CN114276020B - Nitrate-free environment-friendly steel plate enamel low-temperature nickel primer, preparation method and application - Google Patents
Nitrate-free environment-friendly steel plate enamel low-temperature nickel primer, preparation method and application Download PDFInfo
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- 210000003298 dental enamel Anatomy 0.000 title claims abstract description 66
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 26
- 239000010959 steel Substances 0.000 title claims abstract description 26
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 18
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 16
- 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 15
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000010453 quartz Substances 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
- 229910000410 antimony oxide Inorganic materials 0.000 claims abstract description 12
- 239000010436 fluorite Substances 0.000 claims abstract description 12
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 12
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims abstract description 12
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021538 borax Inorganic materials 0.000 claims abstract description 10
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 10
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 10
- 229910052656 albite Inorganic materials 0.000 claims abstract description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims description 27
- 230000008018 melting Effects 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 15
- 239000005388 borosilicate glass Substances 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- 239000010433 feldspar 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
- 239000011521 glass Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- 238000005553 drilling Methods 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 74
- 229910002651 NO3 Inorganic materials 0.000 abstract description 43
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 43
- 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
- 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
- 239000000126 substance Substances 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
- 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
- 238000005245 sintering Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 230000008033 biological extinction 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
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- Glass Compositions (AREA)
Abstract
The invention discloses nitrate-free environment-friendly steel plate enamel low-temperature nickel primer, a preparation method and application thereof, wherein the formula comprises the following components in parts by mass: 16-20 parts of quartz, 25-27 parts of borax zero water, 12-14 parts of sodium carbonate, 1.5-3.5 parts of potassium carbonate, 3.5-5.0 parts of calcium carbonate, 11-13 parts of fluorite, 21-23 parts of potassium feldspar, 1-2 parts of albite, 0.7-0.9 part of nickel oxide, 0.5-0.6 part of antimony oxide and 2.4-3.0 parts of manganese oxide. The formula of the invention does not contain nitrate, and adopts a pure oxygen combustion mode in the melting process, thereby fundamentally solving the problem that the existing steel plate enamel low-temperature nickel primer produces Nitrogen Oxide (NO) in the production process x ) The gas discharge 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 low-temperature nickel primer, 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 applicant 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 invention CN201810677390.4 provides a preparation technique of phosphosilicate enamel, chinese invention 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 invention CN201310166353.4 discloses a high-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 sintering points, which completely violates the safety requirement of daily application and is forbidden in industry, and simultaneously, the invention 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 invention 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 invention CN201711361365.7 discloses a matt sand-lined enamel core glaze and a production method thereof, wherein the core glaze does not seem to involve the use of nitrate, but is essentially a matting agent, and needs to be matched with the real glazeThe material is used in combination to achieve the extinction purpose of the glaze, is not an 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 invention provides the nitrate-free environment-friendly steel plate enamel low-temperature nickel 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 physical and chemical properties of the enamel are kept unchanged.
The technical scheme adopted by the invention is as follows: the nitrate-free environment-friendly steel plate enamel low-temperature nickel primer comprises the following components in parts by mass: 16-20 parts of quartz, 25-27 parts of borax zero water, 12-14 parts of sodium carbonate, 1.5-3.5 parts of potassium carbonate, 3.5-5.0 parts of calcium carbonate, 11-13 parts of fluorite, 21-23 parts of potassium feldspar, 1-2 parts of albite, 0.7-0.9 part of nickel oxide, 0.5-0.6 part of antimony oxide and 2.4-3.0 parts of manganese oxide.
In the nitrate-free environment-friendly steel plate enamel low-temperature nickel primer, 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 Ni in nickel oxide is more than or equal to 95%, the purity of the antimony oxide is more than or equal to 99.5%, and other raw materials are industrial-grade purity.
The preparation method of the nitrate-free environment-friendly steel plate enamel low-temperature nickel primer comprises the following steps of:
(1) Weighing the following raw materials in parts by mass;
16-20 parts of quartz, 25-27 parts of borax zero water, 12-14 parts of sodium carbonate, 1.5-3.5 parts of potassium carbonate, 3.5-5.0 parts of calcium carbonate, 11-13 parts of fluorite, 21-23 parts of potassium feldspar, 1-2 parts of albite, 0.7-0.9 part of nickel oxide, 0.5-0.6 part of antimony oxide and 2.4-3.0 parts of manganese 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-temperature nickel 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-temperature nickel primer is applied to a blank with a steel plate as a matrix, and the sintering temperature of a finished product is 760-790 ℃.
The principle of the invention 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 invention, namely, after nitrate is removed, fluxing property in the enamel can still be ensured.
Compared with the prior art, the invention has the beneficial effects that:
the invention 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 invention 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 invention 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 the enamel low temperature nickel primer of the present invention applied thereto.
FIGS. 2-4 are pages 1-3 of the test report for the application of the low temperature nickel primer for steel enamels according to the invention, respectively.
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:
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 invention, 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:
18.0kg of quartz, 25.0kg of borax zero water, 13.0kg of calcined soda, 3.5kg of potassium carbonate, 3.5kg of calcium carbonate, 11.5kg of fluorite, 22.0kg of potassium feldspar, 1.2kg of albite, 0.6kg of antimony oxide, 0.8kg of nickel oxide and 2.6kg of manganese 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 Ni in nickel oxide is more than or equal to 95%, the purity of the antimony oxide is more than or equal to 99.5%, and other raw materials are 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: 18.0kg of quartz, 25.5kg of borax zero water, 13.0kg of calcined soda, 2.8kg of potassium carbonate, 4.0kg of calcium carbonate, 11.9kg of fluorite, 22.0kg of potassium feldspar, 1.6kg of albite, 0.6kg of antimony oxide, 0.8kg of nickel oxide and 2.6kg of manganese 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: 18.0kg of quartz, 26.0kg of borax zero water, 13.0kg of calcined soda, 1.5kg of potassium carbonate, 4.7kg of calcium carbonate, 12.5kg of fluorite, 22.0kg of potassium feldspar, 2.0kg of albite, 0.6kg of antimony oxide, 0.8kg of nickel oxide and 2.6kg of manganese 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: 20.0kg of quartz, 26.5kg of borax zero water, 14.0kg of sodium carbonate, 1.5kg of potassium carbonate, 4.3kg of calcium carbonate, 11.0kg of fluorite, 21.0kg of potassium feldspar, 1.5kg of albite, 0.5kg of antimony oxide, 0.7kg of nickel oxide and 2.4kg of manganese 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: 16.0kg of quartz, 27.0kg of borax zero water, 12.0kg of calcined soda, 1.5kg of potassium carbonate, 5.0kg of calcium carbonate, 13.0kg of fluorite, 23.0kg of potassium feldspar, 1.0kg of albite, 0.55kg of antimony oxide, 0.9kg of nickel oxide and 3.0kg of manganese oxide.
The product prepared by the invention 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 an enamel low-temperature nickel primer for a steel sheet prepared in example 2 of the present invention applied to an enamel 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 invention2And 1-3 pages of detection report of the application of the low-temperature nickel primer of the prepared steel plate enamel. 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-temperature nickel primer produced by the method does not contain nitrogen oxides in the preparation process, 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-temperature nickel primer, the purpose of removing nitrate from the environment-friendly steel plate enamel low-temperature nickel primer is realized, and the problem that Nitrogen Oxides (NO) are generated in the production and processing processes of the existing steel plate enamel low-temperature nickel primer is fundamentally solved x ) The technical problem of environmental pollution caused by gas discharge.
Claims (3)
1. The preparation method of the nitrate-free environment-friendly steel plate enamel low-temperature nickel primer comprises the following steps:
(1) Weighing the following raw materials in parts by mass;
16-20 parts of quartz, 25-27 parts of borax zero water, 12-14 parts of sodium carbonate, 1.5-3.5 parts of potassium carbonate, 3.5-5.0 parts of calcium carbonate, 11-13 parts of fluorite, 21-23 parts of potassium feldspar, 1-2 parts of albite, 0.7-0.9 part of nickel oxide, 0.5-0.6 part of antimony oxide and 2.4-3.0 parts of manganese 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 method for preparing the nitrate-free environment-friendly steel plate enamel low-temperature nickel primer according to claim 1, which is characterized in that: 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 Ni in nickel oxide is more than or equal to 95%, the purity of the antimony oxide is more than or equal to 99.5%, and other raw materials are industrial-grade purity.
3. The method for preparing the nitrate-free environment-friendly steel plate enamel low-temperature nickel primer according to claim 1, which is characterized in that: the quenching in the step (5) is a water quenching or tabletting process method.
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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 |
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| CN103693850A (en) * | 2013-12-09 | 2014-04-02 | 常熟市永达化工设备厂 | Preparation technology of nanocrystalline enamel |
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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 |
| CN103693850A (en) * | 2013-12-09 | 2014-04-02 | 常熟市永达化工设备厂 | Preparation technology of nanocrystalline enamel |
| CN107892479A (en) * | 2017-12-18 | 2018-04-10 | 娄底湘信新材料科技有限公司 | A kind of matt sand streak vitreous enamel core glaze and production method |
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