CN114368912B - Nitrate-free environment-friendly steel plate enamel medium-temperature acid-resistant transparent glaze and preparation method thereof - Google Patents
Nitrate-free environment-friendly steel plate enamel medium-temperature acid-resistant transparent glaze and preparation method thereof Download PDFInfo
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- 210000003298 dental enamel Anatomy 0.000 title claims abstract description 66
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 26
- 239000010959 steel Substances 0.000 title claims abstract description 26
- 239000002253 acid Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 22
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 14
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000010436 fluorite Substances 0.000 claims abstract description 12
- 239000010453 quartz Substances 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-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 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 11
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 11
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005245 sintering Methods 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims description 24
- 230000008018 melting Effects 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- 239000005388 borosilicate glass Substances 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 4
- 238000005553 drilling Methods 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 68
- 229910002651 NO3 Inorganic materials 0.000 abstract description 42
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 42
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 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
- 230000000694 effects Effects 0.000 description 11
- 229910052573 porcelain Inorganic materials 0.000 description 9
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 235000010215 titanium dioxide Nutrition 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000010309 melting process Methods 0.000 description 5
- 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
- 230000007613 environmental effect Effects 0.000 description 4
- 238000010304 firing Methods 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
- 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
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000004323 potassium nitrate Substances 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
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution 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
- 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
- 241000283690 Bos taurus Species 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
- 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
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 230000004907 flux 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
- 238000007689 inspection Methods 0.000 description 1
- 239000002932 luster Substances 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
- AHYBQDWHRPRCKD-UHFFFAOYSA-N potassium nitric acid nitrate Chemical compound [K+].O[N+]([O-])=O.[O-][N+]([O-])=O AHYBQDWHRPRCKD-UHFFFAOYSA-N 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
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011734 sodium Substances 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
- 239000010936 titanium Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/06—Frit compositions, i.e. in a powdered or comminuted form containing halogen
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2207/00—Compositions specially applicable for the manufacture of vitreous enamels
- C03C2207/04—Compositions specially applicable for the manufacture of vitreous enamels for steel
Abstract
The invention discloses a nitrate-free environment-friendly steel plate enamel medium-temperature acid-resistant transparent glaze and a preparation method thereof, which belong to the technical field of enamel, wherein the formula comprises the following components in parts by mass: 23-26 parts of borax zero water, 39-41 parts of quartz, 10-13 parts of sodium carbonate, 4-6 parts of titanium dioxide, 6-8 parts of aluminum oxide, 5-7 parts of fluorite and 3-5 parts of barium carbonate. The raw materials are uniformly mixed according to the proportion, and are melted under the conditions of 1260+/-10 ℃ and pure oxygen, and the sintering temperature of the finished product is 800-840 ℃. The formula does not contain nitrate, and fundamentally solves the problem that the conventional steel plate enamel medium-temperature acid-resistant transparent glaze generates 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 medium-temperature acid-resistant transparent glaze and a preparation method thereof.
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 nitrates (especially alkali metal nitrates) are indeed indispensable raw materials 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. Nitrate has good effect in enamel glaze, but can decompose to generate a large amount of nitrogen oxides at high temperature, so as to 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,under the high temperature condition, the nitrate has good oxidation effect, so that the oxide is ensured not to be reduced into simple substance in the melting process, and meanwhile, common nitrate sodium nitrate and common nitrate potassium nitrate are decomposed at high temperature to obtain products 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. The invention CN201711361365.7 discloses a matte 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 the matting purpose of the glaze is achieved by combining with the real glaze, so that the core glaze is not an independent glaze and cannot be used independently. In addition, in the "initial practice of nitrate-free enamel glaze" (Xie Xuexin, limited practice of Xinjin Jincrouch cattle in Chengdu City)In company, glass and enamel 2007,35 (1), this document uses a method of increasing the air flow rate in order to intensify the oxidation, which, although not involving the use of nitrates, does not start from the aim of reducing nitrogen oxides, but rather of solving the problem of sufficient oxidation of the Ti-containing overglaze, is achieved for this purpose 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
One of the purposes of the invention is to provide the nitrate-free environment-friendly steel plate enamel medium-temperature acid-resistant transparent glaze on the premise of not reducing various performance indexes of the product aiming at the environmental protection problem existing in the traditional nitrate-containing acid-resistant enamel glaze.
The invention relates to nitrate-free environment-friendly steel plate enamel medium-temperature acid-resistant transparent glaze, which comprises the following components in parts by mass: 23-26 parts of borax zero water, 39-41 parts of quartz, 10-13 parts of sodium carbonate, 4-6 parts of titanium dioxide, 6-8 parts of aluminum oxide, 5-7 parts of fluorite and 3-5 parts of barium carbonate.
Further, in quartz, siO 2 The content of the ferric oxide is more than or equal to 98 percent and less than or equal to 0.05 percent.
Further, in fluorite, caF 2 The content is more than or equal to 95 percent.
The second aim of the invention is to provide a preparation method of the nitrate-free environment-friendly steel plate enamel medium-temperature acid-resistant transparent glaze.
The invention relates to a preparation method of nitrate-free environment-friendly steel plate enamel medium-temperature acid-resistant transparent glaze, which comprises the following steps:
(1) Weighing the following raw materials in parts by mass;
23-26 parts of borax zero water, 39-41 parts of quartz, 10-13 parts of sodium carbonate, 4-6 parts of titanium dioxide, 6-8 parts of aluminum oxide, 5-7 parts of fluorite and 3-5 parts of barium carbonate;
(2) Stirring and mixing the raw materials in the step (1) uniformly;
(3) Adding the uniformly mixed materials into a melting furnace, and melting under the pure oxygen condition, wherein the melting temperature is controlled to be 1260+/-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.
The nitrate-free environment-friendly steel plate enamel medium-temperature acid-resistant transparent glaze is applied to blanks taking steel plates as matrixes, and the sintering temperature of finished products is 800-840 ℃.
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.
The invention has the beneficial effects that:
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.
In addition, the flux components and the dosage of other non-nitrate are adjusted in the formula, so that even if nitrate is not used for fluxing in enamel, 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.
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 in the series of enamel glaze manufacturers of the applicant do not contain nitrate, the residual approximately 20% of the products can not completely remove nitrate, but the use amount of nitrate can be reduced by more than 50%. The nitrate consumption is reduced to about 100 tons from 1000 tons in the original year, and the reduction rate is about 90 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 performance (porcelain surface, luster, firing temperature) of the product after nitrate removal is unchanged, and the quality detection requirement of the national enamel product is met. Therefore, the technical scheme of the invention has extremely important environmental benefit, social benefit and popularization and application significance.
Drawings
FIG. 1 is a photograph showing the application of the product obtained in example 3 of the present invention to an enamel plate made of a steel plate.
Figures 2 to 4 are photographs of pages 1 to 3, respectively, of a test report for the application of the product obtained in example 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific experimental 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.
The purity of the raw materials used in the embodiment of the invention meets the requirements of industrial grade.
Example 1
(1) Weighing the following raw materials in parts by mass:
23.2KG of borax zero water, 40KG of quartz, 12.5KG of sodium carbonate, 5KG of titanium dioxide, 7KG of alumina, 6.8KG of fluorite and 4KG of barium carbonate;
(2) Stirring and mixing the raw materials uniformly;
(3) Adding the uniformly mixed materials into a melting furnace for melting under the pure oxygen condition, wherein the melting temperature is controlled to be 1260+/-10 ℃;
(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 (3) quenching (tabletting) the melted borosilicate glass body 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: 24.6KG of borax zero water, 40KG of quartz, 10.8KG of sodium carbonate, 5KG of titanium dioxide, 7KG of alumina, 6.5KG of fluorite and 4KG of barium carbonate.
In the step (5), the molten borosilicate glass body is quenched by adopting a water quenching 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: 25.9KG of borax zero water, 40KG of quartz, 11.7KG of sodium carbonate, 5KG of titanium dioxide, 7KG of alumina, 5.2KG of fluorite and 4KG of barium carbonate.
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: borax zero water 23KG, quartz 39KG, sodium carbonate 10KG, titanium white 4KG, alumina 6KG, fluorite 5KG and barium carbonate 3KG.
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: borax zero water 26KG, quartz 41KG, sodium carbonate 13KG, titanium white powder 6KG, alumina 8KG, fluorite 7KG and barium carbonate 5KG.
The product prepared by the invention is applied to a blank taking a steel plate as a matrix, and the sintering temperature of the finished product is 800-840 ℃.
Taking the product obtained in example 3 as an example, the performance was evaluated as follows:
referring to fig. 1, the product obtained in the embodiment 3 of the invention is applied to porcelain glaze made of steel plates, the porcelain surface is smooth and fine, the color is uniform and attractive, and the requirements of users are completely met.
Referring to fig. 2 to 4, there are test reports of the product application obtained in example 3 of the present invention. The detection unit is a national glass enamel product quality inspection and detection center.
Experiments and detection results prove that the nitrate-free environment-friendly steel plate enamel produced by the method has medium temperature resistanceThe acid transparent glaze is free from nitrogen oxide in the preparation process, various properties (porcelain surface, gloss, acid resistance, firing temperature) and the like of the obtained product all meet the requirements of the steel plate enamel intermediate temperature acid resistant transparent glaze, the purpose of removing nitrate by the environment-friendly steel plate enamel intermediate temperature acid resistant transparent glaze is realized, and the problem that Nitrogen Oxide (NO) is generated in the production and processing processes of the traditional steel plate enamel intermediate temperature acid resistant transparent glaze is fundamentally solved x ) The technical problem of environmental pollution caused by gas discharge.
Claims (6)
1. The nitrate-free environment-friendly steel plate enamel medium-temperature acid-resistant transparent glaze is characterized by comprising the following components in parts by mass: 23-26 parts of borax zero water, 39-41 parts of quartz, 10-13 parts of sodium carbonate, 4-6 parts of titanium dioxide, 6-8 parts of aluminum oxide, 5-7 parts of fluorite and 3-5 parts of barium carbonate.
2. The nitrate-free environment-friendly steel plate enamel medium-temperature acid-resistant transparent glaze as claimed in claim 1, wherein SiO 2 The content of the ferric oxide is more than or equal to 98 percent and less than or equal to 0.05 percent.
3. The nitrate-free environment-friendly steel plate enamel medium-temperature acid-resistant transparent glaze as claimed in claim 1, wherein in fluorite, caF 2 The content is more than or equal to 95 percent.
4. A method for preparing the nitrate-free environment-friendly steel plate enamel medium-temperature acid-resistant transparent glaze as claimed in any one of claims 1 to 3, which comprises the following steps:
(1) Weighing the following raw materials in parts by mass;
23-26 parts of borax zero water, 39-41 parts of quartz, 10-13 parts of sodium carbonate, 4-6 parts of titanium dioxide, 6-8 parts of aluminum oxide, 5-7 parts of fluorite and 3-5 parts of barium carbonate;
(2) Stirring and mixing the raw materials in the step (1) uniformly;
(3) Adding the uniformly mixed materials into a melting furnace, and melting under the pure oxygen condition, wherein the melting temperature is controlled to be 1260+/-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.
5. The method for preparing the nitrate-free environment-friendly steel plate enamel medium-temperature acid-resistant transparent glaze, which is characterized in that: the quenching in the step (5) is a water quenching or tabletting process method.
6. Use of a nitrate-free environment-friendly steel sheet enamel medium temperature acid resistant transparent enamel according to any of claims 1 to 3, characterized in that: the method is applied to blanks taking steel plates as matrixes, and the sintering temperature of finished products is 800-840 ℃.
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