CN108975411A - A kind of iron oxide red production method - Google Patents
A kind of iron oxide red production method Download PDFInfo
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- CN108975411A CN108975411A CN201810941445.8A CN201810941445A CN108975411A CN 108975411 A CN108975411 A CN 108975411A CN 201810941445 A CN201810941445 A CN 201810941445A CN 108975411 A CN108975411 A CN 108975411A
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- iron oxide
- oxide red
- seed crystal
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 75
- 239000002002 slurry Substances 0.000 claims abstract description 49
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000001301 oxygen Substances 0.000 claims abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 33
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 32
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 28
- 230000003647 oxidation Effects 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 25
- 229910017604 nitric acid Inorganic materials 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000007791 liquid phase Substances 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 69
- 239000000049 pigment Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 3
- 238000010792 warming Methods 0.000 abstract 2
- 239000000428 dust Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 29
- 239000002245 particle Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000001054 red pigment Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- -1 reacting for 90min Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of iron oxide red production methods, belong to technical field of chemical pigments.This method includes being added to metallic iron and water in closed crystal seed reactor, is warming up to scheduled initial reaction temperature；Dust technology is added into the crystal seed reactor, while being passed through oxygen and carrying out reacting obtained iron oxide red seed crystal slurries；The iron oxide red seed crystal slurries and water, ferrous salt and metallic iron are added in closed second oxidation reactor or the iron oxide red seed crystal slurries and water, ferrous nitrate and alkali are added in closed second oxidation reactor；It is passed through oxygen, and is warming up to second oxidation reaction predetermined temperature and carries out oxidation reaction, iron oxide red is made.The present invention solves the problems, such as nitrogen oxides pollution discharge from technique source.Moreover, it is also fewer than consumed by other techniques using ferrous nitrate consumed by production method production per kilogram iron oxide red, production cost is reduced, it is economical and practical.
Description
Technical Field
The invention belongs to the technical field of chemical pigments, and particularly relates to a production method of iron oxide red.
Background
The iron oxide red has strong tinting strength, strong covering power, no toxicity and stable physical and chemical properties, can be widely used as pigment in paint, printing ink, ceramics, building materials, plastics and papermaking, and can also be used in the fields of catalysis, battery anode materials and the like. The performance of the iron oxide red is closely related to the primary particle size of the iron oxide red crystal, and different requirements are imposed on the primary particle size and the distribution of the iron oxide red crystal in different application fields. The particle size and the particle size distribution of the iron oxide red product are closely related to the production process conditions, and the change of the production process conditions can cause the change of the crystal particle size and the distribution of the crystal particle size of the product, thereby affecting the performance of the product, so that the production process conditions are strictly controlled for producing the high-quality iron oxide red pigment.
The iron oxide red prepared by the dry method has coarse and hard particle size, difficult regulation and control of crystal particle size, morphology and color and poor pigment performance, and the wet method is generally adopted to produce the iron oxide red pigment industrially. The wet preparation of iron oxide red pigment includes sulfuric acid process, nitric acid process and mixed acid process, and the sulfuric acid process adopts ferrous sulfate solution for seed crystal preparation and two-step oxidation, so that the produced iron oxide red pigment has dark color and poor pigment performance. The iron oxide red product produced by the nitric acid method is bright in color and optimal in pigment performance, the iron oxide red product produced by the mixed acid method has acceptable pigment performance and can be accepted by the market, but the existing nitric acid method and mixed acid method can produce a large amount of nitrogen oxide gas in the production process, the nitrogen oxide is toxic to human bodies, can damage the atmospheric ozone layer under ultraviolet radiation when being discharged into the atmosphere, and is a strong greenhouse effect gas, and in order to avoid the direct discharge of the produced nitrogen oxide into the atmosphere, CN104628043B provides treatment measures such as ultraviolet irradiation, nitric acid absorption, Selective Catalytic Reduction (SCR) and the like. CN108176203A proposes five-step methods of cooling and dedusting, concentrated nitric acid oxidation, dilute nitric acid absorption, alkali absorption and Selective Catalytic Reduction (SCR) to treat nitrogen oxide tail gas, and the terminal treatment investment and treatment cost are high.
Therefore, the invention provides a method for producing iron oxide red by eliminating nitrogen oxides from a process source.
Disclosure of Invention
The invention aims to provide a method for producing iron oxide red, which eliminates nitrogen oxides from a process source, realizes energy conservation and consumption reduction, and overcomes the defects of large amount of nitrogen oxide waste gas generated by the existing iron oxide red production process, large investment for end treatment and high treatment cost.
The technical scheme of the invention is as follows:
a production method of iron oxide red comprises the preparation of iron oxide red seed crystal slurry and two-step oxidation; wherein,
the preparation of the iron oxide red seed crystal slurry comprises the following steps:
step A1: adding metallic iron and water into a closed seed crystal reactor, and heating to a preset seed crystal reaction starting temperature;
step A2: adding dilute nitric acid into the seed crystal reactor, introducing oxygen into the seed crystal reactor, enabling the oxygen to circularly enter a seed crystal reaction liquid phase by using a first circulating device, and preparing iron oxide red seed crystal slurry after the reaction is finished;
the two-step oxidation comprises the following steps:
step B1: adding metallic iron, the iron oxide red seed crystal slurry and water into a closed two-step oxidation reactor;
step B2: heating to the preset temperature of the second-step oxidation reaction, adding ferrous salt at least comprising ferrous nitrate into the second-step oxidation reactor, introducing oxygen, and enabling the oxygen to circularly enter the liquid phase of the second-step oxidation reaction by using a second circulating device until the reaction is finished when the color is slightly similar to that of a standard sample to prepare iron oxide red slurry;
step B3: filtering, washing and drying the iron oxide red slurry to obtain an iron oxide red finished product;
or,
step C1: adding the iron oxide red seed crystal slurry into a closed two-step oxidation reactor, and heating to a preset temperature for two-step oxidation reaction;
step C2: adding ferrous nitrate and alkali into the two-step oxidation reactor, introducing oxygen, and enabling the oxygen to circularly enter a liquid phase of the two-step oxidation reaction by using a third circulating device until the color is slightly similar to that of a standard sample, and finishing the reaction to prepare iron oxide red slurry;
step C3: and filtering, washing and drying the iron oxide red slurry to obtain an iron oxide red finished product.
Preferably, the seed crystal reaction preset temperature in the step A1 is 85-160 ℃.
Preferably, the adding of the ferrous salt in the step B2 and the adding of the ferrous nitrate in the step C2 are carried out in a single step before the reaction or in batches or continuously during the reaction.
Further preferably, the concentrations of the ferrous salt added in the step B2 and the ferrous nitrate added in the step C2 are kept between 5 and 80 g/L.
Preferably, the base in step C2 comprises one or more of sodium hydroxide, potassium hydroxide, calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, ammonia or aqueous ammonia.
It is further preferred that the pH of the liquid phase is maintained between 1 and 4.5 by the addition of a base in step C2.
Preferably, the purity of the oxygen introduced in the step A2, the step B2 and the step C2 is in the range of 80-100%.
Preferably, the first circulation device in step a2, the second circulation device in step B2, and the third circulation device in step C2 are air compressors, self-priming stirrers, or venturi ejectors.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects or advantages:
in the process of reaction, the reaction container is closed, no waste gas is discharged basically, the nitrogen oxide is consumed gradually in the reaction process, and only a small amount of waste gas is discharged when the reaction is finished. Compared with the existing method for preparing the iron oxide red, the method solves the problem of nitrogen oxide pollution emission from a process source, and simultaneously reduces the consumption of steam in production. In addition, the ferrous nitrate consumed by producing each kilogram of iron oxide red by adopting the production method of the iron oxide red provided by the invention is less than that consumed by other processes, so that the production cost is reduced, and the method is economical and practical.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
Preparing iron oxide red seed crystal slurry:
adding 14.32Kg of iron sheet and 110Kg of water into a seed crystal reactor, heating the medium in the seed crystal reactor to 85 ℃, sealing the seed crystal reactor, adding 18Kg of 32% dilute nitric acid, introducing oxygen into the seed crystal reactor at the same time, keeping the oxygen partial pressure in the container above 0.1MPa, dispersing the gas in the seed crystal reactor into a liquid phase by using a self-suction stirrer, and continuing to react for 90min after the nitric acid is added to prepare the iron oxide red seed crystal slurry. Through measurement, the slurry iron oxide red crystal seed is 13.76Kg, and the content of nitrogen oxide (by NO) in tail gas2Calculated) is 496mg/m3. A slurry containing 2.39Kg of iron oxide red seeds per kilogram of nitric acid was obtained.
Example 2
Preparing iron oxide red seed crystal slurry:
adding 14.41Kg of iron sheet and 110Kg of water into a seed crystal reactor, heating the medium in the seed crystal reactor to 85 ℃, sealing the reactor, adding 17.2Kg of dilute nitric acid with the concentration of 32%, and introducing oxygen into the container at the same time to keep the oxygen partial pressure in the container above 0.06MPa, pressurizing the gas in the seed crystal reactor by using an air compressor, and then blowing the gas into a liquid phase, wherein the circulating flow of the gas is 0.4m3After the nitric acid is added, the gas is continuously circulated for 90min, the reaction is finished, the gas circulation is stopped, and the slurry contains 13.87Kg of iron oxide red crystal seeds and the content of nitrogen oxides (by NO) in tail gas is measured2Calculated) is 287mg/m3. 2.52Kg of iron red seed crystal can be obtained per kilogram of nitric acid.
Example 3
Preparing iron oxide red seed crystal slurry:
adding 14.5Kg of iron sheet and 110Kg of water into a seed crystal reactor, heating the medium in the seed crystal reactor to 160 ℃, sealing the reactor, adding 17.5Kg of 32% dilute nitric acid, and introducing oxygen into the container to maintain the oxygen partial pressure in the container above 0.08MPa, and using a Venturi tube ejector to reversely seed crystalAnd circularly dispersing the gas in the reactor in the liquid phase, reacting for 90min, and finishing the reaction. The measured slurry contains 13.82Kg of iron oxide red crystal seeds and the content of nitrogen oxides (by NO) in tail gas2Calculated) is 352mg/m3. A slurry containing 2.46Kg of iron oxide red seeds per kilogram of nitric acid was prepared.
Example 4
Preparing iron oxide red seed crystal slurry:
adding 14.40Kg of iron sheet and 110Kg of water into a seed crystal reactor, heating the medium in the seed crystal reactor to 115 ℃, sealing the seed crystal reactor, adding 17.3Kg of 32% dilute nitric acid, introducing oxygen into the seed crystal reactor at the same time, keeping the oxygen partial pressure in the container at 0.07MPa, circularly dispersing the gas in the seed crystal reactor into a liquid phase by using a Venturi tube ejector, and continuously reacting for 90min after the nitric acid is added to prepare the iron oxide red seed crystal slurry. Through measurement, the slurry iron oxide red crystal seed is 13.70Kg, and the content of nitrogen oxide (by NO) in tail gas2Calculated) is 338mg/m3. A slurry containing 2.47Kg of iron oxide red seeds per kilogram of nitric acid was obtained.
Example 5
Preparing iron oxide red seed crystal slurry:
adding 14.43Kg of iron sheet and 110Kg of water into a seed crystal reactor, heating the medium in the seed crystal reactor to 135 ℃, sealing the seed crystal reactor, adding 17.0Kg of 32% dilute nitric acid, introducing oxygen into the seed crystal reactor at the same time, keeping the oxygen partial pressure in the container at 0.09MPa, dispersing the gas in the seed crystal reactor into a liquid phase by using a self-suction stirrer, and continuing to react for 90min after the nitric acid is added to prepare the iron oxide red seed crystal slurry. Through measurement, the slurry iron oxide red crystal seed is 13.70Kg, and the content of nitrogen oxide (by NO) in tail gas2Calculated) is 368mg/m3. A slurry containing 2.51Kg of iron oxide red seeds per kilogram of nitric acid was prepared.
Example 6
And (2) two-step oxidation:
in a two-step oxidation reactor, 206.3kg of iron sheet and 1.6m3Water, iron oxide red seed crystal slurry (solid content is 32Kg) and ferrous nitrate solution make the medium contain 32g/L ferrous nitrate, the reaction medium is heated to 70 ℃, an exhaust valve is closed, oxygen is introduced, the reaction temperature is continuously heated to 85 ℃, gas is pressurized and blown into the liquid phase by an air compressor, and the circulating flow of the gas is 9.3m3H, continuously introducing oxygen to keep the oxygen partial pressure in the container at 0.05MPa, reacting until the content of iron ions is lower than 0.1g/L, and after the reaction is finished, the content of nitrogen oxides in tail gas is 163mg/m3The slurry is filtered, washed and dried to obtain 161.5Kg of iron oxide red finished product, and each kilogram of ferrous nitrate can prepare 2.13Kg of iron oxide red.
Example 7
And (2) two-step oxidation:
adding water, iron oxide red seed crystal slurry (solid content is 28.3kg) and ferrous nitrate solution into a two-step oxidation reactor with a stirring self-suction device, starting stirring, heating the solution to 70 ℃, closing an exhaust valve, starting to introduce oxygen, continuing to heat to the reaction temperature of 85 ℃, adding a proper amount of sodium hydroxide into the solution to ensure that the pH value of the solution is between 1.5 and 4, stirring and self-suction by using a self-suction stirrer to disperse gas into a liquid phase, continuously introducing oxygen to ensure that the oxygen partial pressure in the container is kept at 0.6MPa, continuously replenishing the ferrous nitrate solution and the sodium hydroxide solution along with the reaction, continuing the reaction until the iron red color is similar to that of a standard sample, and after the reaction is finished, ensuring that the content of nitrogen oxides in tail gas is 87mg/m3And filtering, washing and drying to obtain the finished product of the iron oxide red.
Example 8
And (2) two-step oxidation:
adding water, iron oxide red seed crystal slurry (containing 352Kg of solid content) and ferrous nitrate (the initial concentration of ferrous nitrate is 46g/L) to 30m3In the two-step oxidation reactor with the circulating pipe (a Parthala clamping groove structure reactor), the solution is heated to 70 ℃, the exhaust valve is closed, oxygen is introduced, the gas is pressurized by the air compressor and then is blown into the liquid phase at the lower end in the circulating pipe, and the circulating flow of the gas is 84m3And h, continuously introducing oxygen to keep the oxygen partial pressure in the container at 0.3 MPa. Adding a proper amount of sodium hydroxide into the solution to ensure that the pH value of the solution is between 1.5 and 4, continuously heating to ensure that the reaction temperature reaches 85 ℃, continuously supplementing the ferrous nitrate solution and the sodium hydroxide solution along with the reaction until the color of the iron oxide red is similar to that of a standard sample, and after the reaction is finished, the content of nitrogen oxides in tail gas is 173mg/m3And filtering, washing and drying the iron oxide red pigment.
Example 9
And (2) two-step oxidation:
mixing 208kg of iron sheet with the diameter of 1.6m3Adding water, iron oxide red seed crystal slurry (containing 28.9Kg of solid content) and ferrous nitrate solution (containing 60.8Kg of ferrous nitrate) into a two-step oxidation reactor, heating the solution to 70 ℃, closing an exhaust valve, starting to introduce oxygen, continuing to heat to enable the reaction temperature to reach 85 ℃, circularly dispersing gas in the reactor into a liquid phase by utilizing a Venturi tube ejector, and continuously introducing oxygen to enable the oxygen partial pressure in the container to be kept at 0.08 MPa. The reaction is continued until the content of ferrous nitrate in the solution is lower than 0.1g/L, and after the reaction is finished, the content of nitrogen oxide in tail gas is 96mg/m3The slurry is filtered, washed and dried to obtain 177.2Kg of finished iron oxide red, and each kilogram of ferrous nitrate can prepare 2.44Kg of iron oxide red.
It should be noted here that, in order to make the reaction fully, in the above examples, the iron sheet added is excessive whether the iron oxide red seed slurry is prepared or the two-step oxidation is carried out; the higher the purity of the introduced oxygen, the better, preferably, the purity range of the oxygen is between 80 and 100 percent, and more preferably, the purity range of the oxygen is between 89 and 100 percent.
In addition, the method for adding the ferrous nitrate in the above examples 6 to 9 is to add the ferrous nitrate once before the reaction or add the ferrous nitrate in batches or continuously in the reaction, so as to ensure that the concentration of the ferrous nitrate is kept between 5 and 80 g/L. In example 7 and example 8, in addition to the sodium hydroxide solution, one or more of potassium hydroxide, calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, ammonia or ammonia water may be added, which is not limited herein.
Comparative example 1
Preparing iron oxide red seed crystal slurry:
adding 14.48Kg of iron sheet and 110Kg of water into a reactor, heating the medium in the reactor to 85 ℃, sealing the reactor, adding 18Kg of dilute nitric acid with the concentration of 32%, continuously reacting under constant pressure for 90min after the nitric acid is added, and keeping the nitrogen oxide content (in NO) in the tail gas2Calculated) is 22450mg/m3And filtering, washing and drying the slurry to obtain 9.9Kg of iron oxide red seed crystal. 1.72Kg of iron red seed crystal can be obtained per kilogram of nitric acid.
Comparative example 2
And (2) two-step oxidation:
in a two-step oxidation reactor, 206.3Kg of fluffy iron sheet, 1.6m of 3 water, iron oxide red seed crystal slurry (containing 32Kg of solid content) and ferrous nitrate solution are added to ensure that the medium contains 32g/L of ferrous nitrate, the reaction medium is heated to 70 ℃, an exhaust valve is closed, air starts to be introduced, and the air flow is maintained at 11.5m3H, continuing heating to enable the reaction temperature to reach 85 ℃, reacting until the content of ferrous nitrate in the solution is lower than 0.1g/L, and after the reaction is finished, the content of nitrogen oxide in tail gas is 18326mg/m3The slurry is filtered, washed and dried to obtain 121.4Kg of finished iron oxide red, and each kilogram of ferrous nitrate can prepare 1.47Kg of iron oxide red.
Compared with the comparative example, the content of the nitrogen oxide waste gas generated in the preparation process of the iron oxide red is greatly reduced, the problem of nitrogen oxide pollution emission is solved from a process source, and the consumption of steam in production is reduced.
Furthermore, the ferrous nitrate consumed by producing each kilogram of iron oxide red by adopting the iron oxide red production method provided by the embodiment of the invention is less than that consumed by other processes, so that the production cost is reduced, and the method is economical and practical.
The invention is not limited to the above alternative embodiments, and any other various forms of products can be obtained by anyone in the light of the present invention, but any changes in shape or structure thereof, which fall within the scope of the present invention as defined in the claims, fall within the scope of the present invention.
Claims (8)
1. The production method of the iron oxide red is characterized by comprising the steps of preparing iron oxide red seed crystal slurry and carrying out two-step oxidation; wherein,
the preparation of the iron oxide red seed crystal slurry comprises the following steps:
step A1: adding metallic iron and water into a closed seed crystal reactor, and heating to a preset seed crystal reaction starting temperature;
step A2: adding dilute nitric acid into the seed crystal reactor, introducing oxygen into the seed crystal reactor, enabling the oxygen to circularly enter a seed crystal reaction liquid phase by using a first circulating device, and preparing iron oxide red seed crystal slurry after the reaction is finished;
the two-step oxidation comprises the following steps:
step B1: adding metallic iron, the iron oxide red seed crystal slurry and water into a closed two-step oxidation reactor;
step B2: heating to the preset temperature of the second-step oxidation reaction, adding ferrous salt at least comprising ferrous nitrate into the second-step oxidation reactor, introducing oxygen, and enabling the oxygen to circularly enter the liquid phase of the second-step oxidation reaction by using a second circulating device until the reaction is finished when the color is slightly similar to that of a standard sample to prepare iron oxide red slurry;
step B3: filtering, washing and drying the iron oxide red slurry to obtain an iron oxide red finished product;
or,
step C1: adding the iron oxide red seed crystal slurry into a closed two-step oxidation reactor, and heating to a preset temperature for two-step oxidation reaction;
step C2: adding ferrous nitrate and alkali into the two-step oxidation reactor, introducing oxygen, and enabling the oxygen to circularly enter a liquid phase of the two-step oxidation reaction by using a third circulating device until the color is slightly similar to that of a standard sample, and finishing the reaction to prepare iron oxide red slurry;
step C3: and filtering, washing and drying the iron oxide red slurry to obtain an iron oxide red finished product.
2. The method for producing iron oxide red according to claim 1, wherein the predetermined temperature of the seed crystal reaction in step a1 is 85 to 160 ℃.
3. The method for producing iron oxide red according to claim 1, wherein the step B2 of adding the ferrous salt and the step C2 of adding the ferrous nitrate are performed in a single step before the reaction or in batches or continuously.
4. The method for producing iron oxide red according to claim 3, wherein the concentrations of the ferrous salt added in step B2 and the ferrous nitrate added in step C2 are maintained at 5-80 g/L.
5. The process for producing iron oxide red according to claim 1, wherein the alkali in step C2 comprises one or more of sodium hydroxide, potassium hydroxide, calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, ammonia or aqueous ammonia.
6. The process for producing iron oxide red according to claim 5, wherein the pH of the liquid phase is maintained between 1 and 4.5 by adding alkali in step C2.
7. The method for producing iron oxide red according to any one of claims 1 to 6, wherein the purity of the oxygen gas introduced in step A2, step B2 and step C2 is in the range of 80 to 100%.
8. The method for producing iron oxide red according to claim 7, wherein the first circulating device in step A2, the second circulating device in step B2, and the third circulating device in step C2 are air compressors, self-priming stirrers, or venturi ejectors.
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| CN1699477A (en) * | 2005-05-27 | 2005-11-23 | 华南理工大学 | Preparation method and product of sulfuric acid seed mixed acid iron oxide red |
| CN101811739A (en) * | 2010-04-15 | 2010-08-25 | 升华集团德清华源颜料有限公司 | Preparation method of low-arsenicred iron oxide pigment |
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| CN1699477A (en) * | 2005-05-27 | 2005-11-23 | 华南理工大学 | Preparation method and product of sulfuric acid seed mixed acid iron oxide red |
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| CN103030181A (en) * | 2011-09-30 | 2013-04-10 | 朗盛德国有限责任公司 | Improved method for producing finely divided haematite and for producing iron oxide red pigments |
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Inventor after: Lin Jiangshun Inventor after: Lin Gaopeng Inventor before: Lin Gaopeng |