CN1142033C - Preparation method of iron ore flotation collector - Google Patents
Preparation method of iron ore flotation collector Download PDFInfo
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- CN1142033C CN1142033C CNB00112563XA CN00112563A CN1142033C CN 1142033 C CN1142033 C CN 1142033C CN B00112563X A CNB00112563X A CN B00112563XA CN 00112563 A CN00112563 A CN 00112563A CN 1142033 C CN1142033 C CN 1142033C
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- iron ore
- basic raw
- flotation collector
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 24
- 238000005188 flotation Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 24
- 239000000194 fatty acid Substances 0.000 claims abstract description 24
- 229930195729 fatty acid Natural products 0.000 claims abstract description 24
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 24
- 239000003921 oil Substances 0.000 claims abstract description 24
- 235000019198 oils Nutrition 0.000 claims abstract description 23
- 239000004088 foaming agent Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 13
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005642 Oleic acid Substances 0.000 claims abstract description 13
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 13
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 7
- 239000008158 vegetable oil Substances 0.000 claims abstract description 7
- 239000013067 intermediate product Substances 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000005670 sulfation reaction Methods 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000005187 foaming Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- KOPMZTKUZCNGFY-UHFFFAOYSA-N 1,1,1-triethoxybutane Chemical compound CCCC(OCC)(OCC)OCC KOPMZTKUZCNGFY-UHFFFAOYSA-N 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims 2
- 230000019635 sulfation Effects 0.000 claims 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims 1
- 239000003925 fat Substances 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 150000001261 hydroxy acids Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000003513 alkali Substances 0.000 abstract description 7
- 239000003814 drug Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 3
- 239000011707 mineral Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 13
- 239000002253 acid Substances 0.000 description 10
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 239000003784 tall oil Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 230000001180 sulfating effect Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- WUOACPNHFRMFPN-VIFPVBQESA-N (R)-(+)-alpha-terpineol Chemical compound CC1=CC[C@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-VIFPVBQESA-N 0.000 description 2
- 241000202567 Fatsia japonica Species 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 oxygen alkanes Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a preparation method of an iron ore flotation collector, which comprises the steps of taking vegetable oil, acidified oil and an intermediate product, namely crude fatty acid or mixed fatty acid, in the process of processing and producing oleic acid as basic raw materials, adding concentrated sulfuric acid with the proportion of 3-50% of the weight of the basic raw materials into the basic raw materials to perform sulfation reaction, adding alkali liquor into a reaction product, adjusting the pH value to 9-11, and then adding a mineral separation foaming agent accounting for 1-15% of the basic raw materials to obtain a product. The method provided by the invention has the advantages of low production cost, wide raw material source, strong collecting capability of the produced medicament and good selectivity.
Description
Technical field
The present invention relates to the preparation method of a kind of iron ore flotation factory collecting agent, specifically is exactly to adopt vegetable oil, acidifying oil and by the intermediate products in their processing oleic acid processes---croude fatty acids, fatty acid mixed are the method that base stock prepares floatation catcher of iron ore.
Background technology
The flotation of iron ore can be adopted direct flotation and two kinds of methods of reverse flotation.The direct flotation foam is an iron ore concentrate, and bottom land goes out gangue; The reverse flotation foam is a gangue, and bottom land produces iron ore concentrate.In anion collecting agent reverse flotation, collecting agent generally adopts the commodity aliphatic acid such as the oleic acid of general maturation on the market, and the general process scheme of preparation oleic acid is: raw material oil foot or the hydrolysis under acidity or alkali condition of acidifying oil generate croude fatty acids; Behind the croude fatty acids branch vibration layer, drying dehydration, distillation, output accounts for the fatty acid mixed of croude fatty acids amount 85%, produces distillation at the bottom of the byproduct still simultaneously; Fatty acid mixed is through freezing squeezing, output final products oleic acid, and its output accounts for fatty acid mixed amount 65%～75%, simultaneously output by-product solid acid.The acidifying oil here refers to, and heats the mixture of preliminary pure aliphatic acid of making and unhydrolysed oil by oil foot through adding acid; Oil foot refers to process the by-product of vegetable and animals oils, promptly divides emulsion layer and the sediment go behind the product oil.Its production cycle is long, power consumption is big, the final products amount is the weak point of this method less, and it is lower also to exist collecting power with oleic acid as collecting agent, the relatively poor and expensive shortcoming of foaming characteristic.The neat mountain of China platform iron ore that assembles troops selects factory, is iron ore anion collecting agent reverse flotation factory maximum on the our times, and the collecting agent of employing is a RA315 anion collecting agent, and the ore dressing effect is better than oleic acid.Composition among the RA315 more than 70% is the chlorinated fatty acid that tall oil forms through chlorination, mixes about 30% auxiliary agent again.The tall oil here is the by-product aliphatic acid of timber papermaking, and has only the pine alkaline process to select paper plant that production is just arranged.At present, owing to be subjected to the influence of country's restriction disafforestation policy, the raw material sources of tall oil are very nervous on the market, have a strong impact on the medicament stock supply and jeopardize the ordinary production of selecting factory.Moreover, paper plant turns to production to make with extra care tall oil gradually and waits industrial chemicals to sell as making lacquer for interests own, makes with extra care tal fibre oil price lattice costliness, and relatively poor as the RA315 ore dressing effect of raw material production.
Summary of the invention
Purpose of the present invention is exactly at the above-mentioned problems in the prior art, and propose a kind of raw material sources extensively, the preparation method of floatation catcher of iron ore that low production cost, stable in properties, collecting power and selectivity are good.
For achieving the above object, the preparation method of floatation catcher of iron ore of the present invention is by following technology, step is carried out: with vegetable oil, acidifying oil reaches by intermediate products---the croude fatty acids in their processing oleic acid processes, one or more of fatty acid mixed are base stock, account for the concentrated sulfuric acid of base stock weight 3%～50% proportioning to its adding, the control reaction temperature is at 30 ℃～60 ℃, after sulfating reaction finishes, through washing, leave standstill, branch vibration layer, in the sulfating reaction thing, add alkali lye, adjust pH value 9～11, the sulfating reaction thing is converted into the sodium salt of carboxylic acid and aliphatic acid; Add the foaming agent for ore dressing that weight is base stock weight 1%～15% proportioning again, promptly become final products.
The preparation method of floatation catcher of iron ore provided by the invention, institute's enriching sulfuric acid amount are that base stock weight 4～20% is for best.Addition is excessive, and the finished product foamability is too strong, and selectivity descends; Addition is too little, and then sulfating reaction is insufficient.The foaming agent for ore dressing that adds is preferentially selected 2%～10% of base stock weight for use.Addition is excessive, and then foaming characteristic is too strong, the selectivity variation; Addition is too small, has then reduced the collecting performance of medicament.The alkali lye amount that adds 10～11 is advisable pH.
The foaming agent for ore dressing of above-mentioned adding can be a kind of in alcohols such as terpenol, polyalcohols ethers such as polypropylene glycol ether, oxygen alkanes such as the triethoxybutane or the foaming agent that has similar quality with above-mentioned a few class foaming agent for ore dressing, as 903 foaming agents, be all present technique field those of ordinary skill and know.Preferentially select No. 2 oil of foaming agent for ore dressing (alcohols, Main Ingredients and Appearance and effective ingredient are terpenol) of extensively selling in the market for use.
Compared with prior art, adopt the floatation catcher of iron ore of method preparation provided by the invention to have the following advantages:
1. as iron ore reverse flotation anion collecting agent, evidence and RA315 compare, and ton concentrate medicament expense can reduce by 15～20%; Give the ore deposit to flotation, select ore deposit per ton collecting agent can reduce consumption 1/4, the consumption of inhibitor starch can reduce 1/3, remarkable benefit.
2. the ore dressing contrast test with RA315 shows, under not desliming reverse flotation condition, the collecting agent collecting ability and the selectivity of the inventive method preparation all are better than RA315, and iron concentrate grade improves 0.85%, and the rate of recovery improves 1.5%.
3. present, it is tall oil and modified product thereof that iron ore reverse flotation anion collecting agent is produced raw materials used, owing to be subjected to the influence of country's restriction disafforestation policy, the tall oil market supply is in an emergency, and has injured the normal operation of production.And the raw materials used wide material sources of the present invention, all base stock croude fatty acids, fatty acid mixed are the processing of farm products by-product---oil foot is the intermediate products that raw material is produced oleic acid, and the price of vegetable oil, acidifying oil is also cheap more than oleic acid.
4. compare with the oleic acid production method, production technology of the present invention is simple, the cycle is short, energy consumption is little, production cost is low, and raw material all can be converted into costly final products.
5. comprised the aliphatic acid of various carbochain length in acidifying oil, croude fatty acids and the fatty acid mixed, not only comprised saturated acid but also comprised unsaturated acids, the product with this raw material is produced both can improve collecting ability, had selectivity preferably again; The sodium salt that contains carboxylic acid and aliphatic acid in the product helps foaming characteristic, collecting ability and optionally raising simultaneously; Add the abundant mixing of low-molecular-weight foaming agent for ore dressing, also promptly participate in more helping the dispersion in ore pulp in the micella molecules align of aliphatic acid, be increased in the coverage rate of mineral surfaces, improved the collecting performance greatly.
The specific embodiment
Below in conjunction with embodiment, method provided by the invention is described in further detail:
Embodiment 1
Get 100 gram acidifying oil, add the 20 gram concentrated sulfuric acids to it, between 20 ℃～60 ℃ of the control reaction temperatures, reaction time is 60 minutes, adds 20 milliliters of cold water (running water) agitator treating then 1～2 minute, leaves standstill about 2 hours, divide and remove following water layer, add the sulfating reaction thing hydroxylating of alkali lye, make pH value=10, under agitation add 2 of 5 grams the upper strata
#Grease separation ore deposit foaming agent promptly becomes product after fully stirring evenly.
Embodiment 2
The addition of the concentrated sulfuric acid is 4 grams, and the reaction time is 20 minutes, and adding alkali lye adjusting pH value is 11, foaming agent for ore dressing 2
#The oil addition is 15 grams, and other is with embodiment 1.
Embodiment 3
Concentrated sulfuric acid addition is 20 grams, and the reaction time is 50 minutes, and adding alkali lye adjusting pH value is 9, foaming agent for ore dressing 2
#The oil addition is 10 grams, and other is with embodiment 1.
Embodiment 4
Concentrated sulfuric acid addition is 3 grams, and the reaction time is 20 minutes, foaming agent for ore dressing 2
#The oil addition is 15 grams, and other is with embodiment 1.
Embodiment 5
Concentrated sulfuric acid addition is 50 grams, foaming agent for ore dressing 2
#The oil addition is 1 gram.Other together
Embodiment 1.
Embodiment 6
Get intermediate products croude fatty acids, each 50 gram of fatty acid mixed of producing oleic acid, the addition of the concentrated sulfuric acid is 8 grams, foaming agent for ore dressing 2
#The addition of oil is 8 grams.Other is with embodiment 1.
Embodiment 7
Get acidifying oil 60 grams, croude fatty acids 20 grams, fatty acid mixed 20 grams, foaming agent for ore dressing is a triethoxybutane.Other is with embodiment 1.
Embodiment 8
Get croude fatty acids 100 grams, foaming agent for ore dressing is a polypropylene glycol ether, and addition is 4 grams, and other is with embodiment 6.
Embodiment 9
Get vegetable oil soybean oil 100 grams, concentrated sulfuric acid addition is 15 grams, and foaming agent for ore dressing is 903 foaming agents, and addition is 5 grams.Other is with embodiment 1.
Embodiment 10
Get vegetable oil rapeseed oil 100 grams, concentrated sulfuric acid addition is 12 grams, and other is with embodiment 1.
Table 1 has been listed the medicament and on-the-spot RA315 chemical concentration closed circuit comparative test result that adopts the inventive method preparation, and sample is that the neat mountain table flotation that assembles troops is selected to the ore deposit.
Table 1
| Institute's adding medicine and consumption (gram/ton) | Mineral processing index (%) | |||||
| Collecting agent | Collecting agent | NaOH | Starch | CaO | Concentrate grade (TFe) | Iron recovery |
| RA315 | 550 | 1125 | 1500 | 375 | 64.50 | 88.96 |
| Embodiment 1 | 375 | 1125 | 625 | 375 | 65.35 | 90.46 |
| Embodiment 2 | 375 | 1125 | 625 | 375 | 65.10 | 90.26 |
| Embodiment 3 | 375 | 1125 | 625 | 375 | 65.06 | 92.40 |
| Embodiment 4 | 375 | 1125 | 625 | 375 | 65.00 | 89.70 |
| Embodiment 5 | 375 | 1125 | 625 | 375 | 65.46 | 90.06 |
| Embodiment 6 | 375 | 1125 | 625 | 375 | 65.10 | 91.48 |
| Embodiment 7 | 375 | 1125 | 625 | 375 | 65.12 | 91.60 |
| Embodiment 8 | 375 | 1125 | 625 | 375 | 65.48 | 91.46 |
| Embodiment 9 | 375 | 1125 | 625 | 375 | 65.60 | 91.06 |
| Embodiment 10 | 375 | 1125 | 625 | 375 | 65.00 | 87.06 |
Find out that from above index its collecting of floatation catcher of iron ore and selectivity that the inventive method is produced are all good than RA315, and starch consumption, collector dosage reduce significantly.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB00112563XA CN1142033C (en) | 2000-09-21 | 2000-09-21 | Preparation method of iron ore flotation collector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB00112563XA CN1142033C (en) | 2000-09-21 | 2000-09-21 | Preparation method of iron ore flotation collector |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1343531A CN1343531A (en) | 2002-04-10 |
| CN1142033C true CN1142033C (en) | 2004-03-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB00112563XA Expired - Fee Related CN1142033C (en) | 2000-09-21 | 2000-09-21 | Preparation method of iron ore flotation collector |
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| Country | Link |
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| CN (1) | CN1142033C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293226B (en) * | 2008-06-16 | 2011-03-30 | 湖北富邦化工科技有限公司 | Inverse floatation collecting agent for carbonate phosphorus ore |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297351C (en) * | 2003-12-05 | 2007-01-31 | 福州大学 | Preparation process for floatation ion collector of heavy spar |
| CN101130181B (en) * | 2006-08-25 | 2011-02-16 | 博兴华润油脂化学有限公司 | Method of producing trapping agent for floatation of iron ore |
| CN101234367B (en) * | 2008-03-04 | 2011-04-06 | 昆明晶石矿冶有限公司 | Siderite floatation collector and preparation thereof |
| CA2729297C (en) | 2008-07-02 | 2017-10-10 | Georgia-Pacific Chemicals Llc | Collectors for mineral ore flotation comprising oxidised fatty acids or maleated and oxidised fatty acids |
| CN101632961B (en) * | 2008-07-22 | 2012-09-12 | 鞍钢集团矿业公司 | Beta-hydroxy fatty acid collecting agent for positive floatation of iron ore and application thereof |
| CN101972708A (en) * | 2010-10-28 | 2011-02-16 | 山东科技大学 | Preparation method of feldspar ore reverse-flotation de-ironing collector |
| CN102755933A (en) * | 2011-04-29 | 2012-10-31 | 沈阳铝镁设计研究院有限公司 | Preparation method of collecting agent suitable for bauxite direct flotation |
| CN106179770A (en) * | 2016-07-18 | 2016-12-07 | 刘合琼 | A kind of copper sulfide ore beneficiation technique |
| CN108246513A (en) * | 2018-01-25 | 2018-07-06 | 包头钢铁（集团）有限责任公司 | The process of iron direct flotation in a kind of oxide ore tailing |
| CN108745651A (en) * | 2018-04-18 | 2018-11-06 | 广东省资源综合利用研究所 | A kind of collecting agent and its preparation method and application |
| CN108722676B (en) * | 2018-05-31 | 2020-11-27 | 广东省资源综合利用研究所 | Collecting agent and preparation method and application thereof |
-
2000
- 2000-09-21 CN CNB00112563XA patent/CN1142033C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293226B (en) * | 2008-06-16 | 2011-03-30 | 湖北富邦化工科技有限公司 | Inverse floatation collecting agent for carbonate phosphorus ore |
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|---|---|
| CN1343531A (en) | 2002-04-10 |
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