WO2023044840A1 - 一种低能耗钾钙镁磷肥的生产方法 - Google Patents
一种低能耗钾钙镁磷肥的生产方法 Download PDFInfo
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- WO2023044840A1 WO2023044840A1 PCT/CN2021/120563 CN2021120563W WO2023044840A1 WO 2023044840 A1 WO2023044840 A1 WO 2023044840A1 CN 2021120563 W CN2021120563 W CN 2021120563W WO 2023044840 A1 WO2023044840 A1 WO 2023044840A1
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- Prior art keywords
- low
- sintered clinker
- magnesium phosphate
- phosphate fertilizer
- calcium magnesium
- Prior art date
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000005265 energy consumption Methods 0.000 title claims abstract description 15
- CSTCWXGYJCUXLP-UHFFFAOYSA-K [Mg+2].[K+].[Ca+2].[O-]P([O-])([O-])=O Chemical compound [Mg+2].[K+].[Ca+2].[O-]P([O-])([O-])=O CSTCWXGYJCUXLP-UHFFFAOYSA-K 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000010433 feldspar Substances 0.000 claims abstract description 14
- 239000010434 nepheline Substances 0.000 claims abstract description 14
- 229910052664 nepheline Inorganic materials 0.000 claims abstract description 14
- 239000000571 coke Substances 0.000 claims abstract description 13
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 9
- 238000010791 quenching Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003830 anthracite Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000002367 phosphate rock Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 238000005188 flotation Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 13
- KMQAPZBMEMMKSS-UHFFFAOYSA-K calcium;magnesium;phosphate Chemical compound [Mg+2].[Ca+2].[O-]P([O-])([O-])=O KMQAPZBMEMMKSS-UHFFFAOYSA-K 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 2
- 239000004480 active ingredient Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000010298 pulverizing process Methods 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- WZRFPEHMOPTIDR-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Mg+2].[Ca+2].[Si+4] Chemical compound P(=O)([O-])([O-])[O-].[Mg+2].[Ca+2].[Si+4] WZRFPEHMOPTIDR-UHFFFAOYSA-K 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B13/00—Fertilisers produced by pyrogenic processes from phosphatic materials
- C05B13/02—Fertilisers produced by pyrogenic processes from phosphatic materials from rock phosphates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Definitions
- the invention belongs to the field of chemical production, and relates to a fertilizer production method, in particular to a production method of low energy consumption potassium calcium magnesium phosphate fertilizer.
- Calcium magnesium phosphate fertilizer contains various nutrients such as phosphorus, calcium, magnesium, silicon, iron, aluminum, etc. needed by crops.
- Calcium magnesium phosphate fertilizer contains various nutrients such as phosphorus, calcium, magnesium, silicon, iron, aluminum, etc. needed by crops.
- its consumption is increasing rapidly.
- the method for producing calcium magnesium phosphate fertilizer in existing blast furnace its raw material adopts phosphate rock, dolomite and serpentine, and fuel adopts coke and coal
- production process is: raw material is crushed, and then the raw material after crushing is promoted and added in blast furnace, in Blast smelting in a blast furnace, and then high-pressure water quenching to obtain semi-finished products, which are reproduced to obtain calcium magnesium phosphate fertilizer.
- the disadvantages of this process are: large fixed investment, high production cost, complex process, low conversion rate of phosphorus in calcium magnesium phosphate fertilizer, high energy consumption and high pollution.
- Phosphate ore required for the production of high-concentration phosphate fertilizer can be obtained by flotation of low- and medium-grade phosphate ore and high-magnesium phosphate ore in addition to direct use of rich phosphate ore.
- the poor behavior has led to a large amount of waste of low-grade phosphate rock, resulting in a waste of phosphate rock resources. Therefore, in the face of the current situation of increasingly scarce phosphorus resources, how to expand the scope of phosphorus resource utilization is of great significance.
- Chinese patent document CN101747090 (application number 200910218353.8) discloses a method for preparing calcium-magnesium phosphate fertilizer by utilizing phosphate ore flotation tailings blast furnace method
- Chinese patent document CN101747091 (application number 200910218354.2) discloses a method using phosphate ore flotation tailings as raw material The method for preparing calcium-magnesium phosphate fertilizer by the cyclone furnace method.
- Both of these two patent documents mix phosphate rock tailings with primary phosphate rock to obtain a phosphate rock raw material with a weight ratio of P 2 O 5 on a dry basis of ⁇ 13%, and then mix it with silica, Serpentine and coke (or coal powder) are roasted to prepare calcium magnesium phosphate fertilizer.
- the production methods of calcium magnesium phosphate fertilizer all have the following disadvantages: the temperature during roasting is relatively high (1350-1450° C.), the energy consumption is large, and the complexity of the process is increased.
- the present invention provides a calcium-magnesium phosphate fertilizer production method with low roasting temperature, low energy consumption and simple process, and opens up a new way for the comprehensive utilization of low-grade phosphate rock resources.
- a method for producing low-energy potassium calcium magnesium phosphate fertilizer comprising the following steps: 1) mixing low-grade phosphate rock with nepheline and feldspar at a mass ratio of 100:20-40:10-30, and then adding low-grade phosphate rock Mix coke or anthracite and coke mixture with nepheline and feldspar with a total weight of 4-5% to obtain a mixed material; 2) put the mixed material prepared in step 1 into a blast furnace and roast at a temperature of 900-1000°C for 30 ⁇ 60 minutes, obtained sintered clinker; 3) the sintered clinker prepared in the above step 2 was water quenched, and the temperature of the sintered clinker dropped to between 80 ⁇ 110°C within 1 ⁇ 20 seconds, and the sintered clinker after water quenching The material is drained, dried, crushed and ground to obtain high silicon calcium magnesium phosphate fertilizer.
- the low-grade phosphate rock is that the P2O5 content in the raw ore is less than 18%, the MgO content is 1%-5%, and the silicate content is more than 20%; or the P2O5 content is 8%-15% phosphate rock Flotation tailings.
- the particle size of the mixed material powder is 60-150 mesh.
- roasting temperature is only 900 ⁇ 1000 °C, roasts 30 ⁇ 60 minutes, is lower than the roasting temperature 1350 ⁇ 1450 °C of prior art production calcium magnesium phosphate fertilizer, roasting time 60-150 minutes, the temperature is low, the time is short, the energy consumption is small, and the process is simple.
- the method of the present invention not only utilizes low-grade phosphate rock with little economic value and phosphate rock flotation tailings that cause environmental pollution, prolongs the service life of mines, contributes to environmental protection, and improves economic benefits.
- the field test shows that the low energy consumption potassium calcium magnesium phosphate fertilizer produced by the invention can increase the yield of crops by 10-20%.
- the particle size of the mixed material powder is 60 mesh; 2) Put the mixed material prepared in step 1 into a blast furnace and roast at 1000°C for 30 minutes to obtain sintered clinker; 3) The sintered clinker prepared in the above step 2 is subjected to water Quenching, the temperature of the sintered clinker drops to 80°C within 20 seconds, and the water-quenched sintered clinker is drained, dried, crushed and ground to obtain low energy consumption potassium calcium magnesium phosphate fertilizer. Field experiments show that it can increase crop yield by 10%.
- the sintered clinker prepared in the above step 2 is subjected to water Quenching, the temperature of the sintered clinker drops to 100°C within 10 seconds, and the water-quenched sintered clinker is drained, dried, crushed and ground to obtain low energy consumption potassium calcium magnesium phosphate fertilizer. Field experiments show that it can increase crop yield by 18%.
- the particle size of the mixed material powder is 80 mesh; 2) Put the mixed material prepared in step 1 into a blast furnace and roast at 900°C for 60 minutes to obtain sintered clinker; 3) The sintered clinker prepared in the above step 2 is subjected to water Quenching, the temperature of the sintered clinker drops to 90°C within 15 seconds, and the water-quenched sintered clinker is drained, dried, crushed and ground to obtain low energy consumption potassium calcium magnesium phosphate fertilizer. Field experiments show that it can increase crop yield by 20%.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
涉及一种低能耗钾钙镁磷肥的生产方法，包括如下步骤：将低品位磷矿与霞石、长石按质量比100：20～40：10～30混合，再加入占低品位磷矿与霞石、长石总重量4～5％的焦炭或无烟煤和焦炭混合物，混合均匀得混合物料；将上述混合物料放入高炉内，900～1000℃温度下焙烧30～60分钟，制得烧结熟料；将上述烧结熟料进行水淬，烧结熟料在1～20秒内温度降至80～110℃之间，水淬后的烧结熟料经沥水、干燥、破碎和粉磨制得优质钙镁磷肥。使用原料少，焙烧温度低，时间短，工艺简单，可操作性强；产品质量稳定，有效成分转化率高，提高作物产量；充分利用低品位磷矿石，延长矿山服务年限，提高经济效益。
Description
本发明属于化工生产领域，涉及一种肥料生产方法，具体涉及一种低能耗钾钙镁磷肥的生产方法。
钙镁磷肥含有农作物所需的磷、钙、镁、硅、铁、铝等多种养分，具有施用后水土流失少，不污染环境，不块结土地，还能改良土壤等优点，特别是近年来以钙镁磷肥为基料的包裹肥技术的发展和应用，其用量正迅速增加。
现有的高炉生产钙镁磷肥的方法，其原料采用磷矿石、白云石和蛇纹石，燃料采用焦炭和煤，生产工艺为：将原料破碎，再将破碎后的原料提升加入高炉中，在高炉中鼓风熔炼，再经过高压水淬得到半成品，由半成品再生产得到钙镁磷肥。本工艺的缺点在于：固定投资大，生产成本高，工艺复杂，钙镁磷肥中磷的转化率低，能耗大，污染高。
生产高浓磷肥所需磷矿除直接使用富磷矿外还可以通过对中低品位磷矿和高镁磷矿浮选得到，随着高浓磷肥产业的快速发展，企业采矿普遍存在采富弃贫的行为，导致低品位磷矿被大量浪费，造成磷矿资源的浪费，因此面对当今磷资源日渐匮乏的现状，如何扩展磷资源利用范围具有重大意义。
中国专利文献CN101747090(申请号200910218353.8)公开了一种利用磷矿浮选尾矿高炉法制备钙镁磷肥的方法，中国专利文献CN101747091(申请号200910218354.2)公开一种以磷矿浮选尾矿为原料旋风炉法制备钙镁磷肥的方法，这两篇专利文献均将磷矿尾矿与原生磷矿混配，得到干基P
2O
5重量比为≥13％的磷矿原料，再与硅石、蛇纹石以及焦炭(或煤粉)焙烧制备钙镁磷肥。
目前钙镁磷肥生产方法，均存在以下不足：焙烧时温度较高(1350～1450℃)，能耗较大，增加了工艺的复杂度。
发明内容
针对现有技术的不足，本发明提供一种焙烧温度低，能耗低，工艺简单的钙镁磷肥生产方法，且为低品位磷矿的资源综合利用开辟一条新的途径。
本发明为解决上述技术问题所采用的方案如下：
一种低能耗钾钙镁磷肥的生产方法,包括如下步骤：1)将低品位磷矿与霞石、长石按质量比100：20～40：10～30混合，再加入占低品位磷矿与霞石、长石总重量4～5％的焦炭或无烟煤和焦炭混合物，混合均匀，得混合物料；2)将步骤1制得的混合物料放入高炉内，900～1000℃温度下焙烧30～60分钟，制得烧结熟料；3)上述步骤2制得的烧结熟料进行水淬，烧结熟料在1～20秒内温度降至80～110℃之间，水淬后的烧结熟料经沥水、干燥、破碎和粉磨制得高硅钙镁磷肥。
所述低品位磷矿为原矿中P
2O
5含量低于18％，MgO含量为1％～5％，硅酸盐含量20％以上；或P
2O
5含量为8％～15％磷矿浮选尾矿。
所述混合物料粉末粒度至60～150目。
本发明具有以下优点和有益效果：
1、本发明所述低能耗钾钙镁磷肥的生产方法，焙烧温度仅为900～1000℃，焙烧30～60分钟，低于现有技术生产钙镁磷肥的焙烧温度1350～1450℃，焙烧时间60～150分钟，温度低，时间短，能耗小，工艺简单。
2、本发明方法既对经济价值小的低品位磷矿和造成环境污染的磷矿浮选尾矿进行了利用，延长了矿山服务年限，也为环保做出了贡献，提高了经济效益。
4、大田试验表明：本发明生产的低能耗钾钙镁磷肥可使农作物产量提高10～20％。
下面结合具体实施例对本发明作进一步详细说明，但本发明并不局限于具体实施例。
实施例1
1)将低品位磷矿与霞石、长石按质量比100：20：10混合，再加入占低品位磷矿与霞石、长石总重量5％的焦炭，混合均匀，得混合物料，混合物料粉末粒度至60目；2)将步骤1制得的混合物料放入高炉内，1000℃温度下焙烧30分钟，制得烧结熟料；3)上述步骤2制得的烧结熟料进行水淬，烧结熟料在20秒内温度降至80℃之间，水淬后的烧结熟料经沥水、干燥、破碎和粉磨制得低能耗钾钙镁磷肥。大田试验表明：可使农作物产量提高10％。
实施例2
1)将低品位磷矿与霞石、长石按质量比100：40：30混合，再加入占低品位磷矿与霞石、长石总重量4.7％无烟煤和焦炭的混合物，混合均匀，得混合物料，其中无烟煤和焦炭按质量 1:1混合物；混合物料粉末粒度至100目；2)将步骤1制得的混合物料放入高炉内，970℃温度下焙烧40分钟，制得烧结熟料；3)上述步骤2制得的烧结熟料进行水淬，烧结熟料在1秒内温度降至110℃之间，水淬后的烧结熟料经沥水、干燥、破碎和粉磨制得低能耗钾钙镁磷肥。大田试验表明：可使农作物产量提高14％。
实施例3
1)将低品位磷矿与霞石、长石按质量比100：28：18混合，再加入占低品位磷矿与霞石、长石总重量4.3％的焦炭，混合均匀，得混合物料，混合物料粉末粒度至150目；2)将步骤1制得的混合物料放入高炉内，950℃温度下焙烧50分钟，制得烧结熟料；3)上述步骤2制得的烧结熟料进行水淬，烧结熟料在10秒内温度降至100℃之间，水淬后的烧结熟料经沥水、干燥、破碎和粉磨制得低能耗钾钙镁磷肥。大田试验表明：可使农作物产量提高18％。
实施例4
1)将低品位磷矿与霞石、长石按质量比100：35：25混合，再加入占低品位磷矿与霞石、长石总重量4％的焦炭，混合均匀，得混合物料，混合物料粉末粒度至80目；2)将步骤1制得的混合物料放入高炉内，900℃温度下焙烧60分钟，制得烧结熟料；3)上述步骤2制得的烧结熟料进行水淬，烧结熟料在15秒内温度降至90℃之间，水淬后的烧结熟料经沥水、干燥、破碎和粉磨制得低能耗钾钙镁磷肥。大田试验表明：可使农作物产量提高20％。
Claims (3)
- 一种低能耗钾钙镁磷肥的生产方法,包括如下步骤：1)将低品位磷矿与霞石、长石按质量比100：20～40：10～30混合，再加入占低品位磷矿与霞石、长石总重量4～5％的焦炭或无烟煤和焦炭混合物，混合均匀，得混合物料；2)将步骤1制得的混合物料放入高炉内，900～1000℃温度下焙烧30～60分钟，制得烧结熟料；3)上述步骤2制得的烧结熟料进行水淬，烧结熟料在1～20秒内温度降至80～110℃之间，水淬后的烧结熟料经沥水、干燥、破碎和粉磨制得低能耗钾钙镁磷肥。
- 根据权利要求1所述的一种低能耗钾钙镁磷肥的生产方法，其特征在于：所述低品位磷矿为原矿中P 2O 5含量低于18％，MgO含量为1％～5％，硅酸盐含量20％以上；或P 2O 5含量为8％～15％磷矿浮选尾矿。
- 根据权利要求1所述的一种低能耗钾钙镁磷肥的生产方法，其特征在于：所述混合物料粉末粒度至60～150目。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111115515.2A CN113735631A (zh) | 2021-09-23 | 2021-09-23 | 一种低能耗钾钙镁磷肥的生产方法 |
| CN202111115515.2 | 2021-09-23 |
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| CN103058739A (zh) * | 2013-01-10 | 2013-04-24 | 山东金正大生态工程股份有限公司 | 一种磷矿尾矿或低品位磷矿窑法生产碱性肥料的方法 |
| CN103086779A (zh) * | 2013-01-10 | 2013-05-08 | 贵州金正大生态工程有限公司 | 一种用磷矿尾矿或低品位磷矿高炉法生产碱性肥料的方法 |
| CN103086778A (zh) * | 2013-01-10 | 2013-05-08 | 贵州金正大生态工程有限公司 | 一种用不溶性含钾岩石窑炉法生产碱性肥料的方法 |
| JP2019172547A (ja) * | 2018-03-29 | 2019-10-10 | Ｊｆｅスチール株式会社 | リン酸質肥料の製造方法およびリン酸肥料 |
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| CN1048972C (zh) * | 1995-05-10 | 2000-02-02 | 陈德荣 | 硅钙镁磷肥及其生产方法 |
| CN101747091B (zh) * | 2009-12-14 | 2013-02-06 | 云南省化工研究院 | 一种以磷矿浮选尾矿为原料旋风炉法制备钙镁磷肥的方法 |
| CN103641516B (zh) * | 2013-12-04 | 2016-01-20 | 宣威市恒邦磷化工业有限公司 | 钙镁高炉实现肥、铁同炉冶炼方法 |
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| CN103058739A (zh) * | 2013-01-10 | 2013-04-24 | 山东金正大生态工程股份有限公司 | 一种磷矿尾矿或低品位磷矿窑法生产碱性肥料的方法 |
| CN103086779A (zh) * | 2013-01-10 | 2013-05-08 | 贵州金正大生态工程有限公司 | 一种用磷矿尾矿或低品位磷矿高炉法生产碱性肥料的方法 |
| CN103086778A (zh) * | 2013-01-10 | 2013-05-08 | 贵州金正大生态工程有限公司 | 一种用不溶性含钾岩石窑炉法生产碱性肥料的方法 |
| JP2019172547A (ja) * | 2018-03-29 | 2019-10-10 | Ｊｆｅスチール株式会社 | リン酸質肥料の製造方法およびリン酸肥料 |
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