CN114315148A - Nitrate-free environment-friendly steel plate enamel high-temperature acid-resistant base glaze, preparation method and application - Google Patents
Nitrate-free environment-friendly steel plate enamel high-temperature acid-resistant base glaze, preparation method and application Download PDFInfo
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- CN114315148A CN114315148A CN202210103548.3A CN202210103548A CN114315148A CN 114315148 A CN114315148 A CN 114315148A CN 202210103548 A CN202210103548 A CN 202210103548A CN 114315148 A CN114315148 A CN 114315148A
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- 210000003298 dental enamel Anatomy 0.000 title claims abstract description 64
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 31
- 239000010959 steel Substances 0.000 title claims abstract description 31
- 239000002253 acid Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 40
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 22
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 20
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 19
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000010453 quartz Substances 0.000 claims abstract description 14
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 13
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010436 fluorite Substances 0.000 claims abstract description 13
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 13
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 11
- 235000017550 sodium carbonate Nutrition 0.000 claims abstract description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 10
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims abstract description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 7
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims description 26
- 230000008018 melting Effects 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000005388 borosilicate glass Substances 0.000 claims description 11
- 239000010433 feldspar Substances 0.000 claims description 9
- 238000001514 detection method Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- 238000005553 drilling Methods 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 71
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 238000010309 melting process Methods 0.000 abstract description 7
- 238000002485 combustion reaction Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 3
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 20
- 239000002585 base Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 230000001590 oxidative effect Effects 0.000 description 9
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 229910052573 porcelain Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229940072033 potash Drugs 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 235000015320 potassium carbonate Nutrition 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- -1 ferrous metal oxides Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004534 enameling Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- MJWMNCORAUQGIX-UHFFFAOYSA-N sodium nitric acid nitrate Chemical compound [Na+].O[N+]([O-])=O.[O-][N+]([O-])=O MJWMNCORAUQGIX-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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Abstract
The invention discloses a nitrate-free environment-friendly steel plate enamel high-temperature acid-resistant base glaze, a preparation method and application thereof, wherein the nitrate-free environment-friendly steel plate enamel high-temperature acid-resistant base glaze comprises the following components in parts by mass: 51-55 parts of quartz, 24-26 parts of borax anhydrous, 4-5 parts of soda ash, 1.5-1.7 parts of manganese oxide, 0.7-0.9 part of nickel oxide, 0.7-0.9 part of cobalt oxide, 4.0-5.5 parts of calcium carbonate, 1.0-1.5 parts of sodium fluosilicate, 2.5-3.5 parts of titanium dioxide, 1.0-1.8 parts of potassium feldspar, 5-6 parts of lithium carbonate and 0.4-0.8 part of fluorite. The formula of the invention does not contain nitrate, and the melting process adopts pure oxygen combustion, thereby fundamentally solving the problem that the prior high-temperature acid-resistant primer glaze for the steel plate enamel generates Nitrogen Oxide (NO) in the production processx) The gas emission pollutes the environment.
Description
Technical Field
The invention belongs to the technical field of enamel, and particularly relates to a nitrate-free environment-friendly steel plate enamel high-temperature acid-resistant base glaze, a preparation method and application.
Background
The enamel glaze is mainly prepared from fire-resistant raw materials such as feldspar and quartz, fusible chemical raw materials such as borax, sodium nitrate, potassium nitrate and soda ash, characteristic raw materials such as non-ferrous metal oxides and the like according to a certain proportion, and is prepared by high-temperature melting and rapid cooling to form granular or flaky borosilicate glass.
The introduction of nitrate (sodium nitrate, potassium nitrate, etc.) as an oxidant and a fluxing agent into the enamel glaze is a common consensus among people in the industry and is an essential enamel glaze raw material in the traditional enamel theory. So far, no safe, colorless, reasonably priced, oxidizing and fluxing raw material is available to replace nitrate. It has long been proven in production practice that nitrates, in particular alkali metal nitrates, are indeed the starting materials which must not be present in the enamel.
In the process of melting the enamel glaze at high temperature, a series of complex physical and chemical reactions are carried out among the raw materials. Wherein nitrate is decomposed at high temperature to generate a large amount of nitrogen oxides, which pollute the atmospheric environment. The nitrogen oxide exceeds the national emission standard by more than 40 times, and if the converter is adopted for production, the instantaneous release concentration of the nitrogen oxide exceeds the national standard by hundreds of thousands of times. As is well known, nitrogen oxides are the main factors of acid rain in the air, and with the increasing awareness of environmental protection, the harm of nitrogen oxides released by nitrates in the production of enamel glaze to the environment is more and more concerned by all parties.
Therefore, the emission of nitrogen oxides reaching the standard and the improvement of the environment are inevitable trends of social responsibility and social economic development of enterprises, and are inevitable choices for the survival of the enterprises. The applicant starts to research the use amount of nitrate in the enamel glaze from 2018, and ensures that the waste gas in the production process of the enamel glaze reaches the emission standard by adding other measures and using no or less nitrate as far as possible on the premise of not influencing the product performance.
The main three technical routes for reducing the emission of nitrogen oxides in the production process of the enamel glaze are as follows: firstly, the use of nitrate is removed or reduced from the source, secondly, nitrogen oxide generated by air in a high-temperature state in the melting process is eliminated, thirdly, the emission of the nitrogen oxide is reduced from the treatment facility, and therefore the national emission standard is achieved.
Prior to this, there have also been technical studies of the single nitrate-removal in enamel formulations, but if nitrate is removed purely for nitrate-removal, the direct consequence is that the quality of the product needs to be sacrificed to some extent, since the fluxing and oxidizing properties of the corresponding nitrate will not be supplemented correspondingly, i.e.: on one hand, the fluxing agent in the formula of the porcelain glaze is reduced, and the smoothness, the leveling property and the expansion coefficient of the porcelain glaze product are directly influenced; on the other hand, since nitrate is oxidizing, removal of nitrate during the glaze melting process results in reduction of some of the metal oxides in the glaze formulation, and the glaze color development and adhesion properties are affected.
From the perspective of the fluxing agent, the compound salt is used for replacing nitrate to serve as a raw material formula of the porcelain glaze, the traditional melting process is used for melting, and the fluxing effect is hopeful to be replaced. However, the use of nitrate removal results in a reduction of the oxidizing atmosphere during the enamel melting process, with the consequent partial reduction of the corresponding metal oxides, which has an effect both on the colour and on the adherence of the enamel product. Therefore, after the nitrate is removed, the supplement of the fluxing effect and the oxidation effect must be considered simultaneously to maintain the original performance of the enamel product.
The specific application of the nitrate in the enamel is mainly sodium nitrate and potassium nitrate, and the nitrate has good oxidation effect under the high-temperature condition, so that oxides can be prevented from being reduced into simple substances in the melting process, and meanwhile, the common products Na of the nitrate sodium nitrate and potassium nitrate after being decomposed at high temperature2O and K2O has good fluxing action.
At present, partial nitrate removal research is explored. The Chinese invention CN201810677390.4 provides a preparation technology of phosphosilicate enamel, and the Chinese invention CN201010608133.9 discloses a high-toughness enamel glaze which is represented by the above materials, and various oxides are directly mixed and melted to obtain an enamel product, so that the use of nitrate is avoided. This may be feasible for theoretical studies. However, under the conditions of the prior art, Na2O and K2O has no industrialized product, and has extremely active activity, poor stability and difficult stable storageAnd (4) storing. Therefore, the method directly uses oxides such as sodium oxide and potassium oxide as raw materials, and cannot realize industrial production at present, so that the method has no practicability. The invention CN201310166353.4 of China discloses a high and low temperature resistant porcelain glaze for enamel, the use of nitrate is not involved in the formula, but the invention introduces the use of heavy metal lead for improving the product quality and reducing the sintering point, which completely violates the safety requirement of daily application and is prohibited by the industry, and simultaneously, the invention also relates to the use of a large amount of sulfate, even if the content is very low, the existence of the sulfate is likely to cause explosion in the quenching link, thereby violating the basic requirement of safe production. In addition, the borate content in the formula is low, and the basic requirement of the enamel industry cannot be met. That is, the invention is claimed to be able to be used for enamels, the conditions of which are practically not reached even without taking into account the aforementioned drawbacks. The Chinese invention CN201711361365.7 discloses a matt sand-grain enamel glaze core glaze and a production method thereof, wherein the core glaze seems not to relate to the use of nitrate, but is a flatting agent in essence, and needs to be combined with a real glaze to achieve the flatting purpose of the glaze, and is not an independent glaze and can not be used independently. Furthermore, in "preliminary practice of nitrate-free enamel" (new academia, new metropolis, glass & enamel 2007,35 (1)), in order to intensify the oxidation, this document uses a method of increasing the air flow rate, which, although not involving the use of nitrates, does not start from the reduction of nitrogen oxides but instead from the solution of the problem of sufficient oxidation of the Ti-containing overglaze, for this purpose it is achieved by means of increasing the air flow rate. However, the increase of the air flow rate can have an obvious cooling effect on the melting furnace, in order to enable the temperature of the melting furnace to meet the requirement, the energy consumption needs to be increased to increase the reaction temperature of the melting furnace, and the air contains a large amount of nitrogen, and under the effect of high temperature, the introduction of a large amount of air can cause the generation of more nitrogen oxides. Research practice shows that the empty burning smelting furnace can cause the content of nitrogen oxides to exceed the national emission standard by more than 2 times. If air is introduced at a high flow rate, the result is more conceivable. Thus, although the document avoids the use of nitratesIn use, but ultimately, the production of nitrogen oxides is exacerbated, contrary to the goal of reducing or eliminating nitrogen oxides.
In conclusion, in the enamel research, the nitrate is removed, the environmental benefit is improved, and simultaneously the excellent quality of the enamel product can be maintained, so that the method is significant and has a difficult task.
Disclosure of Invention
In order to solve the technical problems, the invention provides a nitrate-free environment-friendly steel plate enamel high-temperature acid-resistant base glaze, a preparation method and application, which can solve the problem that nitrogen oxide discharged in the production process of enamel glaze pollutes the environment and can ensure that the original physical and chemical properties of the enamel glaze are kept unchanged.
The technical scheme adopted by the invention is as follows: the nitrate-free environment-friendly steel plate enamel high-temperature acid-resistant base glaze comprises the following components in parts by mass: 51-55 parts of quartz, 24-26 parts of borax anhydrous, 4-5 parts of soda ash, 1.5-1.7 parts of manganese oxide, 0.7-0.9 part of nickel oxide, 0.7-0.9 part of cobalt oxide, 4.0-5.5 parts of calcium carbonate, 1.0-1.5 parts of sodium fluosilicate, 2.5-3.5 parts of titanium dioxide, 1.0-1.8 parts of potassium feldspar, 5-6 parts of lithium carbonate and 0.4-0.8 part of fluorite.
In the nitrate-containing environment-friendly steel plate enamel high-temperature acid-resistant ground coat, SiO in quartz2The mass ratio of the components is more than or equal to 99.5 percent, and SiO is contained in the potassium feldspar2The mass ratio of the titanium dioxide is more than or equal to 71 percent, the mass ratio of the calcium fluoride in the fluorite is more than or equal to 95 percent, the mass ratio of the titanium dioxide in the titanium dioxide is more than or equal to 99.0 percent, the mass ratio of the Co in the cobalt oxide is more than or equal to 71 percent, the mass ratio of the Ni in the nickel oxide is more than or equal to 71 percent, and other raw materials have industrial-grade purity.
The preparation method of the nitrate-free environment-friendly steel plate enamel high-temperature acid-resistant base glaze comprises the following steps:
(1) weighing the following raw materials in parts by mass;
51-55 parts of quartz, 24-26 parts of borax anhydrous, 4-5 parts of soda ash, 1.5-1.7 parts of manganese oxide, 0.7-0.9 part of nickel oxide, 0.7-0.9 part of cobalt oxide, 4.0-5.5 parts of calcium carbonate, 1.0-1.5 parts of sodium fluosilicate, 2.5-3.5 parts of titanium dioxide, 1.0-1.8 parts of potassium feldspar, 5-6 parts of lithium carbonate and 0.4-0.8 part of fluorite;
(2) stirring and uniformly mixing the raw materials in the step (1);
(3) adding the uniformly mixed materials into a melting furnace for melting, wherein the melting furnace adopts a pure oxygen environment and the temperature is controlled at 1290 +/-10 ℃;
(4) and (3) obtaining a borosilicate glass body after the materials in the step (3) are completely melted, drilling the melted borosilicate glass body, and rapidly drawing 1.2-1.5 m glass fibers for detection, wherein the detection requirements are as follows: continuously melting the glass fiber within 1 m for 20 minutes to finish melting;
(5) and (3) quenching the molten borosilicate glass body to obtain the product.
In the preparation method of the nitrate-free environment-friendly steel plate enamel high-temperature acid-resistant base glaze, the quenching in the step (5) is a water quenching or tabletting process.
The application of the nitrate-free environment-friendly steel plate enamel high-temperature acid-resistant base glaze is applied to a blank taking a steel plate as a matrix, and the firing temperature of a finished product is 850-880 ℃.
The principle of the invention for preventing the emission of nitrogen oxide in the production process is as follows:
taking sodium nitrate commonly used in the enamel glaze of the traditional steel plate containing nitrate as an example, the chemical reaction of nitrate in the production of the enamel glaze is as follows:
the nitrate is decomposed during heating to generate nitrite and release oxygen, thereby preventing the metal oxide from generating reduction reaction during melting, converting the metal oxide to a low valence state, and even reducing the metal oxide to elemental metal, thereby changing the components, the physical and chemical properties and the process performance of the enamel glaze.
At high temperature or at discharge, nitrogen and oxygen can be combined into NOx. With respect to NOxThe mechanism of formation of (A) is N in air at high temperature2The oxidation generates NO, and the generation rate thereof has a large relationship with the gas concentration and the combustion temperature. Practice shows that the temperature reaches over 1000 ℃, and the furnace is sintered in an empty stateAlso results in higher levels of nitrogen oxides being formed. Therefore, the invention adopts pure oxygen to replace air, on one hand, the oxidizing atmosphere in the melting process can be increased, and on the other hand, the zero emission of nitrogen oxides generated in the combustion process is realized.
On the other hand, the components and the dosage of the non-nitrate fluxing agent are adjusted in the formula, so that the melting can be completed as required even if no nitrate fluxing agent exists in the enamel glaze. The key technical innovation point of the invention is that after nitrate is removed, the fluxing property in the enamel glaze can still be ensured.
Compared with the prior art, the invention has the beneficial effects that:
the invention removes the nitrate from the enamel glaze, realizes the industrialization, solves the problem that the environment is polluted by nitrogen oxide discharged in the production process of the enamel glaze, and ensures that the original physical and chemical properties of the enamel glaze are kept unchanged. Experimental practice proves that when 80% of products of enamel glaze manufacturers of the applicant of the invention do not contain nitrate, the residual products of about 20% can ensure that the use amount of the nitrate is reduced by more than 50% although the nitrate cannot be completely removed. The usage amount of the nitrate is reduced to about 100 tons from the original annual usage amount of 800 tons, and the reduction rate is close to 85 percent. Nitrate removal alone directly reduces the nitrogen oxide emissions by 500 tons per year, and does not include the conversion of nitrogen in the air to nitrogen oxides. In addition, the performance (porcelain surface, adherence, fluidity, acid resistance and luster) of the product without nitrate is not changed, and the quality detection requirement of the national enamel product is met. Therefore, the technical scheme of the invention has extremely important environmental protection effect, social benefit and popularization and application significance.
Drawings
FIG. 1 is a photograph of the high temperature acid-resistant primer for steel plate enameling, applied to an enamel-strike plate made of a steel plate.
FIGS. 2-4 are pages 1-3 of the test report for the application of the high temperature acid-resistant primer for steel plate enamel of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The equipment used in the embodiment of the invention is as follows:
preparing materials: adopts a full-automatic batching and mixing system. The system is fully-automatic computer control, and has the characteristics of accurate weighing, uniform mixing and high batching efficiency.
Melting: an automatic feeding system, a pure oxygen combustion system and an automatic discharging system are adopted. Because the effect of the oxidant is removed after the nitrate is removed, the combustion condition of the smelting furnace is improved, pure oxygen combustion is changed, and the effect of the oxidant can also meet the requirement after the nitrate is removed. This is also the key point in the invention, namely the removal of nitrate, but the performance of the oxidant is not changed.
Packaging: an automatic packaging system is used.
Example 1
(1) Weighing the following raw materials in parts by mass:
53kg of quartz, 24kg of borax anhydrous, 5.0kg of soda ash, 1.5kg of manganese oxide, 0.8kg of nickel oxide, 0.8kg of cobalt oxide, 5.3kg of calcium carbonate, 1.0kg of sodium fluosilicate, 3.0kg of titanium dioxide, 1.7kg of potash feldspar, 5.8kg of lithium carbonate and 0.8kg of fluorite.
SiO in quartz2The mass ratio of the components is more than or equal to 99.5 percent, and SiO is contained in the potassium feldspar2The mass ratio of the titanium dioxide is more than or equal to 71 percent, the mass ratio of the calcium fluoride in the fluorite is more than or equal to 95 percent, the mass ratio of the titanium dioxide in the titanium dioxide is more than or equal to 99.0 percent, the mass ratio of the Co in the cobalt oxide is more than or equal to 71 percent, the mass ratio of the Ni in the nickel oxide is more than or equal to 71 percent, and other raw materials have industrial-grade purity.
(2) The raw materials are stirred and mixed evenly.
(3) And adding the uniformly mixed materials into a melting furnace for melting, wherein the melting furnace adopts a pure oxygen environment during melting, and the temperature is controlled to 1290 +/-10 ℃ for melting.
(4) Obtaining a borosilicate glass body after the above materials are completely melted, drilling the melted borosilicate glass body, and rapidly drawing 1.2-1.5 m glass fiber to detect, wherein the detection requirement is as follows: and continuously melting the glass fiber within 1 m for 20 minutes to finish melting.
(5) And (3) quenching the molten borosilicate glass body with water to obtain the product.
Example 2
This example is prepared substantially identically to example 1, except that: the mass parts of the components in the step (1) are as follows: 53kg of quartz, 24.8kg of borax anhydrous, 4.7kg of soda ash, 1.5kg of manganese oxide, 0.8kg of nickel oxide, 0.8kg of cobalt oxide, 4.4kg of calcium carbonate, 1.2kg of sodium fluosilicate, 3.5kg of titanium dioxide, 1.4kg of potash feldspar, 5.8kg of lithium carbonate and 0.6kg of fluorite.
In the step (5), the rapid cooling of the molten borosilicate glass body adopts a tabletting process.
Example 3
This example is prepared substantially identically to example 1, except that: the mass parts of the components in the step (1) are as follows: 53kg of quartz, 26kg of borax anhydrous, 4.0kg of sodium carbonate, 1.5kg of manganese oxide, 0.8kg of nickel oxide, 0.8kg of cobalt oxide, 4.0kg of calcium carbonate, 1.4kg of sodium fluosilicate, 3.0kg of titanium dioxide, 1.1kg of potash feldspar, 5.8kg of lithium carbonate and 0.4kg of fluorite.
Example 4
This example is prepared substantially identically to example 1, except that: the mass parts of the components in the step (1) are as follows: 51kg of quartz, 25kg of borax anhydrous, 4.5kg of soda ash, 1.7kg of manganese oxide, 0.9kg of nickel oxide, 0.7kg of cobalt oxide, 5.5kg of calcium carbonate, 1.5kg of sodium fluosilicate, 3.5kg of titanium dioxide, 1.0kg of potash feldspar, 5kg of lithium carbonate and 0.7kg of fluorite.
Example 5
This example is prepared substantially identically to example 1, except that: the mass parts of the components in the step (1) are as follows: 55kg of quartz, 25kg of borax anhydrous, 4.5kg of soda ash, 1.6kg of manganese oxide, 0.7kg of nickel oxide, 0.9kg of cobalt oxide, 4.8kg of calcium carbonate, 1.0kg of sodium fluosilicate, 2.5kg of titanium dioxide, 1.8kg of potash feldspar, 6kg of lithium carbonate and 0.5kg of fluorite.
The product prepared by the invention is applied to a blank taking a steel plate as a substrate, and the firing temperature of the finished product is 850-.
FIG. 1 is a photograph of a steel plate enamel high-temperature acid-resistant primer prepared in example 2 of the present invention applied to an enamel firing plate made of a steel plate. The porcelain surface is smooth and fine, is closely adhered with grade I, has acid resistance and grade A, has uniform and beautiful color, and the hue completely meets the requirements of users.
Fig. 2 to 4 are pages 1 to 3 of the test report of the application of the high temperature acid-proof primer for steel plate enamel prepared in example 2 of the present invention, respectively. The detection unit is the national glasses and glass detection center.
Experiments and detection results prove that the nitrate-free environment-friendly steel plate enamel high-temperature acid-resistant base glaze produced by the method does not generate nitrogen oxide in the preparation process, various properties (porcelain surface, luster, whiteness, hue, sintering temperature) and the like of the obtained product meet the requirements of the steel plate enamel high-temperature acid-resistant base glaze, the aim of removing the nitrate from the environment-friendly steel plate enamel high-temperature acid-resistant base glaze is fulfilled, and the problem that Nitrogen Oxide (NO) is generated in the production and processing process of the traditional steel plate enamel high-temperature acid-resistant base glaze is fundamentally solvedx) The gas emission pollutes the environment.
Claims (5)
1. The nitrate-free environment-friendly steel plate enamel high-temperature acid-resistant base glaze is characterized by comprising the following components in parts by mass: 51-55 parts of quartz, 24-26 parts of borax anhydrous, 4-5 parts of soda ash, 1.5-1.7 parts of manganese oxide, 0.7-0.9 part of nickel oxide, 0.7-0.9 part of cobalt oxide, 4.0-5.5 parts of calcium carbonate, 1.0-1.5 parts of sodium fluosilicate, 2.5-3.5 parts of titanium dioxide, 1.0-1.8 parts of potassium feldspar, 5-6 parts of lithium carbonate and 0.4-0.8 part of fluorite.
2. The nitrate-containing environment-friendly steel plate enamel high-temperature acid-resistant primer glaze as claimed in claim 1, wherein SiO in quartz is SiO2The mass ratio of the components is more than or equal to 99.5 percent, and SiO is contained in the potassium feldspar2The mass ratio of the titanium dioxide is more than or equal to 71 percent, the mass ratio of the calcium fluoride in the fluorite is more than or equal to 95 percent, the mass ratio of the titanium dioxide in the titanium dioxide is more than or equal to 99.0 percent, the mass ratio of the Co in the cobalt oxide is more than or equal to 71 percent, the mass ratio of the Ni in the nickel oxide is more than or equal to 71 percent, and other raw materials have industrial-grade purity.
3. The method for preparing the nitrate-free environment-friendly steel plate enamel high-temperature acid-resistant primer as claimed in claim 1 or 2, comprising the steps of:
(1) weighing the following raw materials in parts by mass;
51-55 parts of quartz, 24-26 parts of borax anhydrous, 4-5 parts of soda ash, 1.5-1.7 parts of manganese oxide, 0.7-0.9 part of nickel oxide, 0.7-0.9 part of cobalt oxide, 4.0-5.5 parts of calcium carbonate, 1.0-1.5 parts of sodium fluosilicate, 2.5-3.5 parts of titanium dioxide, 1.0-1.8 parts of potassium feldspar, 5-6 parts of lithium carbonate and 0.4-0.8 part of fluorite;
(2) stirring and uniformly mixing the raw materials in the step (1);
(3) adding the uniformly mixed materials into a melting furnace for melting, wherein the melting furnace adopts a pure oxygen environment and the temperature is controlled at 1290 +/-10 ℃;
(4) and (3) obtaining a borosilicate glass body after the materials in the step (3) are completely melted, drilling the melted borosilicate glass body, and rapidly drawing 1.2-1.5 m glass fibers for detection, wherein the detection requirements are as follows: continuously melting the glass fiber within 1 m for 20 minutes to finish melting;
(5) and (3) quenching the molten borosilicate glass body to obtain the product.
4. The method for preparing the nitrate-free environment-friendly steel plate enamel high-temperature acid-resistant base coat as claimed in claim 3, wherein the method comprises the following steps: and (5) quenching in water or tabletting.
5. The application of the nitrate-free environment-friendly steel plate enamel high-temperature acid-resistant primer as claimed in claim 1, wherein: the method is applied to a blank taking a steel plate as a substrate, and the firing temperature of the finished product is 850-880 ℃.
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| CN101921063A (en) * | 2010-08-05 | 2010-12-22 | 奇瑞汽车股份有限公司 | Enamel and preparation method thereof |
| CN101967042A (en) * | 2010-06-29 | 2011-02-09 | 蔡文仁 | Electrostatic enamel powder and preparation method thereof |
| CN102659318A (en) * | 2012-04-20 | 2012-09-12 | 湖南信诺颜料科技有限公司 | Cracking preventing porcelain glaze of enamel and preparation of cracking preventing porcelain glaze |
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| CN101967042A (en) * | 2010-06-29 | 2011-02-09 | 蔡文仁 | Electrostatic enamel powder and preparation method thereof |
| CN101921063A (en) * | 2010-08-05 | 2010-12-22 | 奇瑞汽车股份有限公司 | Enamel and preparation method thereof |
| CN102659318A (en) * | 2012-04-20 | 2012-09-12 | 湖南信诺颜料科技有限公司 | Cracking preventing porcelain glaze of enamel and preparation of cracking preventing porcelain glaze |
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