經滴部中央標準局员工消費合作社印^ 五、發明説明（/ ) 本發明是有關於由含硫酸廢流中製造石膏’特定是一 種由工業的含硫酸廢流中製造高純度石膏的方法。 從含硫酸的酸類廢流中製造石膏’通常是使用一個或 是二個步驟的方法來實行，在這二種方法之間的關鍵不同 處，是在石膏沈澱產生處的PH値。在一個步驟的方法中 ，酸類流的pH値爲增加，典型是在4到6的範圍，並且 經由分離及/或是過濾處理的範圍回收此石膏V產生的石膏 具有低的石膏含量，典型爲少於90%，並且少於80¾也非 稀奇。所製造的石膏同樣也有小的結晶大小。這些因素都 使得它成爲不適合在石膏或是其他較高價値產品的製造中 使用。來自於此種方法的石膏，通常是便用在土壤的修復 或是作爲一種水泥的硬化控制劑。 在二個步驟的方法中，經由在二個不同的pH値下沈澱 ，由含硫酸廢流中回收石膏。石膏初始的回收，典型爲經 由添加石灰到酸類流中，增加pH値到2至2.4的範圍。沈 激的石膏一般爲高純度，典型爲大於90%，並且具有一個 使用在製造加工方法中可接受的粒子大小分佈。此方法目 前是使用在由氧化鈦的製造之中所產生的廢酸流來回收石 膏。所製造的石膏有足夠的純度，可使用在石膏板的製造 中。 在第一個沈激步驟之後，經由添加石灰，再次增加pH 値，以使得流的pH値約爲6。在此pH値下所沈澱的石膏 爲低的純度，其含有明顯數量的鐵以及其他雜質，其同樣 也存在此酸類流中s在此第二沈澱步驟的產品，通常是稱 __________________ 本紙張尺度適用中國國家標準（CNS ) Λ4况格（210X 297公嫠） - ·· I ^^^1 —^1 --*—- ί I I $. i A- · {誚先閱讀背而之洼念麥項呼峭巧本頁) 經滴部中央標準局員工消費合作社印製 44〇552 , B7 五、發明説明（二） 之爲”紅石膏”，並且主要是使用在土壤的修復，或是作爲 一種水泥的添加物。 本發明的g標是，克服或是減輕一項或是多項習知技 術方法的缺點，並且提供由含硫酸廢流，增進高純度石膏 的回收。 根據本發明，提供了一種由含硫酸廢流製造石膏的方 法，其包括有： (A) 添加含鈣的鹼性材料到該廢流中，以使得pH値在 約爲2.0至2.7的範圍之內，以沈澱出石膏，並且從廢流中 回收此沈澱的石膏，以及 (B) 添加鹼性材料到此廢流中，以使得pH値在約爲3.0 至3.4的範圍之內，以沈澱出雜質，並且將沈澱出的雜質 從廢流中移除，以及 (C) 添加含鈣的鹼性材料到該廢流中，以使得pH値在 約爲4至6的範圍之內，以沈澱出石膏，並且從廢流中回 收此沈澱的石膏。 根據本發明的方法，經由包含一種中間沈澱步驟，在 其中雜質可被移除，使得高純度石膏在二個階段中被回收 。該雜質包括有鐵和鋁。在這二個階段所回收的石膏，同 樣也具有使用在多種製造加I方法中可接受的粒子大小， 例如石膏扳和以石膏爲基材產品的製造，或是一種水泥的 添加物。 在本文中所使用的”鹼性材料”一詞，是指任何有能力 中和硫酸的鹼性材料，合適的鹼性材料例子，包括了鹼金 1J —i -=' nJK^^^^1 ^^^^1 nn ^^^^1 1 J 、v5 {"1閱讀背而之注悫Ψ項'""〈巧木頁) 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X29·?公# ) 經满部中央標隼局貝工消費合作杜印製 440552 ΑΊ H? 五、發明説明（3 ) 屬的氫氧化物，例如氫氧化鈉(NaOH)和氫氧化鉀(KOH)， 鹼土金屬的氬氧化物，例如氫氧化鎂(Mg(OH):)和氫氧化鈣 (Ca(OH)2),鹼性氧化物，例如氧化鈉(Na20)、氧化鎂 (MgO)和氧化鈣(CaO)，以及碳酸鹽和碳酸氫鹽，例如碳酸 鈉(Na2C03)、碳酸氫鈉(MaHC03_碳酸鈣(CaC03)。 在本文中所使用的”含鈣鹼性材料”一詞，是指一種如 上面所定義其含有鈣原子或是陽離子的鹼性材料。台適的 含鈣鹼性材料例子，包括了氬氧化鈣、碳酸鈣、氧化鈣和 石灰，包括熟石灰和生石灰。較爲適合的含鈣鹼性材料是 氫氧化鈣或是石灰。 在本文中所使用的”含硫酸廢流-詞，是指使用或是 製造硫酸的任何工業加工方法所產生的一種廢流，因此， 在此廢流中含有過童的或是廢棄的硫酸。該工業加工方法 包括了二氧化鈦、活性膠質黏土、樹薯粉澱粉、檸檬酸、 乳酸和酒石酸的製造，以及kevlar(芳香聚醯胺纖維的商標 名稱)的製造。 在本文中所使用的”高純度”和”高純的”一詞，當使用 在與回收的石膏相關時，是指具有一個大於85%的純度。 在此方法的步驟A中，其較爲適合的是，使得廢酸流 的pH値在2到2.4的範圍之內。爲了使回收量爲最大而含 有高純度，其較爲適合的是使得pH値在約爲2.4。 爲確保純石膏的最大回收量，其較爲合適的是*含鈣 鹼性材料在廢酸流中的停留時間，是在30分鐘到2個小時 之間。它同樣也可能經由加入石膏到廢酸流中，以在石膏 ^^^^1 n^i ί I - - at H1^ 一· i"t間讀背而之注"事項4"-，"本^) 本紙張尺度適用中國國家標準（CNS ) Λ4规格（210X29：；公总） 440552 ^ Η" 五、發明説明（4 ) 的沈澱”植入晶種”。在此方法中的植入晶種，可以增加石 膏沈澱的重量，或是改變結晶的大小，或二者都有。 爲了提供更好的結晶成長，以及增加石膏的粒子大小 ，其較爲適合的是，鹼性材料以及/或是含鈣鹼性材料爲高 度的分散。此可以經由包括硏磨或是溶解之任何合適的裝 置來達成。 使用在習知技術中已知的方法，例如經由過濾、澄淸( 淨化)或是離心作用，可以由廢酸流中將石膏回收i 經濟部中央標準局員.t消費合作社印輩 ---.-------ti-- (邻先聞讀背而之注意肀項¢4¾本τ];) 在步驟B中，使得廢酸流的pH値在約爲3.0到3.4的 範圍之內，以約爲3.0較爲適合。可以選擇較高的pH値， 然而，此將會減少石膏的全部回收量·在某些狀態中，其 可能爲有益的是，使用較高的pH値以移除不想要的雜質 。在這點上，由二氧化鈦加工方法之含硫酸廢流中製造’紅 石膏'，通常含有明顯數量的放射性物質。爲了移除這些放 射性雜質，在步驟B中，廢流的pH値可能需要高於3.4， 在某些其他的狀況下，其可能同樣也有利的是，使用較高 的pH値，以移除不想要的雜質，雖然在步驟C中，較高 的pH値降低了石膏的回收量- 在步驟B中，沈澱出的雜質可以使用習知技術中已知 的任何合適的裝置來移除◊在一個較爲適合的方法中是使 用凝聚劑《此凝聚劑可能是陽離子、陰離子或是非離子-合適的凝聚劑包括有丙烯醯胺聚合物、聚氨基丙烯酸聚合 物和磺化聚苯乙烯、·較爲適合的凝聚劑是陰離子…-種較 爲台適的陰離子凝聚劑是Ndco化學公司的Nalco 本紙張尺度適用中國國家標準（CNS ) Λ4規柢（210X297公ft ) ^7*^^44 05 5 2Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Distillation V. Description of the Invention (/) The present invention relates to the production of gypsum from a sulfuric acid-containing waste stream ', and is specifically a method for manufacturing high-purity gypsum from an industrial sulfuric acid-containing waste stream. The manufacture of gypsum from a sulfuric acid-containing acid waste stream is usually carried out using a one- or two-step process. The key difference between these two methods is the pH at the place where the gypsum precipitates. In a one-step process, the pH of the acid stream is increased, typically in the range of 4 to 6, and the gypsum produced by recovering this gypsum V through a separation and / or filtration process has a low gypsum content, typically It is not uncommon for less than 90% and less than 80¾. The manufactured gypsum also has a small crystal size. These factors make it unsuitable for use in the manufacture of gypsum or other higher value concrete products. Gypsum from this method is usually used for soil repair or as a hardening control agent for cement. In a two step process, gypsum is recovered from a sulfuric acid-containing waste stream by precipitation at two different pH levels. The initial recovery of gypsum is typically by adding lime to the acid stream and increasing the pH to a range of 2 to 2.4. Stimulated gypsum is generally of high purity, typically greater than 90%, and has a particle size distribution acceptable for use in manufacturing processes. This method currently uses a waste acid stream produced during the manufacture of titanium oxide to recover gypsum. The manufactured gypsum has sufficient purity to be used in the manufacture of gypsum boards. After the first incubation step, the pH 再次 was increased again by adding lime so that the pH 流 of the stream was about 6. The gypsum precipitated at this pH is of low purity, it contains a significant amount of iron and other impurities, and it also exists in this acid stream. The product of this second precipitation step is usually called __________________ This paper size Applicable to Chinese National Standards (CNS) Λ4 condition grid (210X 297 male)-·· I ^^^ 1 — ^ 1-* —- ί II $. I A- Xianghu Qiaoqiao page) Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Labor 44504552, B7 V. Description of the Invention (2) It is "red plaster" and is mainly used for soil restoration or as a kind of Additives to cement. The g standard of the present invention is to overcome or alleviate the shortcomings of one or more conventional technical methods, and to provide a high-purity gypsum recovery from a sulfuric acid-containing waste stream. According to the present invention, there is provided a method for producing gypsum from a sulfuric acid-containing waste stream, comprising: (A) adding a calcium-containing alkaline material to the waste stream so that the pH is in the range of about 2.0 to 2.7 Gypsum is precipitated, and the precipitated gypsum is recovered from the waste stream, and (B) an alkaline material is added to the waste stream so that the pH is in the range of about 3.0 to 3.4 to precipitate out Impurities, and remove the precipitated impurities from the waste stream, and (C) add a calcium-containing alkaline material to the waste stream so that the pH is in the range of about 4 to 6 to precipitate out Gypsum, and this precipitated gypsum is recovered from the waste stream. According to the method of the present invention, by including an intermediate precipitation step in which impurities can be removed, high-purity gypsum is recovered in two stages. The impurities include iron and aluminum. The gypsum recovered in these two stages also has particle sizes acceptable for use in a variety of manufacturing methods, such as the manufacture of gypsum boards and gypsum-based products, or a cement additive. The term "alkaline material" as used herein refers to any alkaline material capable of neutralizing sulfuric acid. Examples of suitable alkaline materials include alkali gold 1J —i-= 'nJK ^^^^ 1 ^^^^ 1 nn ^^^^ 1 1 J, v5 {" 1 Read the note below and back to the item '" " 〈巧 木 页) This paper size applies the Chinese National Standard (CNS) Λ4 specification ( 210X29 ·? 公 #) Printed by 440552 Α 隼 H? By the Ministry of Standards and Technology of the People ’s Republic of China. 5. Description of the invention (3) Hydroxides of the genus, such as sodium hydroxide (NaOH) and potassium hydroxide (KOH ), Argon oxides of alkaline earth metals, such as magnesium hydroxide (Mg (OH) :) and calcium hydroxide (Ca (OH) 2), basic oxides, such as sodium oxide (Na20), magnesium oxide (MgO), and Calcium oxide (CaO), and carbonates and bicarbonates, such as sodium carbonate (Na2C03), sodium bicarbonate (MaHC03_calcium carbonate (CaC03). The term "calcium-containing alkaline material" as used herein is Refers to an alkaline material as defined above that contains calcium atoms or cations. Examples of suitable calcium-containing alkaline materials include calcium argon oxide, calcium carbonate, calcium oxide, and lime, including mature stones And quicklime. A more suitable calcium-containing alkaline material is calcium hydroxide or lime. As used herein, the term "sulfuric acid-containing waste stream" refers to one produced by any industrial processing method that uses or makes sulfuric acid. The waste stream, therefore, contains waste or waste sulfuric acid in this waste stream. This industrial process includes the production of titanium dioxide, activated colloidal clay, tapioca starch, citric acid, lactic acid and tartaric acid, and kevlar (fragrant Polyamide fiber (trade name)). As used herein, the terms "high purity" and "high purity" when used in connection with recycled gypsum means having a purity greater than 85%. In step A of this method, it is more suitable to make the pH of the waste acid stream in the range of 2 to 2.4. In order to maximize the recovery and contain high purity, it is more suitable to make the pH値 is about 2.4. In order to ensure the maximum recovery of pure gypsum, it is more suitable * The residence time of the calcium-containing alkaline material in the waste acid stream is between 30 minutes and 2 hours. It is also the same May be added Gypsum into the waste acid stream in order to read gypsum ^^^^ 1 n ^ i ί I--at H1 ^ i " t " Matter 4 "-, " this ^) paper The scale applies to the Chinese National Standard (CNS) Λ4 specification (210X29 :; total) 440552 ^ Η " V. Description of the invention (4) precipitation "implanted seed". In this method, the implanted seed can increase gypsum The weight of the precipitate, or the size of the crystals, or both. In order to provide better crystal growth and increase the particle size of gypsum, it is more suitable that alkaline materials and / or calcium-containing alkaline materials are highly dispersed. This can be achieved by any suitable means including honing or dissolving. Gypsum can be recovered from the waste acid stream using methods known in the art, such as filtration, clarification (purification), or centrifugation. Member of the Central Standards Bureau of the Ministry of Economic Affairs.t Consumer Cooperative, India. ------- ti-- (near the first to read and pay attention to the item ¢ 4¾ this τ];) In step B, make the pH of the waste acid stream 値 in the range of about 3.0 to 3.4 It is more suitable to be about 3.0. A higher pH 値 can be selected, however, this will reduce the overall recovery of gypsum. In some states, it may be beneficial to use a higher pH 値 to remove unwanted impurities. In this regard, the manufacture of 'red gypsum' from a sulfuric acid-containing waste stream of a titanium dioxide processing method usually contains a significant amount of radioactive material. In order to remove these radioactive impurities, in step B, the pH of the waste stream may need to be higher than 3.4. In some other conditions, it may also be advantageous to use a higher pH to remove unwanted Essential impurities, although in step C, a higher pH will reduce the amount of gypsum recovered-in step B, the precipitated impurities can be removed using any suitable device known in the art A more suitable method is to use a coagulant. This coagulant may be cationic, anionic or non-ionic-suitable coagulants include acrylamide polymers, polyaminoacrylic polymers and sulfonated polystyrene, A suitable flocculant is an anionic ...-a more suitable anionic flocculant is Nalco of Ndco Chemical Co., Ltd. This paper applies Chinese National Standard (CNS) Λ4 Regulations (210X297 ft) ^ 7 * ^^ 44 05 5 2
A7 B7 ^c#4,rur_” ：..令案修正後是否變更原實質内容 經濟部智慧財產局員工消費合作社印製 五、發明說明（s) Opiimer® 9960。移除雜質的其他方法，例如離心分離，同 樣也可能。從酸類廢流中移除雜質，可以如问廢渣埋塡來 使用。假如在步驟B中使用一種含鈣鹼性材料，然後產品 將含有石膏，也有其他雜質。也可以使用強烈地攪拌以及/ 或是降低額定工作性能(deration)，以促進鐵和其他雜質的 氧化，藉此幫助這些雜質的移除。 在步驟C中，使得酸類廢流的pH値在約爲4到6的 範圍之內，以約爲6較爲適合。爲了確保最大的回收量， 停留時間可能需要在約二到四個小時之間。如同步驟A， 石膏的沈澱可以使用”植入晶種”，以增加回收量以及/或是 調整所製造的結晶大小。如同步驟A的產物，在步驟C中 回收的石膏爲高純度，並且具有製造加工方法之合適的粒 子大小分佈。 本發明的方法，使得由含硫酸廢流中製造石膏’其爲 高純度，並且具有使用在製造加工方法中可接受的粒子大 小。在這點上*從步驟A和C的方法中所回收的石膏’可 以具有大於85。/。的純度，以大於90%較爲適合’並且以大 於92%最爲適合。根據本發明所製造的高純度石膏，同樣 也可以具有可接受的粒子大小，使其適合使用在製造加工 方法中。在這點上，石膏粒子可以具有一個平均在20到 120微米之間的大小，較佳在40到120微米之間’並且最 佳在60到120微米之間。 爲了促進對本發明的了解，即將要提到的附加實例， 敘述本發明的一個具體實施例。然而其可了解到’下面敘 8 ______ ----OS* --- (請先閱讀背面之注意事項再填寫本頁) ί Γ •务- ί 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） 經濟部中央標準局員Η消费合作社印裝 ^40552 五、發明説明（6 ) 述的特定性’並不是要取代本發明在上面所敘述的一般法 則。 實例 在活性膠質黏土的製造中所產生的含硫酸廢流，從其 中將石膏回收。除了硫酸之外，溶液含有鐵和其他的溶解 的物質。 廢酸流的pH値初始爲pH 1.64。在經由添加粉碎良好 的氫氧化鈣而將pH値增加到2.42之前，將溶液過濾以移 除殘留的固體。在過濾以移除沈澱的石膏之前，使得溶液 混合6〇分鐘。從此步驟的回收量，每公升酸類廢液中有 3.5公克，並且石膏的純度91.7。。=石膏被故置在一邊沒有 淸洗，以在後面的步驟中使用·-. 經由添加氫氧化鈣，溶液的pH値大槪增加到3.0，並 且加人一種陰離子凝聚劑(Optimer® 9960)，以幫助離子和 其雜質的分離。在過濾之前，此溶液激烈地攪拌60分鐘。 此步驟的回收量，在每公升廢液中爲6.1公克。含有鐵或 其他雜質的沈澱部份，對於石膏的使用上是有害的、' 然後使用粉碎良好的氫氧化鈣，將過濾物中和到pH値 爲6·15，並且加入在第一個階段中所製造之一部份石膏， 以增加結晶的速率。在過濾之前，使得溶液混合120分鐘 ;從沈澱中整體的回收量，在每公升中爲18.7公克。所製 造之石膏的純度爲93.6% :乾燥的石膏顏色爲乳脂色，並 且具有平均的粒子大小爲53微米- 熟悉此技術者將可理解到*在本文中所敘述的發明， -'J^n H. - 1· .H--0 ("1間讀背而之注"f#填$本頁) 本紙浪尺度適用中國國家標準（CNS ) Λ4規掊（210X297公疗） 游 40552 a， Η 7 五、發明説明（1 ) 有可能受到與特定敘述不同的變化和修正。其可了解到， 本發明包括了所有的該變化與修正f本發明同樣也包括了 在此說明書中所提及或是顯示的所有步驟和特徵，個別地 或是共同地，以及任二個或是更多個該步驟或待徵之任何 和全部的結合。 i^A7 B7 ^ c # 4, rur_ ”: whether the original content of the order is changed after the amendment of the order. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (s) Opiimer® 9960. Other methods to remove impurities, such as Centrifugation is also possible. Removal of impurities from the acid waste stream can be used as buried waste. If a calcium-containing alkaline material is used in step B, then the product will contain gypsum and other impurities. It is also possible Use vigorous agitation and / or derating to promote the oxidation of iron and other impurities, thereby helping to remove these impurities. In step C, the pH of the acid waste stream is brought to about 4 In the range of 6, it is suitable to be about 6. In order to ensure the maximum recovery, the residence time may need to be between about two to four hours. As in step A, the gypsum can be precipitated by using "implanted seeds" "To increase the amount of recovery and / or adjust the size of the crystals produced. Like the product of step A, the gypsum recovered in step C is of high purity and has suitable granules for the manufacturing process. Size distribution. The method of the present invention enables the manufacture of gypsum from a sulfuric acid-containing waste stream which is of high purity and has a particle size acceptable for use in manufacturing processes. In this regard * from the methods of steps A and C The recovered gypsum 'can have a purity of more than 85%, and is more suitable for more than 90%' and is most suitable for more than 92%. The high-purity gypsum produced according to the present invention can also have acceptable particles. Size, making it suitable for use in manufacturing processes. In this regard, gypsum particles may have an average size between 20 and 120 microns, preferably between 40 and 120 microns, and most preferably between 60 and 120 In order to promote the understanding of the present invention, an additional example to be mentioned will describe a specific embodiment of the present invention. However, it can be understood that 'the following 8 ______ ---- OS * --- (Please first Read the notes on the reverse side and fill in this page) ί Γ • 务-ί The paper size is applicable to the Chinese National Standard (CNS) A4 (210 x 297 mm) Printed by a member of the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives ^ 40552 2. The specificity described in the description of the invention (6) is not intended to replace the general principles described above in the present invention. Examples The sulfuric acid-containing waste stream produced in the production of activated colloidal clay is used to recover gypsum from it. In addition, the solution contains iron and other dissolved substances. The pH of the spent acid stream is initially at pH 1.64. Before the pH is increased to 2.42 by the addition of pulverized calcium hydroxide, the solution is filtered to remove residual solids The solution was allowed to mix for 60 minutes before filtering to remove the precipitated gypsum. The recovered amount from this step was 3.5 grams per liter of acid waste and the purity of the gypsum was 91.7. = Gypsum is placed on one side without washing for use in subsequent steps.-. By adding calcium hydroxide, the pH of the solution is increased to 3.0, and an anionic coagulant (Optimer® 9960) is added. To help the separation of ions and their impurities. This solution was stirred vigorously for 60 minutes before filtering. The recovery amount in this step was 6.1 grams per liter of waste liquid. The precipitated part containing iron or other impurities is harmful to the use of gypsum. Then, use the crushed calcium hydroxide to neutralize the filter to pH 6 6.15, and add it in the first stage Part of the gypsum produced to increase the rate of crystallization. Prior to filtration, the solution was allowed to mix for 120 minutes; the overall recovery from the precipitate was 18.7 grams per liter. The purity of the manufactured gypsum is 93.6%: the dry gypsum is creamy and has an average particle size of 53 microns. Those skilled in the art will understand that * the invention described in this article, -'J ^ n H.-1 · .H--0 (" 1 note read back " f # fill in this page) The standard of this paper is applicable to the Chinese National Standard (CNS) Λ4 Regulation (210X297 Public Therapy) Travel 40552 a, Η 7 V. Description of the Invention (1) It may be subject to changes and amendments different from the specific description. It can be understood that the present invention includes all such changes and modifications. The present invention also includes all steps and features mentioned or shown in this specification, individually or collectively, and any two or It is a combination of any and all of this step or pending. i ^
T 經濟部中央標準局負工消費合作社印製 本紙張尺度適用中國國家標窣（CXS ) Λ4規梠（2丨OX 297公#_ )T Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper standard is applicable to China National Standards (CXS) Λ4 Regulations (2 丨 OX 297 公 #_)