CN85107440A - 磷酸盐矿物的泡沫浮选工艺流程及其使用的试剂 - Google Patents
磷酸盐矿物的泡沫浮选工艺流程及其使用的试剂 Download PDFInfo
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Abstract
本发明提出了从磷酸盐矿，特别是从磷酸盐碳酸盐矿中，通过浮选，分离出磷酸盐矿物的工艺流程和工艺过程中建议使用的试剂。根据本发明，在浮选时，除了捕集剂外，采用了象甲阶酚醛树脂或酚醛清漆那样的酚聚合物。尤其是相对于碳酸盐矿物而言，这种酚聚合物可提高磷酸盐矿物的产额和选择性。
Description
本发明涉及在捕集剂存在下，用浮选法从磷酸盐矿石，特别是从磷酸盐-碳酸盐混合矿中分离出磷酸盐矿物的工艺流程。
目前，已有许多工艺过程和化合物，可以选择性地将磷酸盐矿物从含磷酸盐的矿中泡沫浮选出来。芬兰专利申请811333号介绍了一种泡沫浮选工艺，它是先将一种阴离子捕集剂，通常是一种脂肪酸，加入到矿石的、或者它的精矿的水淤浆中，淤浆经浮选，从精矿石中除去含硅酸盐的残渣。接着用碱处理淤浆，以便从矿物表面除去捕集剂复盖物，最后，为了得到尽可能纯的磷酸盐精矿，用PH是中性或弱酸性的阳离子捕集剂，通常是胺型捕集剂，浮选化合的精矿。
从芬兰专利申请790725号，也了解到一种两性表面活性剂，用作捕集剂。通过合适的氨基化合物，例如甲基丙氨酸或甲基氨基乙酸与环氧化合物或氯乙醇化合物发生反应，已经获得了这种捕集剂。为了得到最佳结果，象其它熟悉的两性试剂一样，捕集剂中的亲水部分和疏水部分可以通过调节碳链的长度，例如醚键的数目，而改变。
此外，在芬兰专利申请783804号中介绍了一种捕集剂混合物，它的基本成份是磺基琥珀酸的单酯和脂肪酸，脂肪酸是植物油或动物油。在该捕集剂混合物中，两种组分的含量范围，按重量计算，从1-99%变化到99-1%。
目前，脂肪酸是最商品化使用的捕集剂。脂肪酸可以是不饱和酸，也可以是工业脂肪酸混合物。也有一些其它的化合物被建议用作捕集剂，如烷基苯的磺酸盐，硫酸烷基酯和各种胺。
为了改善磷酸盐矿物与碳酸盐矿物分离的选择性，提高产额，在浮选中也常常使用各种调节剂。使用添加剂也常常可降低化学试剂的总消耗和（或）成本。通常使用的调节剂有水玻璃、玉米淀粉、阿拉伯树胶、羧甲基纤维素、中性油、气体二氧化碳或气体二氧化硫、各种乳化剂和起沫剂。假如以提高回收为目的，尤其在碳酸盐矿物与磷酸盐矿物一块浮选的情况，那末，目前已有的工艺流程和使用的试剂就不能提高磷酸盐精矿的品位。
本发明的目的是提出一种工艺流程，使如磷灰石这样的磷酸盐矿物能选择性地、有效地与其它矿物分离。同时本发明还意外地发现，在浮选时，除捕集剂外再加入苯酚聚合物，能产生协合作用，可改善磷酸盐矿物的回收和选择性，特别是相对于碳酸盐矿物而言。
根据本发明，要提高选择性可选用的试剂是各种酚-甲醛共聚物，如：甲阶酚醛树脂、酚醛清漆和改良的苯酚聚合物，如：蜜胺改良的酚醛清漆。
甲阶酚醛树脂和酚醛清漆是合成聚合物，可以相当方便地调节其骨架结构、各种官能团之间的距离和组份的比例。按照A.A.K.怀特豪斯，E.G.K.普利切特和G.布兰耐特，酚醛树脂，1967，艾利夫书刊有限公司，伦敦，996-91，尤其是P.7介绍的，这类聚合物可定义如下，譬如：
甲阶酚醛树脂是一种合成树脂，它由酚和醛组成，它的分子中含有羟甲基活性基团或取代的羟甲基基团。
酚醛清漆是一种可溶性的、易熔的合成酚醛树脂，它不含有羟甲基活性基团或取代的羟甲基基团。
根据文献记载，用酸作催化剂，由酚和甲醛反应可制备酚醛清漆。羟甲基酚的酸催化形成是一个相当缓慢的过程，但是，羟甲基酚与酚缩合成二羟基二苯基甲烷是很快速的，因此，在酚醛清漆中，主要是二羟基二苯基甲烷，其反应式见（1）。
上述反应可以连锁进行，从而形成多核酚链，下述结构式表示出多核酚链中的一部分。
酚醛清漆本身是上述多核酚链的异构化合物，未起反应的苯酚总是留在反应混合物中。
根据文献报道，如在碱催化剂等存在下，苯酚和甲醛反应可以制得甲阶酚醛树脂，酚和甲醛的碱催化加成反应要比其后的缩合反应快，这样，羟甲基酚便是主要的中间产物，反应式见（2）。
含有活性羟甲基基团的羟甲基酚或者与其余的羟甲基基团进一步缩合，形成醚键，或者，较常见的是与苯环的活泼原子（邻位或对位）反应，形成象在酚醛清漆中那样的亚甲基桥。在这两种情况下，反应中都生成水。
甲阶酚醛树脂平均说来也许有三至四个苯环，下面的结构式可以作为一个例子：
除了水外，或许遇有酚、羟甲基酚和甲醛聚合物作为残留物存在于甲阶酚醛树脂中。
当浮选中使用这种类型的苯酚聚合物时，选择性、精砂的纯度和回收、以及泡沫的质量都得到改善。使用苯酚聚合物还能够有效地利用一般的非选择性的捕集剂，象脂肪酸、氨基酸和磺酸，或上述诸酸的混合物。浮选时，遇有可能使用工艺中所熟悉的普通调节剂，如抑制剂、乳化剂、分散剂和起沫油。普通的物理条件如温度和淤浆的酸碱度，也可采用浮选工艺中常用的方法得到调节。
下面用实例对本发明进行说明：
例1：
一种磷酸盐和碳酸盐矿石，含有6.9%氟磷灰石和30.8%碳酸盐，其余是硅酸盐矿物，将这种矿石粉碎至颗粒度小于三毫米，取一公斤经均化处理的该矿石一份，用0.7升水磨碎至其37%的粒度为74微米。磨碎的物料用3升水搅成淤浆状，淤浆中加入甲阶酚醛树脂的比例为125克/吨，妥尔油脂肪酸比例为50克/吨，三乙氧基丁烷（TEB）的加入比例为10克/吨，该淤浆被保持10分钟。随后在一个3升容器中进行较粗的浮选，得到的较粗的精砂再在一个1.5升的容器中经过三次更洁净的浮选，从而得到如下结果：
% P2O5回收%
矿石 4.0
磷灰石精砂 35.9 80.6
利用例1介绍的工艺流程，同时，改变使用的化学试剂和（或）它们的量，可得到下面的结果。
Claims (5)
1、在捕集剂存在下，用泡沫浮选法从磷酸盐矿石，主要是从磷酸盐-碳酸盐矿中分离出磷酸盐矿物的工艺流程，其特点是，在浮选时，另外使用一种试剂，它可以提高选择性和回收，这类试剂是酚聚合物，主要是酚--甲醛共聚物。
2、根据权利要求1的工艺流程，其特点是，用于提高选择性的试剂是甲阶酚醛树脂，酚醛清漆，或者一种改性的酚聚合物。
3、根据权利要求1或2的工艺过程，其特点是，使用的捕集剂是一种含有脂肪酸基团、氨基酸基团或者磺酸基因的化合物。
4、在磷酸盐矿物的浮选中，使用的是苯酚聚合物，特别是采用酚甲醛共聚物。
5、权利要求4中所用的苯酚聚合物为甲阶酚醛树脂，酚醛清漆或一种蜜胺（三聚氰酰胺）改性的酚醛清漆。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI843991A FI71885C (fi) | 1984-10-11 | 1984-10-11 | Foerfarande foer flotation av ett fosfatmineral och ett medel avsett att anvaendas daeri. |
| FI843991 | 1984-10-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN85107440A true CN85107440A (zh) | 1986-04-10 |
Family
ID=8519724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198585107440A Pending CN85107440A (zh) | 1984-10-11 | 1985-10-09 | 磷酸盐矿物的泡沫浮选工艺流程及其使用的试剂 |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US4687571A (zh) |
| CN (1) | CN85107440A (zh) |
| BR (1) | BR8505041A (zh) |
| FI (1) | FI71885C (zh) |
| SU (1) | SU1537126A3 (zh) |
| ZA (1) | ZA857286B (zh) |
| ZW (1) | ZW15385A1 (zh) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101484246A (zh) * | 2006-06-23 | 2009-07-15 | 佐治亚-太平洋化工品有限公司 | 改性胺-醛树脂及其在分离工艺中的用途 |
| CN102470289A (zh) * | 2009-08-11 | 2012-05-23 | 栗田工业株式会社 | 水处理方法和水处理混凝剂 |
| CN101795778B (zh) * | 2007-06-29 | 2012-11-14 | 佐治亚-太平洋化工品有限公司 | 改性的胺醛树脂以及它们在分离过程中的用途 |
| CN101128264B (zh) * | 2004-12-23 | 2013-05-29 | 佐治亚-太平洋化学有限责任公司 | 改性的胺-醛树脂及其在分离工艺中的应用 |
| CN103920596A (zh) * | 2014-04-25 | 2014-07-16 | 中蓝连海设计研究院 | 一种胶磷矿组合浮选捕收剂及其制法与用途 |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5314073A (en) * | 1993-05-03 | 1994-05-24 | Eastman Kodak Company | Phosphate flotation using sulfo-polyesters |
| US5858214A (en) * | 1996-10-17 | 1999-01-12 | Arr-Maz Products, L.P. | Phosphate beneficiation process using polymers as slime flocculants |
| US8702993B2 (en) * | 2004-12-23 | 2014-04-22 | Georgia-Pacific Chemicals Llc | Amine-aldehyde resins and uses thereof in separation processes |
| US7913852B2 (en) * | 2004-12-23 | 2011-03-29 | Georgia-Pacific Chemicals Llc | Modified amine-aldehyde resins and uses thereof in separation processes |
| US8757389B2 (en) * | 2004-12-23 | 2014-06-24 | Georgia-Pacific Chemicals Llc | Amine-aldehyde resins and uses thereof in separation processes |
| US8127930B2 (en) * | 2004-12-23 | 2012-03-06 | Georgia-Pacific Chemicals Llc | Amine-aldehyde resins and uses thereof in separation processes |
| CN102240603B (zh) * | 2010-05-12 | 2014-08-13 | 北京君致清科技有限公司 | 地沟油制备的捕收剂用于磷灰石浮选的方法 |
| CN104117220B (zh) * | 2014-07-04 | 2016-01-20 | 南开大学 | 一种泡沫精馏纯化方法 |
| US11638923B1 (en) | 2020-09-10 | 2023-05-02 | King Saud University | Flotation reagents from acidic olive oil |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3403783A (en) * | 1965-11-22 | 1968-10-01 | Zuplatec A G Ges Fur Tech Plan | Flotation of phosphate-containing materials |
| US3634230A (en) * | 1969-08-06 | 1972-01-11 | Reichhold Chemicals Inc | Process for removal of inorganic and organic matter from waste water systems |
| US3974116A (en) * | 1974-03-20 | 1976-08-10 | Petrolite Corporation | Emulsion suspensions and process for adding same to system |
| SE441740B (sv) * | 1983-05-27 | 1985-11-04 | Berol Kemi Ab | Forfarande for flotation av fosfatmalm |
| US4486301A (en) * | 1983-08-22 | 1984-12-04 | Tennessee Valley Authority | Method of beneficiating high carbonate phosphate ore |
-
1984
- 1984-10-11 FI FI843991A patent/FI71885C/fi not_active IP Right Cessation
-
1985
- 1985-09-13 ZW ZW153/85A patent/ZW15385A1/xx unknown
- 1985-09-23 ZA ZA857286A patent/ZA857286B/xx unknown
- 1985-10-09 CN CN198585107440A patent/CN85107440A/zh active Pending
- 1985-10-10 BR BR8505041A patent/BR8505041A/pt unknown
- 1985-10-10 SU SU853964936A patent/SU1537126A3/ru active
- 1985-10-10 US US06/786,411 patent/US4687571A/en not_active Ceased
-
1988
- 1988-02-08 US US07/154,568 patent/USRE32875E/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101128264B (zh) * | 2004-12-23 | 2013-05-29 | 佐治亚-太平洋化学有限责任公司 | 改性的胺-醛树脂及其在分离工艺中的应用 |
| CN101484246A (zh) * | 2006-06-23 | 2009-07-15 | 佐治亚-太平洋化工品有限公司 | 改性胺-醛树脂及其在分离工艺中的用途 |
| CN101484246B (zh) * | 2006-06-23 | 2013-07-31 | 佐治亚-太平洋化工品有限公司 | 矿石的选矿方法及纯化煤矿石的方法 |
| CN101795778B (zh) * | 2007-06-29 | 2012-11-14 | 佐治亚-太平洋化工品有限公司 | 改性的胺醛树脂以及它们在分离过程中的用途 |
| CN102470289A (zh) * | 2009-08-11 | 2012-05-23 | 栗田工业株式会社 | 水处理方法和水处理混凝剂 |
| CN102470289B (zh) * | 2009-08-11 | 2014-11-05 | 栗田工业株式会社 | 水处理方法和水处理混凝剂 |
| CN103920596A (zh) * | 2014-04-25 | 2014-07-16 | 中蓝连海设计研究院 | 一种胶磷矿组合浮选捕收剂及其制法与用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| FI71885C (fi) | 1990-06-12 |
| FI71885B (fi) | 1986-11-28 |
| ZW15385A1 (en) | 1986-02-19 |
| ZA857286B (en) | 1986-05-28 |
| FI843991L (fi) | 1986-04-12 |
| BR8505041A (pt) | 1986-07-29 |
| SU1537126A3 (ru) | 1990-01-15 |
| FI843991A0 (fi) | 1984-10-11 |
| US4687571A (en) | 1987-08-18 |
| USRE32875E (en) | 1989-02-21 |
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