CN116813985B - Early warning material for hydrogen sulfide gas and preparation method thereof - Google Patents
Early warning material for hydrogen sulfide gas and preparation method thereof Download PDFInfo
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- CN116813985B CN116813985B CN202310865149.5A CN202310865149A CN116813985B CN 116813985 B CN116813985 B CN 116813985B CN 202310865149 A CN202310865149 A CN 202310865149A CN 116813985 B CN116813985 B CN 116813985B
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 70
- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000007789 gas Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000012544 monitoring process Methods 0.000 claims abstract description 39
- 239000000654 additive Substances 0.000 claims abstract description 37
- 230000000996 additive effect Effects 0.000 claims abstract description 30
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 21
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 19
- 229920000615 alginic acid Polymers 0.000 claims abstract description 19
- 230000008859 change Effects 0.000 claims abstract description 17
- -1 alginic acid polysaccharide Chemical class 0.000 claims abstract description 16
- 239000000783 alginic acid Substances 0.000 claims abstract description 15
- 229960001126 alginic acid Drugs 0.000 claims abstract description 15
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 15
- 239000005017 polysaccharide Substances 0.000 claims abstract description 15
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 47
- 239000007864 aqueous solution Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 12
- 239000001110 calcium chloride Substances 0.000 claims description 12
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 10
- 239000002798 polar solvent Substances 0.000 claims description 10
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 9
- 239000000661 sodium alginate Substances 0.000 claims description 9
- 235000010413 sodium alginate Nutrition 0.000 claims description 9
- 229940005550 sodium alginate Drugs 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 5
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 4
- 229940072056 alginate Drugs 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000737 potassium alginate Substances 0.000 claims description 4
- 235000010408 potassium alginate Nutrition 0.000 claims description 4
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 239000003349 gelling agent Substances 0.000 claims 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 5
- 239000008188 pellet Substances 0.000 description 12
- 239000000017 hydrogel Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000012456 homogeneous solution Substances 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 229910001447 ferric ion Inorganic materials 0.000 description 4
- 239000007863 gel particle Substances 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 208000012902 Nervous system disease Diseases 0.000 description 1
- 208000025966 Neurological disease Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses an early warning material for hydrogen sulfide gas and a preparation method thereof. The early warning material for monitoring the hydrogen sulfide comprises a matrix material, a first additive and a second additive, wherein the matrix material accounts for 70-99.99 wt% of the total content of the two additives, and the total content of the two additives is 0.01-30 wt%, and the molar ratio of the first additive to the second additive is 0.1-30; the matrix material is alginic acid polysaccharide; the first additive is 4'- (4-hydroxyphenyl) -2,2':6', 2' -terpyridine; the second additive is water-soluble ferric salt. The invention has the advantages of rapid response to hydrogen sulfide, obvious color change, easy observation by naked eyes, no need of instruments and equipment, convenient and quick use, uniform color change in the form of particles, continuous color after color change for several hours, convenient observation and use, and the main component of the material is alginic acid polysaccharide, and has biocompatibility and good degradability.
Description
Technical Field
The invention relates to the technical field of environmental protection and gas detection, in particular to an early warning material for monitoring hydrogen sulfide and a preparation method thereof.
Background
With the acceleration of industrialization and urbanization, organic waste generated by human activities is increasing. When these organic wastes are anaerobically decomposed in natural environments or in landfills, harmful gases such as hydrogen sulfide are generated. Hydrogen sulfide gas is a colorless gas with strong pungent odor and has serious threat to human health. It can damage the respiratory tract, eyes and skin and can cause neurological diseases, and long-term exposure can also lead to chronic toxic reactions, which can be fatal in severe cases.
In addition, the generation of hydrogen sulfide gas is not limited to the decay of organic matter. In many industrial processes, such as the exploitation and refining of petroleum and natural gas, the production of gas, the utilization of biogas, and the processing of food products, waste gases containing hydrogen sulfide are released. The production and release of hydrogen sulfide constitutes a great potential risk to the environment and public health. The environment emission of hydrogen sulfide gas and the safe contact concentration of workplaces are strictly regulated in China, and the maximum allowable concentration of hydrogen sulfide in the air of workplaces is 10 mg/m.
In view of the harmfulness of the hydrogen sulfide gas and the widely existing characteristics thereof, it is extremely important to detect the hydrogen sulfide gas rapidly in real time and send out early warning in time when the concentration thereof exceeds the safety standard. Currently, methods for detecting hydrogen sulfide include gas chromatography, electrochemical analysis, sulfide precipitation, lead acetate reaction rate, detection tube, gas detector, hydrogen sulfide sensor, and the like. However, these methods often require complex sample pretreatment processes in practical applications and rely on sophisticated instrumentation. These factors limit the application range and real-time performance of these detection methods, and it is difficult to achieve the effect of rapid early warning. Therefore, a new method or material which is simple, efficient and capable of realizing real-time monitoring and early warning of hydrogen sulfide without precise instruments and equipment is needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for monitoring hydrogen sulfide and a material preparation method thereof, which are low in cost, quick in response, visual in color change, free of instruments and equipment and convenient to use, so as to realize quick early warning of the hydrogen sulfide. The material can be prepared into various forms such as spheres, needles, sheets and the like, and also can be prepared into composite paper, gel, paint and coating, thereby being convenient for monitoring and early warning functions of hydrogen sulfide gas in different occasions.
The invention provides an early warning material for monitoring hydrogen sulfide, which comprises a matrix material, a first additive and a second additive, wherein the matrix material accounts for 70-99.99 wt% of the total content of the two additives, and the total content of the two additives is 0.01-30 wt%, and the molar ratio of the first additive to the second additive is 0.1-30;
the matrix material is alginic acid polysaccharide, the first additive is 4'- (4-hydroxyphenyl) -2,2':6', 2' -terpyridine, and the second additive is water-soluble ferric salt.
Preferably, the alginic acid polysaccharide comprises alginate and oxidized alginate. Preferably, the alginic acid polysaccharide is at least one of sodium alginate, potassium alginate, oxidized sodium alginate and oxidized potassium alginate, and has a number average molecular weight of 1000 to 1000000.
Preferably, the water-soluble ferric salt is at least one of ferric chloride, ferric nitrate and ferric sulfate.
The invention also provides a preparation method of the early warning material for monitoring the hydrogen sulfide, which comprises the following steps:
(1) Dissolving a first additive in a polar solvent, wherein the mass fraction of the solute is in the range of 0.001-10wt% to obtain a polar solvent solution; the second additive is dissolved in water, and the solute mass fraction range is 0.001-10wt% to obtain an aqueous solution; uniformly mixing a polar solvent solution and an aqueous solution to obtain a transparent solution, wherein the volume ratio of the polar solvent solution to the aqueous solution is 1: (0.01-100), preferably 1: (0.1-10), most preferably 1:1, preferably the polar solvent is ethanol;
(2) Dissolving a matrix material in water to form a substrate aqueous solution, wherein the solute mass fraction range is 0.001-10wt%, and dripping the transparent solution obtained in the step one into the substrate aqueous solution to form a uniform dispersion solution, wherein the volume ratio of the transparent solution to the substrate aqueous solution is 1: (0.01-10000), preferably 1: (0.1-10);
(3) Preparing an aqueous solution containing a gel, wherein the gel is a water-soluble salt containing divalent or multivalent cations, the mass fraction of the cations in the aqueous solution is 0.1-20wt%, and then dripping the dispersion solution obtained in the second step into the cationic aqueous solution to form colloidal particles, wherein the volume ratio of the dispersion solution to the cationic aqueous solution is 1: (0.01-100); preferably, the divalent or polyvalent cation is Ca 2+ 、Zn 2+ 、Al 3+ Preferably the water soluble salt containing a divalent or multivalent cation is at least one of calcium chloride, zinc chloride, aluminum chloride, calcium nitrate, zinc nitrate, aluminum nitrate, calcium sulfate, zinc sulfate and aluminum sulfate;
(4) Drying to obtain the early warning material for monitoring hydrogen sulfide. The content percentage of the matrix material in the finally obtained early warning material for monitoring the hydrogen sulfide is controlled to be 70-99.99 wt percent, and the molar ratio of the first additive to the second additive is controlled to be 0.1-30.
The invention also provides a method for monitoring hydrogen sulfide, which comprises the following steps: immersing the early warning material for monitoring the hydrogen sulfide in water for 10-60s, taking out and placing the early warning material in an air or water phase environment possibly containing the hydrogen sulfide, standing for 5-120s, preferably 10-30s, observing the color change condition of the early warning material for monitoring the hydrogen sulfide, and if the color is changed from colorless or light pink to black, indicating that the hydrogen sulfide gas exists, wherein the detection limit of the hydrogen sulfide is 100ppm.
Specifically, the specific roles of the raw materials in the early warning material for monitoring hydrogen sulfide are as follows:
the matrix material alginic acid polysaccharide has abundant hydroxyl and carboxyl groups, can form hydrogen bond action with the first additive 4'- (4-hydroxyphenyl) -2,2':6', 2' -terpyridine, and can play a role in space restriction and dispersion on the first additive 4'- (4-hydroxyphenyl) -2,2':6', 2' -terpyridine by combining the gel property of the matrix material alginic acid polysaccharide. The first additive 4' - (4-hydroxyphenyl) -2,2':6',2 "-terpyridine in a dispersed state can effectively complex with iron ions in the water-soluble ferric salt of the second additive. At a low concentration (10 -3 Under the condition of M), the respective solution of the additives is transparent and colorless, but after the first additive 4'- (4-hydroxyphenyl) -2,2':6', 2' -terpyridine is complexed with ferrous iron in the water-soluble ferric salt of the second additive, the complex is obviously purple and is easy to observe. The water-soluble ferric salt can provide ferric ions, the ferric ions have oxidability, and the hydrogen sulfide has reducibility, when the ferric ions are contacted with the hydrogen sulfide, oxidation-reduction reaction is easy to occur in an aqueous solution environment, so that ferrous ions are formed, and the generated trace ferrous ions have obvious ink color due to complexing with 4'- (4-hydroxyphenyl) -2,2':6', 2' -terpyridine, and are convenient to observe. In addition, the matrix material alginic acid polysaccharide is easy to have a gelling effect with divalent or multivalent cations and the like in water, and the formed hydrogel not only provides an ideal aqueous solution reaction environment for the oxidation-reduction process of ferric ions and hydrogen sulfide gas, but also can avoid aggregation or loss of internal doping components, so that the detection process is more convenient.
The early warning material for monitoring the hydrogen sulfide has the beneficial effects that:
1. the material has extremely rapid response to hydrogen sulfide, obvious color change, easy observation by naked eyes, no need of instruments and equipment, and convenience and rapidness.
2. The colloidal particles of the material have uniform color change, and the color can be kept for a plurality of hours after the color change, thereby being convenient for observation and use.
3. The main component alginic acid polysaccharide of the material has biocompatibility and good degradability, is low in cost and rich in source, has the advantage of environmental protection, and is easy to obtain on a large scale.
The early warning material for monitoring the hydrogen sulfide gas can be prepared into various forms such as spheres, needles, sheets and the like, and can also be prepared into composite paper, gel, paint and coating, thereby being convenient for monitoring and early warning the hydrogen sulfide gas in different occasions.
Drawings
For a clearer description of embodiments of the invention or of the solutions of the prior art, the drawings that are needed in the description of the embodiments or of the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, from which, without inventive effort, a person skilled in the art can obtain further drawings, fig. 1:
FIG. 1-a is a graph of hydrogel particles obtained after soaking in water for 30s, which is the early warning material for monitoring hydrogen sulfide prepared in example 1;
FIG. 1-b gel particle diagram of hydrogel particles obtained after soaking 30s in water of the early warning material for monitoring hydrogen sulfide in example 1 was placed in hydrogen sulfide environment.
Detailed Description
The contents of the present invention can be more easily understood by referring to the following detailed description of preferred embodiments of the present invention and examples included. 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. In case of conflict, the present specification, definitions, will control. The following examples illustrate the invention in more detail and are not intended to limit the invention to these examples.
Example 1:
(1) 4' - (4-hydroxyphenyl) -2,2':6',2 "-terpyridine 1.63mg was dissolved in 1ml ethanol (10) -3 M), 0.8mg of ferric trichloride was dissolved in 5ml of water (10) -3 M), the two solutions were mixed uniformly and stirred at 50 degrees for 5 minutes to give a transparent solution.
(2) 20mg of sodium alginate was dissolved in 10mL of water to obtain a homogeneous aqueous solution (2 mg/mL), and the transparent solution obtained in the first step was dropped into the matrix material solution and stirred to form a homogeneous solution.
(3) 1.2g of an aqueous solution of calcium chloride (30 ml; 4 wt%) was prepared. Dripping the solution prepared in the second step into the calcium chloride aqueous solution (4 wt%) and standing for 4h after the dripping is finished to obtain colloidal particles;
(4) And drying the colloidal particles to remove the solvent to obtain light pink microsphere particles with stable shapes, namely the early warning material for monitoring the hydrogen sulfide.
Performance test: the obtained pre-warning material particles for monitoring hydrogen sulfide are immersed in water for 30s and taken out, and the corresponding figure 1-a is a hydrogel particle diagram obtained after soaking the pre-warning material particles for monitoring hydrogen sulfide prepared in the example 1 in water for 30 s. Then the gel particles are placed in an aqueous phase environment with the temperature of 25 ℃ and the concentration of hydrogen sulfide of 200ppm, and are kept stand for 8 seconds, so that the color of the particles is obviously changed (from light pink to black), and the gel particles correspond to a gel particle diagram of the hydrogel particles obtained after the hydrogel particles are immersed in the early warning material water for monitoring hydrogen sulfide in the embodiment 1 of the figure 1-b for 30 seconds, and then the hydrogel particles are placed in the hydrogen sulfide environment.
Example 2:
(1) 4' - (4-hydroxyphenyl) -2,2':6',2 "-terpyridine 1.63mg was dissolved in 1ml ethanol (10) -3 M), 0.8mg of ferric trichloride was dissolved in 5ml of water (10) -3 M), the two solutions were mixed uniformly and stirred at 50 degrees for 5 minutes to give a transparent solution.
(2) 20mg of sodium alginate was dissolved in 20mL of water to obtain a homogeneous aqueous solution (1 mg/mL), and the transparent solution obtained in the first step was dropped into the matrix material solution and stirred to form a homogeneous solution.
(3) 1.2g of an aqueous solution of calcium chloride (30 ml; 4 wt%) was prepared. And (3) dripping the solution prepared in the second step into the prepared calcium chloride aqueous solution, and standing for 4 hours after dripping to obtain the light pink microsphere particles with stable shapes.
(4) After wetting the pellets in water for 30s, the pellets were left to stand in an aqueous environment at 25℃and a hydrogen sulfide concentration of 200ppm for 8s, with a significant change in pellet color (from pale pink to black).
Example 3:
(1) 4' - (4-hydroxyphenyl) -2,2':6',2 "-terpyridine 1.63mg was dissolved in 1ml ethanol (10) -3 M), 0.8mg of ferric trichloride was dissolved in 5ml of water (10) -3 M), the two solutions were mixed uniformly and stirred at 50 degrees for 5 minutes to give a transparent solution.
(2) 20mg of sodium alginate was dissolved in 10mL of water to prepare a homogeneous aqueous solution (2 mg/mL), and the transparent solution was dropped into the matrix material solution in the first step, and stirred to form a homogeneous solution.
(3) 30ml (3 wt%) of an aqueous solution of 0.9g of calcium chloride was prepared. And (3) dripping the solution prepared in the second step into the prepared calcium chloride aqueous solution, and standing for 4 hours after dripping to obtain the light pink microsphere particles with stable shapes.
(4) After wetting the pellets in water for 30s, the pellets were left to stand in an aqueous environment at 25℃and a hydrogen sulfide concentration of 200ppm for 8s, with a significant change in pellet color (from pale pink to black).
Example 4:
(1) 4' - (4-hydroxyphenyl) -2,2':6',2 "-terpyridine 1.63mg was dissolved in 1ml ethanol (10) -3 M), 1.6mg of ferric trichloride are dissolved in 10ml of water (10) -3 M), the two solutions were mixed uniformly and stirred at 50 degrees for 5 minutes to give a transparent solution.
(2) 20mg of sodium alginate was dissolved in 10mL of water to obtain a homogeneous aqueous solution (2 mg/mL), and the transparent solution obtained in the first step was dropped into the matrix material solution and stirred to form a homogeneous solution.
(3) 1.2g of an aqueous solution of calcium chloride (30 ml; 4 wt%) was prepared. And (3) dripping the solution prepared in the second step into the prepared calcium chloride aqueous solution, and standing for 4 hours after dripping to obtain the light pink microsphere particles with stable shapes.
(4) After wetting the pellets in water for 30s, the pellets were left to stand in an aqueous environment at 25℃and a hydrogen sulfide concentration of 200ppm for 8s, with a significant change in pellet color (from pale pink to black).
Example 5:
(1) 4' - (4-hydroxyphenyl) -2,2':6',2 "-terpyridine 3.26mg was dissolved in 1ml ethanol (10) -3 M), 3.2mg of ferric trichloride are dissolved in 5ml of water (10) -3 M), the two solutions were mixed uniformly and stirred at 50 degrees for 10 minutes to give a transparent solution.
(2) 40mg of sodium alginate was dissolved in 10mL of water to obtain a homogeneous aqueous solution (4 mg/mL), and the transparent solution obtained in the first step was dropped into the matrix material solution and stirred to form a homogeneous solution.
(3) 1.2g of an aqueous solution of calcium chloride (30 ml; 4 wt%) was prepared. And (3) dripping the solution prepared in the second step into a prepared calcium chloride aqueous solution (4 wt%) and standing for 4 hours after dripping to obtain the light pink microsphere particles with stable shapes.
(4) After wetting the pellets in water for 30s, the pellets were left to stand in an aqueous environment at 25℃and a hydrogen sulfide concentration of 100ppm for 8s, with a significant change in pellet color (from pale pink to black).
The invention provides an early warning material for monitoring hydrogen sulfide, which has a plurality of remarkable advantages and can meet the actual demands. Firstly, the material has extremely high response speed to hydrogen sulfide, obvious color change, easy visual observation, no need of any instrument and equipment, and convenient and quick use. Secondly, the material exists in a granular form, the color is uniform, the color after the color change can last for a plurality of hours, the observation and the use process are convenient, and the reliability and the durability of the monitoring result are ensured.
The main component of the material is alginic acid polysaccharide, and the natural component has biocompatibility and good degradability. Furthermore, alginic acid polysaccharide has the advantages of low cost and continuous production, and is easy to realize large-scale production due to abundant sources and outstanding environmental protection advantages.
In conclusion, the invention is remarkably superior in monitoring hydrogen sulfide, ensures the high efficiency and reliability of the monitoring process by the characteristics of rapid response, obvious color change, convenient and quick observation by naked eyes, uniform color change and durability of colloidal particles and the biocompatibility and degradability of alginic acid polysaccharide. Therefore, the early warning material can meet the actual demands and bring important progress to the field of hydrogen sulfide monitoring.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The early warning material for monitoring the hydrogen sulfide is characterized by comprising a matrix material, a first additive and a second additive, wherein the matrix material accounts for 70-99.99 wt% of the total content of the two additives, and the total content of the two additives is 0.01-30 wt%, and the molar ratio of the first additive to the second additive is 0.1-30;
the matrix material is alginic acid polysaccharide;
the first additive is 4'- (4-hydroxyphenyl) -2,2':6', 2' -terpyridine;
the second additive is water-soluble ferric salt.
2. The warning material for monitoring hydrogen sulfide as claimed in claim 1, wherein the alginic acid polysaccharide includes alginate and oxidized alginate.
3. The early warning material for monitoring hydrogen sulfide according to claim 2, wherein the alginic acid polysaccharide is at least one of sodium alginate, potassium alginate, oxidized sodium alginate and oxidized potassium alginate, and has a number average molecular weight of 1000 to 1000000.
4. The early warning material for monitoring hydrogen sulfide according to claim 1, wherein the water-soluble ferric salt is at least one of ferric chloride, ferric nitrate and ferric sulfate.
5. A method for preparing an early warning material for monitoring hydrogen sulfide gas as claimed in any one of claims 1 to 4, comprising the steps of:
(1) Dissolving a first additive in a polar solvent, wherein the mass fraction of the solute is in the range of 0.001-10wt% to obtain a polar solvent solution;
the second additive is dissolved in water, and the solute mass fraction range is 0.001-10wt% to obtain an aqueous solution;
uniformly mixing a polar solvent solution and an aqueous solution to obtain a transparent solution;
(2) Dissolving a matrix material in water to form a matrix aqueous solution, wherein the solute mass fraction range is 0.001-10wt%;
dripping the transparent solution obtained in the step one into a substrate water solution to form a uniform dispersion solution;
(3) Preparing an aqueous solution containing a gelling agent, wherein the gelling agent is a water-soluble salt containing divalent or multivalent cations, and the mass fraction of the cations in the aqueous solution is 0.1-20wt%;
dripping the dispersion solution obtained in the second step into a cation water solution to form colloidal particles;
(4) And (5) drying.
6. The method for preparing an early warning material for monitoring hydrogen sulfide as claimed in claim 5, wherein the volume ratio of the polar solvent solution to the aqueous solution in the first step is 1: (0.01-100), wherein the polar solvent is ethanol.
7. The method for preparing an early warning material for monitoring hydrogen sulfide as claimed in claim 5, wherein the volume ratio of the transparent solution to the aqueous solution of the substrate in the second step is 1: (0.01-10000).
8. The method for preparing an early warning material for monitoring hydrogen sulfide according to claim 5, wherein the volume ratio of the dispersion solution to the cationic aqueous solution in the third step is 1: (0.01-100); the divalent or polyvalent cation is Ca 2+ 、Zn 2+ 、Al 3+ At least one of them.
9. The method for preparing a warning material for monitoring hydrogen sulfide as claimed in claim 8, wherein the water-soluble salt containing divalent or polyvalent cations is at least one of calcium chloride, zinc chloride, aluminum chloride, calcium nitrate, zinc nitrate, aluminum nitrate, calcium sulfate, zinc sulfate and aluminum sulfate.
10. A method of monitoring hydrogen sulfide comprising the steps of: immersing an early warning material for monitoring hydrogen sulfide according to any one of claims 1-4 in water for 10-60s, taking out and placing in air or water phase environment possibly containing hydrogen sulfide, standing for 5-120s, observing the color change condition of the early warning material for monitoring hydrogen sulfide, and if the color changes from colorless or light pink to black, indicating that hydrogen sulfide gas exists in the environment.
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