CN111960393A - Preparation method of nitric acid without yellow smoke - Google Patents
Preparation method of nitric acid without yellow smoke Download PDFInfo
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- CN111960393A CN111960393A CN202010866838.4A CN202010866838A CN111960393A CN 111960393 A CN111960393 A CN 111960393A CN 202010866838 A CN202010866838 A CN 202010866838A CN 111960393 A CN111960393 A CN 111960393A
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- nitric acid
- hydrogen peroxide
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- yellow smoke
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910017604 nitric acid Inorganic materials 0.000 title claims abstract description 95
- 239000000779 smoke Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 183
- 239000003381 stabilizer Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 claims description 21
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 18
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 18
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 229910021389 graphene Inorganic materials 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 238000007865 diluting Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- -1 perfluoro Chemical group 0.000 claims description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- QFVGCVZHAQQIMT-UHFFFAOYSA-L nickel(2+);prop-2-enoate Chemical compound [Ni+2].[O-]C(=O)C=C.[O-]C(=O)C=C QFVGCVZHAQQIMT-UHFFFAOYSA-L 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 210000003298 dental enamel Anatomy 0.000 claims description 5
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 11
- 150000004706 metal oxides Chemical class 0.000 abstract description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000004383 yellowing Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000005374 membrane filtration Methods 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 238000001471 micro-filtration Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- SKHRWYIOPCHLGQ-UHFFFAOYSA-N formaldehyde thiourea 1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC(N)=S.NC1=NC(N)=NC(N)=N1 SKHRWYIOPCHLGQ-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 235000001465 calcium Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
- C01B21/46—Purification; Separation ; Stabilisation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of fine chemical engineering, in particular to a preparation method of nitric acid without yellow smoke; the method comprises the following steps: oxidation and rectification; the invention adopts the cheap hydrogen peroxide oxidant to oxidize and remove the nitric oxide in the nitric acid to generate the nitric acid, solves the problems of yellowing and yellow smoke generation of industrial nitric acid solution and has great significance for further standing of the nitric acid; according to the invention, the superfine active metal oxide is added into the hydrogen peroxide solution as the hydrogen peroxide stabilizer, so that the decomposition of hydrogen peroxide can be effectively prevented, the stability of hydrogen peroxide is increased, the reaction time can be increased in the reaction process, the superfine active metal oxide is fully contacted with nitric oxide in a nitric acid solution, the use efficiency of hydrogen peroxide is increased, and the use amount of hydrogen peroxide is reduced; the method is an economic and cheap method for treating the industrial nitric acid, the nitric acid treated by the method can reduce the process steps of further purifying the nitric acid, simplify the treatment procedure and greatly save the treatment cost.
Description
Technical Field
The invention relates to the field of fine chemical engineering, in particular to a preparation method of nitric acid without yellow smoke.
Background
Nitric acid is strong acid with strong oxidizing property and corrosiveness, belongs to unitary inorganic strong acid, is one of six inorganic strong acids, and is also an important chemical raw material. Can be used for preparing chemical fertilizers, pesticides, explosives, dyes, salts and the like in industry. The requirement for nitric acid in the electronics industry is very high, and industrial grade nitric acid needs to be purified before use.
CN109835877A discloses an electronic grade high-purity nitric acid purification method, which comprises a rectifying tower, wherein a heating coil is arranged in the rectifying tower, the heating coil is made of metallic nickel, polypropylene Raschig ring packing is filled in the rectifying tower, the diameter of the rectifying tower is 150-280mm, and the height of the rectifying tower is 3-15 m; the diameter of the rectifying tower is set to be 150-280mm, the height of the rectifying tower is set to be 3-15m, the reflux ratio is controlled to be 1: 2-1: 5, a heating coil pipe material in the rectifying tower is set to be metallic nickel, and polypropylene Raschig ring packing is filled in the rectifying tower. The method can achieve the final electronic grade high-purity nitric acid product by one-time distillation, saves resources and reduces pollution.
CN109835924A adopts a double decomposition method of calcium nitrate solution and potassium chloride, potassium nitrate is produced by freezing, and calcium chloride is a byproduct. Compared with the prior art: has the characteristics of short process flow, simple equipment, high product purity, high potassium chloride conversion rate, low energy consumption, low production cost, good byproduct sale and the like. And no equipment corrosion, no waste gas, waste water and waste residue pollution are generated in the production process. The calcium nitrate is generated by the reaction of dilute nitric acid and ground limestone (high-purity limestone or common limestone) powder, so that the cost is low; the reaction is carried out under the conditions of normal temperature and normal pressure, the energy consumption is low, and the process conditions are easy to control. Limestone powder can be replaced by other calcium sources (such as heavy calcium, light calcium, quicklime, slaked lime, carbide slag, or calcium carbonate converted from phosphogypsum). The calcium carbonate converted from the scale gypsum is used for producing potassium nitrate, so that the economic and social benefits are greater.
CN103601163B discloses a preparation method of high-purity nitric acid, which comprises the steps of taking industrial-grade nitric acid as a raw material, adding metal nitrate for reaction, carrying out membrane filtration through a microfiltration membrane to remove impurity anions in the nitric acid, carrying out membrane filtration through a melamine-formaldehyde-thiourea resin/polyacrylic resin composite membrane to remove impurity cations in the nitric acid, and carrying out rectification, high-purity water blending, whitening blowing and microfiltration membrane filtration on filtrate to obtain a target product. The content of the high-purity nitric acid obtained by the method is 69-70 wt%, the content of impurity metal ions is lower than 1ppb, the number of dust particles larger than 0.5 micron is lower than 5/ml, the high-purity nitric acid meets the standard of SEMI C8, the microfiltration membrane is used for membrane filtration, and the melamine-formaldehyde-thiourea resin/polyacrylic resin composite membrane is used for membrane filtration, so that the impurity anions and cations in industrial-grade nitric acid can be effectively removed, the raw materials for preparing the composite membrane can be reused, the product purity is good, and the method is suitable for industrial production.
The industrial nitric acid contains a large amount of oxynitride, so that the nitric acid solution is yellow, yellow smoke is generated, oxynitride smoke pollutes the environment and has great harm to human bodies, and in addition, the existence of oxynitride has great influence on the further refining of the nitric acid.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of nitric acid without yellow smoke.
A preparation method of nitric acid without yellow smoke comprises the following operation:
step one, oxidizing, namely adding 200 parts by mass of 60-80% industrial-grade nitric acid into an oxidation reaction kettle, adding 4-15 parts by mass of 30-35% hydrogen peroxide solution, and carrying out a circular reaction for 3-5 hours; the hydrogen peroxide solution contains hydrogen peroxide stabilizer, and the method comprises the following steps:
adding 20-50 parts by mass of hydrogen peroxide solution into an ultrasonic mixing kettle, adding 0.00001-0.00005 part by mass of hydrogen peroxide stabilizer, stirring and mixing uniformly at room temperature, and performing ultrasonic treatment for 30-60min to obtain the product;
and step two, rectification, namely introducing the treated nitric acid into a rectification tower after oxidation reaction, rectifying at the tower top temperature of 110-125 ℃ under the condition of a reflux ratio of 1:2.1-3.2, condensing by a tower top condenser, introducing the collected rectification liquid into an intermediate tank, and diluting and blending the rectification liquid into the nitric acid without yellow smoke by using ultrapure water.
The invention relates to a method for removing a yellow NOx compound in nitric acid, which comprises the steps of adding hydrogen peroxide into nitric acid containing NOx by using the oxidation of hydrogen peroxide, and reacting the hydrogen peroxide with the NOx as follows, so that the purpose of removing the yellow NOx compound in the nitric acid is achieved.
2NO2+H2O2=2HNO3
2NO+3H2O2=2HNO3+2H2O
The hydrogen peroxide stabilizer is an ultrafine active metal oxide, and the preparation method comprises the following steps:
step 1: mixing 1-4 parts of graphite oxide and 5-12 parts of allyltrimethoxysilane by weight, adding 100-300 parts of solvent oil, and reacting at 80-90 ℃ for 1-5 h; and then adding 12-30 parts of hydrazine hydrate and 50-80 parts of ammonia water, reacting for 2-5 hours at 70-90 ℃, filtering, washing, and drying in vacuum to obtain the allyltrimethoxysilane grafted graphene.
Step 2: adding 20-30 parts of manganese dioxide, 200-300 parts of solvent oil, 1.2-3.2 parts of allyl trimethoxy silane grafted graphene, 1-5 parts of nickel acrylate and 0.1-0.5 part of potassium persulfate, introducing nitrogen, mixing and stirring at 60-70 ℃ for 2-5 hours, filtering, and drying to obtain the hydrogen peroxide stabilizer.
The soluble metal salt is magnesium chloride or aluminum chloride or zirconium chloride.
The hydroxypropyl cellulose is high-substituted hydroxypropyl cellulose.
The oxidation reaction kettle is a perfluoro material lining reaction kettle or an enamel reaction kettle.
The ultrasonic frequency of the ultrasonic treatment is 10-20 kHz.
The average particle size of the hydrogen peroxide stabilizer is 20-50 μm.
According to the preparation method of the nitric acid without yellow smoke, nitric oxide in the nitric acid is oxidized and removed by adopting a cheap hydrogen peroxide oxidant to generate the nitric acid, so that the problems of yellowing and yellow smoke generation of an industrial nitric acid solution are solved, and the preparation method has great significance for further standing of the nitric acid; according to the invention, the superfine active metal oxide is added into the hydrogen peroxide solution as the hydrogen peroxide stabilizer, so that the decomposition of hydrogen peroxide can be effectively prevented, the stability of hydrogen peroxide is increased, the reaction time can be increased in the reaction process, the superfine active metal oxide is fully contacted with nitric oxide in a nitric acid solution, the use efficiency of hydrogen peroxide is increased, and the use amount of hydrogen peroxide is reduced; the method is an economic and cheap method for treating the industrial nitric acid, the nitric acid treated by the method can reduce the process steps of further purifying the nitric acid, simplify the treatment procedure and greatly save the treatment cost.
Detailed Description
The invention is further illustrated by the following specific examples:
the method for testing the stabilizing effect of the hydrogen peroxide stabilizer prepared in the experiment on hydrogen peroxide is as follows: adding 1.5ppm of hydrogen peroxide stabilizer into 30% hydrogen peroxide according to an experimental method, then heating at 90 ℃ for 60min, measuring the concentration of hydrogen peroxide at 30min and 60min, and calculating the hydrogen peroxide stability rate according to the hydrogen peroxide stability rate% = the hydrogen peroxide concentration before heating/the hydrogen peroxide concentration after heating.
Example 1
A preparation method of nitric acid without yellow smoke comprises the following operation:
step one, oxidizing, namely adding 200kg of industrial nitric acid with the mass percentage content of 60-80% into an oxidation reaction kettle, adding 4kg of hydrogen peroxide solution with the mass percentage content of 30%, and carrying out cyclic reaction for 3 hours; the hydrogen peroxide solution contains hydrogen peroxide stabilizer, and the method comprises the following steps:
adding 20kg of hydrogen peroxide solution into an ultrasonic mixing kettle, adding 0.00001kg of hydrogen peroxide stabilizer, stirring and mixing uniformly at room temperature, and performing ultrasonic treatment for 30min to obtain the product;
and step two, rectification, namely introducing the treated nitric acid into a rectification tower after oxidation reaction, rectifying at the tower top temperature of 110 ℃ under the condition of a reflux ratio of 1:2.1, condensing by a condenser at the tower top, introducing the collected rectification liquid into an intermediate tank, and diluting and blending the rectification liquid into the nitric acid without yellow smoke by using ultrapure water.
The hydrogen peroxide stabilizer is an ultrafine active metal oxide, and the preparation method comprises the following steps:
step 1: mixing 1kg of graphite oxide and 5kg of allyltrimethoxysilane, adding 100kg of solvent oil, and reacting for 1h at 80 ℃; and then adding 12kg of hydrazine hydrate and 50kg of ammonia water, reacting for 2 hours at 70 ℃, filtering, washing, and drying in vacuum to obtain the allyltrimethoxysilane grafted graphene.
Step 2: adding 20kg of manganese dioxide into 200kg of solvent naphtha, 1.2kg of allyl trimethoxy silane grafted graphene, 1kg of nickel acrylate and 0.1kg of potassium persulfate, introducing nitrogen, mixing and stirring for 2 hours at 60 ℃, filtering and drying to obtain the hydrogen peroxide stabilizer.
The soluble metal salt is magnesium chloride.
The hydroxypropyl cellulose is high-substituted hydroxypropyl cellulose.
The oxidation reaction kettle is a perfluoro material lining reaction kettle.
The ultrasonic frequency of the ultrasonic treatment is 10 kHz.
The average particle size of the hydrogen peroxide stabilizer is 20 μm.
The electronic grade nitric acid after the experiment is a colorless transparent solution, no yellow smoke is generated, the chromaticity and the impurity ion content of the nitric acid product are shown in an attached table, the 30-min hydrogen peroxide stability rate is 99.2%, and the 60-min hydrogen peroxide stability rate is 99.0%.
Example 2
A preparation method of nitric acid without yellow smoke comprises the following operation:
step one, oxidizing, namely adding 240kg of industrial nitric acid with the mass percentage content of 70% into an oxidation reaction kettle, adding 8kg of hydrogen peroxide solution with the mass percentage content of 33%, and circularly reacting for 4 hours; the hydrogen peroxide solution contains hydrogen peroxide stabilizer, and the method comprises the following steps:
adding 40kg of hydrogen peroxide solution into an ultrasonic mixing kettle, adding 0.00003kg of hydrogen peroxide stabilizer, stirring and mixing uniformly at room temperature, and performing ultrasonic treatment for 45min to obtain the product;
and step two, rectification, namely introducing the treated nitric acid into a rectification tower after oxidation reaction, rectifying at the tower top temperature of 120 ℃ under the condition of a reflux ratio of 1:2.8, condensing by a tower top condenser, introducing the collected rectification liquid into an intermediate tank, and diluting and blending the rectification liquid into the nitric acid without yellow smoke by using ultrapure water.
The hydrogen peroxide stabilizer is an ultrafine active metal oxide, and the preparation method comprises the following steps:
step 1: mixing 2kg of graphite oxide and 7kg of allyltrimethoxysilane, adding 200kg of solvent oil, and reacting for 2 hours at 85 ℃; and then adding 18kg of hydrazine hydrate and 70kg of ammonia water, reacting for 4 hours at 80 ℃, filtering, washing, and drying in vacuum to obtain the allyltrimethoxysilane grafted graphene.
Step 2: adding 23kg of manganese dioxide into 250kg of solvent naphtha, 1.8kg of allyl trimethoxy silane grafted graphene, 3kg of nickel acrylate and 0.2kg of potassium persulfate, introducing nitrogen, mixing and stirring for 3 hours at 65 ℃, filtering and drying to obtain the hydrogen peroxide stabilizer.
The soluble metal salt is aluminum chloride.
The hydroxypropyl cellulose is high-substituted hydroxypropyl cellulose.
The oxidation reaction kettle is an enamel reaction kettle.
The ultrasonic frequency of the ultrasonic treatment is 15 kHz.
The average particle size of the hydrogen peroxide stabilizer is 30 μm.
The electronic grade nitric acid after the experiment is a colorless transparent solution, no yellow smoke is generated, the chromaticity and the impurity ion content of the nitric acid product are shown in an attached table, the 30-min hydrogen peroxide stability rate is 99.4%, and the 60-min hydrogen peroxide stability rate is 99.1%.
Example 3
A preparation method of nitric acid without yellow smoke comprises the following operation:
step one, oxidizing, namely adding 300kg of industrial nitric acid with the mass percentage content of 80% into an oxidation reaction kettle, adding 15kg of hydrogen peroxide solution with the mass percentage content of 35%, and circularly reacting for 5 hours; the hydrogen peroxide solution contains hydrogen peroxide stabilizer, and the method comprises the following steps:
adding 50kg of hydrogen peroxide solution into an ultrasonic mixing kettle, adding 0.00005kg of hydrogen peroxide stabilizer, stirring and mixing uniformly at room temperature, and performing ultrasonic treatment for 60min to obtain the product;
and step two, rectification, namely introducing the treated nitric acid into a rectification tower after oxidation reaction, rectifying at the tower top temperature of 125 ℃ under the condition of a reflux ratio of 1:3.2, condensing by a condenser at the tower top, introducing the collected rectification liquid into an intermediate tank, and diluting and blending the rectification liquid into the nitric acid without yellow smoke by using ultrapure water.
The hydrogen peroxide stabilizer is an ultrafine active metal oxide, and the preparation method comprises the following steps:
step 1: mixing 4kg of graphite oxide and 12kg of allyltrimethoxysilane, adding 300kg of solvent oil, and reacting for 5 hours at 90 ℃; and then adding 30kg of hydrazine hydrate and 80kg of ammonia water, reacting for 5 hours at 90 ℃, filtering, washing, and drying in vacuum to obtain the allyltrimethoxysilane grafted graphene.
Step 2: adding 30kg of manganese dioxide into 300kg of solvent naphtha, 3.2kg of allyl trimethoxy silane grafted graphene, 5kg of nickel acrylate and 0.5kg of potassium persulfate, introducing nitrogen, mixing and stirring for 5 hours at 70 ℃, filtering and drying to obtain the hydrogen peroxide stabilizer.
The soluble metal salt is zirconium chloride.
The hydroxypropyl cellulose is high-substituted hydroxypropyl cellulose.
The oxidation reaction kettle is an enamel reaction kettle.
The ultrasonic frequency of the ultrasonic treatment is 20 kHz.
The average particle size of the hydrogen peroxide stabilizer is 50 μm.
The electronic grade nitric acid after the experiment is a colorless transparent solution, no yellow smoke is generated, the chromaticity and the impurity ion content of the nitric acid product are shown in an attached table, the 30-min hydrogen peroxide stability rate is 99.7%, and the 60-min hydrogen peroxide stability rate is 99.6%.
Example 4
A preparation method of nitric acid without yellow smoke comprises the following operation:
step one, oxidizing, namely adding 200kg of industrial nitric acid with the mass percentage content of 60-80% into an oxidation reaction kettle, adding 4kg of hydrogen peroxide solution with the mass percentage content of 30%, and carrying out cyclic reaction for 3 hours; the hydrogen peroxide solution contains hydrogen peroxide stabilizer, and the method comprises the following steps:
adding 20kg of hydrogen peroxide solution into an ultrasonic mixing kettle, adding 0.00001kg of hydrogen peroxide stabilizer, stirring and mixing uniformly at room temperature, and performing ultrasonic treatment for 30min to obtain the product;
and step two, rectification, namely introducing the treated nitric acid into a rectification tower after oxidation reaction, rectifying at the tower top temperature of 110 ℃ under the condition of a reflux ratio of 1:2.1, condensing by a condenser at the tower top, introducing the collected rectification liquid into an intermediate tank, and diluting and blending the rectification liquid into the nitric acid without yellow smoke by using ultrapure water.
The hydrogen peroxide stabilizer is an ultrafine active metal oxide, and the preparation method comprises the following steps:
step 1: mixing 1kg of graphite oxide and 12kg of allyltrimethoxysilane, adding 100kg of solvent oil, and reacting for 5 hours at 80 ℃; and then adding 12kg of hydrazine hydrate and 80kg of ammonia water, reacting for 5h at 70 ℃, filtering, washing, and drying in vacuum to obtain the allyltrimethoxysilane grafted graphene.
Step 2: adding 30kg of manganese dioxide into 300kg of solvent naphtha, 1.2kg of allyl trimethoxy silane grafted graphene, 1kg of nickel acrylate and 0.5kg of potassium persulfate, introducing nitrogen, mixing and stirring for 2 hours at 70 ℃, filtering and drying to obtain the hydrogen peroxide stabilizer.
The soluble metal salt is zirconium chloride.
The hydroxypropyl cellulose is high-substituted hydroxypropyl cellulose.
The oxidation reaction kettle is an enamel reaction kettle.
The ultrasonic frequency of the ultrasonic treatment is 20 kHz.
The average particle size of the hydrogen peroxide stabilizer is 50 μm.
The electronic grade nitric acid after the experiment is a colorless transparent solution, no yellow smoke is generated, the chromaticity and the impurity ion content of the nitric acid product are shown in table 1, the 30-min hydrogen peroxide stability rate is 99.3%, and the 60-min hydrogen peroxide stability rate is 99.1%.
Comparative example 1
A preparation method of nitric acid without yellow smoke comprises the following operation:
step one, oxidizing, namely adding 200kg of industrial nitric acid with the mass percentage content of 60-80% into an oxidation reaction kettle, adding 4kg of hydrogen peroxide solution with the mass percentage content of 30%, and carrying out cyclic reaction for 3 hours; the hydrogen peroxide solution contains hydrogen peroxide stabilizer, and the method comprises the following steps:
adding 20kg of hydrogen peroxide solution into an ultrasonic mixing kettle, adding 0.00001kg of hydrogen peroxide stabilizer, stirring and mixing uniformly at room temperature, and performing ultrasonic treatment for 30min to obtain the product;
and step two, rectification, namely introducing the treated nitric acid into a rectification tower after oxidation reaction, rectifying at the tower top temperature of 110 ℃ under the condition of a reflux ratio of 1:2.1, condensing by a condenser at the tower top, introducing the collected rectification liquid into an intermediate tank, and diluting and blending the rectification liquid into the nitric acid without yellow smoke by using ultrapure water.
The hydrogen peroxide stabilizer is an ultrafine active metal oxide, and the preparation method comprises the following steps:
adding 20kg of manganese dioxide into 200kg of solvent naphtha, 1.2kg of graphene, 1kg of nickel acrylate and 0.1kg of potassium persulfate, introducing nitrogen, mixing and stirring for 2 hours at 60 ℃, filtering and drying to obtain the hydrogen peroxide stabilizer.
The soluble metal salt is magnesium chloride.
The hydroxypropyl cellulose is high-substituted hydroxypropyl cellulose.
The oxidation reaction kettle is a perfluoro material lining reaction kettle.
The ultrasonic frequency of the ultrasonic treatment is 10 kHz.
The electronic grade nitric acid subjected to the experiment is a colorless transparent solution, no yellow smoke is generated, the hydrogen peroxide stability rate is 85.4% in 30min, and the hydrogen peroxide stability rate is 82.6% in 60 min.
Comparative example 2
A preparation method of nitric acid without yellow smoke comprises the following operation:
step one, oxidizing, namely adding 200kg of industrial nitric acid with the mass percentage content of 60-80% into an oxidation reaction kettle, adding 4kg of hydrogen peroxide solution with the mass percentage content of 30%, and carrying out cyclic reaction for 3 hours; the hydrogen peroxide solution contains hydrogen peroxide stabilizer, and the method comprises the following steps:
adding 20kg of hydrogen peroxide solution into an ultrasonic mixing kettle, adding 0.00001kg of hydrogen peroxide stabilizer, and stirring and mixing uniformly at room temperature to obtain the product;
and step two, rectification, namely introducing the treated nitric acid into a rectification tower after oxidation reaction, rectifying at the tower top temperature of 110 ℃ under the condition of a reflux ratio of 1:2.1, condensing by a condenser at the tower top, introducing the collected rectification liquid into an intermediate tank, and diluting and blending the rectification liquid into the nitric acid without yellow smoke by using ultrapure water.
The hydrogen peroxide stabilizer is an ultrafine active metal oxide, and the preparation method comprises the following steps:
step 1: mixing 1kg of graphite oxide and 5kg of allyltrimethoxysilane, adding 100kg of solvent oil, and reacting for 1h at 80 ℃; and then adding 12kg of hydrazine hydrate and 50kg of ammonia water, reacting for 2 hours at 70 ℃, filtering, washing, and drying in vacuum to obtain the allyltrimethoxysilane grafted graphene.
Step 2: adding 20kg of manganese dioxide into 200kg of solvent naphtha, 1.2kg of allyl trimethoxy silane grafted graphene and 0.1kg of potassium persulfate, introducing nitrogen, mixing and stirring for 2 hours at 60 ℃, filtering and drying to obtain the hydrogen peroxide stabilizer.
The soluble metal salt is magnesium chloride.
The hydroxypropyl cellulose is high-substituted hydroxypropyl cellulose.
The oxidation reaction kettle is a perfluoro material lining reaction kettle.
The average particle size of the hydrogen peroxide stabilizer is 20 μm.
The electronic grade nitric acid after the experiment is a colorless transparent solution, no yellow smoke is generated, the hydrogen peroxide stability rate is 96.3% in 30min and 94.7% in 60 min.
Comparative example 3
A preparation method of nitric acid without yellow smoke comprises the following operation:
step one, oxidizing, namely adding 200kg of industrial nitric acid with the mass percentage content of 80% into an oxidation reaction kettle, adding 4kg of hydrogen peroxide solution with the mass percentage content of 30%, and circularly reacting for 3 hours; the method comprises the following steps:
adding 20kg of hydrogen peroxide solution into an ultrasonic mixing kettle, adding 0.00001kg of hydrogen peroxide stabilizer, stirring and mixing uniformly at room temperature, and performing ultrasonic treatment for 30min to obtain the product;
and step two, rectification, namely introducing the treated nitric acid into a rectification tower after oxidation reaction, rectifying at the tower top temperature of 110 ℃ under the condition of a reflux ratio of 1:2.1, condensing by a condenser at the tower top, introducing the collected rectification liquid into an intermediate tank, and diluting and blending the rectification liquid into the nitric acid without yellow smoke by using ultrapure water.
The soluble metal salt is magnesium chloride.
The hydroxypropyl cellulose is high-substituted hydroxypropyl cellulose.
The oxidation reaction kettle is a perfluoro material lining reaction kettle.
The ultrasonic frequency of the ultrasonic treatment is 10 kHz.
The average particle size of the hydrogen peroxide stabilizer is 20 μm.
The electronic grade nitric acid after the experiment is a colorless transparent solution, no yellow smoke is generated, the hydrogen peroxide stability rate is 98.1% in 30min and 96.7% in 60 min.
Table 1 example electronic grade nitric acid index
Claims (7)
1. A preparation method of nitric acid without yellow smoke comprises the following operation:
step one, oxidizing, namely adding 200 parts by mass of 60-80% industrial-grade nitric acid into an oxidation reaction kettle, adding 4-15 parts by mass of 30-35% hydrogen peroxide solution, and carrying out a circular reaction for 3-5 hours; the hydrogen peroxide solution contains hydrogen peroxide stabilizer, and the method comprises the following steps:
adding 20-50 parts by mass of hydrogen peroxide solution into an ultrasonic mixing kettle, adding 0.00001-0.00005 part by mass of hydrogen peroxide stabilizer, stirring and mixing uniformly at room temperature, and performing ultrasonic treatment for 30-60min to obtain the product;
and step two, rectification, namely introducing the treated nitric acid into a rectification tower after oxidation reaction, rectifying at the tower top temperature of 110-125 ℃ under the condition of a reflux ratio of 1:2.1-3.2, condensing by a tower top condenser, introducing the collected rectification liquid into an intermediate tank, and diluting and blending the rectification liquid into the nitric acid without yellow smoke by using ultrapure water.
2. The method of claim 1 for the production of nitric acid with no yellow smoke, comprising: the preparation method of the hydrogen peroxide stabilizer comprises the following steps:
step 1: mixing 1-4 parts of graphite oxide and 5-12 parts of allyltrimethoxysilane by weight, adding 100-300 parts of solvent oil, and reacting at 80-90 ℃ for 1-5 h; then adding 12-30 parts of hydrazine hydrate and 50-80 parts of ammonia water, reacting for 2-5 hours at 70-90 ℃, filtering, washing, and drying in vacuum to obtain the allyltrimethoxysilane grafted graphene;
step 2: adding 20-30 parts of manganese dioxide, 200-300 parts of solvent oil, 1.2-3.2 parts of allyl trimethoxy silane grafted graphene, 1-5 parts of nickel acrylate and 0.1-0.5 part of potassium persulfate, introducing nitrogen, mixing and stirring at 60-70 ℃ for 2-5 hours, filtering, and drying to obtain the hydrogen peroxide stabilizer.
3. The method of claim 2, wherein the nitric acid is prepared by: the soluble metal salt is magnesium chloride or aluminum chloride or zirconium chloride.
4. The method of claim 2, wherein the nitric acid is prepared by: the hydroxypropyl cellulose is high-substituted hydroxypropyl cellulose.
5. The method of claim 1 for the production of nitric acid with no yellow smoke, comprising: the oxidation reaction kettle is a perfluoro material lining reaction kettle or an enamel reaction kettle.
6. The method of claim 1 for the production of nitric acid with no yellow smoke, comprising: the ultrasonic frequency of the ultrasonic treatment is 10-20 kHz.
7. The method of claim 1 for the production of nitric acid with no yellow smoke, comprising: the average particle size of the hydrogen peroxide stabilizer is 20-50 μm.
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