CN104341008B - Preparation method of ferric nitrate solution with low NOx emission - Google Patents
Preparation method of ferric nitrate solution with low NOx emission Download PDFInfo
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- CN104341008B CN104341008B CN201310334110.7A CN201310334110A CN104341008B CN 104341008 B CN104341008 B CN 104341008B CN 201310334110 A CN201310334110 A CN 201310334110A CN 104341008 B CN104341008 B CN 104341008B
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- iron
- oxygen
- nitric acid
- reaction
- nitrate solution
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- 238000002360 preparation method Methods 0.000 title claims description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 title abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 74
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000001301 oxygen Substances 0.000 claims abstract description 51
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 229910052742 iron Inorganic materials 0.000 claims abstract description 36
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 35
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 22
- 229910001868 water Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 9
- 229910002089 NOx Inorganic materials 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000012544 monitoring process Methods 0.000 claims abstract description 8
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010521 absorption reaction Methods 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 230000000740 bleeding effect Effects 0.000 claims description 9
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 53
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000002386 leaching Methods 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
Landscapes
- Compounds Of Iron (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to a method for preparing ferric nitrate solution with low NOx emission; adding metal iron sheets or scrap iron and deionized water into a reaction kettle, introducing oxygen into the kettle, and closing an oxygen supply valve and an exhaust valve when the mass of oxygen in gas flowing out of an exhaust port reaches 99.9%; adding a nitric acid solution with the mass concentration of 5-65% into a kettle in batches, and introducing oxygen; the molar ratio of the metallic iron to the nitric acid is 1: 3.1-4.5; the reaction temperature of the dissolved iron is 30-100 ℃; keeping the pressure of 0.1-1.0 Mpa, keeping the temperature at 50-150 ℃ in the later period, opening an exhaust valve after the reaction is finished, and monitoring the content of nitrogen dioxide in tail gas after the tail gas is washed by water in a washing tank and then in an absorption tube; the method is characterized in that nitric oxide generated by nitric acid is converted into nitric acid under the condition of oxygen, the nitric acid continuously participates in the oxidation leaching reaction process of metals, a water washing process is added in tail gas emission, the emission of nitric oxide is controlled to meet the environmental protection requirement, and water washing water can be recycled.
Description
Technical field
The present invention relates to field of material preparation, the preparation method of a kind of industrial iron nitrate solution.
Background technology
Catalyst preparation process is commonly used nitrate, such as oxidative dehydrogenation process are used ferric nitrate, molten iron
During Bei, nitric acid and metallic iron react generation nitrogen oxides, it is well known that environment and human body are made by nitrogen oxides
Becoming the biggest harm, therefore, environmental emission standard-required nitrogen oxides controls at 200mg/m3Hereinafter, conventional nitrogen
Oxide Treatment process uses urea absorption technology, but this technology cannot meet current environmental protection mark
Accurate, it is therefore desirable to seek the nitrogen oxides that molten iron produces by new method and strictly control.
Nitrogen oxides is administered and is recycled it has been reported that wherein disclose in Patent No. CN101029357A
" during gold smelting, nitrogen oxides is administered and the method recycled ", it is miscellaneous that the method only relates to gold smelting
The process of matter, and process tail gas through 20% NaOH wash liquid process can be only achieved discharge standard.The present invention
Relating to the preparation of nitrate, tail gas only just can reach emission request by water-washing process, and these washings are recycled to
Nitric acid dilution, is not required to administer further.
The present invention proposes the ferric nitrate preparation method of a kind of environmental type.
Summary of the invention
It is an object of the invention to provide the iron nitrate solution preparation method of a kind of low NOx drainage, this method can
So that discharged nitrous oxides is directly reduced or avoided, reduces raw material nitric acid simultaneously and consume；And react high without high temperature
Pressure, equipment is simple, invests little, easily realizes industrialized production, has good application prospect, it is possible to extensively
It is applied to iron nitrate solution preparing technical field.
The iron nitrate solution preparation method of described a kind of low NOx drainage of the present invention, comprises the following steps:
(1) metal iron plate or iron filings and deionized water are joined in reactor, close kettle cover, open reaction
The oxygen supply valve of still, is passed through oxygen in still, with air in replacement of oxygen still, until exhaust outlet eluting gas oxygen
When quality reaches 99.9%, close oxygen supply valve and air bleeding valve；
(2) by mass concentration be 5～65% salpeter solution loading hopper add the most in batches in still in still,
In still, oxygen it is passed through while adding nitric acid；The mol ratio of metallic iron and nitric acid is 1:3.1-4.5；
(3) molten iron reaction temperature controls at 30-100 DEG C；
(4) keeping 0.1～1.0Mpa pressure after nitric acid all adds, in the molten iron process later stage, temperature controls
50-150 DEG C, after reaction thoroughly terminates, opening air bleeding valve, tail gas washes the monitoring of laggard absorption tube through water washing tank
Nitrogen dioxide content.
The preferred 1:3.1-3.3 of mol ratio of described metallic iron and nitric acid.
Described employing closed pressure vessel is as reacting environment, and its operating pressure is provided by oxygen, preferably 0.2-0.5
Mpa。
The described preferred 10-30% of salpeter solution concentration.
Described molten iron reaction temperature is 30-50 DEG C.
Described nitric acid reacts the later stage with iron, and temperature controls at 70-100 DEG C.
The principle of the present invention:
The chemical reaction of nitric acid and iron can be described as follows by reaction equation:
Fe+4HNO3→Fe(NO3)3+NO+2H2O (1)
After being passed through oxygen in closed pressure vessel, nitric acid and iron react the nitric oxide produced and react, and retouch
State as follows:
NO+1/2O2→NO2(2)
Owing to reaction is carried out in closed pressure vessel, contact with water after nitrogen dioxide generation and react, describe
As follows:
2NO2+H2O→HNO2+HNO3(3)
Thereafter, there is again following reaction:
3HNO2→2NO+HNO3+H2O (4)
The NO that reactions steps (4) produces reacts again (2), and NO is progressively converted dangerous by circular response successively
To the greatest extent.
Airtight face oxygen under the conditions of, nitric acid and iron react total equation and are:
Fe+0.75O2+3HNO3→Fe(NO3)3+1.5H2O
During reclaiming nitrogen oxides in situ, there is a certain amount of nitrous acid in system, the system temperature raising of needs promotes nitrous
Acid decomposition produces nitric oxide then, and nitric oxide continues and oxygen reaction ultimately generates nitric acid.
After reaction terminates, by water-washing process before exhaust emissions, washing water reuse dilution nitric acid, the method is true
Just achieve environmental protection and prepare ferric nitrate.
Detailed description of the invention
Embodiment 1
75 grams of iron plates or iron filings and 500g deionized water are put into reactor simultaneously；It is sealed reactor, uses oxygen
Air in displacement still；During until the content of exhaust outlet eluting gas oxygen reaches 99.9%, close oxygen supply valve and air bleeding valve；
In batches the nitric acid of the 54% of 400ml is added reactor by loading hopper, be passed through oxygen off and on, and protect
Holding pressure in still is 0.3Mpa, and course of reaction leads to condensed water, keeps reaction temperature to be 30-40 DEG C, after reaction
Phase, raising temperature in the kettle, to 80 DEG C, promotes nitrous acid to decompose and produces nitric oxide, and nitric oxide continues and oxygen
Solid/liquid/gas reactions ultimately generates nitric acid.Treat that vessel temp is down to room temperature, open reactor blow-off valve, utilize oxygen in container
Liquid complete for reaction is discharged by atmospheric pressure, obtains nitrate solution.Monitoring tail gas NO2Content is 77.6
mg/m3。
Embodiment 2
75 grams of iron plates or iron filings and 500g deionized water are put into reactor simultaneously；It is sealed reactor, uses oxygen
Air in displacement still, during until the content of exhaust outlet eluting gas oxygen reaches 99.9%, closes oxygen supply valve and air bleeding valve；
In batches the nitric acid of the 54% of 380ml is added reactor by loading hopper, be continually fed into oxygen, and keep
In still, pressure is 0.4Mpa, and course of reaction leads to condensed water, keeps reaction temperature to be 40-50 DEG C, reacts the later stage,
Raising temperature in the kettle, to 90 DEG C, promotes nitrous acid to decompose and produces nitric oxide, and nitric oxide continues and oxygen is anti-
Nitric acid should be ultimately generated.Treat that vessel temp is down to room temperature, open reactor blow-off valve, utilize oxygen pressure in container
Liquid complete for reaction is discharged by power, obtains nitrate solution.Monitoring tail gas NO2Content is 58.36mg/m3。
Embodiment 3
75 grams of iron plates or iron filings and 500g deionized water are put into reactor simultaneously；It is sealed reactor, uses oxygen
Air in displacement still；During until the content of exhaust outlet eluting gas oxygen reaches 99.9%, close oxygen supply valve and air bleeding valve；
In batches the nitric acid of the 54% of 450ml is added reactor by loading hopper, be continually fed into oxygen, and keep
In still, pressure is 0.5Mpa, and course of reaction leads to condensed water, keeps reaction temperature to be 30-40 DEG C, reacts the later stage,
Raising temperature in the kettle, to 100 DEG C, promotes nitrous acid to decompose and produces nitric oxide, and nitric oxide continues and oxygen
Reaction ultimately generates nitric acid.Treat that vessel temp is down to room temperature, open reactor blow-off valve, utilize oxygen in container
Liquid complete for reaction is discharged by pressure, obtains nitrate solution.Monitoring tail gas NO2Content is 96.8mg/m3。
Embodiment 4
75 grams of iron plates or iron filings 500g deionized water are put into reactor simultaneously；It is sealed reactor, puts with oxygen
Change air in still；During until the content of exhaust outlet eluting gas oxygen reaches 99.9%, close oxygen supply valve and air bleeding valve；
In batches the nitric acid of the 54% of 480ml is added reactor by loading hopper, be passed through oxygen off and on, and protect
Holding pressure in still is 0.4Mpa, and course of reaction leads to condensed water, keeps reaction temperature to be 30-40 DEG C, after reaction
Phase, raising temperature in the kettle, to 90 DEG C, promotes nitrous acid to decompose and produces nitric oxide, and nitric oxide continues and oxygen
Solid/liquid/gas reactions ultimately generates nitric acid.Treat that vessel temp is down to room temperature, open reactor blow-off valve, utilize oxygen in container
Liquid complete for reaction is discharged by atmospheric pressure, obtains nitrate solution.Monitoring tail gas NO2Content is 64.7
mg/m3。
Embodiment 5
75 grams of iron plates or iron filings 500g deionized water are put into reactor simultaneously；It is sealed reactor, puts with oxygen
Change air in still；During until the content of exhaust outlet eluting gas oxygen reaches 99.9%, close oxygen supply valve and air bleeding valve；
In batches the nitric acid of the 54% of 510ml is added reactor by loading hopper, be continually fed into oxygen, and keep
In still, pressure is 0.4Mpa, and course of reaction leads to condensed water, keeps reaction temperature to be 30-40 DEG C, reacts the later stage,
Raising temperature in the kettle, to 90 DEG C, promotes nitrous acid to decompose and produces nitric oxide, and nitric oxide continues and oxygen is anti-
Nitric acid should be ultimately generated.Treat that vessel temp is down to room temperature, open reactor blow-off valve, utilize oxygen pressure in container
Liquid complete for reaction is discharged by power, obtains nitrate solution.Monitoring tail gas NO2Content is 64.7mg/m3。
Claims (4)
1. the method that prepared by the iron nitrate solution of low NOx drainage, is characterized in that:
(1) metal iron plate or iron filings and deionized water are joined in reactor, close kettle cover, open the confession of reactor
Oxygen valve, is passed through oxygen in still, with air in replacement of oxygen still, until the quality of exhaust outlet eluting gas oxygen reaches 99.9%
Time, close oxygen supply valve and air bleeding valve；
(2) by mass concentration be 5～65% salpeter solution loading hopper add the most in batches in still, add nitric acid
While in still, be passed through oxygen；The mol ratio of metallic iron and nitric acid is 1:3.1-4.5；
(3) molten iron reaction temperature controls at 30-100 DEG C；
(4) using closed pressure vessel as reacting environment, nitric acid keeps 0.2-0.5MPa pressure after all adding, molten
In the iron process later stage, temperature controls at 50-100 DEG C, after reaction thoroughly terminates, opens air bleeding valve, and tail gas is through water washing tank water
Wash laggard absorption tube monitoring nitrogen dioxide content.
The iron nitrate solution preparation method of low NOx drainage the most according to claim 1, is characterized in that: metallic iron and nitric acid
Mol ratio is 1:3.2-3.5.
The iron nitrate solution preparation method of low NOx drainage the most according to claim 1, is characterized in that: during described molten iron
Salpeter solution mass concentration is 10-30%.
The iron nitrate solution preparation method of low NOx drainage the most according to claim 1, is characterized in that: after nitric acid reacts with iron
Phase, temperature controls at 70-100 DEG C.
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| CN201310334110.7A CN104341008B (en) | 2013-08-02 | 2013-08-02 | Preparation method of ferric nitrate solution with low NOx emission |
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| CN201310334110.7A CN104341008B (en) | 2013-08-02 | 2013-08-02 | Preparation method of ferric nitrate solution with low NOx emission |
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| CN104341008B true CN104341008B (en) | 2016-09-07 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107601572A (en) * | 2017-11-09 | 2018-01-19 | 佛山市华希盛化工有限公司 | A kind of preparation method of high pure nitric acid ferrous solution and its serialization |
| CN109264788A (en) * | 2018-11-15 | 2019-01-25 | 湖北省宏源药业科技股份有限公司 | A kind of preparation facilities and method of ferric nitrate |
| CN111068476A (en) * | 2019-12-14 | 2020-04-28 | 汪子夏 | NO in process of dissolving metal by nitric acidXTail gas treatment device and method and terminal |
| CN112479245B (en) * | 2020-12-15 | 2022-12-20 | 先导薄膜材料（广东）有限公司 | Preparation method of indium nitrate solution |
| CN113926418A (en) * | 2021-11-19 | 2022-01-14 | 广东长信精密设备有限公司 | Nitric acid and pure metal reaction device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2193114A (en) * | 1986-06-02 | 1988-02-03 | Ici Plc | Catalysts |
| US4808393A (en) * | 1987-09-18 | 1989-02-28 | Mineral Research And Development Corp. | Process for manufacture of ferric nitrate |
| CN101746733A (en) * | 2008-12-11 | 2010-06-23 | 中科合成油技术有限公司 | Method and equipment for continuous preparation of metallic oxide material and catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100957855B1 (en) * | 2008-03-31 | 2010-05-14 | (주) 휴브글로벌 | Method of manufacturing ferric nitrate |
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2013
- 2013-08-02 CN CN201310334110.7A patent/CN104341008B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2193114A (en) * | 1986-06-02 | 1988-02-03 | Ici Plc | Catalysts |
| US4808393A (en) * | 1987-09-18 | 1989-02-28 | Mineral Research And Development Corp. | Process for manufacture of ferric nitrate |
| CN101746733A (en) * | 2008-12-11 | 2010-06-23 | 中科合成油技术有限公司 | Method and equipment for continuous preparation of metallic oxide material and catalyst |
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