CN116444054B - Boiler water treatment agent and preparation method thereof - Google Patents
Boiler water treatment agent and preparation method thereof Download PDFInfo
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- CN116444054B CN116444054B CN202310700414.4A CN202310700414A CN116444054B CN 116444054 B CN116444054 B CN 116444054B CN 202310700414 A CN202310700414 A CN 202310700414A CN 116444054 B CN116444054 B CN 116444054B
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- water treatment
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002245 particle Substances 0.000 claims abstract description 46
- 239000011521 glass Substances 0.000 claims abstract description 37
- 229910052742 iron Inorganic materials 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 30
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000011069 regeneration method Methods 0.000 claims abstract description 26
- 230000008929 regeneration Effects 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000000853 adhesive Substances 0.000 claims abstract description 14
- 230000001070 adhesive effect Effects 0.000 claims abstract description 14
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- QANIADJLTJYOFI-UHFFFAOYSA-K aluminum;magnesium;carbonate;hydroxide;hydrate Chemical compound O.[OH-].[Mg+2].[Al+3].[O-]C([O-])=O QANIADJLTJYOFI-UHFFFAOYSA-K 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 16
- 229960001545 hydrotalcite Drugs 0.000 claims description 15
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000003480 eluent Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 5
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229920000858 Cyclodextrin Polymers 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 27
- 229910052760 oxygen Inorganic materials 0.000 description 27
- 239000001301 oxygen Substances 0.000 description 27
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 20
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 20
- 239000011575 calcium Substances 0.000 description 20
- 229910001424 calcium ion Inorganic materials 0.000 description 20
- 229910001425 magnesium ion Inorganic materials 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 18
- 239000000126 substance Substances 0.000 description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229960004887 ferric hydroxide Drugs 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000005337 ground glass Substances 0.000 description 5
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 5
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 5
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000005550 wet granulation Methods 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 3
- 229920002261 Corn starch Polymers 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- -1 and meanwhile Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
Abstract
The invention relates to the technical field of boiler water treatment, and particularly discloses a boiler water treatment agent and a preparation method thereof. The treating agent comprises: 42-55 parts of zeolite particles, 24-31 parts of carbonate hydrotalcite powder, 10-16 parts of glass powder, 11-18 parts of sponge iron particles and 16-20 parts of adhesive. The preparation method comprises the following steps: (1) Mixing the zeolite particles, the talcum powder, the glass powder, the sponge iron particles and the adhesive uniformly, and granulating to form a precursor. (2) Sintering the dried precursor in the temperature condition of being higher than the melting point of the glass powder and lower than 500 ℃ and in an oxygen-isolated environment, and cooling to room temperature after the sintering to obtain the boiler water treatment agent. The treating agent disclosed by the invention not only can effectively play a role in softening boiler water and deoxidizing the boiler water, but also can obviously reduce toxic, harmful or impurities with obvious side effects introduced into the boiler water, and meanwhile, the treating agent has the characteristic of good regeneration and reuse.
Description
Technical Field
The invention relates to the technical field of boiler water treatment, in particular to a boiler water treatment agent and a preparation method thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Boilers are widely used in industry as heat exchange devices that transfer heat released from fuel to water to form high temperature steam, which is then supplied to downstream equipment. The water quality is very important for the safe operation of the boiler, the most common and most harmful is the scaling problem of the boiler water, especially for the hard water with higher calcium and magnesium ion content, the damage to the boiler system is extremely great, the heat transfer efficiency of the boiler can be greatly reduced, and even the pipeline is blocked and exploded. Therefore, the treatment of water entering the boiler system is an important measure to ensure safe operation of the boiler system.
At present, a method of directly adding a treating agent into boiler water is generally adopted, for example, a scale inhibitor, a scale remover, a corrosion inhibitor, an deoxidizer and the like are added into the water. These agents dissolve in the water and enter the boiler system together. However, this approach has the disadvantage that the introduction of various agents itself affects the quality of the water, changing the physicochemical properties of the boiler water, such as hydrazine (N) 2 H 4 ) The deoxidizer such as oxime (general formula R-c=noh) is a toxic and harmful substance, has poor safety and is unfavorable for controlling the water quality safety. For another example, the added trisodium phosphate, organic phosphate and other scale inhibitors cause the discharged boiler wastewater to contain a large amount of phosphorus elements, so that the wastewater discharge capacity is high, and the problem that the phosphorus-containing wastewater is difficult to treat is faced. Therefore, the search for new boiler water treatment methods is an important issue facing enterprises.
Disclosure of Invention
The invention provides a boiler water treatment agent and a preparation method thereof, which not only can effectively play roles in softening boiler water and deoxidizing the boiler water, but also can obviously reduce toxic, harmful or impurities with obvious side effects introduced into the boiler water. Meanwhile, the treating agent has the characteristic of good regeneration and reuse. In order to achieve the above purpose, the present invention discloses the following technical solutions.
Firstly, the invention provides a boiler water treatment agent, which comprises the following raw materials in parts by weight: 42-55 parts of zeolite particles, 24-31 parts of hydrotalcite powder, 10-16 parts of glass powder, 11-18 parts of sponge iron particles and 16-20 parts of adhesive. Wherein: the melting point of the glass powder is 440-460 ℃. The hydrotalcite is carbonate type hydrotalcite.
Further, the adhesive includes any one of water glass, starch, cyclodextrin, hydroxymethyl cellulose, and the like. The method is mainly used for bonding the raw materials together and granulating. In addition, the use of the starch, cyclodextrin, hydroxymethyl cellulose, etc. as a binder also contributes to an increase in the porosity in the resulting treatment agent, making the hydrotalcite and sponge iron particles more fully contacted with boiler water.
Further, the hydrotalcite includes Mg 6 Al 2 (OH) 16 CO 3 ·4H 2 O、Mg 4 Al 2 (OH) 12 CO 3 ·4H 2 O、Zn 6 Cr 2 (OH) 16 CO 3 ·4H 2 O、Zn 4 Cr 2 (OH) 12 CO 3 ·4H 2 O、Ni 6 Fe 2 (OH) 16 CO 3 ·4H 2 O、Co 4 Cr 2 (OH) 14 CO 3 ·4H 2 O, etc. Optionally, the particle size of the hydrotalcite powder is 300-500 meshes. The hydrotalcite has good effect of removing carbonate ions and bicarbonate ions in water after subsequent sintering modification, and has the characteristic of regeneration and reuse.
Further, the particle size of the zeolite particles is 200-300 meshes. The zeolite particles have a large number of nano-scale mesopores, have good adsorption capacity on calcium and magnesium ions, can effectively reduce the concentration of the calcium and magnesium ions in boiler water, and are beneficial to preventing the boiler pipeline system from scaling.
Further, the particle size of the glass powder is 200-300 meshes. The low-melting-point glass is adopted to soften and melt in the subsequent high-temperature sintering process, so that each component can be bonded, and the obtained treating agent can be solidified and shaped after cooling and hardening, so that the low-melting-point glass has good volume stability, chemical stability and thermal stability, and the damage to the pore structure of zeolite particles due to the fact that the sintering temperature is too high is avoided.
Further, the particle size of the sponge iron particles is 200-300 meshes. The sponge iron can consume oxygen in boiler water, and reduce oxygen corrosion caused by the sponge iron. Meanwhile, the sponge iron is also convenient for magnetic recovery of the treating agent.
Secondly, the invention provides a preparation method of the boiler water treatment agent, which comprises the following steps:
(1) Mixing the zeolite particles, the talcum powder, the glass powder, the sponge iron particles and the adhesive, uniformly stirring, granulating by a wet method to form a granular precursor, and drying for later use.
(2) Sintering the dried granular precursor in a temperature condition which is higher than the melting point of the glass powder and lower than 500 ℃ and in an oxygen-isolated environment, and cooling to room temperature after the sintering to obtain the boiler water treatment agent.
Further, in the step (2), the sintering temperature is 460-490 ℃ and the sintering time is 30-50 min.
Further, in the step (2), the oxygen-isolation environment is created for a protective atmosphere, and optionally, the protective atmosphere includes nitrogen or inert atmosphere, etc.
Further, the method further comprises the step of regenerating the treating agent after being treated by the boiler water: the treating agent is firstly placed in eluent for ultrasonic cleaning, and then is leached by fresh eluent. And drying to remove residual eluent after completion. And then placing the obtained treating agent in a hydrogen atmosphere at 400-430 ℃ for reduction and regeneration, and cooling to room temperature after the completion of the reduction and regeneration.
Further, the eluent includes any one of water, methanol, ethanol and the like. Optionally, the ultrasonic cleaning time is 40-60 min, the power is 350-500W, and the rinsing time is 30-40 min. And desorbing calcium and magnesium ions adsorbed in the treating agent into eluent through ultrasonic washing, and further removing residual calcium and magnesium ions in the adsorbing treating agent by utilizing the leaching, so that the treating agent can be reused conveniently.
Further, the reduction regeneration time is 1.0-1.5 hours. The ferric hydroxide and ferrous hydroxide formed on the surface of the sponge iron are converted into oxides through regeneration treatment under the hydrogen and high-temperature environment and then reduced into nano iron simple substance, and meanwhile, water, carbonate and bicarbonate are absorbed in the use process and the hydrotalcite recovered is removed again, so that the recycling of the hydrotalcite is realized.
Compared with the prior art, the invention has the beneficial technical effects that: the boiler water treatment agent prepared by taking the zeolite particles, the carbonate hydrotalcite, the glass powder and the sponge iron as raw materials can effectively reduce substances such as calcium and magnesium ions, carbonate radicals, bicarbonate radicals and the like in water, which are easy to cause boiler system scaling, and can consume oxygen dissolved in water to reduce oxygen corrosion caused. In addition, the boiler water treatment agent has the characteristic of good recycling after regeneration. The reason for this is that: first, the formation of scale in boiler water is mainly due to carbonate precipitation formed by dissolved calcium and magnesium ions and carbonate precipitation formed by decomposition of bicarbonate formed by calcium and magnesium ions and bicarbonate at the temperature of boiler water. Therefore, calcium and magnesium ions in water are adsorbed by the nano-scale mesopores of the zeolite particles, so that conditions for forming the scale are blocked. Further, since carbonate and bicarbonate in water may form precipitates with other metal ions, the zeolite has poor effect of removing such anions. Therefore, the invention uses the high temperature condition of the treating agent prepared by sintering molding to carry out reversible modification treatment on the carbonate hydrotalcite. In the process, interlayer water molecules and carbonate in the hydrotalcite are decomposed and removed, the formed vacancies enable the hydrotalcite to form a reversible structure capable of being repeatedly regenerated and recovered, and when the treating agent enters boiler water, the vacancies absorb water and carbonate or bicarbonate to form hydrotalcite again, so that carbonate ions and bicarbonate ions in the water are removed. In addition, in the treating agent, the reaction of the sponge iron with oxygen in the boiler water and water is utilized to form ferrous hydroxide and/or ferric hydroxide, so that the boiler water is deoxidized to prevent oxygen corrosion caused by dissolved oxygen. In addition, the sponge iron also enables the treating agent prepared by the invention to be regenerated and reused after being magnetically recovered. The glass powder is softened and melted in the high-temperature sintering process, and then all the components are bonded, and the obtained treating agent is solidified and shaped after cooling and hardening, so that the treating agent has good volume stability, chemical stability and thermal stability, and is convenient for adapting to the subsequent regeneration process. Compared with the traditional mode of directly adding chemical agents into water, the treating agent has the advantages that toxic, harmful or obvious side effect chemical agents introduced into the boiler water can be obviously reduced, impurity ions in the boiler water can be carried out by the treating agent by utilizing the characteristics of the treating agent, the mode can more thoroughly block the conditions of forming scale formation and oxygen corrosion, and meanwhile, the purity of the boiler water is better kept.
In addition, the invention utilizes high temperature to decompose ferrous hydroxide and/or ferric hydroxide formed on the surface of the sponge body to form oxide, so as to reduce the oxide into nano-scale high-activity iron simple substance, thereby recovering the consumed part of the iron simple substance of the sponge, and the dissolved oxygen in the sponge can be consumed again after the sponge enters boiler water. Meanwhile, as the ferrous hydroxide and/or ferric hydroxide are insoluble in water, the ferrous hydroxide and/or ferric hydroxide can be carried out from water along with the recovery of the treating agent, so that on one hand, impurities are prevented from being introduced into boiler water, on the other hand, the part of sponge iron which is consumed and converted into other substances is convenient to recover and regenerate, the loss of the sponge iron is reduced, and the service life of the treating agent is prolonged. Meanwhile, the invention further utilizes the high temperature condition for regenerating the sponge iron to simultaneously realize the reversible modification treatment for recovering the hydrotalcite structure due to the treatment of the boiler water, so that the reversible structure capable of being repeatedly regenerated and recovered is formed again, and the treating agent prepared by the invention has the characteristic of good regeneration and reutilization.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof. The technical scheme of the invention is further described through specific implementation.
Example 1:
a preparation method of a boiler water treatment agent comprises the following steps:
(1) The following raw materials were prepared: 49 parts by weight of zeolite particles, mg 6 Al 2 (OH) 16 CO 3 ·4H 2 27 parts of O-water talcum powder, 14 parts of glass powder, 15 parts of sponge iron particles and 18 parts of water glass adhesive. Wherein: the glass powder is obtained by grinding waste glass with the melting point of 440-460 ℃ and sieving the ground glass with a 200-mesh sieve. The particle size of the zeolite particles is 300 meshes, the particle size of the talcum powder is 400 meshes, and the particle size of the sponge iron particles is 200 meshes.
(2) Mixing the zeolite particles, the talcum powder, the glass powder, the sponge iron particles and the adhesive, uniformly stirring, then placing into a granulator for wet granulation to form a granular precursor with the particle size of 0.8-1.2 cm, and then drying at 60 ℃ for 1 hour for later use.
(3) Placing the dried granular precursor in a heating furnace, and performing high-temperature sintering in a nitrogen atmosphere: heating to 480 ℃ at a heating rate of 15 ℃/min and maintaining for 40min. And cooling to room temperature in the nitrogen atmosphere after the completion of the reaction to obtain the boiler water treatment agent.
Performance test: the boiler water treatment agent prepared in this embodiment was added to boiler water (total calcium and magnesium ion concentration 0.05mmol/L, bicarbonate concentration 0.1mmol/L, dissolved oxygen 0.12 mg/L) at a ratio of 2.5g/L, followed by standing for 2 hours. And testing various indexes in the boiler water, and calculating the removal rate delta= (B-A)/A, wherein A is the initial concentration of the indexes in the boiler water, and B is the concentration of the indexes after being treated by the boiler water treatment agent.
And (3) displaying a calculation result: the calcium and magnesium ion removal rate is 96.31%, the bicarbonate removal rate is 97.29%, and the dissolved oxygen removal rate is 99.18%. It can be seen that the boiler water treatment agent prepared by the embodiment can effectively remove scaling substances and dissolved oxygen in water, thereby reducing the scaling rate and the oxygen corrosion rate of a boiler system.
Example 2:
a preparation method of a boiler water treatment agent comprises the following steps:
(1) The following raw materials were prepared: 42 parts by weight of zeolite particles, zn 6 Cr 2 (OH) 16 CO 3 ·4H 2 24 parts of O-water talcum powder, 10 parts of glass powder, 11 parts of sponge iron particles and 16 parts of hydroxymethyl cellulose binder. Wherein: the glass powder is obtained by grinding waste glass with the melting point of 440-460 ℃ and sieving the ground glass with a 300-mesh sieve. The particle size of the zeolite particles is 250 meshes, the particle size of the hydrotalcite powder is 300 meshes, and the particle size of the sponge iron particles is 300 meshes.
(2) Mixing the zeolite particles, the talcum powder, the glass powder, the sponge iron particles and the adhesive, uniformly stirring, then placing into a granulator for wet granulation to form a granular precursor with the particle size of 1-1.5 cm, and then drying at 55 ℃ for 1.5 hours for later use.
(3) Placing the dried granular precursor in a heating furnace, and performing high-temperature sintering in a nitrogen atmosphere: heating to 460 ℃ at a heating rate of 15 ℃/min for 50min. And cooling to room temperature in the nitrogen atmosphere after the completion of the reaction to obtain the boiler water treatment agent.
The boiler water treatment agent prepared in this example was found to have a calcium and magnesium ion removal rate of 97.04%, a bicarbonate radical removal rate of 97.83% and a dissolved oxygen removal rate of 99.34% with respect to boiler water by the same method as in example 1. It can be seen that the boiler water treatment agent prepared by the embodiment can effectively remove scaling substances and dissolved oxygen in water.
Example 3:
a preparation method of a boiler water treatment agent comprises the following steps:
(1) The following raw materials were prepared: 55 parts by weight of zeolite particles, ni 6 Fe 2 (OH) 16 CO 3 ·4H 2 31 parts by weight of O hydrotalcite powder, 16 parts by weight of glass powder and micro sponge iron18 parts of granules and 20 parts of corn starch binder. Wherein: the glass powder is obtained by grinding waste glass with the melting point of 440-460 ℃ and sieving the ground glass with a 300-mesh sieve. The particle size of the zeolite particles is 200 meshes, the particle size of the talcum powder is 500 meshes, and the particle size of the sponge iron particles is 200 meshes.
(2) Mixing the zeolite particles, the talcum powder, the glass powder, the sponge iron particles and the adhesive, uniformly stirring, then placing into a granulator for wet granulation to form a granular precursor with the particle size of 1.5-2 cm, and then drying at the temperature of 60 ℃ for 1.5 hours for later use.
(3) Placing the dried granular precursor in a heating furnace, and performing high-temperature sintering in a nitrogen atmosphere: heating to 490 ℃ at a heating rate of 15 ℃/min for 20min. And cooling to room temperature in the nitrogen atmosphere after the completion of the reaction to obtain the boiler water treatment agent.
The boiler water treatment agent prepared in this example was found to have a calcium and magnesium ion removal rate of 96.77%, a bicarbonate radical removal rate of 98.44% and a dissolved oxygen removal rate of 99.51% with respect to boiler water by the same method as in example 1. It can be seen that the boiler water treatment agent prepared by the embodiment can effectively remove scaling substances and dissolved oxygen in water.
Example 4:
a regeneration method of a boiler water treatment agent comprises the following steps:
(1) The boiler water treatment agent used for treating the boiler water in the embodiment 1 is placed in clear water for ultrasonic cleaning: the time was 45min and the power was 400W. And after the completion, washing the boiler water treatment agent for 30min by using new clean water, and then placing the obtained boiler water treatment agent in an oven to dry for 1.5 hours at 60 ℃ for later use.
(2) The dried boiler water treatment agent is placed in a hydrogen atmosphere for reduction and regeneration treatment: the temperature was 420℃and the time was 1.5 hours. And cooling to room temperature after finishing in the hydrogen atmosphere, thus obtaining the regenerated boiler water treatment agent.
The boiler water treatment agent prepared in this example was found to have a calcium and magnesium ion removal rate of 96.16%, a bicarbonate radical removal rate of 97.36% and a dissolved oxygen removal rate of 99.13% with respect to boiler water by the same method as in example 1. It can be seen that the boiler water treatment agent prepared in example 1 still has good effect of removing scaling substances and dissolved oxygen in water after regeneration.
Example 5:
a regeneration method of a boiler water treatment agent comprises the following steps:
(1) The boiler water treatment agent used for treating the boiler water in the embodiment 4 is placed in ethanol with the mass percentage of 75% for ultrasonic cleaning: the time was 60min and the power was 350W. And after the completion, washing the boiler water treatment agent for 35min by using new clean water, and then placing the obtained boiler water treatment agent in an oven to dry for 0.5 hour at 60 ℃ for standby.
(2) Placing the dried boiler water treatment agent in a hydrogen atmosphere for reduction and regeneration treatment: the temperature was 400℃and the time was 1.5 hours. And cooling to room temperature after finishing in the hydrogen atmosphere, thus obtaining the regenerated boiler water treatment agent.
The boiler water treatment agent prepared in this example was found to have a calcium and magnesium ion removal rate of 96.03%, a bicarbonate radical removal rate of 97.18% and a dissolved oxygen removal rate of 98.94% with respect to boiler water by the same method as in example 1. It can be seen that the boiler water treatment agent prepared in example 1 still has good effect of removing scaling substances and dissolved oxygen in water after two regenerations.
Example 6:
a regeneration method of a boiler water treatment agent comprises the following steps:
(1) The boiler water treatment agent used for treating the boiler water in the embodiment 5 is placed in 75% of methanol by mass for ultrasonic cleaning: the time was 40min and the power was 500W. And after the completion, washing the boiler water treatment agent for 40min by using new clean water, and then placing the obtained boiler water treatment agent in an oven to dry for 0.5 hour at 60 ℃ for standby.
(2) Placing the dried boiler water treatment agent in a hydrogen atmosphere for reduction and regeneration treatment: the temperature was 430℃and the time was 1.0 hour. And cooling to room temperature after finishing in the hydrogen atmosphere, thus obtaining the regenerated boiler water treatment agent.
The boiler water treatment agent prepared in this example was found to have a calcium and magnesium ion removal rate of 95.87%, a bicarbonate radical removal rate of 97.12% and a dissolved oxygen removal rate of 99.06% with respect to boiler water by the same method as in example 1. It can be seen that the boiler water treatment agent prepared in the embodiment 1 still has good effect of removing scaling substances and dissolved oxygen in water after three regenerations, which indicates that the treatment agent can maintain stable treatment capacity of boiler water after regeneration.
Example 7:
a preparation method of a boiler water treatment agent comprises the following steps:
(1) The following raw materials were prepared: 42 parts of zeolite particles, 10 parts of glass powder, 11 parts of sponge iron particles and 16 parts of hydroxymethyl cellulose binder. Wherein: the glass powder is obtained by grinding waste glass with the melting point of 440-460 ℃ and sieving the ground glass with a 300-mesh sieve. The particle size of the zeolite particles is 250 meshes, and the particle size of the sponge iron particles is 300 meshes.
(2) Mixing the zeolite particles, the glass powder, the sponge iron particles and the adhesive, uniformly stirring, then placing into a granulator for wet granulation to form a granular precursor with the particle size of 1-1.5 cm, and then drying at 55 ℃ for 1.5 hours for later use.
(3) Placing the dried granular precursor in a heating furnace, and performing high-temperature sintering in a nitrogen atmosphere: heating to 460 ℃ at a heating rate of 15 ℃/min for 50min. And cooling to room temperature in the nitrogen atmosphere after the completion of the reaction to obtain the boiler water treatment agent.
The boiler water treatment agent prepared in this example was found to have a calcium and magnesium ion removal rate of 95.49%, a bicarbonate radical removal rate of 65.21% and a dissolved oxygen removal rate of 99.27% with respect to boiler water by the same method as in example 1. It can be seen that the boiler water treatment agent prepared in this example has significantly reduced removal of scaling substances from boiler water.
Example 8:
a preparation method of a boiler water treatment agent comprises the following steps:
(1) The following raw materials were prepared: 55 parts by weight of zeolite particles, ni 6 Fe 2 (OH) 16 CO 3 ·4H 2 31 parts of O hydrotalcite powder, 16 parts of glass powder and 20 parts of corn starch adhesive. Wherein: the glass powder is obtained by grinding waste glass with the melting point of 440-460 ℃ and sieving the ground glass with a 300-mesh sieve. The particle size of the zeolite particles is 200 meshes, and the particle size of the talcum powder is 500 meshes.
(2) Mixing the zeolite particles, the water talcum powder, the glass powder and the adhesive, uniformly stirring, then placing in a granulator for wet granulation to form a granular precursor with the particle size of 1.5-2 cm, and then drying at the temperature of 60 ℃ for 1.5 hours for later use.
(3) Placing the dried granular precursor in a heating furnace, and performing high-temperature sintering in a nitrogen atmosphere: heating to 490 ℃ at a heating rate of 15 ℃/min for 20min. And cooling to room temperature in the nitrogen atmosphere after the completion of the reaction to obtain the boiler water treatment agent.
The boiler water treatment agent prepared in this example was found to have a calcium and magnesium ion removal rate of 96.56%, a bicarbonate radical removal rate of 98.02% and a dissolved oxygen removal rate of 14.67% with respect to boiler water by the same method as in example 1. It can be seen that the deoxidizing capability of the boiler water by the boiler water treatment agent prepared by the embodiment is greatly reduced.
Example 9:
the preparation method of the boiler water treatment agent is the same as that of the embodiment 2, and the difference is that: placing the dried granular precursor in a heating furnace, and performing high-temperature sintering in a nitrogen atmosphere: heating to 600 ℃ at a heating rate of 15 ℃/min for 50min. And cooling to room temperature in the nitrogen atmosphere after the completion of the reaction to obtain the boiler water treatment agent.
The boiler water treatment agent prepared in this example was measured to have a calcium and magnesium ion removal rate of 96.80%, a bicarbonate radical removal rate of 32.14% and a dissolved oxygen removal rate of 99.21% with respect to boiler water by the same method as in example 1. It can be seen that the boiler water treatment agent prepared in this example has significantly reduced bicarbonate removal capability from boiler water.
Example 10:
a regeneration method of a boiler water treatment agent comprises the following steps:
(1) The boiler water treatment agent used for treating the boiler water in the embodiment 9 is placed in clear water for ultrasonic cleaning: the time was 50min and the power was 450W. And after the completion, washing the boiler water treatment agent for 35min by using new clean water, and then placing the obtained boiler water treatment agent in an oven to dry for 1.5 hours at 60 ℃ for later use.
(2) Placing the dried boiler water treatment agent in a hydrogen atmosphere for reduction and regeneration treatment: the temperature was 410℃and the time was 1.5 hours. And cooling to room temperature after finishing in the hydrogen atmosphere, thus obtaining the regenerated boiler water treatment agent.
The boiler water treatment agent prepared in this example was found to have a calcium and magnesium ion removal rate of 96.23%, a bicarbonate radical removal rate of 20.56% and a dissolved oxygen removal rate of 98.94% with respect to boiler water by the same method as in example 1. It can be seen that the boiler water treatment agent prepared in example 10 did not improve the removal capacity of bicarbonate in boiler water after regeneration, and a significant decrease occurred, mainly because the sintering temperature was too high, the structure of hydrotalcite was destroyed, and the removal capacity of bicarbonate was significantly decreased when the boiler water treatment agent was prepared in example 9.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The boiler water treatment agent is characterized by comprising the following raw materials in parts by weight: 42-55 parts of zeolite particles, 24-31 parts of hydrotalcite powder and glass10-16 parts of glass powder, 11-18 parts of sponge iron particles and 16-20 parts of adhesive; wherein: the melting point of the glass powder is 440-460 ℃; the hydrotalcite is carbonate hydrotalcite and comprises Mg 6 Al 2 (OH) 16 CO 3 ·4H 2 O、Mg 4 Al 2 (OH) 12 CO 3 ·4H 2 O、Zn 6 Cr 2 (OH) 16 CO 3 ·4H 2 O、Zn 4 Cr 2 (OH) 12 CO 3 ·4H 2 O、Ni 6 Fe 2 (OH) 16 CO 3 ·4H 2 O、Co 4 Cr 2 (OH) 14 CO 3 ·4H 2 O is any one of the following;
the boiler water treatment agent is prepared by the following method:
(1) Uniformly mixing the zeolite particles, the talcum powder, the glass powder, the sponge iron particles and the adhesive, granulating by a wet method to form a granular precursor, and drying for later use;
(2) Sintering the dried granular precursor in a temperature condition which is higher than the melting point of the glass powder and lower than 500 ℃ and in an oxygen-isolated environment, and cooling to room temperature after the sintering to obtain the boiler water treatment agent.
2. The boiler water treatment agent according to claim 1, characterized in that the zeolite particles have a particle size of 200 to 300 mesh; the particle size of the sponge iron particles is 200-300 meshes.
3. The boiler water treatment agent according to claim 1, characterized in that the particle size of the hydrotalcite powder is 300-500 mesh.
4. The boiler water treatment agent according to claim 1, characterized in that the particle size of the glass powder is 200-300 mesh.
5. The boiler water treatment agent according to claim 1, characterized in that the binder comprises any one of water glass, starch, cyclodextrin, and hydroxymethyl cellulose.
6. The boiler water treatment agent according to claim 1, characterized in that in step (2), the sintering temperature is 460-490 ℃ for 30-50 min; the oxygen-isolated environment is nitrogen or inert atmosphere.
7. The boiler water treatment agent according to any one of claims 1 to 6, further comprising the step of regenerating the treatment agent after being subjected to the treatment of boiler water: the treating agent is firstly placed in eluent for ultrasonic cleaning, and then is leached by fresh eluent; drying to remove residual eluent after completion; and then placing the obtained treating agent in a hydrogen atmosphere at 400-430 ℃ for reduction and regeneration, and cooling to room temperature after the completion of the reduction and regeneration.
8. The boiler water treatment agent according to claim 7, characterized in that the eluent is selected from any one of water, methanol, ethanol; the ultrasonic cleaning time is 40-60 min, the power is 350-500W, and the rinsing time is 30-40 min; the reduction regeneration time is 1.0-1.5 hours.
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| CN1600690A (en) * | 2004-10-13 | 2005-03-30 | 浙江大学 | Method for preparing oxide of bimetal and hydrotalcite by using Bayer red mud as raw material |
| CN102976434A (en) * | 2012-12-11 | 2013-03-20 | 常州大学 | Method for treating lead-containing wastewater |
| CN104289185A (en) * | 2014-10-28 | 2015-01-21 | 北京林业大学 | Granular filtering material for adsorbing and removing heavy metals in water and preparation method thereof |
| CN106219660A (en) * | 2016-08-24 | 2016-12-14 | 北京德同源生态科技有限公司 | A kind of hydrolysis slow releasing agent for aquaculture water purifying and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1600690A (en) * | 2004-10-13 | 2005-03-30 | 浙江大学 | Method for preparing oxide of bimetal and hydrotalcite by using Bayer red mud as raw material |
| CN102976434A (en) * | 2012-12-11 | 2013-03-20 | 常州大学 | Method for treating lead-containing wastewater |
| CN104289185A (en) * | 2014-10-28 | 2015-01-21 | 北京林业大学 | Granular filtering material for adsorbing and removing heavy metals in water and preparation method thereof |
| CN106219660A (en) * | 2016-08-24 | 2016-12-14 | 北京德同源生态科技有限公司 | A kind of hydrolysis slow releasing agent for aquaculture water purifying and preparation method thereof |
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