Disclosure of Invention
The invention aims to solve the technical problems of poor separation effect of iron ions and chromium ions in the existing pickling waste liquid and difficulty in thorough separation, and provides a method for separating chromium from iron in the pickling waste liquid.
The above purpose of the invention is realized by the following technical scheme:
a method for separating chromium and iron from pickling waste liquid comprises the following steps:
s1, extracting ferric iron: adding an organic iron extractant into the pickling waste liquid to extract ferric ions to obtain a ferric organic phase and a water phase containing ferrous ions and chromium ions;
s2 back extracting ferric iron: back extracting the ferric iron in the ferric iron organic phase by using a sulfuric acid solution;
s3, extracting chromium ions: adjusting the pH value of a water phase containing ferrous ions and chromium ions to 1.0-2.5, and adding a chromium organic extracting agent to obtain a chromium-containing organic phase and a water solution containing ferrous ions;
s4. chromium ion stripping: the chromium ions in the chromium-containing organic phase are back-extracted with a sulfuric acid solution.
In order to further improve the separation of chromium and iron in the pickling waste liquid, ferric iron which can be extracted together with chromium is extracted and separated from the solution, the separation effect is relatively thorough, the phenomenon that the ferric iron is not completely reduced in a reduction method is avoided, the extracted ferric iron is relatively pure, the impurity content in the iron solution obtained after back extraction is not higher than 0.5%, the iron solution can be reused for industrial production, and the content of the ferric ion in the organic phase which is left after back extraction is below 25ppm, so that the iron ion can be recycled, and the extraction cost is saved.
The chromium ion extraction of the invention adopts the primary amine extractant which has large extraction capacity, is cheap and easy to obtain, and the reaction can be carried out under the acidic condition, thereby saving the consumption of alkali in the process of adjusting pH; the extracted chromium enters the water phase after the back extraction, the components are pure, the impurity content is not higher than 0.1 percent, the high-price chromium salt product can be prepared through concentration and crystallization treatment, the organic phase recovered by the back extraction can be further reused in the extraction of the chromium, and the chromium extraction cost is saved.
The reasons for adjusting the pH of the ferrous ion and chromium ion water phases to 1.0-2.5 are as follows: the pH is too low, the extraction efficiency of the extractant is low, and chromium ions are easy to precipitate when the pH is too high, so that the extraction operation is influenced. For example, the pH of the ferrous and chromium ion aqueous phases may be adjusted to 1.0, 1.6, 1.8, 2.2 or 2.5. The ferrous acid solution after chromium removal can be used for preparing an iron water purifying agent, and circular economy is realized.
The concentration of the sulfuric acid solution for back extraction of the ferric iron is preferably 0.3-3.0 mol/L, and the concentration of the sulfuric acid for back extraction of the chromium is preferably 1.0-5.0 mol/L. Too low sulfuric acid concentration can cause poor extraction effect, the increase of the sulfuric acid concentration can improve the extraction amount, but the too high sulfuric acid concentration can increase the extraction cost on one hand and the production cost in actual operation on the other hand, and the high-concentration sulfuric acid has strong oxidizability and can oxidize certain components in the organic extractant, so that the organic extractant cannot be recycled, and the treatment cost is increased.
Preferably, the iron organic extractant in S1 is a mixture of an extractant and a diluent, and the extractant accounts for 1-50% of the total volume of the iron organic extractant. For example, it may be 1%, 40% or 50%. The diluent is added into the extractant, so that the fluidity of the related extractant can be improved, the full fusion of the extractant and the extracted substances is promoted, and the extraction effect is improved. The extraction agent with too high content can not achieve good dilution effect, the improvement of the fluidity is not obvious, and the extraction potential energy of the whole body can be influenced by too low content of the extraction agent, so that the extraction is insufficient, and the extraction separation can not be realized. The extracting agent is preferably one or more of trioctyl tertiary amine, dodecyl tertiary amine, tributyl phosphate, dodecyl dimethyl tertiary amine, N-dimethyl hexadecyl tertiary amine or octadecyl dimethyl tertiary amine, and the diluent is preferably one or more of sulfonated kerosene, xylene or toluene.
Preferably, the extractant accounts for 40-50% of the total volume of the organic iron extractant.
Preferably, the addition amount of the organic iron extractant in the S1 is 0.5-3.0 times of the mass of the pickling waste liquid. For example, the amount may be.5 times, 1.4 times, 1.6 times, or 3.0 times.
Preferably, the extraction time in S1 is 5-10 min, and the extraction rotation speed is 200-300 r/min.
Preferably, the addition amount of the sulfuric acid solution in the stripping in the S2 is 0.5-5.0 times of the mass of the ferric iron organic phase. The reason is to ensure that the extracted substances can be fully extracted, and ensure that the extractant can be utilized to the maximum extent, thereby avoiding the waste of the extractant.
Preferably, the back extraction time in S2 is 3-5 min, and the extraction rotation speed is 200-300 r/min.
Preferably, the chromium organic extractant in S3 is a mixture of an extractant and a diluent, wherein the extractant accounts for 20-80% of the total volume of the chromium organic extractant. The dilution treatment of the chromium extractant also needs to take the extraction effect of chromium and the fluidity of the extractant into consideration, and because the chromium extract liquid of the invention is carried out in the raffinate for extracting ferric iron in S1, which contains ferrous ions and chromium ions, the flow property and the extraction effect of the extractant need to be determined by comprehensively considering the overall properties of the solution, unlike the chromium extraction alone. The chromium extracting agent is preferably one or more of methyl amyl butanone, dodecyl primary amine, decyl primary amine, hexadecyl primary amine and coco alkyl primary amine, and the diluent is preferably one or more of sulfonated kerosene, xylene and toluene.
Preferably, the extractant accounts for 60-80% of the total volume of the chromium organic extractant. For example, it may be 60%, 65% or 80%.
Preferably, the addition amount of the chromium organic extractant in S3 is 0.5-2.5 times of the mass of the ferrous ions and the chromium ions in the water phase. For example, it may be 0.5 times, 1.0 times, 1.5 times, 2.0 times or 2.5 times.
Preferably, the extraction time in S3 is 15-30 min, the extraction temperature is 50-70 ℃, and the extraction rotation speed is 200-300 r/min. The extraction of chromium is a heat absorption process, and the extraction is carried out under a certain temperature condition, so that the fluidity of an extracting agent is improved, and the mass transfer process and the two-phase layering are promoted; on the other hand, the external heat energy is helpful to promote the extraction reaction to proceed in the forward and reverse reaction direction, and the extraction efficiency is improved. Too low extraction temperature can slow down the mass transfer process, reduces the extraction effect, and too high extraction temperature can lead to the quick volatilization of organic extractant, causes the waste of extractant. The protected extraction time of chromium is optimized, and insufficient extraction can be caused by too short extraction time, so that the extraction efficiency is influenced; too long extraction time can cause emulsification, form bubble layer, and influence the extraction process.
Preferably, the addition amount of the back extraction sulfuric acid solution in the S4 is 0.5-4.0 times of the mass of the chromium ion organic phase. For example, it may be 0.5 times, 1 times, 2 times or 4 times.
Preferably, the back extraction time in S4 is 15-25 min, the temperature is 40-60 ℃, and the extraction speed is 200-300 r/min. The back extraction is carried out under a certain temperature condition, on one hand, the fluidity of an extracting agent is improved, and the mass transfer process and two-phase layering are promoted; on the other hand, the external heat energy is helpful to promote the reverse reaction direction of the back extraction reaction, and the extraction efficiency is improved. Too low extraction temperature can slow down the mass transfer process and reduce the back extraction effect, and too high extraction temperature can cause the waste of the extractant. The protected extraction time of chromium is optimized, and insufficient extraction can be caused by too short extraction time, so that the extraction efficiency is influenced; too long extraction time can cause emulsification, form bubble layer, and influence the extraction process.
The method for separating chromium and iron from waste acid is used for separating chromium and iron ions of various waste acids, is particularly suitable for separating chromium and iron from stainless steel pickling waste liquid, and is preferably suitable for separating chromium and iron from the pickling waste liquid with the chromium ion concentration of 0.5-5 g/L, the ferric ion concentration of 0-8 g/L and the ferrous ion concentration of 10-80 g/L.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for separating chromium and iron from pickling waste liquor, which comprises the steps of firstly separating and obtaining ferric ions through organic extraction and sulfuric acid back-extraction, avoiding the phenomenon that ferric ions are not completely reduced in a reduction method, avoiding the influence of ferric ions on the extraction and separation of the chromium ions, further separating and obtaining chromium ions and ferrous solution through a specific extraction-back-extraction system, and preparing a high-price chromium salt product through concentration and crystallization treatment, wherein the ferrous acid solution after chromium removal can be used for preparing an iron water purifying agent.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
The method for detecting the contents of the chromium ions and the iron ions comprises the following steps:
the chromium ion is determined by electric heating atomic absorption spectrometry, and the iron ion is determined by potassium dichromate titration "
Example 1
The raw material of this example was 400 kg of stainless steel pickling wastewater, and the acidity (acidity of sulfuric acid) was found to be 5.3%, the content of chromium ions was 4.5g/L, the content of ferric iron was 2.8 g/L, and the content of ferrous iron was 75 g/L.
A method for separating chromium and iron from pickling waste liquid comprises the following steps:
s1, extracting ferric iron: adding an iron organic extractant into the acid pickling waste liquid, and carrying out continuous centrifugal extraction at normal temperature to separate ferric ions to obtain a ferric organic phase and a ferrous ion and chromium ion water phase, wherein the ferric extractant contains 20% of trioctyl tertiary amine, 20% of dodecyl dimethyl tertiary amine, 10% of tributyl phosphate and 50% of sulfonated kerosene, and the addition amount is 0.5 times of the mass of the acid pickling waste liquid;
s2 back extracting ferric iron: utilizing a sulfuric acid solution to back extract the ferric iron in the ferric iron organic phase, wherein the concentration of the sulfuric acid solution is 0.5mol/L, the adding amount is 1 time of the mass of the ferric iron organic phase, and the organic extractant can be pumped back to the reaction tank for recycling;
s3, extracting chromium ions: adding soda ash to adjust the pH value of the ferrous ion and the chromium ion water phase to 1.6, and adding a chromium organic extracting agent to obtain a chromium ion organic phase and a ferrous ion water solution, wherein the chromium organic extracting agent comprises the following components: the method comprises the following steps of (1) carrying out primary extraction on 30% of dodecyl primary amine, 20% of decyl primary amine, 10% of methyl amyl ethyl ketone and 40% of sulfonated kerosene, wherein the addition amount of the dodecyl primary amine is 1 time of the mass of a ferrous ion water phase and a chromium ion water phase, the addition amount of the decyl primary amine is 0.5 time of the mass of the ferrous ion water phase and the chromium ion water phase, the secondary extraction is carried out, continuous centrifugal extraction separation is carried out at the temperature of 50 ℃, the extraction rotation speed is 300r/min, and raffinate (iron ion solution) can be used for industrial production of iron-based flocculants;
s4. chromium ion stripping: and (2) carrying out back extraction on chromium ions in the chromium ion organic phase by using a sulfuric acid solution, wherein the concentration of the sulfuric acid solution is 2.0mol/L, the adding amount is 1 time of the mass of the chromium ion organic phase, carrying out primary extraction, the adding amount is 0.5 time of the mass of the chromium ion organic phase, carrying out secondary extraction, the extraction temperature is 60 ℃, the extraction rotation speed is 300r/min, and the organic phase can be directly returned to an extraction working section for utilization.
Detecting the content of iron ions in raffinate (chromium and ferrous ion solution) in S1, wherein the content of iron ions is as follows: 55 ppm.
The content of iron ions in the organic phase in S2 was measured, and the content of iron ions was reduced to 25 ppm.
Detecting the content of chromium ions in the raffinate in the S3, wherein the content of the chromium ions is 6 ppm;
the chromium ion concentration of the organic phase after back extraction in S4 was measured, and the chromium ion content was 13 ppm.
Example 2
The raw material of this example was 500 kg of stainless steel pickling wastewater, and the acidity (acidity of sulfuric acid) was found to be 4.1%, the content of chromium ions was 2.1g/L, the content of ferric iron was 7.8 g/L, and the content of ferrous iron was 71 g/L.
A method for separating chromium and iron from pickling waste liquid comprises the following steps:
s1, extracting ferric iron: adding an iron organic extractant into the acid pickling waste liquid, and carrying out continuous centrifugal extraction at normal temperature to separate ferric ions to obtain a ferric organic phase and a ferrous ion and chromium ion water phase, wherein the ferric extractant contains 15% of dodecyl tertiary amine, 20% of N, N-dimethyl hexadecyl tertiary amine, 5% of tributyl phosphate and 60% of sulfonated kerosene, and the addition amount is 1.6 times of the mass of the acid pickling waste liquid;
s2 back extracting ferric iron: utilizing a sulfuric acid solution to back extract the ferric iron in the ferric iron organic phase, wherein the concentration of the sulfuric acid solution is 0.7mol/L, the adding amount is 0.6 times of the mass of the ferric iron organic phase, and the organic extractant can be pumped back to the reaction tank for recycling;
s3, extracting chromium ions: adding soda ash to adjust the pH value of the ferrous ion and the chromium ion water phase to 1.8, and adding a chromium organic extracting agent to obtain a chromium ion organic phase and a ferrous ion water solution, wherein the chromium organic extracting agent comprises the following components: the method comprises the following steps of (1) carrying out primary extraction by adding 20% of coconut alkyl primary amine, 40% of hexadecyl primary amine, 5% of methyl amyl ethyl ketone and 35% of sulfonated kerosene, wherein the adding amount of the sulfonated kerosene is 1 time of the mass of ferrous ions and chromium ions in a water phase, carrying out continuous centrifugal extraction separation at 55 ℃, wherein the extraction speed is 300r/min, and raffinate (iron ion solution) can be used for industrial production of iron-based flocculants;
s4. chromium ion stripping: and (2) carrying out back extraction on chromium ions in the chromium ion organic phase by using a sulfuric acid solution, wherein the concentration of the sulfuric acid solution is 1.5mol/L, the addition amount of the sulfuric acid solution is 1 time of the mass of the chromium ion organic phase, the extraction temperature is 60 ℃, the extraction rotation speed is 300r/min, and the organic phase can be directly returned to an extraction section for utilization.
Detecting the content of iron ions in raffinate (chromium and ferrous ion solution) in S1, wherein the content of iron ions is as follows: 42 ppm.
The content of iron ions in the organic phase in S2 was measured, and the content of iron ions was reduced to 16 ppm.
Detecting the content of chromium ions in the raffinate in the S3, wherein the content of the chromium ions is 13 ppm;
the chromium ion concentration of the organic phase after back extraction in S4 was measured, and the chromium ion content was 22 ppm.
Example 3
The raw material of this example was 1000 kg of stainless steel pickling wastewater, and the acidity (acidity of sulfuric acid) was found to be 3.8%, the content of chromium ions was 4.8g/L, the content of ferric iron was 7.0 g/L, and the content of ferrous iron was 65 g/L.
A method for separating chromium and iron from pickling waste liquid comprises the following steps:
s1, extracting ferric iron: adding an iron organic extractant into the acid pickling waste liquid, and carrying out continuous centrifugal extraction at normal temperature to separate ferric ions to obtain a ferric organic phase and a ferrous ion and chromium ion water phase, wherein the ferric extractant contains 30% of trioctyl tertiary amine, 10% of dodecyl tertiary amine, 10% of tributyl phosphate and 50% of sulfonated kerosene, and the adding amount is 1.4 times of the mass of the acid pickling waste liquid;
s2 back extracting ferric iron: back extracting the ferric iron in the ferric iron organic phase by using a sulfuric acid solution, wherein the concentration of the sulfuric acid solution is 2.0mol/L, the adding amount is 0.5 times of the mass of the ferric iron organic phase, and the organic extractant can be pumped back to the reaction tank for recycling;
s3, extracting chromium ions: adding soda ash to adjust the pH value of the ferrous ion and the chromium ion water phase to 2.2, and adding a chromium organic extracting agent to obtain a chromium ion organic phase and a ferrous ion water solution, wherein the chromium organic extracting agent comprises the following components: the method comprises the steps of adding 40% of dodecyl primary amine, 30% of decyl primary amine, 10% of methyl amyl ethyl ketone and 20% of sulfonated kerosene, wherein the adding amount of the dodecyl primary amine, the 30% of decyl primary amine, the 10% of methyl amyl ethyl ketone and the 20% of sulfonated kerosene is 1.5 times of the mass of ferrous ions and chromium ions in a water phase, extracting, and carrying out continuous centrifugal extraction separation at 55 ℃, wherein the extraction speed is 300r/min, and raffinate (iron ion solution) can be used for industrial production of iron-based flocculants;
s4. chromium ion stripping: and (2) carrying out back extraction on chromium ions in the chromium ion organic phase by using a sulfuric acid solution, wherein the concentration of the sulfuric acid solution is 5mol/L, the adding amount of the sulfuric acid solution is 0.5 times of the mass of the chromium ion organic phase, the extraction temperature is 40 ℃, the extraction rotating speed is 200r/min, and the organic phase can be directly returned to an extraction section for utilization.
Detecting the content of iron ions in raffinate (chromium and ferrous ion solution) in S1, wherein the content of iron ions is as follows: 45 ppm.
The content of iron ions in the organic phase in S2 was measured, and the content of iron ions was reduced to 12 ppm.
Detecting the content of chromium ions in the raffinate in S3, wherein the content of chromium ions is 18 ppm;
the chromium ion concentration of the organic phase after the back extraction in S4 was measured, and the chromium ion content was 28 ppm.
Example 4
A method for separating chromium and iron from a pickling waste liquid, which is basically the same as that in the embodiment 1, except that: in the S1, the extraction agent trioctyl tertiary amine accounts for 1 percent of the total volume of the ferric organic extraction agent, and the addition amount is 3.0 times of the mass of the pickling waste liquid.
Detecting the content of iron ions in raffinate (chromium and ferrous ion solution) in S1, wherein the content of iron ions is as follows: 12 ppm.
The content of iron ions in the organic phase in S2 was measured, and the content of iron ions was reduced to 20 ppm.
Detecting the content of chromium ions in the raffinate in the S3, wherein the content of the chromium ions is 10 ppm;
the chromium ion concentration of the organic phase after back extraction in S4 was measured, and the chromium ion content was 16 ppm.
Example 5
A method for separating chromium and iron from a pickling waste liquid, which is basically the same as that in the embodiment 1, except that: the amount of sulfuric acid solution added in the stripping in S2 was 5 times the mass of the ferric organic phase.
Detecting the content of iron ions in raffinate (chromium and ferrous ion solution) in S1, wherein the content of iron ions is as follows: 48 ppm.
The content of iron ions in the organic phase in S2 was measured, and the content of iron ions was reduced to 6 ppm.
Detecting the content of chromium ions in the raffinate in the S3, wherein the content of the chromium ions is 15 ppm;
the chromium ion concentration of the organic phase after back extraction in S4 was measured, and the chromium ion content was 12 ppm.
Example 6
A method for separating chromium and iron from a pickling waste liquid, which is basically the same as that in the embodiment 1, except that: s3 adjusts the pH of the ferrous and chromium ion aqueous phases to 1.0.
Detecting the content of iron ions in raffinate (chromium and ferrous ion solution) in S1, wherein the content of iron ions is as follows: 53 ppm.
The content of iron ions in the organic phase in S2 was measured, and the content of iron ions was reduced to 22 ppm.
Detecting the content of chromium ions in the raffinate in S3, wherein the content of chromium ions is 24 ppm;
the chromium ion concentration of the organic phase after back extraction in S4 was measured, and the chromium ion content was 10 ppm.
Example 7
A method for separating chromium and iron from a pickling waste liquid, which is basically the same as that in the embodiment 1, except that: in S3, the extraction agent dodecyl primary amine accounts for 20% of the total volume of the chromium organic extraction agent, and the addition amount of the chromium organic extraction agent is 2.5 times of the volume of the ferrous ions and the chromium ions in the water phase.
Detecting the content of iron ions in raffinate (chromium and ferrous ion solution) in S1, wherein the content of iron ions is as follows: 15 ppm.
The content of iron ions in the organic phase in S2 was measured, and the content of iron ions was reduced to 26 ppm.
Detecting the content of chromium ions in the raffinate in the S3, wherein the content of the chromium ions is 8 ppm;
the chromium ion concentration of the organic phase after back extraction in S4 was measured, and the chromium ion content was 12 ppm.
Example 8
A method for separating chromium and iron from a pickling waste liquid, which is basically the same as that in the embodiment 1, except that: in S3, the extraction agent dodecyl primary amine accounts for 80% of the total volume of the chromium organic extraction agent, and the addition amount of the chromium organic extraction agent is 0.5 times of the volume of the ferrous ions and the chromium ions in the water phase.
Detecting the content of iron ions in raffinate (chromium and ferrous ion solution) in S1, wherein the content of iron ions is as follows: 41 ppm.
The content of iron ions in the organic phase in S2 was measured, and the content of iron ions was reduced to 19 ppm.
Detecting the content of chromium ions in the raffinate in S3, wherein the content of chromium ions is 29 ppm;
the chromium ion concentration of the organic phase after back extraction in S4 was measured, and the chromium ion content was 15 ppm.
Example 9
A method for separating chromium and iron from a pickling waste liquid, which is basically the same as that in the embodiment 1, except that: the amount of the back-extracted sulfuric acid solution in S4 added was 4.0 times that of the chromium ion organic phase.
Detecting the content of iron ions in raffinate (chromium and ferrous ion solution) in S1, wherein the content of iron ions is as follows: 39 ppm.
The content of iron ions in the organic phase in S2 was measured, and the content of iron ions was reduced to 22 ppm.
Detecting the content of chromium ions in the raffinate in S3, wherein the content of chromium ions is 11 ppm;
the chromium ion concentration of the organic phase after back extraction in S4 was measured, and the chromium ion content was 6 ppm.
Example 10
A method for separating chromium and iron from a pickling waste liquid, which is basically the same as that in the embodiment 1, except that: the concentration of the sulfuric acid solution in S4 was 1.0 mol/L.
Detecting the content of iron ions in raffinate (chromium and ferrous ion solution) in S1, wherein the content of iron ions is as follows: 42 ppm.
The content of iron ions in the organic phase in S2 was measured, and the content of iron ions was reduced to 18 ppm.
Detecting the content of chromium ions in the raffinate in the S3, wherein the content of the chromium ions is 10 ppm;
the chromium ion concentration of the organic phase after back extraction in S4 was measured, and the chromium ion content was 22 ppm.
Comparative example 1
A method for separating chromium and iron from a pickling waste liquid, which is basically the same as that in the embodiment 1, except that: the concentration of the sulfuric acid solution in S2 was 0.2 mol/L.
Detecting the content of iron ions in raffinate (chromium and ferrous ion solution) in S1, wherein the content of iron ions is as follows: 54 ppm.
The content of iron ions in the organic phase in S2 was measured, and the content of iron ions was reduced to 71 ppm.
Detecting the content of chromium ions in the raffinate in the S3, wherein the content of the chromium ions is 12 ppm;
the chromium ion concentration of the organic phase after back extraction in S4 was measured, and the chromium ion content was 15 ppm.
Comparative example 2
A method for separating chromium and iron from a pickling waste liquid, which is basically the same as that in the embodiment 1, except that: the concentration of the sulfuric acid solution in S4 was 0.8 mol/L.
Detecting the content of iron ions in raffinate (chromium and ferrous ion solution) in S1, wherein the content of iron ions is as follows: 46 ppm.
The content of iron ions in the organic phase in S2 was measured, and the content of iron ions was reduced to 26 ppm.
Detecting the content of chromium ions in the raffinate in S3, wherein the content of chromium ions is 11 ppm;
the chromium ion concentration of the organic phase after back extraction in S4 was measured, and the chromium ion content was 63 ppm.
Comparative example 3
A method for separating chromium and iron from a pickling waste liquid, which is basically the same as that in the embodiment 1, except that: the pH of the aqueous phase containing ferrous ions and chromium ions is adjusted to 4 in S3.
Detecting the content of iron ions in raffinate (chromium and ferrous ion solution) in S1, wherein the content of iron ions is as follows: 54 ppm.
The content of iron ions in the organic phase in S2 was measured and was reduced to 24 ppm.
Detecting the content of chromium ions in the raffinate in S3, wherein the content of the chromium ions is 58 ppm;
the chromium ion concentration of the organic phase after back extraction in S4 was measured, and the chromium ion content was 10 ppm.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.