CN106044730A - Method for producing wet-process phosphoric acid from high-grade phosphate ore - Google Patents
Method for producing wet-process phosphoric acid from high-grade phosphate ore Download PDFInfo
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- CN106044730A CN106044730A CN201610392154.9A CN201610392154A CN106044730A CN 106044730 A CN106044730 A CN 106044730A CN 201610392154 A CN201610392154 A CN 201610392154A CN 106044730 A CN106044730 A CN 106044730A
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229910019142 PO4 Inorganic materials 0.000 title description 3
- 239000010452 phosphate Substances 0.000 title description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title description 3
- 239000002367 phosphate rock Substances 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 239000010440 gypsum Substances 0.000 claims abstract description 53
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 53
- 238000005406 washing Methods 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 238000004064 recycling Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 23
- 239000007790 solid phase Substances 0.000 claims description 9
- 239000006210 lotion Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 21
- 239000011575 calcium Substances 0.000 abstract description 21
- 229910052791 calcium Inorganic materials 0.000 abstract description 21
- 238000001556 precipitation Methods 0.000 abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 15
- 239000011574 phosphorus Substances 0.000 abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 15
- 238000000926 separation method Methods 0.000 abstract description 13
- 238000007039 two-step reaction Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract 2
- 238000012993 chemical processing Methods 0.000 abstract 1
- 239000006228 supernatant Substances 0.000 abstract 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 13
- 239000012066 reaction slurry Substances 0.000 description 10
- 239000012141 concentrate Substances 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- CKRORYDHXIRZCH-UHFFFAOYSA-N phosphoric acid;dihydrate Chemical compound O.O.OP(O)(O)=O CKRORYDHXIRZCH-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002311 subsequent effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/222—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
本发明公开了一种利用高品位磷矿生产湿法磷酸的方法，属于磷化工加工领域，该方法是采用两步反应，逆流洗涤流程，由高品位磷矿生产高浓度磷酸和工业级石膏，包括以下步骤：加压酸解反应步骤，酸解产物分离工序、清液沉钙反应工序和洗涤液循环利用工序。本发明的方法能够把高品位磷矿中的磷元素生产成高浓度的磷酸同时，还能够把磷矿中的钙元素生产成工业级石膏，达到节能目的与钙元素的价值化利用。
The invention discloses a method for producing wet-process phosphoric acid by using high-grade phosphate rock, which belongs to the field of phosphorus chemical processing. The method adopts a two-step reaction and a countercurrent washing process to produce high-concentration phosphoric acid and industrial-grade gypsum from high-grade phosphate rock. The method comprises the following steps: a pressurized acidolysis reaction step, an acidolysis product separation process, a supernatant liquid calcium precipitation reaction process and a washing liquid recycling process. The method of the invention can produce high-concentration phosphoric acid from the phosphorus element in the high-grade phosphate rock, and can also produce the calcium element in the phosphate rock into industrial-grade gypsum, so as to achieve the purpose of energy saving and the value utilization of the calcium element.
Description
技术领域technical field
本发明涉及磷化工技术领域，具体涉及利用高品位磷矿生产湿法磷酸的方法。The invention relates to the technical field of phosphorus chemical industry, in particular to a method for producing wet-process phosphoric acid by using high-grade phosphate rock.
背景技术Background technique
湿法磷酸工艺是以无机酸(主要是硫酸)分解磷矿制造磷酸的过程，即用硫酸与磷矿反应生成硫酸钙结晶和磷酸溶液，再进行液固分离，得到磷酸。其中无机酸也可以是硝酸和盐酸。湿法磷酸工艺存在一些难以克服的缺陷，由于加工工艺粗放，矿石中的有害杂质大部分进入磷酸中。特别是氟元素，一旦进入液相，将很难分离出来。更严重的是，产生大量的磷石膏废料，造成严重的污染和浪费。The wet-process phosphoric acid process is the process of decomposing phosphate rock with inorganic acid (mainly sulfuric acid) to produce phosphoric acid, that is, reacting sulfuric acid with phosphate rock to form calcium sulfate crystals and phosphoric acid solution, and then separating liquid and solid to obtain phosphoric acid. Among them, the inorganic acid can also be nitric acid and hydrochloric acid. There are some insurmountable defects in the wet process phosphoric acid process. Due to the extensive processing technology, most of the harmful impurities in the ore enter the phosphoric acid. Especially fluorine, once it enters the liquid phase, it will be difficult to separate out. What's more serious is that a large amount of phosphogypsum waste is produced, causing serious pollution and waste.
后经学者研究对湿法磷酸工艺过程进行了改进，将其分两步进行反应，首先采用磷酸浸取分解磷矿石，其次提供适宜的结晶条件，降低副产物磷石膏中的杂质含量。目前磷酸分解磷矿在二水法磷酸和料浆法重钙工艺中已有应用基础，After scholars' research, the process of wet phosphoric acid was improved, and the reaction was divided into two steps. First, phosphoric acid was used to leaching and decomposed phosphate rock, and second, suitable crystallization conditions were provided to reduce the impurity content in the by-product phosphogypsum. At present, phosphoric acid decomposition of phosphate rock has been applied in dihydrate phosphoric acid and slurry heavy calcium process.
中国专利申请CN102001636B公开了一种利用中低品位磷矿湿法生产宽浓度磷酸和洁净石膏的方法，在该方法的磷酸分解磷矿工序中，酸解反应温度小于105℃，从而造成磷矿分解反应不完全，同时，中低品位磷矿由于反应活性较低，磷矿在磷酸体系中也分解不完全，未反应完全的磷矿仍然需要用硫酸再次分解，采用中低品位磷矿，由于磷矿中杂质含量高，反应浆液粘度极大，料液中析出固相堵塞过滤设备，未反应完全的磷矿和液相的分离是一个工业化技术难题，基本没有工业化的可能。同时上述方法存在磷矿反应余渣与石膏的分离困难，生产的石膏杂质含量高的问题。Chinese patent application CN102001636B discloses a method for producing wide-concentration phosphoric acid and clean gypsum by using a medium and low-grade phosphate rock wet method. In the process of phosphoric acid decomposition of phosphate rock in this method, the acidolysis reaction temperature is less than 105°C, resulting in decomposition of phosphate rock The reaction is incomplete. At the same time, due to the low reactivity of medium and low-grade phosphate rock, the decomposition of phosphate rock in the phosphoric acid system is not complete. The unreacted phosphate rock still needs to be decomposed again with sulfuric acid. The impurity content in the ore is high, the viscosity of the reaction slurry is extremely high, the solid phase precipitated in the feed liquid blocks the filter equipment, and the separation of the unreacted phosphate rock and the liquid phase is a technical problem in industrialization, and there is basically no possibility of industrialization. At the same time, the above method has the problems of difficulty in separating the phosphate rock reaction residue and gypsum, and the produced gypsum has high impurity content.
发明内容Contents of the invention
本发明的目的在于克服现有技术中所存在的上述不足，利用高品位磷矿生产湿法磷酸的方法。该方法通过控制磷矿酸解的工艺条件，利用高品位磷矿直接生产高浓度磷酸，并副产高质量工业石膏，使高品位磷矿得以更好的价值化利用。The purpose of the present invention is to overcome the above-mentioned shortcomings existing in the prior art, and utilize high-grade phosphate rock to produce the method for wet-process phosphoric acid. By controlling the process conditions of acid hydrolysis of phosphate rock, the method utilizes high-grade phosphate rock to directly produce high-concentration phosphoric acid, and by-products high-quality industrial gypsum, so that high-grade phosphate rock can be better valued and utilized.
为了实现上述发明目的，本发明提供了以下技术方案：In order to realize the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
利用高品位磷矿生产湿法磷酸的方法，包括以下步骤：The method for producing wet-process phosphoric acid by utilizing high-grade phosphate rock comprises the following steps:
S1将磷矿浆与磷酸加入到酸解反应设备中，加压至0.2～0.5MPa，于105～200℃下反应1～5h得到酸解浆液，将所述酸解浆液进行分离得到清液和固体相；S1 Add phosphate rock slurry and phosphoric acid to the acidolysis reaction equipment, pressurize to 0.2-0.5MPa, react at 105-200°C for 1-5h to obtain acidolysis slurry, and separate the acidolysis slurry to obtain clear liquid and solid phase;
S2向所述清液中加入硫酸，于50～100℃下反应，沉淀分层，分离得到P2O5含量为36％以上的磷酸和半成品工业级石膏；S2 adding sulfuric acid to the clear liquid, reacting at 50-100°C, precipitating and stratifying, and separating to obtain phosphoric acid with a P2O5 content of 36% or more and semi - finished industrial-grade gypsum;
S3将所述固体相经过硫酸酸洗分离后，洗涤液进入步骤S1循环利用；将所述半成品工业级石膏用水洗涤得到工业级石膏和石膏洗液，所述石膏洗液进入步骤S1循环利用。S3 After the solid phase is separated by acid washing with sulfuric acid, the washing solution enters step S1 for recycling; the semi-finished industrial-grade gypsum is washed with water to obtain industrial-grade gypsum and gypsum lotion, and the gypsum lotion enters step S1 for recycling.
本发明提供的方法是采用两步反应，逆流洗涤流程，由高品位磷矿生产高浓度磷酸和工业级石膏。上述步骤中磷酸酸解磷矿的反应速率不像第二步结晶反应那样能够迅速完成，而后续得到工业级石膏的品质和高浓度磷酸的效果是由磷酸分解磷矿来实现的。通过加压和提高反应温度的方式，能够极大地提高酸解反应速率和转化率，使酸解反应进行得更为彻底，从而能够极大地缓解酸解反应后清液和固体相的分离困难，避免造成反应浆液粘度极大，料液中析出固相堵塞过滤设备。申请人经过大量的试验研究发现，在反应压力为0.2～0.5MPa，反应温度为105～200℃时，酸解反应速率相较现有技术能够提高40～50％，同时磷矿的转化率能达到97％以上。The method provided by the invention adopts two-step reaction and countercurrent washing process to produce high-concentration phosphoric acid and industrial-grade gypsum from high-grade phosphate rock. The reaction rate of phosphoric acid hydrolysis of phosphate rock in the above steps is not as rapid as the second crystallization reaction, and the subsequent effect of obtaining the quality of industrial grade gypsum and high concentration of phosphoric acid is achieved by phosphoric acid decomposition of phosphate rock. By pressurizing and increasing the reaction temperature, the acidolysis reaction rate and conversion rate can be greatly improved, and the acidolysis reaction can be carried out more thoroughly, which can greatly alleviate the separation difficulty of the clear liquid and the solid phase after the acidolysis reaction. Avoid causing the viscosity of the reaction slurry to be extremely high, and the solid phase precipitated in the feed liquid to block the filter equipment. After a large number of experimental studies, the applicant found that when the reaction pressure is 0.2-0.5MPa and the reaction temperature is 105-200°C, the acidolysis reaction rate can be increased by 40-50% compared with the existing technology, and the conversion rate of phosphate rock can be Reach above 97%.
进一步地，步骤S1中磷矿浆的水分含量为1～20wt％，磷矿中P2O5含量为30～38wt％，MgO含量为0.1～1.0wt％，Al2O3和Fe2O3含量和为0.1～1.5wt％。Further, in step S1, the moisture content of the phosphate rock slurry is 1-20wt%, the P2O5 content in the phosphate rock is 30-38wt %, the MgO content is 0.1-1.0wt % , and the Al2O3 and Fe2O3 The content sum is 0.1-1.5wt%.
选用上述方案中的高品位磷矿能够保证酸解反应的反应活性，磷矿中杂质含量低，酸解反应浆液粘度适中，料液中不易堵塞过滤设备，能够很好实现未反应完全的磷矿和液相的分离，达到工业化生产的目的。The selection of high-grade phosphate rock in the above scheme can ensure the reactivity of the acidolysis reaction. The impurity content in the phosphate rock is low, the viscosity of the acid hydrolysis reaction slurry is moderate, and the feed liquid is not easy to block the filter equipment, which can well realize the unreacted phosphate rock. and liquid phase separation to achieve the purpose of industrial production.
进一步地，步骤S1中酸解反应所用磷酸的P2O5含量大于36wt％。Further, the P 2 O 5 content of the phosphoric acid used in the acidolysis reaction in step S1 is greater than 36 wt%.
进一步地，步骤S2中离心分离所使用的设备为旋流分离器或者卧螺式离心机。Further, the equipment used for centrifugation in step S2 is a cyclone separator or a decanter centrifuge.
选用上述方案中的离心分离设备是因为该设备在酸解浆液的固液分离步骤中不易堵塞过滤设备。The centrifugal separation equipment in the above scheme is selected because the equipment is not easy to block the filter equipment in the solid-liquid separation step of the acid hydrolyzed slurry.
进一步地，步骤S3中酸洗分离所用硫酸的浓度为5～55wt％。Further, the concentration of sulfuric acid used for acid washing and separation in step S3 is 5-55 wt%.
进一步地，步骤S3中洗涤液和石膏洗液进入步骤S1循环利用前还包括加热浓缩的步骤。Further, before the washing liquid and gypsum washing liquid enter step S1 for recycling in step S3, the step of heating and concentrating is also included.
进一步地，上述加热浓缩后的洗液中P2O5含量大于36wt％，浓缩洗液的温度为90～100℃。Further, the content of P 2 O 5 in the washing liquid after heating and concentration is greater than 36 wt%, and the temperature of the concentrated washing liquid is 90-100°C.
该温度范围内的浓缩洗液在进入加压酸解反应设备后能够实现酸解过程热量平衡，而当浓缩洗液中P2O5含量小于36wt％时，酸解反应的分解率差。The concentrated lotion in this temperature range can achieve heat balance in the acidolysis process after entering the pressurized acidolysis reaction equipment, and when the P 2 O 5 content in the concentrated lotion is less than 36wt%, the decomposition rate of the acidolysis reaction is poor.
与现有技术相比，本发明的有益效果：Compared with prior art, the beneficial effect of the present invention:
本发明提供的利用高品位磷矿生产湿法磷酸的方法，在酸解磷矿的步骤中，通过加压和提高反应温度的方式，极大地提高了反应速率和转化率，使酸解反应进行得更为彻底，酸解反应速率相较现有技术能够提高40～50％，同时磷矿的转化率能达到97％以上，从而能够极大地缓解酸解反应后清液和固体相的分离困难，避免造成反应浆液粘度极大，料液中析出固相堵塞过滤设备。同时由于改进了酸解工艺提高了后续沉钙所得白膏的质量。采用本发明提出的高浓度湿法磷酸与工业石膏联产生产工艺，利用高品位磷矿湿法生产高浓度磷酸和工业石膏有非常好的经济效益。生产1吨P2O5磷酸，可以产出3.2吨工业石膏，在减少3.2吨石膏堆放压力的同时，还可以实现320元的石膏销售收入。The method for producing wet-process phosphoric acid using high-grade phosphate rock provided by the present invention, in the step of acid-decomposing phosphate rock, by pressurizing and raising the reaction temperature, the reaction rate and conversion rate are greatly improved, so that the acid-hydrolysis reaction proceeds The acid hydrolysis reaction rate can be increased by 40-50% compared with the existing technology, and the conversion rate of phosphate rock can reach more than 97%, which can greatly alleviate the separation difficulty of the clear liquid and the solid phase after the acid hydrolysis reaction , to avoid the extremely high viscosity of the reaction slurry, and the precipitation of solid phase in the feed liquid to block the filter equipment. At the same time, the quality of the white paste obtained by subsequent calcium precipitation is improved due to the improvement of the acid hydrolysis process. By adopting the high-concentration wet-process phosphoric acid and industrial gypsum joint production process proposed by the present invention, the high-concentration phosphoric acid and industrial gypsum are produced by the high-grade phosphate rock wet process, which has very good economic benefits. The production of 1 ton of P 2 O 5 phosphoric acid can produce 3.2 tons of industrial gypsum. While reducing the stacking pressure of 3.2 tons of gypsum, it can also achieve a sales income of 320 yuan for gypsum.
附图说明Description of drawings
图1为本发明所述利用高品位磷矿生产湿法磷酸方法的工艺流程图。Fig. 1 is a process flow diagram of the method for producing wet-process phosphoric acid by using high-grade phosphate rock according to the present invention.
图2为本发明的实施例1的工艺流程图。Fig. 2 is the process flow chart of embodiment 1 of the present invention.
具体实施方式detailed description
下面结合试验例及具体实施方式对本发明作进一步的详细描述。但不应将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明内容所实现的技术均属于本发明的范围。The present invention will be further described in detail below in conjunction with test examples and specific embodiments. However, it should not be understood that the scope of the above subject matter of the present invention is limited to the following embodiments, and all technologies realized based on the content of the present invention belong to the scope of the present invention.
实施例1Example 1
本实施例的工艺流程如附图2所示。某磷矿的P2O5品位为31wt％，磷矿中MgO含量为0.5wt％，磷矿中Al2O3+Fe2O3含量之和为1wt％，把磷矿磨成矿浆，用卧螺式离心机把矿浆水分离心分离到16wt％。把浓缩来的P2O5含量为37wt％的95℃磷酸与含水分16wt％的磷矿浆在加压反应槽R1内进行酸解反应，加入的干基磷矿1000份，酸解反应操作条件为：温度为117℃，反应压力0.3MPa，反应时间2小时。反应完的酸解料浆进入分离器F1，进行固液分离，得到的固体渣在洗涤器R2进行水洗过程，获得含磷洗水1000份，其中P2O5含量100份，得到的清液进入沉钙槽C1，加入硫酸进行沉钙反应，充分沉钙反应后，反应料浆经真空过滤器F2分离出白色工业石膏和浓磷酸，白色工业石膏洗涤以后获得干净的石膏与含磷洗涤水，经干燥得到干净工业石膏650～750份，同时得到P2O5浓度为40％的磷酸550～570份，含磷酸洗水混合以后，进入浓缩器C2浓缩，95℃浓缩液返回加压反应槽R1作为循环磷酸。The process flow of this embodiment is shown in Figure 2. The P2O5 grade of a phosphate rock is 31wt%, the MgO content in the phosphate rock is 0.5wt%, and the sum of the Al2O3 + Fe2O3 content in the phosphate rock is 1wt%. A horizontal screw centrifuge centrifugally separates the pulp water to 16wt%. The concentrated P2O5 content of 95°C phosphoric acid with a content of 37wt% and the phosphate rock slurry with a water content of 16wt% were acidolysis reaction in the pressurized reaction tank R1, and 1000 parts of dry base phosphate rock were added, and the acid hydrolysis reaction operation The conditions are: the temperature is 117° C., the reaction pressure is 0.3 MPa, and the reaction time is 2 hours. The reacted acidolysis slurry enters the separator F1 for solid-liquid separation, and the obtained solid slag is washed in the scrubber R2 to obtain 1000 parts of phosphorus - containing washing water, including 100 parts of P2O5 , and the obtained clear liquid Enter the calcium precipitation tank C1, add sulfuric acid to carry out the calcium precipitation reaction, after the sufficient calcium precipitation reaction, the reaction slurry is separated through the vacuum filter F2 to separate white industrial gypsum and concentrated phosphoric acid, and after the white industrial gypsum is washed, clean gypsum and phosphorus-containing washing water are obtained After drying, 650-750 parts of clean industrial gypsum can be obtained, and at the same time, 550-570 parts of phosphoric acid with a P2O5 concentration of 40% can be obtained. After mixing the washing water containing phosphoric acid, it enters the concentrator C2 to concentrate, and the 95°C concentrate returns to pressurization reaction Tank R1 acts as a circulating phosphoric acid.
实施例2Example 2
本实施例的工艺流程如附图2所示。某磷矿的P2O5品位为36wt％，磷矿中MgO含量为0.4wt％，磷矿中Al2O3和Fe2O3的含量总和为0.9wt％，把磷矿磨成矿浆，用卧螺式离心机把矿浆水分离心分离到12％。把浓缩来的含P2O5为37wt％的90℃磷酸与含水分16wt％的磷矿浆在加压反应槽R1内进行酸解反应，加入的干基磷矿1000份，酸解反应操作条件为：温度为105℃，反应压力0.2MPa，反应时间为3小时。反应完的酸解料浆进入分离器F1，进行固液分离，得到的渣在洗涤器R2进行水洗过程，获得含磷洗水1000份，其中P2O5含量100份，得到的清液进入沉钙槽C1，加入硫酸进行沉钙反应，充分沉钙反应后，反应料浆经真空过滤器F2分离出白色工业石膏和浓磷酸，白色工业石膏洗涤以后获得干净的石膏与含磷洗涤水，经干燥得到干净工业石膏650～750份，同时得到P2O5浓度为42％的磷酸550～570份，含磷酸洗水混合以后，进入浓缩器C2浓缩，90℃浓缩液返回加压反应槽R1作为循环磷酸。The process flow of this embodiment is shown in Figure 2. The P2O5 grade of a certain phosphate rock is 36wt%, the MgO content in the phosphate rock is 0.4wt%, the total content of Al2O3 and Fe2O3 in the phosphate rock is 0.9wt %, and the phosphate rock is ground into a pulp, Use a decanter centrifuge to centrifugally separate the pulp water to 12%. The 90°C phosphoric acid containing 37wt% of P2O5 and the phosphate rock slurry containing 16wt % of water are carried out acidolysis reaction in the pressurized reaction tank R1, and 1000 parts of dry base phosphate rock are added, and the acid hydrolysis reaction operation The conditions are: the temperature is 105° C., the reaction pressure is 0.2 MPa, and the reaction time is 3 hours. The reacted acidolysis slurry enters the separator F1 for solid-liquid separation, and the obtained slag is washed in the scrubber R2 to obtain 1000 parts of phosphorus - containing washing water, including 100 parts of P2O5 , and the obtained clear liquid enters Calcium precipitation tank C1, adding sulfuric acid to carry out calcium precipitation reaction, after sufficient calcium precipitation reaction, the reaction slurry is separated by vacuum filter F2 to separate white industrial gypsum and concentrated phosphoric acid, after washing the white industrial gypsum, clean gypsum and phosphorus-containing washing water are obtained, After drying, 650-750 parts of clean industrial gypsum are obtained, and at the same time, 550-570 parts of phosphoric acid with a P 2 O 5 concentration of 42% are obtained. After mixing the washing water containing phosphoric acid, it enters the concentrator C2 to concentrate, and the concentrated solution returns to the pressurized reaction tank at 90°C R1 acts as a cyclic phosphate.
实施例3Example 3
本实施例的工艺流程如附图2所示。某磷矿的P2O5品位为33％，磷矿中MgO含量为0.6wt％，磷矿中Al2O3+Fe2O3含量之和为1wt％，把磷矿磨成矿浆，用卧螺式离心机把矿浆水分离心分离到2wt％。把浓缩来的含P2O5为37wt％的95℃磷酸与含水分2wt％的磷矿浆在加压反应槽R1内进行酸解反应，加入的干基磷矿1000份，酸解反应操作条件为：温度为140℃，反应压力0.3MPa，反应时间5小时。反应完的酸解料浆进入分离器F1，进行固液分离，得到的渣在洗涤器R2进行水洗过程，获得含磷洗水1000份，其中P2O5含量100份，得到的清液进入沉钙槽C1，加入硫酸进行沉钙反应，充分沉钙反应后，反应料浆经真空过滤器F2分离出白色工业石膏和浓磷酸，白色工业石膏洗涤以后获得干净的石膏与含磷洗涤水，经干燥得到干净工业石膏650～750份，同时得到P2O5浓度为42％的磷酸550～570份，含磷酸洗水混合以后，进入浓缩器C2浓缩，95℃浓缩液返回加压反应槽R1作为循环磷酸。The process flow of this embodiment is shown in Figure 2. The P 2 O 5 grade of a phosphate rock is 33%, the MgO content in the phosphate rock is 0.6wt%, the sum of the Al 2 O 3 +Fe 2 O 3 content in the phosphate rock is 1wt%, and the phosphate rock is ground into a slurry, and the The horizontal screw centrifuge centrifugally separates the pulp water to 2wt%. The 95°C phosphoric acid with 37wt% of P2O5 concentrated and the phosphate rock slurry containing 2wt% of water are subjected to acidolysis reaction in the pressurized reaction tank R1. The conditions are: the temperature is 140° C., the reaction pressure is 0.3 MPa, and the reaction time is 5 hours. The reacted acidolysis slurry enters the separator F1 for solid-liquid separation, and the obtained slag is washed in the scrubber R2 to obtain 1000 parts of phosphorus - containing washing water, including 100 parts of P2O5 , and the obtained clear liquid enters Calcium precipitation tank C1, adding sulfuric acid to carry out calcium precipitation reaction, after sufficient calcium precipitation reaction, the reaction slurry is separated by vacuum filter F2 to separate white industrial gypsum and concentrated phosphoric acid, after washing the white industrial gypsum, clean gypsum and phosphorus-containing washing water are obtained, After drying, 650-750 parts of clean industrial gypsum are obtained, and at the same time, 550-570 parts of phosphoric acid with a P 2 O 5 concentration of 42% are obtained. After mixing the washing water containing phosphoric acid, it enters the concentrator C2 to concentrate, and the 95°C concentrate returns to the pressurized reaction tank R1 acts as a cyclic phosphate.
实施例4Example 4
本实施例的工艺流程如附图2所示。某磷矿的P2O5品位为32wt％，磷矿中MgO含量为0.8wt％，磷矿中Al2O3+Fe2O3含量之和为0.5wt％，把磷矿磨成矿浆，用卧螺式离心机把矿浆水分离心分离到18wt％。把浓缩来的P2O5含量为37wt％的98℃磷酸与含水分18wt％的磷矿浆在加压反应槽R1内进行酸解反应，加入的干基磷矿1000份，酸解反应操作条件为：温度为110℃，反应压力0.3MPa，反应时间2小时。反应完的酸解料浆进入分离器F1，进行固液分离，得到的固体渣在洗涤器R2进行水洗过程，获得含磷洗水1000份，其中P2O5含量100份，得到的清液进入沉钙槽C1，加入硫酸进行沉钙反应，充分沉钙反应后，反应料浆经真空过滤器F2分离出白色工业石膏和浓磷酸，白色工业石膏洗涤以后获得干净的石膏与含磷洗涤水，经干燥得到干净工业石膏650～750份，同时得到P2O5浓度为43％的磷酸550～570份，含磷酸洗水混合以后，进入浓缩器C2浓缩，98℃浓缩液返回加压反应槽R1作为循环磷酸。The process flow of this embodiment is shown in Figure 2. The P2O5 grade of a phosphate rock is 32wt%, the MgO content in the phosphate rock is 0.8wt%, the sum of the Al2O3 + Fe2O3 content in the phosphate rock is 0.5wt%, and the phosphate rock is ground into a pulp, Centrifuge the pulp water to 18wt% with a decanter centrifuge. The concentrated P2O5 content of 98 ° C phosphoric acid with a content of 37wt% and the phosphate rock slurry with a moisture content of 18wt% are carried out in the pressurized reaction tank R1 for acidolysis reaction, and 1000 parts of dry base phosphate rock are added. The conditions are: the temperature is 110° C., the reaction pressure is 0.3 MPa, and the reaction time is 2 hours. The reacted acidolysis slurry enters the separator F1 for solid-liquid separation, and the obtained solid slag is washed in the scrubber R2 to obtain 1000 parts of phosphorus - containing washing water, including 100 parts of P2O5 , and the obtained clear liquid Enter the calcium precipitation tank C1, add sulfuric acid to carry out the calcium precipitation reaction, after the sufficient calcium precipitation reaction, the reaction slurry is separated through the vacuum filter F2 to separate white industrial gypsum and concentrated phosphoric acid, and after the white industrial gypsum is washed, clean gypsum and phosphorus-containing washing water are obtained After drying, 650-750 parts of clean industrial gypsum can be obtained, and at the same time, 550-570 parts of phosphoric acid with a P2O5 concentration of 43% can be obtained. After mixing the washing water containing phosphoric acid, it enters the concentrator C2 to concentrate, and the 98°C concentrate returns to pressurization reaction Tank R1 acts as a circulating phosphoric acid.
对比例1Comparative example 1
本实施例的工艺流程如附图2所示。某磷矿的P2O5品位为31wt％，磷矿中MgO含量为0.5wt％，磷矿中Al2O3+Fe2O3含量之和为1wt％，把磷矿磨成矿浆，用卧螺式离心机把矿浆水分离心分离到16wt％。把浓缩来的P2O5含量为37wt％的95℃磷酸与含水分16wt％的磷矿浆在加压反应槽R1内进行酸解反应，加入的干基磷矿1000份，酸解反应操作条件为：温度为117℃，反应压力为常压，反应时间为2小时。反应完的酸解料浆进入分离器F1，进行固液分离，得到的固体渣在洗涤器R2进行水洗过程，获得含磷洗水1000份，其中P2O5含量100份，得到的清液进入沉钙槽C1，加入硫酸进行沉钙反应，充分沉钙反应后，反应料浆经真空过滤器F2分离出白色工业石膏和浓磷酸，白色工业石膏洗涤以后获得干净的石膏与含磷洗涤水，经干燥得到干净工业石膏650～750份，同时得到磷酸550～570份，含磷酸洗水混合以后，进入浓缩器C2浓缩，95℃浓缩液返回加压反应槽R1作为循环磷酸。The process flow of this embodiment is shown in Figure 2. The P2O5 grade of a phosphate rock is 31wt%, the MgO content in the phosphate rock is 0.5wt%, and the sum of the Al2O3 + Fe2O3 content in the phosphate rock is 1wt%. A horizontal screw centrifuge centrifugally separates the pulp water to 16wt%. The concentrated P2O5 content of 95°C phosphoric acid with a content of 37wt% and the phosphate rock slurry with a water content of 16wt% were acidolysis reaction in the pressurized reaction tank R1, and 1000 parts of dry base phosphate rock were added, and the acid hydrolysis reaction operation The conditions are: the temperature is 117° C., the reaction pressure is normal pressure, and the reaction time is 2 hours. The reacted acidolysis slurry enters the separator F1 for solid-liquid separation, and the obtained solid slag is washed in the scrubber R2 to obtain 1000 parts of phosphorus - containing washing water, including 100 parts of P2O5 , and the obtained clear liquid Enter the calcium precipitation tank C1, add sulfuric acid to carry out the calcium precipitation reaction, after the sufficient calcium precipitation reaction, the reaction slurry is separated through the vacuum filter F2 to separate white industrial gypsum and concentrated phosphoric acid, and after the white industrial gypsum is washed, clean gypsum and phosphorus-containing washing water are obtained After drying, 650-750 parts of clean industrial gypsum are obtained, and 550-570 parts of phosphoric acid are obtained at the same time. After the washing water containing phosphoric acid is mixed, it enters the concentrator C2 to concentrate, and the 95°C concentrated solution is returned to the pressurized reaction tank R1 as circulating phosphoric acid.
对比例2Comparative example 2
本实施例的工艺流程如附图2所示。某磷矿的P2O5品位为31wt％，磷矿中MgO含量为0.5wt％，磷矿中Al2O3+Fe2O3含量之和为1wt％，把磷矿磨成矿浆，用卧螺式离心机把矿浆水分离心分离到25wt％。把浓缩来的P2O5含量为30wt％的80℃磷酸与含水分25wt％的磷矿浆在加压反应槽R1内进行酸解反应，加入的干基磷矿1000份，酸解反应操作条件为：温度为95℃，反应压力0.1MPa，反应时间1.5小时。反应完的酸解料浆进入分离器F1，进行固液分离，得到的固体渣在洗涤器R2进行水洗过程，获得含磷洗水1000份，其中P2O5含量100份，得到的清液进入沉钙槽C1，加入硫酸进行沉钙反应，充分沉钙反应后，反应料浆经真空过滤器F2分离出白色工业石膏和浓磷酸，白色工业石膏洗涤以后获得干净的石膏与含磷洗涤水，经干燥得到干净工业石膏650～750份，同时得到磷酸550～570份，含磷酸洗水混合以后，进入浓缩器C2浓缩，80℃浓缩液返回加压反应槽R1作为循环磷酸。The process flow of this embodiment is shown in Figure 2. The P2O5 grade of a phosphate rock is 31wt%, the MgO content in the phosphate rock is 0.5wt%, and the sum of the Al2O3 + Fe2O3 content in the phosphate rock is 1wt%. The horizontal screw centrifuge centrifugally separates the pulp water to 25wt%. The concentrated P2O5 content of 80°C phosphoric acid with a content of 30wt% and the phosphate rock slurry with a water content of 25wt% were acidolysis reaction in the pressurized reaction tank R1, and 1000 parts of dry base phosphate rock were added, and the acid hydrolysis reaction operation The conditions are: the temperature is 95° C., the reaction pressure is 0.1 MPa, and the reaction time is 1.5 hours. The reacted acidolysis slurry enters the separator F1 for solid-liquid separation, and the obtained solid slag is washed in the scrubber R2 to obtain 1000 parts of phosphorus - containing washing water, including 100 parts of P2O5 , and the obtained clear liquid Enter the calcium precipitation tank C1, add sulfuric acid to carry out the calcium precipitation reaction, after the sufficient calcium precipitation reaction, the reaction slurry is separated through the vacuum filter F2 to separate white industrial gypsum and concentrated phosphoric acid, and after the white industrial gypsum is washed, clean gypsum and phosphorus-containing washing water are obtained After drying, 650-750 parts of clean industrial gypsum are obtained, and 550-570 parts of phosphoric acid are obtained at the same time. After the washing water containing phosphoric acid is mixed, it enters the concentrator C2 to concentrate, and the 80°C concentrated solution is returned to the pressurized reaction tank R1 as circulating phosphoric acid.
将实施例1-4及对比例1-2制备的磷酸的浓度，工业石膏的含量，磷矿酸解的转化率和酸解反应时间四方面进行对比分析，结果如下表一所示：The concentration of the phosphoric acid prepared by embodiment 1-4 and comparative example 1-2, the content of industrial gypsum, the conversion rate of phosphate rock acid hydrolysis and the four aspects of acid hydrolysis reaction time are comparatively analyzed, and the results are shown in the following table one:
从上表可以看出，本发明技术方案内的实施例1-4中利用高品位磷矿生产湿法磷酸的方法，其第一步酸解反应中，磷矿的转化率均达到97.5％以上，同时酸解反应时间也大大缩短，在120～210min内即可完成，同时制备的湿法磷酸的浓度均在39wt％以上，副产工业石膏中CaSO4·1/2H2O与CaSO4·2H2O的总含量均达到70wt％以上，可以直接投入使用。而反观对比例1及对比例2的制备方法中，酸解磷矿的反应耗时在360～480min，而最终的转化率只有80％，两步反应产出的工业石膏中主产物的含量在51wt％以下，石膏中存在未分解的磷矿，氟化物等多种杂质，性能较差，不能投入使用。As can be seen from the above table, in the method for producing wet-process phosphoric acid using high-grade phosphate rock in Examples 1-4 in the technical solution of the present invention, in the first step of acidolysis reaction, the conversion rate of phosphate rock reaches more than 97.5%. At the same time, the acidolysis reaction time is also greatly shortened, and it can be completed within 120 to 210 minutes. The concentration of wet-process phosphoric acid prepared at the same time is above 39wt%, and CaSO 4 ·1/2H 2 O and CaSO 4 ·in the by-product industrial gypsum The total content of 2H 2 O reaches more than 70wt% and can be directly put into use. On the other hand, in the preparation methods of Comparative Example 1 and Comparative Example 2, the reaction time of acidolysis phosphate rock was 360-480min, and the final conversion rate was only 80%. The content of the main product in the industrial gypsum produced by the two-step reaction was Below 51wt%, there are many impurities such as undecomposed phosphate rock and fluoride in the gypsum, and the performance is poor, so it cannot be put into use.
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| CN109292744A (en) * | 2018-09-04 | 2019-02-01 | 安徽六国化工股份有限公司 | A kind of method that middle-low grade phosphate produces phosphoric acid by wet process and half water ardealite of α |
| CN109628239A (en) * | 2018-12-17 | 2019-04-16 | 武汉飞博乐环保工程有限公司 | Produce method, ceramic cleaning agent and its production method of ceramic cleaning agent coproduction ultrawhite ardealite |
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