TW202122146A - High-concentration iron-based flocculant and manufacturing method thereof - Google Patents
High-concentration iron-based flocculant and manufacturing method thereof Download PDFInfo
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Abstract
Description
本發明係關於一種使用於廢水處理之高濃度的鐵系凝集劑及其製造方法。 The present invention relates to a high-concentration iron-based coagulant used in wastewater treatment and its manufacturing method.
本案專利申請人係以獨自開發出之鐵系無機高分子凝集劑「聚鐵」(註冊商標)作為中心而進行廢水處理藥劑之販賣，並具有一些關於此之專利。 The patent applicant in this case is selling waste water treatment chemicals with the iron-based inorganic polymer coagulant (registered trademark) as the center, and has some patents on this.
此等專利之中，在專利文獻1係已記載於作為鐵系原料之硫酸鐵(II)(FeSO4)溶液添加亞硝酸鈉及氧化劑作為觸媒，而以常溫常壓耗費約10小時左右的時間進行氧化反應，以獲得聚硫酸鐵(III)([Fe2(OH)n(SO4)3-n/2]m，其中，0<n≦2，m為自然數)溶液之方法。 Among these patents, Patent Document 1 describes that iron (II) sulfate (FeSO 4 ) as an iron-based raw material is added with sodium nitrite and an oxidizing agent as a catalyst, and it takes about 10 hours at room temperature and pressure. Time to perform oxidation reaction to obtain polyiron(III) sulfate ([Fe 2 (OH) n (SO 4 ) 3-n/2 ] m , where 0<n≦2, m is a natural number) solution.
惟，該方法在反應時需要長時間，故尋求藉由某些方法使反應時間縮短化。 However, this method requires a long time during the reaction, so some methods are sought to shorten the reaction time.
又，在專利文獻2所記載之鐵系無機凝集劑的製造方法係使用磁鐵礦(Fe3O4)作為鐵系原料，調整硫酸根離子與鐵離子之莫耳比後，在密閉容器中以120至180℃之溫度使其反應的方法。該方法係藉由在高溫高壓下進行反應，以達成反應時間縮短化為目標之製造方法，但即使如此，亦仍需要0.8至1.5小時之反應時間。
In addition, the method for producing an iron-based inorganic coagulant described in
在專利文獻3係揭示一種鐵系凝集劑之製造方法，其係使作為鐵系原料之三氧化二鐵(Fe2O3)溶解於過剩之硫酸中而生成硫酸鐵(III)(Fe2(SO4)3)，將此以含水的三氧化二鐵進行部分中和。 Patent Document 3 discloses a method for producing an iron-based coagulant, which dissolves iron trioxide (Fe 2 O 3 ) as an iron-based raw material in excess sulfuric acid to produce iron (III) sulfate (Fe 2 ( SO 4 ) 3 ), this is partially neutralized with hydrated iron trioxide.
惟，由於該方法係由使三氧化二鐵溶解於硫酸之步驟、及將所生成之硫酸鐵(III)進行部分中和之步驟的2種步驟所構成，故有製造步驟變複雜，無法有效率地生成聚硫酸鐵(III)溶液之困難點。在實施例係必須以加熱至100℃之狀態保持3小時左右，並進行反應。 However, since this method is composed of two steps: a step of dissolving ferric oxide in sulfuric acid and a step of partially neutralizing the produced iron(III) sulfate, the manufacturing steps become complicated and cannot be used. Difficulties in efficiently generating polyiron(III) sulfate solution. In the example, it is necessary to keep the state heated to 100°C for about 3 hours before proceeding with the reaction.
[先前技術文獻] [Prior Technical Literature]
[專利文獻] [Patent Literature]
專利文獻1：日本特公昭51-17516號公報 Patent Document 1: Japanese Patent Publication No. 51-17516
專利文獻2：日本專利第3379204號公報 Patent Document 2: Japanese Patent No. 3379204
專利文獻3：日本專利第2741137號公報 Patent Document 3: Japanese Patent No. 2741137
如上述，在習知技術中，曾嚐試過選擇各式各樣的種類之鐵化合物作為鐵系原料，以各種的反應形態進行反應而製造聚硫酸鐵(III)溶液，但不僅游離硫酸或反應殘渣產生較多等之問題，尚殘留有用以製造耐用之聚硫酸鐵(III)溶液的製造時間變長之問題。 As mentioned above, in the prior art, attempts have been made to select various types of iron compounds as iron-based raw materials, and react in various reaction forms to produce polyiron(III) sulfate solutions, but not only free sulfuric acid or reaction There are many problems such as the generation of residues, and there is still a problem that the production time for making durable polyiron(III) sulfate solution becomes longer.
又，詳細內容係後述，但在鐵系凝集劑中，總鐵濃度愈高，作為凝集劑之特性會愈高。接著，本案專利申請人係製造販賣鐵系無機高分子凝集劑「聚鐵」(商 標註冊)，其總鐵濃度大概為11.0至12.5%(稱為「一般品」)。鐵系無機高分子凝集劑若其總鐵濃度為高濃度，則具有高的凝集能力與脫水性，故在近年，遂製造販賣總鐵濃度為12.5以上者作為「高濃度品」。 In addition, the details are described later, but in the iron-based coagulant, the higher the total iron concentration, the higher the characteristics of the coagulant. Next, the patent applicant in this case manufactures and sells iron-based inorganic polymer coagulant "polyiron" (commercial Standard registration), its total iron concentration is approximately 11.0 to 12.5% (called "general products"). Iron-based inorganic polymer flocculants have high aggregation power and dehydration if the total iron concentration is high. Therefore, in recent years, those with a total iron concentration of 12.5 or more have been manufactured and sold as "high-concentration products."
然而，即使製造總鐵濃度高的凝集劑，與上述之製造時間變長的問題亦為相關，頂多以總鐵濃度為12.7%左右(未達13%)者為極限，並無法製造13.0%以上之聚硫酸鐵(III)溶液作為市售品。 However, even if a flocculant with a high total iron concentration is manufactured, it is related to the aforementioned problem of longer manufacturing time. At most, the total iron concentration is about 12.7% (less than 13%) as the limit, and 13.0% cannot be manufactured. The above polyiron(III) sulfate solution is a commercially available product.
又，除了明確記載莫耳濃度的情形以外，本發明中之濃度全部意指重量%，[T-Fe]表示總鐵之重量濃度，[SO4 2-]表示硫酸根離子之重量濃度。 In addition, unless the molar concentration is clearly stated, the concentration in the present invention all means wt%, [T-Fe] represents the weight concentration of total iron, and [SO 4 2- ] represents the weight concentration of sulfate ions.
在此所謂總鐵濃度不僅包含溶解於原料之鐵，亦包含未溶解而以固體(粉體等)的形式存在於原料液中之鐵。即使為存在於原料液中之鐵系粉末，亦有助於聚硫酸鐵(III)溶液之製造反應，故鐵的濃度亦包含未溶解於原料液中之鐵系成分為合理。 The total iron concentration here includes not only the iron dissolved in the raw material, but also the undissolved iron that exists in the raw material liquid in the form of a solid (powder, etc.). Even if the iron-based powder exists in the raw material liquid, it contributes to the production reaction of the polyiron(III) sulfate solution, so it is reasonable that the concentration of iron includes iron-based components that are not dissolved in the raw material liquid.
惟，在本發明所製造之聚硫酸鐵(III)溶液，雖然亦以總鐵濃度表示濃度，但鐵當然已完全溶解。 However, in the polyferric(III) sulfate solution produced by the present invention, although the concentration is also expressed by the total iron concentration, the iron is of course completely dissolved.
本發明係為解決此等課題而研創者，在於提供一種相較於習知品，可以短時間製造總鐵濃度高的聚硫酸鐵(III)溶液之製造方法。 The present invention is a researcher and creator to solve these problems, and is to provide a method for producing a polyiron(III) sulfate solution with a high total iron concentration in a short time compared to conventional products.
為解決此等之課題，本發明係由如下之技術的手段所構成者。 In order to solve these problems, the present invention is constituted by the following technical means.
(1)一種鐵系凝集劑之製造方法，該鐵系凝集劑含有聚硫酸鐵(III)溶液，而該製造方法包含使滿足下列條件之包含硫酸鐵(II)及硫酸的原料液在密閉容器中於高溫高壓條件下進行反應； (1) A method of manufacturing an iron-based coagulant, the iron-based coagulant containing a polyiron(III) sulfate solution, and the manufacturing method includes placing a raw material liquid containing iron(II) sulfate and sulfuric acid in a closed container that satisfies the following conditions The reaction is carried out under the conditions of high temperature and high pressure;
總鐵與硫酸根離子之莫耳比(SO4 2-/T-Fe)為1.2以上， The molar ratio of total iron to sulfate ion (SO 4 2- /T-Fe) is 1.2 or more,
將硫酸根離子之重量濃度設為[SO4 2-]時，[SO4 2-]為35重量%以下。 When the weight concentration of sulfate ions is [SO 4 2- ], [SO 4 2- ] is 35% by weight or less.
(2)如(1)所述之鐵系凝集劑的製造方法，係在密閉容器中進一步加入硝酸或亞硝酸鹽作為觸媒。 (2) The method for producing an iron-based coagulant as described in (1), wherein nitric acid or nitrite is further added as a catalyst in a closed container.
(3)如(1)或(2)所述之鐵系凝集劑的製造方法，其中，高溫高壓之反應條件為溫度100℃以上、壓力0.3MPa以上。 (3) The method for producing an iron-based coagulant as described in (1) or (2), wherein the high-temperature and high-pressure reaction conditions are a temperature of 100°C or higher and a pressure of 0.3 MPa or higher.
(4)一種鐵系凝集劑，係總鐵濃度為13至16重量%之高濃度聚硫酸鐵(III)溶液。 (4) An iron-based coagulant, which is a high-concentration polyiron(III) sulfate solution with a total iron concentration of 13 to 16% by weight.
本發明之超高濃度鐵系凝集劑的特徵在於，相較於本發明之申請人目前市售之高濃度的鐵系凝集劑為高濃度，且具有高的凝集能力與脫水性。又，與一般品比較，因含有水分少，故可降低製品運輸成本。 The ultra-high-concentration iron-based coagulant of the present invention is characterized in that it has a higher concentration than the high-concentration iron-based coagulant currently commercially available by the applicant of the present invention, and has high coagulation ability and dehydration. In addition, compared with general products, it contains less water, so product transportation costs can be reduced.
又，若依據本發明之鐵系凝集劑的製造方法，可大幅縮短在習知之方法需要10小時以上的製造時間，且可進行鐵系凝集劑之有效率的製造。 In addition, according to the method of manufacturing the iron-based coagulant of the present invention, the manufacturing time required for 10 hours or more in the conventional method can be greatly shortened, and the iron-based coagulant can be efficiently manufactured.
圖1係可以高溫高壓反應製造聚硫酸鐵(III)之區域。 Figure 1 shows the area where polyiron(III) sulfate can be produced by high-temperature and high-pressure reaction.
圖2係產生沉澱物之試樣經過濾後之濃度偏移。 Figure 2 shows the concentration shift of the sample with precipitate after filtration.
圖3係未產生沉澱物之試樣的濃縮後之濃度偏移。 Figure 3 shows the concentration shift of the sample without precipitation after concentration.
在此，說明有關本發明之鐵系凝集劑的製造方法之技術性特徵之前，首先，說明有關無機系凝集劑。 Before describing the technical features of the method for producing the iron-based coagulant of the present invention, first, the description will be made on the inorganic coagulant.
一般，在下水污泥處理中，以凝集劑使污泥中之懸浮粒子或膠體狀粒子凝集而進行脫水處理以固液分離。下水污泥中之懸浮粒子或膠體狀粒子，其表面通常為帶負電，藉由因表面電荷所產生之排斥力及水合而為安定狀態。凝集劑係具有下述作用的藥劑：被吸附於此等粒子表面而將表面電荷中和，減弱粒子間之排斥力而使其凝集。 Generally, in sewage sludge treatment, the suspended particles or colloidal particles in the sludge are aggregated with a flocculant to undergo dehydration treatment for solid-liquid separation. The suspended particles or colloidal particles in sewage sludge are usually negatively charged on the surface, and are in a stable state due to the repulsive force and hydration generated by the surface charge. The aggregating agent is a drug that has the effect of being adsorbed on the surface of these particles to neutralize the surface charge, and weaken the repulsive force between the particles to make them agglomerate.
鐵系凝集劑係代表性的無機系凝集劑，以帶正電之鐵離子將懸浮粒子或膠體狀粒子等懸浮物質的表面之負電荷中和而進行凝集作用。因此，鐵系凝集劑若存在有鐵離子，一定具有凝集作用，但若鐵離子濃度增高，懸浮物質之凝集能力會提高，故減少凝集劑之添加量即可。 The iron-based coagulant is a representative inorganic coagulant that uses positively charged iron ions to neutralize the negative charges on the surface of suspended particles such as suspended particles or colloidal particles to perform agglomeration. Therefore, if the iron-based coagulant has iron ions, it must have agglomeration effect, but if the concentration of iron ions increases, the coagulation ability of the suspended matter will increase, so the amount of the coagulant added can be reduced.
又，為了使凝集劑中之鐵離子安定地存在，必須存在一定程度量的負離子。鐵系凝集劑之情形，通常由硫酸根離子承擔該作用。負離子若與鐵離子量為適當的莫耳比之關係，鐵系凝集劑為安定，但負離子量為過剩時或不足時會變得不安定，而析出結晶等。 In addition, in order for the iron ions in the coagulant to exist stably, a certain amount of negative ions must be present. In the case of iron-based coagulants, sulfate ions usually assume this role. If the amount of negative ions and the amount of iron ions have an appropriate molar ratio, the iron-based coagulant is stable, but when the amount of negative ions is excessive or insufficient, it becomes unstable and crystals are precipitated.
又，使用如此之鐵系凝集劑進行下水污泥的處理時，鐵離子會吸附於懸浮粒子或膠體狀粒子表面而被分離回收為固形物，但硫酸根離子係殘留於被處理水中。 In addition, when using such an iron-based coagulant for sewage sludge treatment, iron ions are adsorbed on the surface of suspended particles or colloidal particles and are separated and recovered as solids, but sulfate ions remain in the water to be treated.
因此，被處理水係成為強酸性，故為了將此放流至河川中，必須以大量之中和劑進行中和，據稱此為提高下水污泥處理之成本的原因之一。亦即，鐵系凝集劑所要求之特徵係要求在凝集劑中所含有的總鐵濃度([T-Fe])高，且硫酸根離子濃度([SO4 2-])低。 Therefore, the treated water system becomes strongly acidic, so in order to release it into the river, it must be neutralized with a large amount of neutralizing agent. This is said to be one of the reasons for increasing the cost of sewage sludge treatment. That is, the characteristics required of the iron-based coagulant are that the total iron concentration ([T-Fe]) contained in the coagulant is high and the sulfate ion concentration ([SO 4 2- ]) is low.
咸認為在以硫酸鐵(II)作為原料之聚硫酸鐵(III)溶液的製造中，係進行下列之化學反應。 It is believed that in the production of polyiron(III) sulfate solution using iron(II) sulfate as a raw material, the following chemical reactions are carried out.
m[2FeSO4+(1-n/2)H2SO4+1/2O2+(n-1)H2O]→[Fe2(OH)n(SO4)3-n/2]m m[2FeSO 4 +(1-n/2)H 2 SO 4 +1/2O 2 +(n-1)H 2 O]→[Fe 2 (OH) n (SO 4 ) 3-n/2 ] m
其中，0<n≦2，m為自然數 Among them, 0<n≦2, m is a natural number
本發明係針對上述之由聚硫酸鐵(III)溶液所構成的鐵系凝集劑，提供一種以短時間形成[T-Fe]高的溶液之方法及藉此所製造之鐵系凝集劑。 The present invention provides a method for forming a high [T-Fe] solution in a short time and an iron-based coagulant produced by the iron-based coagulant composed of the above-mentioned polyiron(III) sulfate solution.
在本發明中，係使用硫酸鐵(II)(FeSO4)作為固體原料，在高溫高壓條件下進行氧化反應時，將投入之原料液的總鐵濃度與硫酸根離子濃度之關係設定於特定之範圍。本發明係藉由使總鐵與硫酸根離子之莫耳比(SO4 2-/T-Fe)為特定值以上，且使硫酸根離子濃度[SO4 2-]為特定值以下者，而達成下列之特別顯著的效果：可以習知技術無法預測之短時間結束反應，而且，所製造之聚硫酸鐵(III)溶液係可製造出在習知技術無法製造之超高濃度的總鐵濃度([T-Fe])。 In the present invention, iron (II) sulfate (FeSO 4 ) is used as a solid raw material. When the oxidation reaction is performed under high temperature and high pressure conditions, the relationship between the total iron concentration of the input raw material liquid and the sulfate ion concentration is set to a specific range. In the present invention, the molar ratio of total iron to sulfate ions (SO 4 2- /T-Fe) is set to a specific value or more, and the sulfate ion concentration [SO 4 2- ] is set to a specific value or less, and The following particularly significant effects are achieved: the reaction can be terminated in a short time that cannot be predicted by the conventional technology, and the produced polyferric sulfate (III) solution can produce an ultra-high concentration of total iron concentration that cannot be produced by the conventional technology ([T-Fe]).
亦即，在本發明中，其特徵係使滿足下列之條件的包含硫酸鐵(II)及硫酸之原料液在高溫高壓條件下反應。 That is, in the present invention, it is characterized in that a raw material liquid containing iron (II) sulfate and sulfuric acid that satisfies the following conditions is reacted under high temperature and high pressure conditions.
總鐵與硫酸根離子之莫耳比(SO4 2-/T-Fe)為1.2以上 The molar ratio of total iron to sulfate ion (SO 4 2- /T-Fe) is 1.2 or more
使硫酸根離子之重量濃度設為[SO4 2-]時，[SO4 2-]為35重量%以下 When the weight concentration of sulfate ion is set to [SO 4 2- ], [SO 4 2- ] is 35% by weight or less
將硫酸鐵(II)之總鐵濃度與硫酸根離子濃度為如此之關係時，不會產生沉澱物，並可以短時間獲得超高濃度之聚硫酸鐵(III)溶液，此乃本發明人等所發現之嶄新見識。 When the total iron concentration of iron (II) sulfate and the sulfate ion concentration are in such a relationship, no precipitate will be generated, and an ultra-high concentration polyferric sulfate (III) solution can be obtained in a short time. This is the inventor of the present invention. New insights discovered.
(高溫高壓反應) (High temperature and high pressure reaction)
在專利文獻1所記載之方法係本發明人等實施之習知的製造方法。咸認為在該方法，反應係在常溫常壓下固相、液相、氣相之三相有相互相關而進行反應者。 理由在於，進行反應之期間，感覺到源自NOx之黃褐色氣體的產生或NOx臭之緣故。 The method described in Patent Document 1 is a conventional manufacturing method performed by the inventors. Xian believes that in this method, the three phases of the solid phase, liquid phase, and gas phase are related to each other and react under normal temperature and pressure. The reason is that, during the reaction, as a tan felt because of the gas from NO x in the NO x or smell it.
惟，本發明之方法係在反應結束後，即使開啟高壓釜，亦感覺不到NOx臭。因此，推測在本發明之高溫高壓反應中，作為固體原料之FeSO4‧7H2O溶解於硫酸液中而進行氧化反應，亦即進行固相與液相相關的反應。 However, in the method of the present invention, after the reaction is completed, even if the autoclave is turned on, no NO x odor is felt. Therefore, it is speculated that in the high-temperature and high-pressure reaction of the present invention, FeSO 4 ‧ 7H 2 O, which is a solid raw material, is dissolved in a sulfuric acid solution to undergo an oxidation reaction, that is, a solid phase and a liquid phase related reaction.
如此一來，咸認為藉由高溫條件下之反應，作為固體原料之FeSO4‧7H2O容易進行溶解，且藉由高壓條件下之反應而使氧分壓會上昇以增大液相中之溶存氧量，藉此，溶存氧直接有助於亞硫酸根離子NO2 -或Fe2+之氧化，急遽促進鐵離子之氧化反應。 In this way, Xian believes that FeSO 4 ‧7H 2 O, which is a solid raw material, is easily dissolved by the reaction under high temperature conditions, and the partial pressure of oxygen will increase by the reaction under high pressure to increase the liquid phase. The amount of dissolved oxygen, thereby, the dissolved oxygen directly contributes to the oxidation of sulfite ion NO 2 - or Fe 2+ , and rapidly promotes the oxidation reaction of iron ions.
(反應溫度與壓力) (Reaction temperature and pressure)
容器內之溫度必須調整至100至150℃之範圍。 The temperature in the container must be adjusted to the range of 100 to 150°C.
若反應溫度未達到100℃，則不會充分進行硫酸鐵(II)之氧化反應。又，若超過150℃，確認出黃色之沉澱物殘存，該沉澱物藉由X射線分析可知為Fe(OH)SO4。 If the reaction temperature does not reach 100°C, the oxidation reaction of iron (II) sulfate will not proceed sufficiently. In addition, if it exceeds 150°C, it is confirmed that a yellow precipitate remains, and the precipitate is found to be Fe(OH)SO 4 by X-ray analysis.
具體的實驗數據係省略，但本發明人等確認出反應壓力愈高，反應愈有效果地進行。此事實係若考量上述之高溫高壓反應的反應機構，可謂當然爾。 Specific experimental data are omitted, but the inventors of the present invention confirmed that the higher the reaction pressure, the more effective the reaction proceeded. This fact is a matter of course if we consider the reaction mechanism of the above-mentioned high temperature and high pressure reaction.
因此，本發明之反應壓力係只要考量製造成本等而設定現實上的條件即可，只要反應壓力為0.3MPa以上即可。 Therefore, the reaction pressure of the present invention only needs to set realistic conditions in consideration of manufacturing costs and the like, as long as the reaction pressure is 0.3 MPa or more.
(觸媒) (catalyst)
為了促進前述之聚硫酸鐵(III)溶液的生成反應，以使用觸媒為較佳。為了促進反應，較佳的觸媒係可列舉硝酸、亞硝酸鹽，亞硝酸鹽係有亞硝酸之鈉鹽、鉀鹽等。從促進反應之功能或成本之面而言，以硝酸為較佳。 In order to promote the formation reaction of the aforementioned polyiron(III) sulfate solution, it is preferable to use a catalyst. In order to promote the reaction, preferred catalyst systems include nitric acid and nitrite, and nitrites include sodium salt and potassium salt of nitrous acid. In terms of the function of promoting the reaction or the cost, nitric acid is preferred.
[實驗1] [Experiment 1]
本發明之發明人等就高溫高壓之反應條件而言，將反應溫度設定為110℃，將反應壓力設定為0.30MPa，將反應時間設定為10分鐘，將包含硫酸鐵(II)及硫酸之原料液調整成為各種之濃度。在其中添加硝酸作為觸媒而進行高溫高壓反應。接著，探討反應時間經過後是否產生沉澱物。 In terms of high temperature and high pressure reaction conditions, the inventors of the present invention set the reaction temperature to 110°C, the reaction pressure to 0.30 MPa, the reaction time to 10 minutes, and the raw materials containing iron(II) sulfate and sulfuric acid The liquid is adjusted to various concentrations. Nitric acid is added as a catalyst to perform a high temperature and high pressure reaction. Next, it was investigated whether or not precipitates were generated after the reaction time passed.
[實驗2] [Experiment 2]
又，就高溫高壓之反應條件而言，將反應溫度設定為120℃，將反應壓力設定為10.00MPa，將反應時間設定為10分鐘，而將包含硫酸鐵(II)及硫酸之原料液調整成為各種之濃度。在其中添加硝酸作為觸媒而進行高溫高壓反應。接著，探討反應時間經過後是否產生沉澱物。 Also, for the high temperature and high pressure reaction conditions, the reaction temperature was set to 120°C, the reaction pressure was set to 10.00 MPa, the reaction time was set to 10 minutes, and the raw material liquid containing iron (II) sulfate and sulfuric acid was adjusted to Various concentrations. Nitric acid is added as a catalyst to perform a high temperature and high pressure reaction. Next, it was investigated whether or not precipitates were generated after the reaction time passed.
將是否產生沉澱物之實驗結果彙整於表1及表2中。 Table 1 and Table 2 summarize the experimental results of whether sediment is generated.
在實驗1之以反應溫度110℃、反應壓力0.30MPa之條件進行的情形、及實驗2之以120℃、10.00MPa進行的情形，可知有關沉澱物之發生為完全相同。亦即，表1與表2之結果係在實驗1與實驗2為共通者。
In the case where the reaction temperature was 110°C and the reaction pressure was 0.30 MPa in Experiment 1, and the case where the reaction was carried out at 120°C and 10.00 MPa in
在表1所示之總鐵濃度[T-Fe]與全硫酸濃度[SO4 2-]之情形，係不形成沉澱物而形成聚硫酸鐵(III)溶液，為本發明之實施例。又，在表2所示之情形，係確認出沉澱物之產生，為本發明之比較例。 In the case of the total iron concentration [T-Fe] and the total sulfuric acid concentration [SO 4 2- ] shown in Table 1, the polyiron(III) sulfate solution is formed without the formation of precipitates, which is an embodiment of the present invention. In addition, in the cases shown in Table 2, the occurrence of precipitates was confirmed, which is a comparative example of the present invention.
[表1]
[表2]
(特定區域) (Specific area)
將彙總此等之結果者表示於圖1中。圖中以○符號劃記的區域係不形成沉澱物而形成有聚硫酸鐵(III)溶液。此為本發明規定之區域，以下係謂「特定區域」。該特定區域所包含之以白色○符號表示之[T-Fe]、[SO4 2-]為本發明之實施例的原 料組成。藉由使該組成物在高溫高壓條件下反應，可獲得聚硫酸鐵(III)之紅褐色的溶液。 The results are summarized in Figure 1. In the area marked with ○ in the figure, no precipitate is formed but a polyiron(III) sulfate solution is formed. This is the area defined by the present invention, and is referred to as "specific area" below. [T-Fe] and [SO 4 2- ] represented by white ○ included in the specific area are the raw material composition of the embodiment of the present invention. By reacting the composition under high temperature and high pressure conditions, a reddish brown solution of polyferric sulfate (III) can be obtained.
另一方面，使用在特定區域的外側之以▲符號表示的原料組成，在高溫高壓下使反應進行者對應本發明之比較例。使用此等之組成物時，任一者皆確認出產生沉澱物，總鐵與硫酸根離子之莫耳比(SO4 2-/T-Fe)低於1.2的區域之試樣中，確認出沉澱物為草黃氫鐵礬(Hydronium jarosite)。 On the other hand, using the raw material composition indicated by the symbol ▲ outside of the specific area, the one that allows the reaction to proceed under high temperature and high pressure corresponds to the comparative example of the present invention. When using these compositions, any one of them was confirmed to produce precipitates, and the molar ratio of total iron to sulfate ions (SO 4 2- /T-Fe) was less than 1.2 in the samples. The precipitate is Hydronium jarosite.
本發明人等係設定為該特定區域由如下之2個式所界定。 The inventors set that the specific area is defined by the following two formulas.
首先，該區域之上限係可設定為硫酸根離子之重量濃度[SO4 2-]為35重量%以下。 First, the upper limit of this region can be set as the weight concentration of sulfate ions [SO 4 2- ] below 35% by weight.
其次，該區域之下限係可由朝右上增加之斜向直線來規定。該斜向直線係將表示總鐵與硫酸根離子之莫耳比(SO4 2-/T-Fe)為1.2以上之關係的直線，換算成縱軸與橫軸為硫酸根離子之重量濃度與總鐵之重量濃度的圖而寫入者。 Secondly, the lower limit of the area can be specified by an oblique straight line increasing to the upper right. This oblique straight line is a straight line representing the relationship between the molar ratio of total iron to sulfate ions (SO 4 2- /T-Fe) of 1.2 or more, and the vertical axis and horizontal axis are converted to the weight concentration of sulfate ions and The graph of the total iron weight concentration was written by the author.
有關本發明特定之上述的[T-Fe]與[SO4 2-]之原料組成的特定區域係表示可在高溫高壓條件下安定地生成聚硫酸鐵(III)溶液之區域。 The above-mentioned specific region of the raw material composition of [T-Fe] and [SO 4 2- ], which is specific to the present invention, refers to a region where a polyiron(III) sulfate solution can be stably generated under high temperature and high pressure conditions.
該特定區域之技術的意義亦可從下列之補充實驗1及2來確認。
The significance of the technology in this specific area can also be confirmed from the following
(補充實驗1) (Supplementary Experiment 1)
在圖1中，[T-Fe]與[SO4 2-]之濃度分別為14%與28%之試樣(以下，標記為(14.0：28.0))、及(15.0：30.0)之試樣係產生沉澱物。對於該試樣進行過濾過以除去沉澱物後，測定溶液的濃度，其溶液之組成係分別為(12.8：27.2)、(14.5：29.8)。 In Figure 1, the samples with the concentrations of [T-Fe] and [SO 4 2- ] being 14% and 28% respectively (hereinafter, marked as (14.0: 28.0)) and (15.0: 30.0) Department of sediment. After filtering the sample to remove the precipitate, the concentration of the solution was measured, and the composition of the solution was (12.8: 27.2) and (14.5: 29.8), respectively.
此為本發明規定之區域內的數值。亦即，可知即使為產生沉澱物之試樣，其溶液之部分係本發明規定之總鐵濃度與全硫酸根離子濃度之特定區域內所包含的組成。在圖2中表示其內容。 This is the value in the area specified by the present invention. That is, it can be seen that even if it is a sample that produces a precipitate, the part of its solution is the composition contained in the specific region of the total iron concentration and the total sulfate ion concentration specified in the present invention. The content is shown in Figure 2.
(補充實驗2) (Supplementary Experiment 2)
(15.0：32.0)(15.0：34.0)之試樣係若依據圖1，任一者皆未產生沉澱物之試樣。將此等試樣於(i)乾燥機內保持在50℃、(ii)實驗室內保持在約20℃、(iii)恆溫箱內保持在10℃之3種環境下觀察1個月後之變化。其結果，只有在(i)乾燥機內保持於50℃之(15.0：34.0)的試樣觀察到沉澱物。 The samples of (15.0:32.0)(15.0:34.0) are the samples that did not produce any precipitates according to Figure 1. These samples were kept at 50°C in the dryer, (ii) kept at about 20°C in the laboratory, and (iii) kept at 10°C in a constant temperature box, and observed for 1 month. Variety. As a result, only the samples kept at 50°C (15.0:34.0) in the (i) dryer were precipitated.
認為此原因係有下列之點。 The reasons for this are considered as follows.
對於在乾燥機內保持於50℃一個月之試樣(15.0：32.0)(15.0：34.0)，再度測定[T-Fe]與[SO4 2-]，各別之測定值為(16.0：34.0)(16.0：36.0)。在圖3表示其內容。 For the sample (15.0: 32.0) (15.0: 34.0) kept at 50 ℃ in the dryer for one month, measure [T-Fe] and [SO 4 2- ] again, and the respective measured values are (16.0: 34.0) ) (16.0: 36.0). The content is shown in Figure 3.
在乾燥機內保持之試樣因水分蒸發而濃縮，但即使經過濃縮，具有本發明規定之區域內的[T-Fe]與[SO4 2-]之濃度關係的試樣亦未檢測出沉澱物。惟，因濃縮而使兩者之濃度關係超出上述區域之試樣，濃縮之結果為產生沉澱物。 The sample held in the dryer is concentrated due to the evaporation of water, but even after concentration, the sample with the concentration relationship between [T-Fe] and [SO 4 2-] in the area specified by the present invention does not detect precipitation Things. However, if the concentration relationship between the two exceeds the above-mentioned area due to concentration, the result of concentration is the generation of sediment.
因此，只有在(i)之條件下的(15.0：34.0)之試樣產生沉澱物。 Therefore, only the sample of (15.0:34.0) under the condition of (i) produces precipitates.
(反應時間) (Reaction time)
藉由專利文獻1所記載之習知技術所進行的製造方法係使硫酸鐵(II)在常溫常壓進行氧化之方法，即使考究觸媒或氧化劑等，亦只不過頂多獲得總鐵濃度([T-Fe])為12.5%左右之溶液，而反應時間亦達到16小時以上。 The production method by the conventional technology described in Patent Document 1 is a method of oxidizing iron (II) sulfate at normal temperature and pressure. Even if a catalyst or oxidant is used, the total iron concentration ( [T-Fe]) is a 12.5% solution, and the reaction time is more than 16 hours.
在本發明係藉由採用高溫高壓法，成功使反應時間大幅縮短。 In the present invention, the high temperature and high pressure method is used to successfully shorten the reaction time.
圖1所示之實施例係從總鐵濃度為12.5%之高濃度溶液至總鐵濃度成為16%之超高濃度溶液為止，在全部之試樣中，使反應在30分鐘以內結束。當然反應時間係依存於總鐵濃度，總鐵濃度為12.5%者係在7.5分鐘結束反應，總鐵濃度為16%者，亦在30分鐘以內結束反應。又，反應之結束係依據測定試樣溶液中之二價鐵濃度來判斷。 The example shown in Fig. 1 ranges from a high-concentration solution with a total iron concentration of 12.5% to an ultra-high-concentration solution with a total iron concentration of 16%. In all samples, the reaction was completed within 30 minutes. Of course, the reaction time depends on the total iron concentration. For a total iron concentration of 12.5%, the reaction ends within 7.5 minutes, and for a total iron concentration of 16%, the reaction ends within 30 minutes. In addition, the end of the reaction is judged by measuring the concentration of divalent iron in the sample solution.
可以如此之短時間進行反應係在習知技術中無法預料之顯著的效果。 The fact that the reaction can be carried out in such a short time is a remarkable effect that cannot be expected in the conventional technology.
(超高濃度溶液) (Super high concentration solution)
聚硫酸鐵(III)溶液為超高濃度，但為確認此效果，對於下列之試料A及試料B進行凝集試驗。試料A係與在習知技術中耗費16小時以上之時間而製造者具有相同的總鐵濃度之試樣。另一方面，試料B係在本發明中所製造之總鐵濃度為超高濃度之試樣。 The polyferric sulfate (III) solution has an ultra-high concentration, but to confirm this effect, an agglutination test was performed on the following sample A and sample B. Sample A is a sample with the same total iron concentration as the manufacturer, which took more than 16 hours in the prior art. On the other hand, the sample B is a sample in which the total iron concentration produced in the present invention is an ultra-high concentration.
[表3]
就模擬液而言，以丙烯酸顏料之帶色水作為被處理液體，並減少試料B之添加量，以使添加之試料A及試料B的總鐵量成為相同，亦即，使以鐵離子所產生之凝集能力為相同，而比較兩者之凝集能力。 For the simulation liquid, use acrylic pigment colored water as the liquid to be treated, and reduce the addition amount of sample B so that the total iron content of sample A and sample B added becomes the same, that is, the total iron content of sample A and sample B is the same, that is, the total iron content of sample A and sample B is the same. The agglutination ability produced is the same, and the agglutination ability of the two is compared.
將凝集試驗之條件表示於表4中。 Table 4 shows the conditions of the agglutination test.
[表4]
由於試料B為超高濃度，故要設為與試料A同等之凝集能力的情形，可將其添加量比試料A減少32%。又，試料B之情形，如表1所示，因[SO4 2-]低，故可抑制凝集處理後之被處理液的pH降低，因此，與使用試料A的情形比較，可將為了中和而添加之苛性鈉的添加量減少47%。 Since sample B has an ultra-high concentration, it is necessary to set the same agglutinating ability as sample A. The amount added can be reduced by 32% compared with sample A. Also, in the case of sample B, as shown in Table 1, since [SO 4 2- ] is low, the pH of the liquid to be treated after the agglutination treatment can be suppressed from lowering. Therefore, compared with the case of using sample A, it can be compared with And the added amount of caustic soda is reduced by 47%.
又，若觀察膠羽形成後的樣子，超高濃度的試料B係膠羽之形成能力高，膠羽之沉降速度亦快。如此，即使試料B將鐵量設為與試料A相同，但試料B係凝集能力高。 In addition, if the appearance of the gel feathers is observed, the ultra-high concentration sample B series gel feathers have a high forming ability, and the settling speed of the gel feathers is also fast. In this way, even if sample B has the same amount of iron as sample A, sample B has a high cohesive ability.
就其理由而能想到者係試料B更進一步聚合物化，有利於膠羽之交聯吸附。此事實係可由試料B之超高濃度試樣的液體之黏度比試料A更高乙事得到佐證。 For this reason, it is conceivable that the sample B is further polymerized, which is beneficial to the cross-linked adsorption of the plume. This fact can be confirmed by the fact that the viscosity of the liquid of the ultra-high concentration sample of sample B is higher than that of sample A.
[產業上之利用領域] [Industrial use field]
有關在下水等之廢水處理中利用的凝集劑，可以短時間製造凝集性能高的凝集劑，故可在廢水處理之領域中廣泛地利用。 Regarding the flocculant used in wastewater treatment such as sewage, a flocculant with high coagulation performance can be produced in a short time, so it can be widely used in the field of wastewater treatment.
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| JP4815082B2 (en) * | 2001-09-28 | 2011-11-16 | 日鉄鉱業株式会社 | Treatment method of iron-containing sulfuric acid solution |
| CN101786708A (en) * | 2010-03-01 | 2010-07-28 | 株式会社东洋贸易 | Iron-based flocculating agent and preparation method thereof |
| CN104071853B (en) * | 2014-07-17 | 2016-04-20 | 广西平果锋华科技有限公司 | Waste Sulfuric Acid and ferrous sulfate oxygen pressing is utilized to produce the method for bodied ferric sulfate |
| CN104355336A (en) * | 2014-10-17 | 2015-02-18 | 陕西华陆化工环保有限公司 | Method of utilizing ferrous sulfate waste residue to prepare polymeric ferric sulfate |
| CN105692717B (en) * | 2016-03-21 | 2018-08-14 | 广西福斯特再生资源环保科技有限公司 | A kind of bodied ferric sulfate and preparation method thereof |
| JP6132965B1 (en) * | 2016-07-12 | 2017-05-24 | 日鉄鉱業株式会社 | Method for producing polyferric sulfate and caking inhibitor for sludge incinerator |
-
2019
- 2019-09-30 JP JP2019179191A patent/JP2021053580A/en active Pending
-
2020
- 2020-09-25 KR KR1020227014081A patent/KR20220069092A/en unknown
- 2020-09-25 WO PCT/JP2020/036337 patent/WO2021065732A1/en active Application Filing
- 2020-09-25 CN CN202080068376.XA patent/CN114466824A/en active Pending
- 2020-09-29 TW TW109133870A patent/TW202122146A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR20220069092A (en) | 2022-05-26 |
| WO2021065732A1 (en) | 2021-04-08 |
| JP2021053580A (en) | 2021-04-08 |
| CN114466824A (en) | 2022-05-10 |
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