CN114315142B - Nitrate-free environment-friendly steel plate enamel low Wen Gunie primer, preparation method and application - Google Patents
Nitrate-free environment-friendly steel plate enamel low Wen Gunie primer, preparation method and application Download PDFInfo
- Publication number
- CN114315142B CN114315142B CN202210103535.6A CN202210103535A CN114315142B CN 114315142 B CN114315142 B CN 114315142B CN 202210103535 A CN202210103535 A CN 202210103535A CN 114315142 B CN114315142 B CN 114315142B
- Authority
- CN
- China
- Prior art keywords
- parts
- nitrate
- oxide
- gunie
- steel plate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 210000003298 dental enamel Anatomy 0.000 title claims abstract description 73
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 30
- 239000010959 steel Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 45
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 45
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 22
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 22
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 17
- 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 17
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000010453 quartz Substances 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 14
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010436 fluorite Substances 0.000 claims abstract description 14
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 14
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910021538 borax Inorganic materials 0.000 claims abstract description 12
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 12
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005751 Copper oxide Substances 0.000 claims abstract description 11
- 229910052656 albite Inorganic materials 0.000 claims abstract description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 11
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims description 32
- 230000008018 melting Effects 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 17
- 239000005388 borosilicate glass Substances 0.000 claims description 15
- 238000001514 detection method Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000010791 quenching Methods 0.000 claims description 9
- 230000000171 quenching effect Effects 0.000 claims description 9
- 239000010433 feldspar Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 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 description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 5
- 238000005553 drilling Methods 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 74
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 238000002485 combustion reaction Methods 0.000 abstract description 6
- 238000010309 melting process Methods 0.000 abstract description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 3
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 11
- 229910052573 porcelain Inorganic materials 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- -1 ferrous metal oxide Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004806 packaging method and process 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
- 238000003723 Smelting Methods 0.000 description 1
- 239000002253 acid Substances 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
- 238000013329 compounding Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 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
- 239000006224 matting agent 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
- 150000002823 nitrates Chemical class 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 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
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Abstract
The application discloses a nitrate-free environment-friendly steel plate enamel low Wen Gunie base glaze, a preparation method and application thereof, wherein the formula of the nitrate-free environment-friendly steel plate enamel low Wen Gunie base glaze comprises the following components in parts by mass: 33-37 parts of quartz, 25-27 parts of borax with zero water, 4-6 parts of sodium carbonate, 1.8-2.5 parts of potassium carbonate, 1.8-2.2 parts of calcium carbonate, 5-6 parts of fluorite, 12.5-14.5 parts of potassium feldspar, 5-6 parts of albite, 1.9-2.1 parts of nickel oxide, 0.9-1.0 parts of copper oxide, 0.9-1.0 parts of cobalt oxide, 1.4-1.6 parts of manganese oxide and 1.4-1.6 parts of ferric oxide. The formula of the application does not contain nitrate, and adopts a pure oxygen combustion mode in the melting process, thereby fundamentally solving the problem that the prior steel plate enamel low Wen Gunie primer produces Nitrogen Oxide (NO) in the production process x ) The gas discharge pollutes the environment.
Description
Technical Field
The application belongs to the technical field of enamel, and particularly relates to nitrate-free environment-friendly steel plate enamel low Wen Gunie base enamel, a preparation method and application.
Background
The enamel glaze is prepared with refractory feldspar, quartz and other material, borax, sodium nitrate, potassium nitrate, sodium carbonate and other fusible chemical material, non-ferrous metal oxide and other characteristic material, and through compounding in certain proportion, high temperature smelting, and rapid cooling into granular or sheet borosilicate glass.
The introduction of nitrate (sodium nitrate, potassium nitrate, etc.) as an oxidizing agent and a fluxing agent into enamel has been a common knowledge for the industry and is an indispensable raw material for enamel in the traditional enamel theory. Up to now, no safe, colorless, reasonably priced raw material with both oxidizing and fluxing properties has been available to replace nitrate. Production practices have long proven that nitrate (especially alkali metal nitrate) is indeed an indispensable raw material in enamel glazes.
In the high-temperature melting process of enamel glaze, a series of complex physical and chemical reactions are carried out between the raw materials. Wherein the nitrate is decomposed at high temperature to generate a large amount of nitrogen oxides, which pollute the atmosphere. 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 times. It is known that nitrogen oxides are a main factor of acid rain generated in air, and as environmental awareness of people is enhanced, the harm of nitrogen oxides released by nitrate in enamel production to the environment is increasingly attracting high attention from all parties.
Therefore, the standard emission of the nitrogen oxides and the improvement of the environment are the indistinct social responsibility and the necessary trend of the social and economic development of enterprises, and are the necessary choice for the survival of the enterprises. The inventor starts to research the nitrate removal amount in the enamel glaze from 2018, ensures that nitrate is not used or is less used as much as possible on the premise of not affecting the product performance, and ensures that the waste gas in the enamel glaze production process reaches the standard and is discharged by other measures.
The reduction of the emission of nitrogen oxides in the enamel production process mainly comprises three technical routes: firstly, nitrate is removed or reduced from the source, secondly, nitrogen oxides generated by air in the high-temperature state in the melting process are removed, and thirdly, the emission of the nitrogen oxides is reduced from treatment facilities, so that the national emission standard is achieved.
Prior art attempts have also been made to simply remove nitrate from enamel formulations, but if nitrate is removed purely for nitrate removal, the immediate face is the need to sacrifice product quality to some extent, since the fluxing and oxidizing properties of the corresponding nitrate are not correspondingly supplemented, namely: on one hand, the fluxing agent in the porcelain glaze formula is reduced, and the flatness, leveling property and expansion coefficient of the porcelain surface of the porcelain glaze product are directly affected; on the other hand, since nitrate is oxidative, removal of nitrate during enamel melting results in reduction of part of the metal oxides in the enamel formulation, and thus enamel color development and adhesion properties are affected.
From the perspective of fluxing agent, the compound salt is used for replacing nitrate to be used as a raw material formula of the porcelain glaze, and the traditional melting process is used for melting, so that the fluxing effect is hopefully replaced. However, the use of nitrate removal results in a reduction of the oxidizing atmosphere during the melting of the enamel, which results in a reduction of the corresponding metal oxide fraction, which has an effect on both the hue and the adhesion of the enamel product. Therefore, after nitrate is removed, the original performance of the enamel product is maintained, and the fluxing effect and the oxidation effect are supplemented simultaneously.
The specific application of nitrate in enamel is mainly sodium nitrate and potassium nitrate, and under the condition of high temperature, the nitrate has good oxidation effect, so that the oxide can be ensured not to be reduced into simple substance in the melting process, and meanwhile, common nitrate sodium nitrate and potassium nitrate are decomposed at high temperature to obtain product Na 2 O and K 2 O has good fluxing action.
There have been studies and studies on partial nitrate removal. Chinese application CN201810677390.4 provides a preparation technique of phosphosilicate enamel, chinese application CN201010608133.9 discloses a high toughness enamel glaze, which is represented by them, and all are obtained by directly mixing various oxides and melting, so as to avoid nitrate use. This may be feasible for theoretical studies. However, under the prior art conditions, na 2 O and K 2 O has no industrial product, and has extremely active activity, poor stability and difficult storage stability. Therefore, the use of oxides such as sodium oxide and potassium oxide as raw materials is not practical because industrial production is not currently possible. The application CN201310166353.4 discloses a high-low temperature resistant porcelain glaze for enamel, the use of nitrate is not involved in the formula, but the application introduces the use of heavy metal lead for improving the product quality and reducing sintering points, which completely violates the safety requirement of daily application and is forbidden in industry, and simultaneously, the application also involves the use of a large amount of sulfate, and the existence of sulfate even if the sulfate is very low, can cause explosion of a quenching link, thereby violating the basic requirement of safe production. In addition, the borate content in the formula is low, and the basic requirements of the enamel industry are not met. That is, the application claims to be applicable to enamels, and in practice, the conditions of enamels are not reached even if the aforementioned drawbacks are not considered. Chinese application CN201711361365.7 discloses a matte sand-lined enamel core glaze and a production method thereofThe core glaze is not seemingly related to the use of nitrate, but is essentially a matting agent, and needs to be used in combination with a real glaze to achieve the matting purpose of the glaze, and is not independent glaze and can not be used independently. Furthermore, in the "preliminary practice of nitrate-free enamel glaze" (Xie Xuexin, glass and enamel 2007,35 (1)) this document uses a method of increasing the air flow rate for the purpose of enhancing the oxidation, although the use of nitrate is not involved, the starting point is not to reduce nitrogen oxides but to solve the problem of sufficient oxidation of Ti-containing overglazes, for which purpose it is achieved by means of a technique of increasing the air flow rate. However, the air flow rate is increased, so that the melting furnace has obvious cooling effect, the reaction temperature of the melting furnace needs to be increased by increasing energy consumption in order to meet the requirement of the melting furnace, and a large amount of nitrogen is contained in the air, so that more nitrogen oxides can be generated by introducing a large amount of air under the high-temperature effect. Research practice shows that the empty firing melting furnace can cause the content of nitrogen oxides to exceed the national emission standard by more than 2 times. The result is even more conceivable if a large flow of air is introduced. Therefore, this document, although avoiding the use of nitrates, eventually aggravates the production of nitrogen oxides, contrary to the aim of reducing or eliminating them.
In summary, in enamel research, nitrate is removed to improve environmental benefit, and meanwhile, the excellent quality of enamel products can be maintained, so that the method is significant and difficult in task.
Disclosure of Invention
In order to solve the technical problems, the application provides the nitrate-free environment-friendly steel plate enamel low Wen Gunie primer, the preparation method and the application, which not only solve the problem of environmental pollution caused by emission of nitric oxide in the enamel glaze production process, but also ensure that the original physicochemical properties of the enamel are kept unchanged.
The technical scheme adopted by the application is as follows:
the environment-friendly steel plate enamel low Wen Gunie primer without nitrate comprises the following components in parts by mass: 33-37 parts of quartz, 25-27 parts of borax with zero water, 4-6 parts of calcined soda, 1.8-2.5 parts of potassium carbonate, 1.8-2.2 parts of calcium carbonate, 5-6 parts of fluorite, 12.5-14.5 parts of potassium feldspar, 5-6 parts of albite, 1.9-2.1 parts of nickel oxide, 0.9-1.0 parts of copper oxide, 0.9-1.0 parts of cobalt oxide, 1.4-1.6 parts of manganese oxide and 1.4-1.6 parts of ferric oxide.
The nitrate-free environment-friendly steel plate enamel is low in Wen Gunie base enamel, and SiO in quartz 2 The mass ratio of the potassium feldspar is more than or equal to 99.5 percent, and SiO in the potassium feldspar 2 The mass ratio of the sodium feldspar is more than or equal to 71 percent, and SiO in the sodium feldspar 2 The mass ratio of the calcium fluoride in fluorite is more than or equal to 71%, the mass ratio of the Co in cobalt oxide is more than or equal to 71%, the mass ratio of the Ni in nickel oxide is more than or equal to 71%, and other raw materials are of industrial-grade purity.
The preparation method of the nitrate-free environment-friendly steel plate enamel low Wen Gunie primer comprises the following steps:
(1) Weighing the following raw materials in parts by mass;
33-37 parts of quartz, 25-27 parts of borax with zero water, 4-6 parts of calcined soda, 1.8-2.5 parts of potassium carbonate, 1.8-2.2 parts of calcium carbonate, 5-6 parts of fluorite, 12.5-14.5 parts of potassium feldspar, 5-6 parts of albite, 1.9-2.1 parts of nickel oxide, 0.9-1.0 parts of copper oxide, 0.9-1.0 parts of cobalt oxide, 1.4-1.6 parts of manganese oxide and 1.4-1.6 parts of ferric oxide;
(2) Stirring and mixing the raw materials in the step (1) uniformly;
(3) Adding the uniformly mixed materials into a melting furnace for melting, wherein a pure oxygen environment is adopted in the melting furnace during melting, and the temperature is controlled at 1230+/-10 ℃;
(4) Obtaining borosilicate glass body after the materials in the step (3) are completely melted, drilling the melted borosilicate glass body, and rapidly drawing glass filaments with the length of 1.2-1.5 m for detection, wherein the detection requirements are as follows: the melting is completed within 1 meter of the glass fiber without knots;
(5) And (5) quenching the melted borosilicate glass body to obtain the product.
In the preparation method of the nitrate-free environment-friendly steel plate enamel low Wen Gunie primer, the quenching in the step (5) is a water quenching or tabletting process method.
The application of the nitrate-free environment-friendly steel plate enamel low Wen Gunie primer is applied to a blank taking a steel plate as a matrix, and the sintering temperature of a finished product is 760-790 ℃.
The principle of the application for preventing the emission of nitrogen oxides in the production process is as follows:
taking sodium nitrate commonly used in traditional nitrate-containing steel plate enamel glaze as an example, the chemical reaction of nitrate in enamel glaze production is as follows:
the nitrate is decomposed to generate nitrite when heating and releases oxygen, thus preventing the metal oxide from generating reduction reaction when melting, leading the metal oxide to be converted into low valence state and even reduced into simple substance metal, thereby changing the components, physical and chemical properties and technological properties of the enamel glaze.
At high temperature or by discharge, nitrogen and oxygen can be combined into NO x . Regarding NO x The generation mechanism of (2) is N in air at high temperature 2 NO is formed by oxidation, and the rate of formation is greatly dependent on the gas concentration and combustion temperature. Practice shows that the temperature reaches above 1000 ℃, and the empty firing melting furnace can also lead to the generation of nitrogen oxides with higher content. Therefore, pure oxygen is adopted to replace air, so that on one hand, the oxidizing atmosphere in the melting process can be increased, and on the other hand, the nitrogen oxide generated in the combustion process is emitted in a zero way.
On the other hand, the components and the dosage of the non-nitrate fluxing agent are adjusted in the formula, so that even if nitrate fluxing is not carried out in the enamel glaze, the melting can be completed according to the requirement. The method is a key technical innovation point in the application, namely, after nitrate is removed, fluxing property in the enamel can still be ensured.
Compared with the prior art, the application has the beneficial effects that:
the application removes nitrate from enamel glaze, can realize industrialization, solves the problem of environmental pollution caused by emission of nitrogen oxides in the production process of enamel glaze, and can ensure that the original physicochemical properties of enamel glaze are kept unchanged. Experimental practice proves that when 80% of the products of enamel glaze manufacturers of the applicant of the application are free of nitrate, the residual products of approximately 20% can not completely remove nitrate, but the use amount of nitrate can be reduced by more than 50%. The nitrate consumption is reduced from 800 tons to about 100 tons in the original annual consumption, and the reduction rate is close to 85 percent. Only nitrate removal directly reduces 500 tons of nitrogen oxide discharge per year, and does not include the discharge of nitrogen in air converted into nitrogen oxide. And the properties (porcelain surface, adhesion, fluidity, acid resistance, gloss) of the product after nitrate removal are unchanged, and the quality detection requirement of national enamel products is met. Therefore, the technical scheme of the application has extremely important environmental protection effect, social benefit and popularization and application significance.
Drawings
FIG. 1 is a photograph of an enamel glazing panel made of a steel sheet with enamel low Wen Gunie primer of the application applied thereto.
FIGS. 2-4 are pages 1-3 of the test report for the application of the low Wen Gunie primer to steel sheet enamel of the application, respectively.
Detailed Description
The present application will be described in further detail with reference to specific examples.
The equipment used in the embodiment of the application is as follows:
and (3) batching: a full-automatic batching and mixing system is adopted. 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. Since the effect of the oxidizing agent is removed after the nitrate is removed, the combustion condition of the furnace is improved, and pure oxygen combustion is changed, so that the effect of the oxidizing agent meets the requirement even though the nitrate is removed. This is also a key point in the application, namely the removal of nitrate, but the performance of the oxidizing agent is not changed.
And (3) packaging: an automatic packaging system is employed.
Example 1
(1) Weighing the following raw materials in parts by mass:
35kg of quartz, 25.5kg of borax zero water, 4kg of sodium carbonate, 2.5kg of potassium carbonate, 2.0kg of calcium carbonate, 5.4kg of fluorite, 14.5kg of potassium feldspar, 6.0kg of albite, 2.0kg of nickel oxide, 1.0kg of copper oxide, 1.0kg of cobalt oxide, 1.5kg of manganese oxide and 1.5kg of ferric oxide.
SiO in quartz 2 The mass ratio of the potassium feldspar is more than or equal to 99.5 percent, and SiO in the potassium feldspar 2 The mass ratio of the sodium feldspar is more than or equal to 71 percent, and SiO in the sodium feldspar 2 The mass ratio of the calcium fluoride in fluorite is more than or equal to 71%, the mass ratio of the Co in cobalt oxide is more than or equal to 71%, the mass ratio of the Ni in nickel oxide is more than or equal to 71%, and other raw materials are of industrial-grade purity.
(2) The raw materials are stirred and mixed uniformly.
(3) And 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 to be 1230+/-10 ℃ for melting.
(4) Obtaining borosilicate glass body after the materials are completely melted, drilling the melted borosilicate glass body, and rapidly drawing the borosilicate glass body into glass filaments of 1.2-1.5 meters for detection, wherein the detection requirements are as follows: the melting is completed within 1 meter of the glass fiber without knots.
(5) And (5) quenching the melted borosilicate glass body with water to obtain the product.
Example 2
The procedure of this example was essentially the same as that of example 1, except that: the mass parts of the components in the step (1) are as follows: 35kg of quartz, 26.1kg of borax zero water, 5.5kg of calcined soda, 1.9kg of potassium carbonate, 2.0kg of calcium carbonate, 5.7kg of fluorite, 13.0kg of potassium feldspar, 5.5kg of albite, 2.0kg of nickel oxide, 1.0kg of copper oxide, 1.0kg of cobalt oxide, 1.5kg of manganese oxide and 1.5kg of ferric oxide.
In the step (5), the melted borosilicate glass body is quenched by adopting a tabletting process.
Example 3
The procedure of this example was essentially the same as that of example 1, except that: the mass parts of the components in the step (1) are as follows: 35kg of quartz, 26.7kg of borax zero water, 5.0kg of calcined soda, 1.8kg of potassium carbonate, 2.0kg of calcium carbonate, 5.9kg of fluorite, 12.5kg of potassium feldspar, 5.0kg of albite, 2.0kg of nickel oxide, 1.0kg of copper oxide, 1.0kg of cobalt oxide, 1.5kg of manganese oxide and 1.5kg of ferric oxide.
Example 4
The procedure of this example was essentially the same as that of example 1, except that: the mass parts of the components in the step (1) are as follows: 37kg of quartz, 25kg of borax zero water, 4.5kg of sodium carbonate, 2.0kg of potassium carbonate, 1.8kg of calcium carbonate, 6.0kg of fluorite, 12.5kg of potassium feldspar, 5.0kg of albite, 1.9kg of nickel oxide, 0.9kg of copper oxide, 0.9kg of cobalt oxide, 1.4kg of manganese oxide and 1.4kg of ferric oxide.
Example 5
The procedure of this example was essentially the same as that of example 1, except that: the mass parts of the components in the step (1) are as follows: 33kg of quartz, 27kg of borax zero water, 6.0kg of sodium carbonate, 2.2kg of potassium carbonate, 2.2kg of calcium carbonate, 5.0kg of fluorite, 13.5kg of potassium feldspar, 5.0kg of albite, 2.1kg of nickel oxide, 0.95kg of copper oxide, 0.95kg of cobalt oxide, 1.6kg of manganese oxide and 1.6kg of ferric oxide.
The product prepared by the application is applied to blanks taking steel plates as matrixes, and the sintering temperature of the finished product is 760-790 ℃.
FIG. 1 is a photograph of a steel sheet enamel low Wen Gunie primer prepared in example 2 of the present application applied to an enamel glazing plate made of a steel sheet. The porcelain face is smooth and fine, the porcelain face is adhered to the first grade, the color is uniform and attractive, and the hue completely meets the requirements of users.
FIGS. 2-4 illustrate embodiments of the application2The prepared steel plate enamel is lower than the 1-3 pages of detection report of Wen Gunie primer application. The detection unit is national glasses and glass detection center.
Experiments and detection results prove that the nitrate-free environment-friendly steel plate enamel low Wen Gunie primer produced by the method has no nitrogen oxide in the preparation process, and various properties (porcelain surface, gloss, whiteness, hue, firing temperature) and the like of the obtained product all meet the requirements of the steel plate enamel low Wen Gunie primer, thereby realizing the purpose of removing nitrate from the environment-friendly steel plate enamel low Wen Gunie primer and fundamentally solving the problems of the prior artSteel plate enamel low Wen Gunie primer produces Nitrogen Oxides (NO) in the production and processing process x ) The technical problem of environmental pollution caused by gas discharge.
Claims (5)
1. An environment-friendly steel plate enamel low Wen Gunie base enamel without nitrate is characterized in that: the formula comprises the following components in parts by mass: 33-37 parts of quartz, 25-27 parts of borax with zero water, 4-6 parts of calcined soda, 1.8-2.5 parts of potassium carbonate, 1.8-2.2 parts of calcium carbonate, 5-6 parts of fluorite, 12.5-14.5 parts of potassium feldspar, 5-6 parts of albite, 1.9-2.1 parts of nickel oxide, 0.9-1.0 parts of copper oxide, 0.9-1.0 parts of cobalt oxide, 1.4-1.6 parts of manganese oxide and 1.4-1.6 parts of ferric oxide;
the preparation method of the nitrate-free environment-friendly steel plate enamel low Wen Gunie primer comprises the following steps:
(1) Weighing the following raw materials in parts by mass;
33-37 parts of quartz, 25-27 parts of borax with zero water, 4-6 parts of calcined soda, 1.8-2.5 parts of potassium carbonate, 1.8-2.2 parts of calcium carbonate, 5-6 parts of fluorite, 12.5-14.5 parts of potassium feldspar, 5-6 parts of albite, 1.9-2.1 parts of nickel oxide, 0.9-1.0 parts of copper oxide, 0.9-1.0 parts of cobalt oxide, 1.4-1.6 parts of manganese oxide and 1.4-1.6 parts of ferric oxide;
(2) Stirring and mixing the raw materials in the step (1) uniformly;
(3) Adding the uniformly mixed materials into a melting furnace for melting, wherein a pure oxygen environment is adopted in the melting furnace during melting, and the temperature is controlled at 1230+/-10 ℃;
(4) Obtaining borosilicate glass body after the materials in the step (3) are completely melted, drilling the melted borosilicate glass body, and rapidly drawing glass filaments with the length of 1.2-1.5 m for detection, wherein the detection requirements are as follows: the melting is completed within 1 meter of the glass fiber without knots;
(5) And (5) quenching the melted borosilicate glass body to obtain the product.
2. The nitrate-free environment-friendly steel sheet enamel low Wen Gunie primer as claimed in claim 1, wherein: siO in quartz 2 The mass ratio of the potassium feldspar is more than or equal to 99.5 percent, and SiO in the potassium feldspar 2 The mass ratio of the sodium feldspar is more than or equal to 71 percent, and SiO in the sodium feldspar 2 The mass ratio of the calcium fluoride in fluorite is more than or equal to 71%, the mass ratio of the Co in cobalt oxide is more than or equal to 71%, the mass ratio of the Ni in nickel oxide is more than or equal to 71%, and other raw materials are of industrial-grade purity.
3. A method for preparing the nitrate-free environment-friendly steel plate enamel low Wen Gunie primer according to claim 1 or 2, comprising the following steps:
(1) Weighing the following raw materials in parts by mass;
33-37 parts of quartz, 25-27 parts of borax with zero water, 4-6 parts of calcined soda, 1.8-2.5 parts of potassium carbonate, 1.8-2.2 parts of calcium carbonate, 5-6 parts of fluorite, 12.5-14.5 parts of potassium feldspar, 5-6 parts of albite, 1.9-2.1 parts of nickel oxide, 0.9-1.0 parts of copper oxide, 0.9-1.0 parts of cobalt oxide, 1.4-1.6 parts of manganese oxide and 1.4-1.6 parts of ferric oxide;
(2) Stirring and mixing the raw materials in the step (1) uniformly;
(3) Adding the uniformly mixed materials into a melting furnace for melting, wherein a pure oxygen environment is adopted in the melting furnace during melting, and the temperature is controlled at 1230+/-10 ℃;
(4) Obtaining borosilicate glass body after the materials in the step (3) are completely melted, drilling the melted borosilicate glass body, and rapidly drawing glass filaments with the length of 1.2-1.5 m for detection, wherein the detection requirements are as follows: the melting is completed within 1 meter of the glass fiber without knots;
(5) And (5) quenching the melted borosilicate glass body to obtain the product.
4. The method for preparing the nitrate-free environment-friendly steel plate enamel low Wen Gunie primer according to claim 3, which is characterized by comprising the following steps: the quenching in the step (5) is a water quenching or tabletting process method.
5. The use of the nitrate-free environment-friendly steel sheet enamel low Wen Gunie primer as claimed in claim 1, wherein: the method is applied to blanks taking steel plates as matrixes, and the sintering temperature of finished products is 760-790 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210103535.6A CN114315142B (en) | 2022-01-28 | 2022-01-28 | Nitrate-free environment-friendly steel plate enamel low Wen Gunie primer, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210103535.6A CN114315142B (en) | 2022-01-28 | 2022-01-28 | Nitrate-free environment-friendly steel plate enamel low Wen Gunie primer, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114315142A CN114315142A (en) | 2022-04-12 |
| CN114315142B true CN114315142B (en) | 2023-11-17 |
Family
ID=81030219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210103535.6A Active CN114315142B (en) | 2022-01-28 | 2022-01-28 | Nitrate-free environment-friendly steel plate enamel low Wen Gunie primer, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114315142B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774761A (en) * | 2010-01-15 | 2010-07-14 | 重庆市硅酸盐研究所 | Composite glaze for enameling and method for adopting composite glaze to carry out bottomless glaze enameling |
| CN101921063A (en) * | 2010-08-05 | 2010-12-22 | 奇瑞汽车股份有限公司 | Enamel and preparation method thereof |
| CN101982444A (en) * | 2010-11-07 | 2011-03-02 | 湖南省无机色釉料工程技术研究中心有限公司 | Technology for preparing nano microcrystalline enamels |
| CN102503575A (en) * | 2011-11-02 | 2012-06-20 | 广东博德精工建材有限公司 | Method for producing transparent clinker capable of being compounded with colored glaze ceramic blank |
| CN102557752A (en) * | 2011-12-14 | 2012-07-11 | 陈新基 | Luminescent gloze material |
| CN103011598A (en) * | 2012-12-18 | 2013-04-03 | 龙门协成新材料有限公司 | Ground coat material of enamel glaze |
| CN103435263A (en) * | 2013-08-30 | 2013-12-11 | 湖南立发釉彩科技有限公司 | Primary enameling glaze and preparation method thereof |
| CN106380077A (en) * | 2016-08-29 | 2017-02-08 | 佛山市高明区诚睿基科技有限公司 | Deodorizing antibacterial low-temperature archaized glaze and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0612316D0 (en) * | 2006-06-21 | 2006-08-02 | United States Borax Inc | Glaze compositions |
-
2022
- 2022-01-28 CN CN202210103535.6A patent/CN114315142B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774761A (en) * | 2010-01-15 | 2010-07-14 | 重庆市硅酸盐研究所 | Composite glaze for enameling and method for adopting composite glaze to carry out bottomless glaze enameling |
| CN101921063A (en) * | 2010-08-05 | 2010-12-22 | 奇瑞汽车股份有限公司 | Enamel and preparation method thereof |
| CN101982444A (en) * | 2010-11-07 | 2011-03-02 | 湖南省无机色釉料工程技术研究中心有限公司 | Technology for preparing nano microcrystalline enamels |
| CN102503575A (en) * | 2011-11-02 | 2012-06-20 | 广东博德精工建材有限公司 | Method for producing transparent clinker capable of being compounded with colored glaze ceramic blank |
| CN102557752A (en) * | 2011-12-14 | 2012-07-11 | 陈新基 | Luminescent gloze material |
| CN103011598A (en) * | 2012-12-18 | 2013-04-03 | 龙门协成新材料有限公司 | Ground coat material of enamel glaze |
| CN103435263A (en) * | 2013-08-30 | 2013-12-11 | 湖南立发釉彩科技有限公司 | Primary enameling glaze and preparation method thereof |
| CN106380077A (en) * | 2016-08-29 | 2017-02-08 | 佛山市高明区诚睿基科技有限公司 | Deodorizing antibacterial low-temperature archaized glaze and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 无焰纯氧燃烧技术在搪瓷釉料窑炉中的应用;刘继雄;蒋伟忠;;玻璃与搪瓷(05);29 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114315142A (en) | 2022-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114409257B (en) | Nitrate-free environment-friendly steel plate enamel medium-temperature titanium creamy yellow overglaze and preparation method thereof | |
| CN114315142B (en) | Nitrate-free environment-friendly steel plate enamel low Wen Gunie primer, preparation method and application | |
| CN114315143B (en) | Environment-friendly steel plate enamel Wen Gunie primer without nitrate, preparation method and application | |
| CN114349341B (en) | Nitrate-free environment-friendly steel plate enamel medium-temperature nickel primer, preparation method and application | |
| CN114276020B (en) | Nitrate-free environment-friendly steel plate enamel low-temperature nickel primer, preparation method and application | |
| CN114315140B (en) | Nitrate-free environment-friendly steel plate enamel high-temperature nickel primer, preparation method and application | |
| CN114315141B (en) | Nitrate-free environment-friendly steel plate enamel low-temperature acid-resistant primer, preparation method and application | |
| CN114315153B (en) | Nitrate-free environment-friendly steel plate enamel high-temperature cobalt-nickel primer, preparation method and application | |
| CN114315150B (en) | Nitrate-free environment-friendly steel plate enamel low-temperature acid-resistant transparent glaze and preparation method thereof | |
| CN114368906B (en) | Nitrate-free environment-friendly cast iron enamel low-temperature ground coat and preparation method thereof | |
| CN114213015B (en) | Nitrate-free environment-friendly steel plate enamel high-temperature acid-resistant transparent glaze and preparation method thereof | |
| CN114394747B (en) | Nitrate-free environment-friendly cast iron enamel low-temperature acid-resistant ground coat and preparation method thereof | |
| CN114368913B (en) | Nitrate-free environment-friendly steel plate enamel high-temperature transparent glaze and preparation method thereof | |
| CN114409256B (en) | Nitrate-free environment-friendly cast iron enamel high-temperature ground glaze and preparation method thereof | |
| CN114368907B (en) | Nitrate-free environment-friendly steel plate enamel low Wen Timu primer and preparation method thereof | |
| CN114315147B (en) | Nitrate-free environment-friendly steel plate enamel medium-temperature acid-resistant primer, preparation method and application | |
| CN114368910B (en) | Nitrate-free environment-friendly steel plate enamel medium-temperature transparent glaze and preparation method thereof | |
| CN114315148B (en) | Nitrate-free environment-friendly steel plate enamel high-temperature acid-resistant primer, preparation method and application | |
| CN114368904B (en) | Nitrate-free environment-friendly cast iron enamel moderate-temperature acid-resistant ground coat and preparation method thereof | |
| CN114394748B (en) | Nitrate-free environment-friendly steel plate enamel nickel-free primer and preparation method thereof | |
| CN114368912B (en) | Nitrate-free environment-friendly steel plate enamel medium-temperature acid-resistant transparent glaze and preparation method thereof | |
| CN114315151B (en) | Nitrate-free environment-friendly cast iron enamel transparent glaze and preparation method thereof | |
| CN114368909B (en) | Wen Deyou in nitrate-free environment-friendly cast iron enamel and preparation method thereof | |
| CN114368903B (en) | Nitrate-free environment-friendly cast iron enamel high-temperature acid-resistant ground coat and preparation method thereof | |
| CN114315146B (en) | Nitrate-free environment-friendly cast iron enamel acid-resistant transparent glaze and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 411200 No. 1, Danfeng South Road, wujiaxiang Industrial Park, Xiangtan County, Xiangtan City, Hunan Province Applicant after: Hunan Xinnuo Technology Co.,Ltd. Address before: 411200 No. 1, Danfeng South Road, wujiaxiang Industrial Park, Xiangtan County, Xiangtan City, Hunan Province Applicant before: SINOPIGMENT & ENAMEL CHEMICALS Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |