CN115197101A - Method for preparing urea by recycling vanadium precipitation wastewater - Google Patents
Method for preparing urea by recycling vanadium precipitation wastewater Download PDFInfo
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 64
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002351 wastewater Substances 0.000 title claims abstract description 46
- 238000001556 precipitation Methods 0.000 title claims abstract description 44
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000004202 carbamide Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000004064 recycling Methods 0.000 title claims abstract description 21
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 23
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011734 sodium Substances 0.000 claims abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 238000010521 absorption reaction Methods 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 238000002386 leaching Methods 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 239000010883 coal ash Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000010881 fly ash Substances 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 239000003245 coal Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000143437 Aciculosporium take Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
- C07C273/04—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds from carbon dioxide and ammonia
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明涉及一种沉钒废水回收利用制取尿素的方法，属于沉钒废水再利用技术领域。本发明所述沉钒废水回收利用制取尿素的方法包括：A.钠化焙烧法沉钒废水的还原；B.SO2的吸收；C.尿素的制备。本发明的沉钒废水回收利用制取尿素的方法，回收效率高，节约了成本。本发明对沉钒废水处理使得后续硫化钠的产率可达到89.3～97.2％，也易被浸出纯化，经过简单的碱液浸出，浓缩干燥后的纯度可达到97.6～99.9％。
The invention relates to a method for preparing urea by recycling vanadium precipitation wastewater, belonging to the technical field of vanadium precipitation wastewater reuse. The method for preparing urea by recycling vanadium precipitation wastewater according to the present invention includes: A. reduction of vanadium precipitation wastewater by sodium roasting method; B. absorption of SO 2 ; C. preparation of urea. The method for preparing urea by recycling vanadium precipitation wastewater of the invention has high recycling efficiency and saves cost. The present invention treats vanadium precipitation wastewater so that the yield of subsequent sodium sulfide can reach 89.3-97.2%, and it is also easy to be leached and purified.
Description
技术领域technical field
本发明涉及一种沉钒废水回收利用制取尿素的方法，属于沉钒废水再利用技术领域。The invention relates to a method for preparing urea by recycling vanadium precipitation wastewater, and belongs to the technical field of vanadium precipitation wastewater reuse.
背景技术Background technique
钒具有众多优异的物理性能和化学性能，用途十分广泛，有金属“维生素”之称。钒的应用范围涵盖了航空航天、化学、电池、颜料、玻璃、光学、医药等众多领域，其中，钒在钢铁工业中的消耗量占其生产总量的85％。钢铁行业的需求直接影响到钒市场行情。大约有10％的钒用于生产航天工业所需的钛合金。钒在钛合金中可以作为稳定剂和强化剂，使钛合金具有很好的延展性和可塑性。此外，钒在化学工业中主要作为催化剂和着色剂。钒还被用于生产可充电氢蓄电池或钒氧化还原蓄电池。此外，国家钢标新条例要求钢中钒含量标准提升原指标25倍。种种原因导致钒需求量剧增，提钒企业全力生产，也就导致提钒所产生的固体废物大量堆积，若不及时处理，不仅仅会让提钒企业或将面临停产危机；提钒尾渣的堆积更是会对环境造成严重污染。Vanadium has many excellent physical and chemical properties, and has a wide range of uses. It is known as a metal "vitamin". The application range of vanadium covers aerospace, chemistry, batteries, pigments, glass, optics, medicine and many other fields. Among them, the consumption of vanadium in the iron and steel industry accounts for 85% of its total production. The demand in the steel industry directly affects the vanadium market. About 10% of vanadium is used in the production of titanium alloys for the aerospace industry. Vanadium can be used as a stabilizer and strengthening agent in titanium alloys, which makes titanium alloys have good ductility and plasticity. In addition, vanadium is mainly used in the chemical industry as a catalyst and a colorant. Vanadium is also used to produce rechargeable hydrogen batteries or vanadium redox batteries. In addition, the new regulations of the national steel standard require that the standard of vanadium content in steel be increased by 25 times the original index. Various reasons have led to a sharp increase in the demand for vanadium, and the vanadium extraction enterprises are fully producing, which also leads to a large amount of solid waste generated by vanadium extraction. The accumulation will cause serious pollution to the environment.
现有工艺对提钒尾渣的处理是对其进行钠化焙烧法提取V2O5，剩余沉钒废水堆积，其中含有氯化铵和硫酸铵，同时含有其他杂质。若不进行妥善处置，不仅造成资源的浪费，不符合清洁生产的要求，长期存放还会引起土壤板结，对周围环境产生明显影响。In the prior art, the vanadium extraction tailings are treated by sodium roasting to extract V 2 O 5 , and the remaining vanadium precipitation wastewater is piled up, which contains ammonium chloride and ammonium sulfate, as well as other impurities. If it is not properly disposed of, it will not only cause waste of resources, but also do not meet the requirements of cleaner production. Long-term storage will also cause soil compaction, which will have a significant impact on the surrounding environment.
发明内容SUMMARY OF THE INVENTION
本发明的第一个目的是提供一种新的沉钒废水回收利用制取尿素的方法。The first object of the present invention is to provide a kind of new method for preparing urea by recycling vanadium precipitation wastewater.
为达到本发明的目的，所述沉钒废水回收利用制取尿素的方法包括：In order to achieve the object of the present invention, the method for preparing urea by recycling the vanadium precipitation wastewater comprises:
A.钠化焙烧法沉钒废水的还原:将提钒后的钒渣用钠化焙烧法提取V2O5，将提取V2O5后的沉钒废水进行梯度焙烧，再加入还原剂后在1000～1150℃的温度下反应1.5～2小时，得到含有硫化钠的固体和SO2、NH3、CO2气体；所述沉钒废水中的水含量9.5wt％以下；A. Reduction of vanadium precipitation wastewater by sodium roasting method: V 2 O 5 is extracted from the vanadium slag after vanadium extraction by sodium roasting method, and the vanadium precipitation wastewater after the extraction of V 2 O 5 is subjected to gradient roasting, and after adding a reducing agent The reaction is carried out at a temperature of 1000-1150° C. for 1.5-2 hours to obtain a solid containing sodium sulfide and SO 2 , NH 3 and CO 2 gas; the water content in the vanadium precipitation wastewater is below 9.5wt%;
所述梯度焙烧首先在1000～1075℃加热0.25～0.3小时，其次是在1085～1135℃加热0.5～0.6小时，最后是在1145～1150℃加热0.75～0.8小时；The gradient roasting is first heated at 1000-1075°C for 0.25-0.3 hours, followed by heating at 1085-1135°C for 0.5-0.6 hours, and finally heated at 1145-1150°C for 0.75-0.8 hours;
B.SO2的吸收：将A步骤中的SO2吸收后，再将CO2和NH3分离；B. Absorption of SO 2 : After absorbing SO 2 in step A, separate CO 2 and NH 3 ;
C.尿素的制备：将分离的CO2和NH3进行反应，得到尿素。C. Preparation of urea: The separated CO 2 and NH 3 are reacted to obtain urea.
所述梯度焙烧首先在1000～1075℃是指回转窑提供的环境温度范围，而不是水的温度范围。The gradient roasting first at 1000-1075°C refers to the ambient temperature range provided by the rotary kiln, not the temperature range of water.
CO2和NH3分离方法可以为常规的分离方法。The CO2 and NH3 separation methods can be conventional separation methods.
例如，将气体通入稀H2SO4，先将NH3吸收，把CO2先分离出来，再向吸收氨气后的溶液中加入NaOH，收集NH3。再例如可采用稀释法、差压法等现有方法分离CO2和NH3，例如CN102688651A公开的氨和二氧化碳混合气体的分离方法。只要能将CO2和NH3分离就可以。For example, pass the gas into dilute H 2 SO 4 , absorb NH 3 first, separate CO 2 first, then add NaOH to the solution after absorbing ammonia gas, and collect NH 3 . For another example, existing methods such as dilution method and differential pressure method can be used to separate CO 2 and NH 3 , for example, the separation method of ammonia and carbon dioxide mixed gas disclosed in CN102688651A. As long as the CO2 and NH3 can be separated.
将分离的CO2和NH3反应生产尿素的方法为常规的二氧化碳汽提法生产尿素工艺，可先将CO2经过净化和压缩，NH3经过降温和冷凝，再进行二氧化碳汽提法生产尿素。The method of reacting the separated CO 2 and NH 3 to produce urea is a conventional carbon dioxide stripping method to produce urea. The CO 2 can be purified and compressed first, and the NH 3 is cooled and condensed, and then the carbon dioxide stripping method can be used to produce urea.
在一种具体实施方式中，所述还原剂为煤粉、粉煤灰中的至少一种。In a specific embodiment, the reducing agent is at least one of pulverized coal and fly ash.
在一种具体实施方式中，A步骤所述沉钒废水进行梯度焙烧后剩余的质量为X，所述X与还原剂的质量的比值为4～5:1。In a specific embodiment, the residual mass of the vanadium precipitation wastewater in step A after gradient roasting is X, and the ratio of X to the mass of the reducing agent is 4-5:1.
在一种具体实施方式中，A步骤所述梯度焙烧至沉钒废水中的水分完全蒸发。In a specific embodiment, the gradient roasting in step A is performed until the water in the vanadium precipitation wastewater is completely evaporated.
在一种具体实施方式中，所述还原剂的粒度大小应保持在7目以下。In a specific embodiment, the particle size of the reducing agent should be kept below 7 mesh.
在一种具体实施方式中，所述方法还包括将含硫化钠的固体用80％的烧碱溶液在温度80～85℃中浸出4～4.5h，取上清液，浓缩干燥得到硫化钠。In a specific embodiment, the method further comprises leaching the solid containing sodium sulfide with 80% caustic soda solution at a temperature of 80-85° C. for 4-4.5 hours, taking the supernatant, concentrating and drying to obtain sodium sulfide.
在一种具体实施方式中，所述硫化钠产率为89.3～97.2％，纯度为97.6～99.9％。In a specific embodiment, the sodium sulfide yield is 89.3-97.2%, and the purity is 97.6-99.9%.
在一种具体实施方式中，B步骤中的SO2用饱和NaHCO3。 In a specific embodiment, the SO2 in step B is saturated NaHCO3 .
在一种具体实施方式中，C步骤所述反应为将CO2压缩到14～15Mpa，将NH3冷凝为液氨，液氨升压16.0～17.5Mpa，再进行二氧化碳汽提法生产尿素。In a specific embodiment, the reaction in step C is to compress CO 2 to 14-15Mpa, condense NH 3 into liquid ammonia, pressurize the liquid ammonia to 16.0-17.5Mpa, and then carry out carbon dioxide stripping to produce urea.
在一种具体实施方式中，C步骤所述反应的温度为180～185℃。In a specific embodiment, the temperature of the reaction in step C is 180-185°C.
有益效果：Beneficial effects:
本发明的沉钒废水回收利用制取尿素的方法，回收效率高，节约了成本。本发明对沉钒废水处理使得后续硫化钠的产率可达到89.3～97.2％，也易被浸出纯化，经过简单的碱液浸出，浓缩干燥后的纯度可达到97.6～99.9％。The method for preparing urea by recycling vanadium precipitation wastewater of the invention has high recycling efficiency and saves cost. The present invention treats vanadium precipitation wastewater so that the yield of subsequent sodium sulfide can reach 89.3-97.2%, and it is easy to be leached and purified.
附图说明Description of drawings
图1为本发明的一种具体实施工艺图。Fig. 1 is a specific implementation process diagram of the present invention.
具体实施方式Detailed ways
为达到本发明的目的，所述沉钒废水回收利用制取尿素的方法包括：In order to achieve the object of the present invention, the method for preparing urea by recycling the vanadium precipitation wastewater comprises:
A.钠化焙烧法沉钒废水的还原:将提钒后的钒渣用钠化焙烧法提取V2O5，将提取V2O5后的沉钒废水进行梯度焙烧，再加入还原剂后在1000～1150℃的温度下反应1.5～2小时，得到含有硫化钠的固体和SO2、NH3、CO2气体；所述沉钒废水中的水含量9.5wt％以下；A. Reduction of vanadium precipitation wastewater by sodium roasting method: V 2 O 5 is extracted from the vanadium slag after vanadium extraction by sodium roasting method, and the vanadium precipitation wastewater after the extraction of V 2 O 5 is subjected to gradient roasting, and after adding a reducing agent The reaction is carried out at a temperature of 1000-1150° C. for 1.5-2 hours to obtain a solid containing sodium sulfide and SO 2 , NH 3 and CO 2 gas; the water content in the vanadium precipitation wastewater is below 9.5wt%;
所述梯度焙烧首先在1000～1075℃加热0.25～0.3小时，其次是在1085～1135℃加热0.5～0.6小时，最后是在1145～1150℃加热0.75～0.8小时；The gradient roasting is first heated at 1000-1075°C for 0.25-0.3 hours, followed by heating at 1085-1135°C for 0.5-0.6 hours, and finally heated at 1145-1150°C for 0.75-0.8 hours;
B.SO2的吸收：将A步骤中的SO2吸收后，再将CO2和NH3分离；B. Absorption of SO 2 : After absorbing SO 2 in step A, separate CO 2 and NH 3 ;
C.尿素的制备：将分离的CO2和NH3进行反应，得到尿素。C. Preparation of urea: The separated CO 2 and NH 3 are reacted to obtain urea.
所述梯度焙烧首先在1000～1075℃是指回转窑提供的环境温度范围，而不是水的温度范围。The gradient roasting first at 1000-1075°C refers to the ambient temperature range provided by the rotary kiln, not the temperature range of water.
将分离的CO2和NH3反应生产尿素的方法可为常规的二氧化碳汽提法生产尿素工艺，可先将CO2经过净化和压缩，NH3经过降温和冷凝，再进行二氧化碳汽提法生产尿素。The method of reacting the separated CO 2 and NH 3 to produce urea can be a conventional carbon dioxide stripping method to produce urea. The CO 2 can be purified and compressed first, NH 3 is cooled and condensed, and then the carbon dioxide stripping method can be used to produce urea. .
在一种具体实施方式中，所述还原剂为煤粉、粉煤灰中的至少一种。In a specific embodiment, the reducing agent is at least one of pulverized coal and fly ash.
在一种具体实施方式中，A步骤所述沉钒废水进行梯度焙烧后剩余的质量为X，所述X与还原剂的质量的比值为4～5:1。In a specific embodiment, the residual mass of the vanadium precipitation wastewater in step A after gradient roasting is X, and the ratio of the mass of X to the reducing agent is 4-5:1.
在一种具体实施方式中，A步骤所述梯度焙烧至沉钒废水中的水分完全蒸发。In a specific embodiment, the gradient roasting in step A is performed until the water in the vanadium precipitation wastewater is completely evaporated.
在一种具体实施方式中，所述还原剂的粒度大小应保持在7目以下。In a specific embodiment, the particle size of the reducing agent should be kept below 7 mesh.
在一种具体实施方式中，所述方法还包括将含硫化钠的固体用80％的烧碱溶液在温度80～85℃中浸出4～4.5h，取上清液，浓缩干燥得到硫化钠。In a specific embodiment, the method further comprises leaching the solid containing sodium sulfide with 80% caustic soda solution at a temperature of 80-85° C. for 4-4.5 hours, taking the supernatant, concentrating and drying to obtain sodium sulfide.
在一种具体实施方式中，所述硫化钠产率为89.3～97.2％，纯度为97.6～99.9％。In a specific embodiment, the sodium sulfide yield is 89.3-97.2%, and the purity is 97.6-99.9%.
在一种具体实施方式中，B步骤中的SO2用饱和NaHCO3。 In a specific embodiment, the SO2 in step B is saturated NaHCO3 .
在一种具体实施方式中，C步骤所述反应为将CO2压缩到14～15Mpa，将NH3冷凝为液氨，液氨升压16.0～17.5Mpa，再进行二氧化碳汽提法生产尿素。In a specific embodiment, the reaction in step C is to compress CO 2 to 14-15Mpa, condense NH 3 into liquid ammonia, pressurize the liquid ammonia to 16.0-17.5Mpa, and then carry out carbon dioxide stripping to produce urea.
在一种具体实施方式中，C步骤所述反应的温度为180～185℃。In a specific embodiment, the temperature of the reaction in step C is 180-185°C.
下面结合实施例对本发明的具体实施方式做进一步的描述，并不因此将本发明限制在所述的实施例范围之中。The specific embodiments of the present invention will be further described below with reference to the examples, but the present invention is not limited to the scope of the described examples.
实施例1Example 1
沉钒废水中的水含量9.1％，先将沉钒废水运送至反应车间焙烧，经过回转室分段梯度连续焙烧，依次在1054℃焙烧0.28h、1100℃焙烧0.55h、1148℃焙烧0.77h。焙烧后水分完全蒸发。回转炉型号KY-LQ600-10m，再与含碳量高的高品质煤粉(煤粉颗粒度小于7目)混合，废水干燥过后的固体质量和煤粉按重量比为5:1。在以煤气为热源、反应温度为1020℃下反应1.8h。反应旋转炉型号为QC-M1800-18IK。设备处理能力5t/台·h。The water content in the vanadium precipitation wastewater is 9.1%. First, the vanadium precipitation wastewater is transported to the reaction workshop for roasting, and is continuously roasted in a segmented gradient in a rotary chamber. The water evaporates completely after roasting. The rotary furnace model KY-LQ600-10m is mixed with high-quality pulverized coal with high carbon content (the particle size of pulverized coal is less than 7 meshes). The reaction was carried out at a reaction temperature of 1020 °C for 1.8 h with coal gas as the heat source. The model of the reaction rotary furnace is QC-M1800-18IK. The equipment processing capacity is 5t/unit h.
旋转炉反应后被还原气体直接通往吸收室，用饱和NaHCO3吸收掉SO2，剩余的NH3和CO2气体通入稀H2SO4，先将NH3吸收，把CO2先分离出来，再向吸收氨气的溶液中加入NaOH，收集NH3，CO2经过升压到约14.4Mpa，从底部送入汽提塔。NH3先压缩为液氨，液氨升压至16.8Mpa8，再经过预热与过滤，然后通入尿素合成塔，最后产生的产物进行蒸发造粒，得到成品尿素。After the reaction in the rotary furnace, the reduced gas directly leads to the absorption chamber, and the SO 2 is absorbed by saturated NaHCO 3 . The remaining NH 3 and CO 2 gases are passed into the dilute H 2 SO 4 , and the NH 3 is absorbed first, and the CO 2 is separated first. , and then add NaOH to the solution absorbing ammonia gas to collect NH 3 , CO 2 is boosted to about 14.4Mpa, and sent to the stripper from the bottom. NH3 is first compressed into liquid ammonia, the liquid ammonia is boosted to 16.8Mpa8, then preheated and filtered, and then passed into the urea synthesis tower, and the final product is evaporated and granulated to obtain the finished urea.
旋转炉反应后剩余的固体冷却至700℃，放入温度为80℃、浓度为80％的NaOH溶液中浸取4.5h，浸取后，取上层清液，经浓缩干燥，得到硫化钠。After the reaction in the rotary furnace, the remaining solid was cooled to 700°C, and then put into a NaOH solution with a temperature of 80°C and a concentration of 80% for leaching for 4.5 hours. After leaching, the supernatant was taken and concentrated and dried to obtain sodium sulfide.
得到硫化钠的产率为96.8％；经检测，硫化钠的纯度为99.2％。The yield of sodium sulfide is 96.8%; after testing, the purity of sodium sulfide is 99.2%.
实施例2Example 2
a、将1kg沉钒废水采用分段梯度连续焙烧，其中以质量分数计算，沉钒废水中Na2SO468.0％，(NH4)2SO4 20.2％，H2O 9.1％，NH4Cl0.8％，其他1.9％。分段梯度连续焙烧的过程为：先在1054℃加热0.25h；再在1100℃加热0.5h；最后在1148℃加热0.75h。分段梯度连续焙烧结束后，沉钒废水中水分完全蒸发；a. 1kg vanadium precipitation wastewater is continuously roasted by staged gradient, in which, calculated by mass fraction, Na 2 SO 4 68.0%, (NH 4 ) 2 SO 4 20.2%, H 2 O 9.1%, NH 4 Cl0 .8%, other 1.9%. The stepwise gradient continuous calcination process is as follows: heating at 1054°C for 0.25h; heating at 1100°C for 0.5h; and finally heating at 1148°C for 0.75h. After the segmented gradient continuous roasting is completed, the water in the vanadium precipitation wastewater is completely evaporated;
b、将煤粉粉碎，至粒径＜7目；b. Pulverize the pulverized coal to a particle size of less than 7 meshes;
c、将分段梯度连续焙烧后的原料和煤粉按重量比为5:1混合，用煤气加热进行还原反应，反应温度为1000℃，反应时间控制在2h，得到固体的预产物和混合气体；c. Mix the raw material and pulverized coal after staged gradient continuous roasting in a weight ratio of 5:1, heat with gas to carry out reduction reaction, the reaction temperature is 1000°C, and the reaction time is controlled at 2h to obtain a solid pre-product and mixed gas ;
d、将预产物冷却至700℃，放入温度为80℃、浓度为80％的NaOH溶液中浸取4.5h，浸取后，取上层清液，经浓缩干燥，得到硫化钠。d. Cool the pre-product to 700°C, put it into a NaOH solution with a temperature of 80°C and a concentration of 80% for leaching for 4.5 hours, after leaching, take the supernatant, concentrate and dry to obtain sodium sulfide.
得到硫化钠的重量为356.1g，产率为95.4％；经检测，硫化钠的纯度为99.5％。The weight of the obtained sodium sulfide was 356.1 g, and the yield was 95.4%; after testing, the purity of the sodium sulfide was 99.5%.
NH3和CO2分离，CO2经过净化压缩，NH3先压缩为液氨，再经过预热与过滤，然后通入尿素合成塔，最后产生的产物进行蒸发造粒，得到成品尿素112g。NH 3 and CO 2 are separated, CO 2 is purified and compressed, NH 3 is first compressed into liquid ammonia, then preheated and filtered, and then passed into the urea synthesis tower. The final product is evaporated and granulated to obtain 112g of finished urea.
对比例1Comparative Example 1
a、取1kg的沉钒废水，废水中Na2SO468.0％，(NH4)2SO420.2％，H2O 9.0％，将沉钒废水在1150℃加热6h后，沉钒废水的含水量为0％。a. Take 1kg of vanadium precipitation wastewater, the waste water contains Na 2 SO 4 68.0%, (NH 4 ) 2 SO 4 20.2%, and H 2 O 9.0%. The amount of water is 0%.
b、将煤粉粉碎，至粒径＜7目；b. Pulverize the pulverized coal to a particle size of less than 7 meshes;
c、将干燥过后的原料和煤粉按重量比为5:1混合，用煤气加热进行还原反应，反应温度为1000℃，反应时间控制在2h，得到预产物；c. Mix the dried raw material and pulverized coal in a weight ratio of 5:1, heat with gas to carry out a reduction reaction, the reaction temperature is 1000°C, and the reaction time is controlled at 2h to obtain a pre-product;
d、将预产物冷却至700℃，放入温度为80℃、浓度为80％的NaOH溶液中浸取4.5h，浸取后，取上层清液，经浓缩干燥，得到硫化钠。d. Cool the pre-product to 700°C, put it into a NaOH solution with a temperature of 80°C and a concentration of 80% for leaching for 4.5 hours, after leaching, take the supernatant, concentrate and dry to obtain sodium sulfide.
得到硫化钠的重量为194.8g，产率为60.2％，经检测，纯度为90.4％。The weight of the obtained sodium sulfide is 194.8 g, the yield is 60.2%, and the purity is 90.4% after testing.
NH3和CO2分离，CO2经过净化压缩，NH3先压缩为液氨，再经过预热与过滤，然后通入尿素合成塔，最后产生的产物进行蒸发造粒，得到成品尿素72g。NH 3 and CO 2 are separated, CO 2 is purified and compressed, NH 3 is first compressed into liquid ammonia, then preheated and filtered, and then passed into the urea synthesis tower, and the final product is evaporated and granulated to obtain 72g of finished urea.
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