to adjust the pH of the wastewater to 11. Next, the same operation as that in Example 01 is performed. No water was seen in the waste water in the container before and after heating. After the heated waste water in the container was filtered through a 0.2 micron membrane filter, the filtrate was analyzed by ICP. As a result, it was found that calcium was 八, and magnesium was Qi iron, and the detection limit was below 1 (mg / i). 1 mg / i, that is, the content of the original waste water was confirmed. ^ It was generated by the precipitation of solid components. Scale. Do not

503223

Comparative Example c A test for confirming the effect of the scale inhibitor was performed under the same conditions as in Example C1, except that the scale inhibitor was changed. In this test, the wastewater is first placed in a container, and a 30% by weight aqueous solution of the scale inhibitor is added in advance under the premise that the concentration of the scale inhibitor in the wastewater can reach 20 mg / 1, and then mixed and stirred. The added scale inhibitor is composed of a copolymer of acrylic acid and ethyl ester of acrylic acid (copolymerization molar ratio: 6/94). The molecular weight of the copolymer is molecular weight distribution MW / MN = 9, acid group concentration was 0.52 meq / g. Next, the same steps as those in the second example C1 are performed. No scale was found in the wastewater in the container before and after heating. The heated wastewater in the container was filtered through a 0.2-micron membrane filter, and the filtrate was analyzed by I CP. As a result, calcium was 丨 mg / 1, magnesium was 1mg / 1, iron was 2mg / l, and copper was 1mg / i, that is, the content of the original wastewater had changed. Therefore, it can be confirmed from the analysis results that it is due to the precipitation of solid components. Scale is formed.

Example D Except for changing the scale preventive agent, the conditions were the same as in Example C1, and an effect test for the effect of the scale preventive agent was performed. In this test, the waste water was first placed in a container, and 30 weight was added in advance under the premise that the scale inhibitor concentration in the waste water could reach 20 mg / l. % Scale inhibitor aqueous solution was mixed and stirred. The added scale inhibitor is composed of a homopolymer of maleic acid, the molecular weight of the homopolymer is 60 0, the molecular weight distribution MW / MN = 1.3, and the acid group concentration is

503223 V. Description of the invention (34) 17. 2meq / g. Next, the same steps as those in the embodiment ci are performed. No scale was found in the wastewater in the container before and after heating. The heated wastewater in the container was filtered through a 0.2-micron membrane filter 'and the filtrate was analyzed by ICP. The result was converted to 1 fflg / 1, magnesium was ling / 1, iron was 7mg / l, and copper was lmg / 1, that is, the content of the original wastewater had hardly changed. Therefore, it can be confirmed from the analysis results that it is not due to solid components. It precipitates to form scale.

Example E The effect confirmation test of a scale inhibitor was performed under the following conditions. The waste water supplied for the test at this time was sample waste water, and the waste water was waste water containing ammonia 2000 mg / l, calcium 3 mg / l, magnesium 1 mg / 1, and carbonate ion 50 mg / l and having a pH of 7. In this test, the waste water is first placed in a container, and 30% by weight of the scale inhibitor water> Valley liquid is added in advance on the premise that the scale inhibitor concentration in the wastewater can reach 0.5 mg / l. . The added scale inhibitor is composed of a homopolymer of sodium acrylate and alkali. The molecular weight of the homopolymer is 5000, the molecular weight distribution is MW / MN = 3, and the acid group concentration is 〇e6meci / g. In addition, '25% by weight sodium hydroxide aqueous solution is then mixed with the wastewater to adjust the pH of the wastewater to 11. Furthermore, the container was hermetically sealed, and the sealed container containing the wastewater was statically placed in a constant temperature heater at 105 C for 3 hours under the premise that the temperature of the wastewater could reach 100 ° C or more. Observing the waste water in the container before heating, no scale was found. And when observing the waste water in the heated container, there was no scale deposit. The waste water in the container was filtered by a 0.2 micron membrane filter, and then separated by 丨

503223 V. Description of the invention (35) Analytical filtrate. As a result, the content is almost free of precipitation of the constituents. [Effect of the invention] Regarding the present invention, the stagnation point organic nitride compound and organic nitrogen compound remain in the treatment solution. The love component of this part is difficult to form, and it is difficult to produce water. From the catalyst, [the diagram is abbreviated to the right] According to the present invention, the symbol is 3 mg / l for fresh and 1 mg / 1 for magnesium. From the analysis results, it was confirmed that no scale was formed due to solids. The method is to remove ammonia and low-boiling point damage to the exhaust gas by removing the ammonia and low-level components in the wastewater. By the above treatment, the amount of the ammonia component and the organic nitrogen compound component can be reduced, and the amount can be improved. In addition, the exhaust gas can also be treated with exhaust gas, so it has very excellent environmental protection effects. ▼ ·-q w π worry that the water in the calendar contains limescale and stable continuous operation. That is to say, scale metals can be dealt with in a timely manner. The reason is that the removal tower will not produce from the removal tower: fly; fixed treatment. The problem of poisoning, etc. will increase. Therefore, it can be solved simply] 1 is shown as a solid silk diagram. A general description of the device configuration example of the method] Wastewater tank; 2 ~ Wastewater supply pump;

503223 V. Description of the invention (36) 3 ~ alkali tank; 4 ~ alkali supply pump; _ 5 ~ scale prevention agent tank; 6 ~ scale prevention agent supply pump; 7 ~ heater; 8 ~ removal tower; 9 ~ air supply 10 ~ heater; 11 ~ steam supply line; 12 ~ cooler; 13 ~ treatment liquid discharge pump; 14 ~ treatment liquid discharge line; 15 ~ gas discharge line; 16 ~ air supply line; 17 ~ heater; 18 ~ exhaust gas treatment device.

Page 40

Claims (1)

Public version of L, ft --- ~ ::.,.: J VI. Scope of patent application 1 · A method of wastewater treatment, the treatment method is for organic nitrogen compounds containing gas and / or low Buddha point after decomposition. Organic nitrogen compound component 50 to 200,000 mg / l, and / or ammonia component 500 to 200'ooomg / i, and / or low &gt; Freud point organic nitrogen compound component 5 0 to 2 0 0, 0 0 0 mg / 1 and waste water that will form metal components that form insoluble substances 〇. 〇2 ~ 300mg / 1 The wastewater is subjected to purification treatment, which is characterized in that: This method is the first process of the removal process and the second process of decomposition and purification Composition: In the first engineering system, the acid group concentration is 1 to 20 meq / g and the molecular weight is The polymer scale inhibitor with a molecular weight distribution of MW / MN = MW / MN = L2 to 7 is added to 60 to 100,000, and is added to the waste water at a ratio of 0.5 to 50 0 mg per 1 liter of wastewater so that the pH of the wastewater is 10 Removal of ammonia and / or low-boiling organic nitrogen compounds under conditions of ~ 14; The second project is to remove ammonia and / or low-boiling organic nitrogen compounds from the gas after the removal process. Use solid catalyst to decompose and purify; and 'In the first project mentioned above, adjust the suppression value of the wastewater before removing the ammonia component and / or low boiling point organic nitrogen compound component, and adjust the pH of the wastewater The polymer scale inhibitor is added at the time and / or before the pH is adjusted. — 2 · The wastewater treatment method described in item 1 of the scope of the patent application, wherein the metal component that will form a poorly soluble substance is selected from calcium, magnesium, aluminum, copper, manganese, iron, chromium, zinc, titanium, vanadium, and nickel More than one metal in the group. Page 41 503223 P VI. Patent application scope 3 · The wastewater treatment method as described in item 2 of the patent application scope, wherein the calcium content in the wastewater is 0 ·:! ~ 200mg / l, and magnesium, aluminum, copper, The content of manganese, iron, chromium, zinc, titanium, vanadium, and nickel are 0.02 to 50 mg / l. The wastewater treatment method according to item 1, 2, or 3 of the scope of patent application, wherein the wastewater is In order to further contain a carbonate ion component of 2 to 100,000 mg / l and / or a phosphoric acid component of 2 to 100,000 mg / 1. 5. The wastewater treatment method according to item 1, 2, or 3 of the scope of the patent application, wherein the i-th project uses a heat exchanger or heater with a total thermal conductivity of 10 to 3,000 kcal / m2h ° C Heated to 30 ~ 100. . Air and / or water vapor is then used to remove ammonia and / or low-boiling organic nitrogen compounds from wastewater. 6. The wastewater treatment method according to item 1 of the scope of the patent application, wherein the wastewater containing at least iron 0.02 to 20 mg / l of a metal component that forms a poorly soluble substance is used to make the wastewater of the first project described above Removal of ammonia and / or low-boiling organic nitrogen compounds at a pH of 12 or lower. 7. The waste water treatment method described in item i, 2 or 3 of the scope of the patent application, where the catalyst used in the reactor in the case where the second project is composed of one reactor or in the second In the case where the engineering system is composed of a plurality of reactors, the catalyst used in the reactor closest to the outlet side is the oxidation of at least one of the groups consisting of the following free radicals, titanium, stone and zirconium Thing and # Sixth, the scope of patent application = lice compounds in the group consisting of free H decoration and iron and / or at least one type of vowel in the group of free platinum, palladium, germanium, and tritium. <_ 所Group 矸 芏 乂 1 metal and / or oxide of the element; and „0: 500 t under the condition of the reactor port closest to the outlet side of the oxygen amount is above the theoretical oxygen relative to human π ammonia amount 8 · The wastewater treatment method according to item 4 of the patent application of Shenyang, wherein the wastewater contains at least iron 0.02 ~ 20mg / i as a metal component capable of forming a poorly soluble substance so that the above In the first project, the pH of the wastewater is below 12 to remove ammonia and / or low-boiling organic nitrogen compounds. · 9 · The wastewater treatment method according to item 5 of the scope of patent application, wherein At least 0. 02 to 20 mg / l of iron is used as a metal component that can form insoluble substances. The ammonia component and / or low-boiling organic nitrogen compound component is carried out under the condition that the pH of the wastewater in the first process is below 12 Its removal treatment. Page 43