OA20300A - Nitrogen oxide absorbent slurry, preparation method therefor and use method thereof. - Google Patents
Nitrogen oxide absorbent slurry, preparation method therefor and use method thereof. Download PDFInfo
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- OA20300A OA20300A OA1202100549 OA20300A OA 20300 A OA20300 A OA 20300A OA 1202100549 OA1202100549 OA 1202100549 OA 20300 A OA20300 A OA 20300A
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- Prior art keywords
- chloride
- absorbent
- ferrie
- gas
- ferrie chloride
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 239000002250 absorbent Substances 0.000 title claims abstract description 143
- 230000002745 absorbent Effects 0.000 title claims abstract description 143
- 239000002002 slurry Substances 0.000 title claims abstract description 59
- 229910052813 nitrogen oxide Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 119
- 239000007789 gas Substances 0.000 claims abstract description 93
- 238000010521 absorption reaction Methods 0.000 claims abstract description 53
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 238000002156 mixing Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229940068911 CHLORIDE HEXAHYDRATE Drugs 0.000 claims description 15
- VOAPTKOANCCNFV-UHFFFAOYSA-M chloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-] VOAPTKOANCCNFV-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- DKAGJZJALZXOOV-UHFFFAOYSA-M chloride;hydrate Chemical compound O.[Cl-] DKAGJZJALZXOOV-UHFFFAOYSA-M 0.000 claims description 11
- 238000005660 chlorination reaction Methods 0.000 claims description 10
- 230000001681 protective Effects 0.000 claims description 10
- NSNHWTBQMQIDCF-UHFFFAOYSA-M chloride;dihydrate Chemical compound O.O.[Cl-] NSNHWTBQMQIDCF-UHFFFAOYSA-M 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000003795 desorption Methods 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- -1 sulfoxide chloride Chemical class 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K Aluminium chloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M Lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 3
- 230000000875 corresponding Effects 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L Cobalt(II) chloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L Copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L Nickel(II) chloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 230000005587 bubbling Effects 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L cacl2 Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000012320 chlorinating reagent Substances 0.000 claims 1
- 150000001805 chlorine compounds Chemical group 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K Iron(III) chloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 5
- 238000003915 air pollution Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 5
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 4
- 230000001172 regenerating Effects 0.000 description 4
- 238000005201 scrubbing Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003462 sulfoxides Chemical class 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 2
- QEHKBHWEUPXBCW-UHFFFAOYSA-N Nitrogen trichloride Chemical compound ClN(Cl)Cl QEHKBHWEUPXBCW-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-M chloride;hydrochloride Chemical compound Cl.[Cl-] IXCSERBJSXMMFS-UHFFFAOYSA-M 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910000856 hastalloy Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L Copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 101710007433 FECH Proteins 0.000 description 1
- 229910002089 NOx Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L Zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000003247 decreasing Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 159000000014 iron salts Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002588 toxic Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 229910052723 transition metal Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
Abstract
A nitrogen oxide absorption slurry and its preparation and use method for the removal of nitric oxide in gas streams, belonging to the technical field of air pollution control and related environmental protection, is characterized in that the absorption slurry contains at least one compound and anhydrous ferric chloride, ferric chloride monohydrate, ferric chloride dihydrate and the complex of ferric chloride and hydrogen chloride. The absorption slurry reacts with the nitric oxide in gas stream, so that the nitric oxide in the gas stream is absorbed by the slurry, thereby achieving the purpose of gas purification. And the absorbent can be recycled after regeneration.
Description
NITROGEN OXIDE ABSORPTION SLURRY AND ITS PREPARATION AND USE METHOD THEREOF
FIELD OF TECHNOLOGY
[0001] The présent disclosure relates to a kind of nitrogen oxide absorption slurry and its préparation and use method thereof, which is used to remove nitric oxide from gas streams, and belongs to the technical field of air pollution control and related environmental protection.
BACKGROUND OF THE INVENTION
[0002] Nitrogen oxides (NOX) produced by human activities mainly includes nitric oxide (NO) and nitrogen dioxide (NO2). Among them, NO generally accounts for more than 95% of NOx produced by the combustion of fossil fuels, and the concentration is generally from tens of ppm to thousands of ppm. NOX - containing exhaust gases are also produced from other industrial processes, such as nitric acid production, building materials, metallurgy, Chemical, pharmaceuticals, métal surface treatment and semiconductor production. NOX has a toxic effect on humans, and a large amount of its * émissions is one of the main causes of atmospheric photochemical fogs and acid rains. [0003] The applicant of the présent invention has disclosed a method (CN105032163A) for removing NOX in a gas stream through a Chemical adsorption reaction between ferrie chloride and nitric oxide. When solid ferrie chloride powders are directly used in the reactor, the utilization of the sorbent of ferrie chloride is low, and it Is easy to be carried away by the gas stream, which leads to the loss of the sorbent and subséquent secondary treatment. Therefore, the présent invention proposes a method by using nitrogen oxide absorption slurry to replace solid sorbent to overcome the technical problems encountered.
SUMMARY OF THE INVENTION
[0004] A nitrogen oxide absorption slurry (absorbent for short), which is used to remove nitric oxide in gas stream, is characterized in that the mass ratio of water to ferrie chloride in the absorbent is from 0.005 to 0.55, and contains at least one of anhydrous ferrie chloride, ferrie chloride monohydrate, ferrie chloride dihydrate, and a complex of ferrie chloride and hydrochloric acid.
[0005] The less the water content and the more anhydrous ferrie chloride crystals in the absorbent, the better the absorption effect on NO removal, and the optimal mass ratio of water to ferrie chloride is from 0.01 to 0.11. However, as the water content decreases, the fluidity of the absorbent at the same température becomes poor and higher préparation and working températures are required to ensure the fluidity of the absorbent. When the mass ratio of water to ferrie chloride is less than 0.005, the absorbent cannot be obtained within the température range of the invention. When the mass ratio is greater than 0.55, and the slurry does not contain at least one of anhydrous ferrie chloride, ferrie chloride monohydrate, ferrie chloride dihydrate, and the complex of ferrie chloride and hydrochloric acid, and the absorbent has no absorption effect on nitric oxide removal.
[0006] The préparation of the absorbent of the présent invention is to mix anhydrous ferrie chloride and water, or anhydrous ferrie chloride and ferrie chloride monohydrate, or anhydrous ferrie chloride and ferrie chloride dihydrate, or anhydrous ferrie chloride and ferrie chloride hexahydrate (or other ferrie chloride containing crystalline water) in a mixing reactor according to the mass ratio as described above. After ail the materials are fully mixed under a certain température and atmosphère, the finally obtained slurry is the absorbent.
[0007] The absorbent can be also prepared by dehydrating ferrie chloride solution. The déhydration can be performed by heating or other Chemical and physical methods.
[0008] The préparation température of the absorbent is 35°C and above. The higher the préparation température, the less water in the absorbent, which resulting in the higher content of effective ferrie chloride. However, when the préparation température is too high, ferrie chloride may undergo hydrolysis to release hydrogen chloride gas, which is négative to absorbent préparation. Therefore, when the absorbent is prepared at high température, it can be performed in a protective atmosphère of hydrogen chloride and in a closed environment to prevent décomposition of ferrie chloride. The absorbent préparation température is usually lower than or equal to 200°C, preferably 65 to 130°C. [0009] The préparation of the absorbent by using anhydrous ferrie chloride and water can be performed as following steps: First weigh anhydrous ferrie chloride powder and water respectively according to a predetermined ratio. Preferably, the mass ratio of ferrie chloride to water is 9:1 to 25:1. Then, ail the water is added into a closed mixing reactor (the same below), and then anhydrous ferrie chloride powder is gradualiy added, mixed and heated to a predetermined température in the presence of inert gas such as air or nitrogen, or in the presence of a protective gas of hydrogen chloride (usually, a protective gas of hydrogen chloride may be used at a température above 60°C, the same below) in the reactor. After ferrie chloride and water are completely mixed, the préparation of the absorbent is completed.
[0010] The préparation of the absorbent by using anhydrous ferrie chloride and ferrie chloride hexahydrate can be performed as following steps: First weigh anhydrous ferrie chloride powder and solid ferrie chloride hexahydrate respectively according to a predetermined ratio. Preferably, the mass ratio of the anhydrous ferrie chloride to the ferrie chloride hexahydrate is about 3.5: 1 to 12: 1. Then, ail the ferrie chloride hexahydrate is added into a mixing reactor, and then anhydrous ferrie chloride powder is gradually added, mixed and heated to a predetermined température in the presence of inert gas such as air or nitrogen, or in the presence of a protective gas of hydrogen chloride in the mixing reactor, and after ail materials are completely mixed, the préparation of the absorbent is completed. When other ferrie chloride hydrates, such as mono- or di-hydrate ferrie chloride, are used as raw materials, the mass ratio these materials can be converted according to the above mentioned proportion.
[0011] In the préparation of the absorbent, hydrochloric acid solution can also be used in place of water to increase the content of anhydrous ferrie chloride in the slurry, and the fluidity of the slurry may be also increased. This is because the chloride ions in the hydrochloric acid solution hâve coordination properties. In addition to the free form of the ferrie chloride crystals existing in the slurry, they can also form complexes with the chloride ions in the hydrochloric acid solution, thereby increasing the content of ferrie chloride in the slurry. When the absorbent Works, the complex of ferrie chloride and hydrogen chloride is decomposed as the hydrogen chloride volatilizes from the slurry, resulting in the increase of the content of ferrie chloride crystals in the slurry. Therefore, the ability of the absorbent to continuously absorb nitric oxide is improved. The absorbent may also be prepared by dehydrating ferrie chloride solution after acidification with hydrogen chloride gas or hydrochloric acid.
[0012] The content of hydrochloric acid in the absorbent has no spécial requirements, depending on actual needs. Commercial hydrochloric acid with the concentration of 30 to 38% is usually used in the préparation. The higher the concentration of the hydrochloric acid used, the better the fluidity of the prepared absorbent slurry at the same température, and the more ferrie chloride in the slurry, the better the nitrogen removal. Compared with the use of water, the content of ferrie chloride (containing complexes) in the absorbent can be increased at least 1 times by using hydrochloric acid solution under the same water content condition, and is proportional to the concentration of hydrochloric acid in the absorbent. The mass ratio of ferrie chloride to water can also reach above 0.99 in the absorbent. Similarly, the higher the préparation température, the higher the ferrie chloride content in the prepared absorbent. The working température of the absorbent (the reaction température between the absorbent and nitrogen oxide) may be also increased, which is bénéficiai for removing nitric oxide from gas strearn at higher températures. Compared with température, the concentration of hydrochloric acid has a greater influence on the content of ferrie chloride in the absorbent.
[0013] The préparation of the absorbent by using a hydrochloric acid solution instead of water is substantially the same. The préparation by using anhydrous ferrie chloride and hydrochloric acid solution can be performed as following steps:
[0014] First weigh the ferrie chloride powder and the hydrochloric acid solution according to a predetermined mass ratio. The mass ratio of the ferrie chloride to the hydrochloric acid solution (take 30% hydrochloric acid as an example, the same below) is usually greater than or equal to 3. The dose of ferrie chloride can be determined according to the concentration of hydrochloric acid and the content of water therein. With the increase of the concentration of hydrochloric used, the dose of ferrie chloride increases, and the mass ratio of ferrie chloride to hydrochloric acid solution is preferably from 10 to 100. In the préparation process, the hydrochloric acid solution can be firstly added to a closed mixing reactor, and then anhydrous ferrie chloride powder is gradually added, mixed and heated to a predetermined température in the presence of inert gas such as air or nitrogen, or in the presence of a protective gas of hydrogen chloride in the mixing reactor, and after ail materials are completely mixed, the préparation of the absorbent is completed.
[0015] The préparation by using ferrie chloride hydrates (ferrie chloride hexahydrate, for example) and hydrochloric acid solution can be performed as following steps: First weigh solid ferrie chloride hexahydrate and hydrochloric acid solution according to a predetermined mass ratio, and then the hydrochloric acid solution is added to a closed mixing reactor, and then ferrie chloride hexahydrate is dissolved in the hydrochloric acid solution, and heated and dehydrated in the presence of a protective gas of hydrogen chloride (hydrogen chloride gas or related mixed gas can be passed into the solution). After the composition in mixture in the reactor reaches the predetermined required mass ratio, the préparation of the absorbent is completed. Generally, the déhydration température is 65°C or higher, and the higher heating température, the faster déhydration process, preferably 110 to 200°C, but it is not limited.
[0016] In order to increase the content of ferrie chloride crystal in the absorbent, sait solutions which hâve the properties of sait effect or chloride ion coordination may also be used in place of water in the préparation of the absorbent Said sait solutions are mainly hydrochloride and sulfate salts of alkali metals, alkaline earth metals or transition metals, and corresponding acid salts, which include sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnésium chloride, zinc chloride, manganèse chloride, cobalt chloride, copper chloride, nickel chloride, aluminum chloride, and corresponding sulfates of the metals. In addition, most of the sait solutions are high boiling point salts, which may increase the working température of the absorbent by about 10°C. When the sait solution is used to prépare the absorbent, there is no spécial requirement for the concentration of the sait solution depending on actual need. The maximum concentration of sait solution is normally the saturation concentration at the working température. Other préparation processes are the same as those using hydrochloric acid as solution. The hydrochloric acid and the sait solution can also be used together, and the effect is better than single one.
[0017] The method for using the absorbent is to introduce the absorbent into an absorption reactor, and nitric oxide in gas stream is absorbed by Chemical reaction with ferrie chloride in the absorbent, thereby achieving the purpose of gas purification. The working température of the absorbent prepared by mixing water with ferrie chloride is from 35°Cto 110°C, preferably from 65°C to 100°C. The working température of the absorbent prepared by using hydrochloric acid or a sait solution instead of water is from 35°C to 130°C, preferably from 70°C to 115°C. The working température is roughly « équivalent to the température of the gas stream being processed. When the working température is high, hydrogen chloride gas may be discharged from the absorption slurry, which may be removed by downstream water or alkali solution absorption.
[0018] The major composition of the absorbent responsible for nitric oxide removal are anhydrous ferrie chloride crystals, and ferrie chloride monohydrate, ferrie chloride dihydrate crystals, or related ferrie chloride hydrochloric acid complex in the absorption slurry may pay a certain absorption effect, and the products of the absorption Chemical reaction are coordination compounds or related salts of nitric oxide and ferrie chloride. Possible reactions are listed below:
FeCI3 + mNO + nH2O Fe(H2O)n(NO)mCI3( 1 )
FeCI3 + H2O + mNO -> Fe(NO)m (OH) Cl2 + HCl(2)
Fe(H2O)nCI3 + mNO Fe(H2O)n(NO)mCI3( 3 )
Where, m + n 6 (usually < 3, depending on the reaction conditions).
[0019] The mass ratio of the dosage of the absorbent to nitric oxide in the gas stream mainly dépends on the content of ferrie chloride crystal in the absorbent, and the
R theoretical reaction molar ratio is about 0.5 to 1 (iron to nitrogen ratio). In practical use, the dosage can be determined according to the water content in the absorbent, reaction température, removal requirements, and régénération cycle. There are no spécial requirements of the mole ratio, and it is usually from 10 to 1000.
[0020] The absorption reactor adopted of the présent invention can be gas-liquid contact reactors such as rotating, spraying, bubbling, and moving bed types that are commonly adopted in Chemical engineering unit operations, and the flow pattern in the reactor can be used arranged in co-current flow, counter-flow, cross-flow and others. The detail design . parameters can refer to the relevant Chemical equipment design manual.
[0021] A rotating absorption reactor for nitrogen oxide absorption is consist of a horizontally placed rotating reactor column, a gas iniet at one end of the reactor column and a gas outlet at the other end, an absorbent iniet at the upper part of the reactor column and an absorbent outlet at the lower part, and the reactor is driven by a transmission System.
[0022] The treatment process is to add the absorbent to the reactor through the absorbent iniet, and to introduce the gas stream containing nitric oxide to the reactor from the gas iniet, and to drive the reactor rotating, so that the absorption slurry in the reactor flows along the inner wall pf the column pf the reactor and is in complété contact with the gas. Nitric oxide in the air stream is then absorbed by the absorbent, and the purified gas stream is discharged from the gas outlet at the other end of the reactor, The used absorbent can be periodically discharged from the absorbent outlet.
[0023] A counter-current absorption column for nitric oxide absorption includes a column body, a gas iniet at the lower part of the column, a gas outlet at the upper part of the column. The upper part of the column is provided with an absorbent iniet and a slurry sprayer, and the lower part is provided with an absorbent storage tank. The absorbent storage tank communicates with the absorbent slurry iniet of the column through a slurry pump and a connecting pipeline. The saturated absorbent after absorption can be sent to régénération by a bypass pipeline.
[0024] The absorbent is still in a slurry State at the working température after the absorption reaction with nitric oxide, but it is in a solid State after cooling down tP room température. When exposed to atmosphère and moisture, the product may be decomposed to release the absorbed nitric oxide gas. The absorbed nitric oxide gas can be removed from the absorbent by heating and/or humidifying. The heating température is usually above 65°C, preferably from 110°C to 180°C. The heating température under négative pressure or vacuum can be lower, and desorption is also faster. Both water vapor fi and hydrogen chloride gas may be generated during the heating process, and nitric oxide gas can be recovered from the desorption process or by-products such as nitric acid can be further prepared from nitric oxide gas. The absorbent after desorption can be regenerated after déhydration and chlorination (acidification with hydrogen chloride or hydrochioric acid, hereinafter the same), and the régénération process is substantially the same as the préparation process of the absorbent described above.
[0025] The régénération of the absorbent can also be implemented by deliquescing the absorbent in wet air or water vapor or dissolving it in solvents such as water or hydrochioric acid solution to release the absorbed nitric oxide gas, and then by déhydration and chlorination. The déhydration and chlorination can be performed by heating the product in the presence of hydrogen chloride gas, which is substantially the same as the préparation process. The heating température is usually above 65°C, preferably from 110°C to 200°C, but unlimited. The heating process can also adopt a stepwise heating method according to the change of iron sait concentration. The higher the concentration, the higher the heating température.
[0026] In addition, the déhydration and chlorination of absorbent can also be performed by using dehydrating agents such as sulfoxide chloride solution. When sulfoxide chloride is used as a dehydrating agent, hydrogen chloride gas is generated in the déhydration, which can also play a chlorinating effect on the absorbent régénération. The reaction is:
SOCI2 + H2O -+ 2HCI + SO2 (4)
[0027] Desorption and régénération of the absorbent can be performed simultaneously. Similar to the préparation of the absorbent, the absorbent is heated and desorbed under the protection of hydrogen chloride gas. Or, with the addition of dehydrating agents such as sulfoxide chloride solution, the absorbent also can be regenerated by simultaneously removing the absorbed nitric oxide and water while the décomposition of iron salts is prevented.
[0028] Compared with prior art, this invention has the advantages that using absorption slurry to replace the solid ferrie chloride powders to absorb and remove the nitric oxide in gas stream. Ferrie chloride in the slurry with the ability to react with nitric oxide can exist in the form of extremely small crystals, which overcomes the low rate of gas-solid reaction and low utilization efficiency of the adsorbent. And the absorbent prepared by using hydrochioric acid solution or sait solutions to replace water, the content of ferrie chloride in the slurry, the working température and the ability of the absorbent to continuously absorb nitric oxide are a|l increased. The absorbent can be recycled after régénération.
BRIEF DESCRIPTION OF THE DRAW1NGS
[0029] Fig. 1 a schematic structural view of a rotating absorption reactor according to Example 2 of the présent disclosure.
[0030] Fig. 2 a schematic structural view of a scrubbing absorption reactor according to Example 3,5 and 8 of the présent disclosure.
DETAILED DESCRIPTION
[0031] The présent invention is further described in detail below with reference to the drawings and embodiments.
[0032] Example 1: A préparation method of the absorbent: First weigh the anhydrous ferrie chloride powder (industrial grade, net content >97%, the same below), water and ferrie chloride hexahydrate (or other ferrie chloride hydrates) respectively, according to predetermined mass ratios, and then the water or ferrie chloride hexahydrate (or other ferrie chloride hydrates) is added to the mixing reactor, and at the same time the température of the reactor is raised to a predetermined température in the presence of air or nitrogen or protective gas of hydrogen chloride (about 10-30% by volume, the same below), and then anhydrous ferrie chloride powder is gradually added into the reactor, stirred and mixed. After ail the materials are completely mixed, the préparation of the absorbent is completed. The mass ratio of materials, préparation température and other operating parameters are shown in table 1.
[0033] Table 1 Operating parameters for the absorbent préparation
| No. | Mass ratio | Température (°C) | Protection gas |
| 1 | FeCI3:H2O=25:1 | 100-110 | HCI |
| 2 | FeCI3:H2O=9:1 | 35-45 | Air |
| 3 | FeCI3:FeCI3*6H2O= 12:1 | 90-100 | n2 |
| 4 | FeCI3:FeCI3«6H2O= 8:1 | 70-80 | n2 |
| 5 | FeCI3:FeCI3’6H2O= 3.5:1 | 45-55 | n2 |
R
FeCl3:FeCl3-H2O=
85-95 HCl
1.5:1
FeCI3:FeCI3*2H2O=
60-70 N2
1:1
[0034] Example 2: A rotating absorption reactor is adopted as shown in Fig. 1. The reactor is consisted of a horizontally placed rotating reactor column (2), a gas inlet (1) at one end ofthe reactor column and a gas outlet (4) at the other end, an absorbent inlet (3) at the upper part of the reactor column and a absorbent outlet (5) at the lower part, and the reactor is driven by a transmission System.
[0035] The Hastelloy made reactor column is with 300mm in diameter, and 1500mm in length, and two ends of the reactor are conical shaped with a gas inlet and an outlet the inlet of both 150 mm in diameter. The rotation speed ofthe column is about 45 to 60 rpm. The gasflow rate of to-be treated gas is about 120m3/h (The résidence time ofthe gas in the reactor is about 3s), and the température of the gas stream in the reactor is adjusted from about 35 to 110 °C, The gas stream before the inlet is composed of nitric oxide 500 ppm, sulfur dioxide about 300 ppm, carbon dioxide about 10%, oxygen about 8% ( by volume, the same below), moisture about 10%, and the balance nitrogen gas. The amount of absorbent added into the reactor is about 30 kg.
[0036] After the absorbent is added to the reactor through the absorbent inlet (3) and the absorbent inlet (3) is closed, the gas stream containing nitric oxide is introduced to the reactor from the gas inlet (1), and the reactor column (2) is driven to rotate by a transmission System, so that the absorption slurry in the reactor flows along the inner wall of the column of the reactor and is in full contact with the gas.
[0037] Nitric oxide in the air stream therefore is absorbed by Chemical reaction with the ferrie chloride in absorbent, and the purified gas stream is discharged from the gas outlet (4) at the other end of the reactor, and the saturated absorbent can be periodically discharged through the absorbent outlet (5). The average removal of nitric oxide for one hour is shown in Table 2.
o
[0038] Table 2 Effect of absorbent on nitric oxide removal
| No. in Table 1 | Gas température (°Q | Average NO removal |
| 1 | 105-110 | 45 |
| 1 | 95-100 | 60 |
| 1 | 85-90 | 70 |
| 2 | 40-45 | 20 |
| 3 | 100-105 | 55 |
| 3 | 90-95 | 65 |
| 3 | 80-85 | 70 |
| 4 | 65-70 | 65 |
| 5 | 35-40 | 20 |
| 6 | 70-75 | 50 |
| 7 | 50-55 | 15 |
[0039] Exampie 3: A scrubbing absorption reactor is adopted as shown in Fig. 2. The reactor is consisted of a column body (13), a gas inlet (1) at the lower part of the column, 5 a gas outlet (4) at the upper part of the column. The upper part of the column is provided with an absorbent inlet (11) and a slurry sprayer (12), and the lower part is provided with an absorbent storage tank (8). The absorbent storage tank communicates with a slurry pump (6) though a connecting pipeline (7), and the slurry pump communicates with the absorbent inlet (11) through an absorbent supplying pipeline (10). The saturated 10 absorbent can be sent to régénération by a bypass pipeline (9).
[0040] The scrubbing column is an empty tower, using Hastelloy as the materlal. The dimension of the absorption column is 300 mm in diameter and 3500mm in height with an effective spray height of about 2000mm. The entire pipeline System is heat insulated.
[0041] The treatment process is to supply the absorbent to absorbent inlet of the 15 scrubbing column through a slurry pump, and then the absorbent slurry is sprayed from the top to bottom in the column by a slurry sprayer, and the gas stream containing nitric oxide is introduced into the column from the gas inlet. The gas stream is in full contact with the absorbent droplets in the column, and the nitric oxide in the gas stream is absorbed. After reaction, the purified gas stream is discharged from the gas outlet of the m
absorption tower, and the absorbent circulâtes by the slurry pump. The saturated absorbent can be sent to a régénération unit by a bypass pipeline.
[0042] The flow rate of gas stream is about 150m3/h (the résidence time of the gas in the reactor is about 2s), and the gas composition is the same as in example 2. The 5 température of the gas stream in the column is about 80~90°C, and the température of absorbent is roughly the same. The absorbent with the serial number of 3 in table 1 is used in the test. The total amount of the absorbent added to the reactor is about 50 kg, and the circulation amount by the absorbent pump is about 350kg/h. The maximum average removal of nitrogen oxides for one hour is about 75%.
[0043] Example 4: A préparation method of the absorbent by mixing anhydrous ferrie chloride with a hydrochloric acid solution of different concentrations: The préparation process is to add a hydrochloric acid solution to a mixing reactor, and then gradually add the ferrie chloride powder, stirred and mixed. The reactor température is from room température to 120°C, and when the reactor température is higher than 60°C, the 15 protective gas of hydrogen chloride (10-30% hydrogen chloride in nitrogen gas) is introduced into the reactor. After ail the matériels are completely mixed, the préparation of the absorbent is completed. The mass ratio of matériels, préparation température and other operating parameters are shown in table 3.
| [0044] Table 3 Mass ratio and operating parameters for the absorbent préparation | ||||
| No. | HCl* Con. (%) | Mass ratio of FeCI3:HCI | Température (°C) | Protection gas |
| 8 | 0 | 15 | 70-75 | n2 |
| 9 | 5 | 20 | 75-80 | HCl |
| 10 | 10 | 35 | 80-85 | HCl |
| 11 | 20 | 45 | 90-95 | HCl |
| 12 | 30 | 70 | 100-105 | HCl |
| 13 | 34 | 80 | 85-90 | HCl |
| 14 | 36 | 50 | 35-40 | HCl |
| 15 | 36 | 100 | 115-120 | HCl |
| 20 |
[0045] Example 5: The reactor shown in figure 2 was adopted. The température of the gas stream in the absorption reactor ranges from about 65 to 120°C, and other conditions are the same as in example 3. The maximum average removal of nitrogen oxide for one hour is shown in Table 4.
[0046] Table 4 Effect of absorbent on nitric oxide removal
| No. in table 3 | Gas température (’C) | Average NO removal (%) |
| 8 | 70-75 | 50 |
| 8 | 80-85 | 35 |
| 9 | 75-80 | 60 |
| 10 | 100-105 | 65 |
| 11 | 90-95 | 70 |
| 11 | 115-120 | 40 |
| 11 | 120-125 | 25 |
| 12 | 90-95 | 75 |
| 13 | 95-100 | 80 |
| 14 | 80-85 | 75 |
| 14 | 100-105 | 65 |
| 15 | 125-130 | 20 |
[0047] Example 6: A préparation method of the absorbent: 30 parts of solid ferrie 5 chloride hexahydrate and 1 part of 36-38% hydrochloric acid solution are weighed respectively according to the mass ratio. The prepared hydrochloric acid solution is first added to a mixing reactor, and then ferrie chloride hexahydrate is added gradually to the reactor, stirred and mixed (the température of the reactor may be raised to about 50~60°C). After ail the added solid ferrie chloride hexahydrate is dissolved, the 10 température of the reactor is increased to about 150-180°C for déhydration in the presence of a mixed gas of nitrogen and hydrogen chloride (Hydrogen chloride about 30-50%). When the water content in the liquid phase decreased to about 4-5% of the material, the préparation of the absorbent is completed.
[0048] Example 7: A préparation method of the absorbent: The absorbent is prepared 15 by mixing anhydrous ferrie chloride with different sait solutions. The préparation is to add a predetermined amount of water and solid sait to a mixing reactor. After the sait is completely dissolved, ferrie chloride powder of a predetermined quality is then gradually added, and the other process is the same as that in above examples. After the ferrie chloride and the sait solution are completely mixed, the préparation of the absorbent is complétée!. The mass ratio of materials and operating parameters are shown in Table 5.
[0049] Table 5 Mass ratio of matériels and operating parameters
| No. | Sait solution | Mass ratio of FeCh : sait solution | Temperature( °C) | Protection gas |
| 16 | 5%NaCI | 30 | 65-70 | n2 |
| 17 | 25%NaCI | 40 | 80-85 | HCl |
| 18 | 30%KCI | 45 | 90-95 | HCl |
| 19 | 40%CaCb | 40 | 120-130 | HCl |
| 20 | 15%MgCI2 | 35 | 95-100 | HCl |
| 21 | 30%MgCI2 | 40 | 110-115 | HCI |
| 22 | 35%MnCI2 | 40 | 115-120 | HCl |
| 23 | 15%Na2SO4 | 35 | 60-65 | n2 |
| 24 | 35%ZnSO4 | 40 | 100-105 | HCl |
| 25 | 35%CuSO4 | 40 | 95-100 | HCl |
| 26 | 15%NaCI+10%HC | 40 | 95-100 | HCl |
| 27 | 15% Na2SO4+10%HCI | 40 | 95-100 | HCl |
| 28 | 30% AICh+20% HCl | 50 | 90-95 | HCl |
| 29 | 60% ZnCl2+20% HCl | 45 | 95-100 | HCl |
[0050] Example 8: The reactor shown in Fig. 2 was adopted. The température of the gas stream in the absorption reactor ranges from about 65 to 130°C, and other conditions are the same as in example 3. The average removal of nitrogen oxide for one hour is shown in Table 6.
[0051] Table 6 Effect of absorbent on nitric oxide removal
| No. in table 5 | Gas température (°C) | Average NO removal (%) |
| 16 | 70-75 | 55 |
| 17 | 80-85 | 75 |
| 18 | 75-80 | 85 |
| 1? | 100-105 | 65 |
| 20 | 90-95 | 70 |
| 21 | 115-120 | 45 |
| 22 | 120-125 | 40 |
| 23 | 65-70 | 60 |
| 24 | 100-105 | 65 |
| 25 | 125-130 | 25 |
| 26 | 85-90 | 80 |
| 27 | 70-75 | 65 |
| 28 | 90-95 | 70 |
| 29 | 100-105 | 75 |
[0052] Example 9 A method for regenerating the absorbent: The reacted absorbent of serial No. 4 used in example 2 is introduced to a régénération reactor (the same as the 5 mixing reactor for absorbent préparation, the same below), and then 20% hydrochloric acid solution with an amount of about 0.1 to 0.3 of the volume of the absorbent is added to the reactor after evacuating the air in the reactor, stirred and mixed, and then the reactor is heated to the température of about 90 to 110°C for a period of maintaining. The nitric oxide gas released from absorbent is recovered during above process. After the release of nitric 10 oxide is completed, a mixed gas of nitrogen and hydrogen chloride is introduced below the liquid surface in the reactor, and the same time, the température of the reactor is raised to about 120~150°C for déhydration. When the water content in liquid phase decreases to about 5-7%, the régénération of the absorbent is completed.
[0053] Example 10 A method for regenerating the absorbent: The reacted absorbent of 15 serial No. 10 used in example 5 is added to a régénération reactor. After the air in the reactor is evacuated, the reactor is heated to the température of about 150 to 160°C for a period of maintaining, and at the same time, nitric oxide gas released from absorbent is recovered. After the release of nitric oxide is completed, a mixed gas of nitrogen and hydrogen çhloride is introduced below the liquid surface in the reactor for chlorination and déhydration. When the water content in the liquid phase decreases to 3-5%, the température of the reactor is adjusted to 100-110°C, and lasts for a period of time, before completing the régénération of the absorbent.
[0054] Example 11 A method for regenerating the absorbent: The reacted absorbent of serial No. 17 used in example 8 is introduced to a régénération reactor, and then 20% hydrochloric acid solution with an amount of about 0.1 to 0.3 of the volume of the absorbent is added to the reactor after the air in the reactor is evacuated, stirred and mixed, and then the reactor is heated to the température of about 100~110°C for a period of maintaining. The nitric oxide gas released from absorbent is recovered during above process. After the release of nitric oxide is completed, a mixed gas of nitrogen and hydrogen çhloride is introduced below the liquid surface in the reactor, and at the same time, the température of the reactor is raised to about 160~180°C for déhydration. When the water content in liquid phase decreases to about 3-5%, the régénération of the absorbent is completed.
[0055] Exampie 12 A method for regenerating the absorbent: The absorbent after the reaction with the serial number 11 used in example 5 was added to the régénération reactor. After the air was evacuated, the température of the reactor was maintained at the température of 95-100°C, and then sulfoxide çhloride liquid was slowly added by dropping to the reactor for déhydration and chlorination, stirring to make the absorbent slurry in the reactor fully contacted with the sulfoxide çhloride liquid. The vaporized sulfoxide çhloride in the reactor is retumed to the reactor by a condensation reflux, and the water vapor, nitric oxide, hydrogen çhloride and sulfur dloxide generated during the reaction process are discharged through the non-condensable gas outlet of the condensation reflux for further treatment. The total dosage of sulfoxide çhloride added to the reactor is about 6-10 times the water removed from absorbent. When the water content in liquid phase decreases to about 2-3%, the régénération of the absorbent is complété.
Claims (12)
1. A nitrogen oxide absorption slurry for removing nitric oxide gas from gas streams, wherein said absorption slurry contains at least one of anhydrous ferrie chloride, ferrie chloride monohydrate, ferrie chloride dihydrate, and a complex of ferrie chloride and hydrpçhlpriç acid, and the mass ratio of water to ferrie chloride in the absorption slurry is from 0.005 to 0.55.
2. The absorption slurry according to claim 1, wherein the absorption slurry is prepared by mixing anhydrous ferrie chloride and water, or mixing anhydrous ferrie chloride and hydrochioric acid, or mixing anhydrous ferrie chloride and ferrie chloride monohydrate, or mixing anhydrous ferrie chloride and ferrie chloride dihydrate, or mixing anhydrous ferrie chloride and ferrie chloride hexahydrate, or mixing anhydrous ferrie chloride and ferrie chloride monohydrate and hydrochioric acid, or mixing anhydrous ferrie chloride and ferrie chloride dihydrate and hydrochioric acid, or mixing anhydrous ferrie chloride and ferrie chloride hexahydrate and hydrochioric acid, respectively according to said mass ratio of water to ferrie chloride.
3. The préparation method of the absorption slurry according to claim 2, wherein the température for preparing the absorbent slurry is not less than 35°C, and the preparing atmosphère is in the presence of air or nitrogen gas or hydrogen chloride protective gas.
4. The préparation method of the absorption slurry according to claim 2, wherein said water is replaced with a sait solution or a mixture of sait and hydrochioric acid, and said sait is a chloride or sulfate of alkali métal, alkaline earth métal or transition métal, which includes sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnésium chloride, zinc chloride, manganèse chloride, cobalt chloride, copper chloride, nickel chloride, aluminum chloride, and the corresponding sulfates.
5. The absorption slurry according to claim 1, wherein the absorption slurry is prepared by the déhydration of the ferrie chloride solution, or by the déhydration of the mixture of ferrie chloride and hydrochioric acid.
6. The préparation method of the absorption slurry according to claim 4, wherein the température for preparing the absorbent slurry is not less than 65°C, and the preparing atmosphère is in the presence of air or nitrogen gas or hydrogen chloride protective gas.
Ifi
7. The absorption slurry according to claim 1, wherein the use method of the absorption slurry is to introduce said slurry into a nitrogen oxide absorption reactor and nitric oxide in gas stream is absorbed by Chemical reaction with ferrie chloride in the absorption slurry.
8. The use method of the absorption slurry according to claim 7, wherein the nitrogen oxide absorption reactor is a rotating, spraying, bubbling or moving bed type gas-liquid contact reactors, and the flow pattern in the reactor is arranged in co-current flow, counter flow or cross flow.
9. The use method of the absorption slurry according to claim 7, wherein the reaction température of the absorbent prepared by water and ferrie chloride is from 35 to 110°C, and is from 35°C to 130°C of the absorbent prepared by hydrochloric acid and/or sait solution instead of water.
10. The absorption slurry according to claim 1, wherein the régénération of the absorbent is implemented by heating or humidifying, or dissolving in water or hydrochloric acid solution to release the absorbed nitric oxide gas from the absorbent, and then followed by déhydration and chlorination process, where the desorption of nitric oxide gas from the absorbent, déhydration and chlorination is performed respectively or simultaneously, and the température of said heating is not less than 65°C.
11. The régénération method of the absorption slurry according to claim 10, wherein the déhydration and chlorination are carried out in the presence of hydrogen chloride gas.
12. The régénération method of the absorption slurry according to claim 10, wherein the déhydration and chlorination are carried out by adding sulfoxide chloride solution as the dehydrator and chlorinating agent as well.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910563992.1 | 2019-06-13 | ||
| CN201910889947.5 | 2019-09-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| OA20300A true OA20300A (en) | 2022-05-10 |
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