CN103651349A - Application of anthraquinone salt in preparation of disinfectant for sterilization or for removing formaldehyde - Google Patents

Application of anthraquinone salt in preparation of disinfectant for sterilization or for removing formaldehyde Download PDF

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Publication number
CN103651349A
CN103651349A CN201310405625.1A CN201310405625A CN103651349A CN 103651349 A CN103651349 A CN 103651349A CN 201310405625 A CN201310405625 A CN 201310405625A CN 103651349 A CN103651349 A CN 103651349A
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disinfectant
salt
application
anthraquinone
sterilization
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Inventor
朱作霖
孙萌
朱振吉
顾康福
孙善庆
解统兴
赵家保
王文海
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Ningbo Yuchen Environmental Protection Technology Co Ltd
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Priority to CN201310405625.1A priority Critical patent/CN103651349A/en
Publication of CN103651349A publication Critical patent/CN103651349A/en
Priority to PCT/CN2014/078085 priority patent/WO2015032219A1/en
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing within the same carbon skeleton a carboxylic group or a thio analogue, or a derivative thereof, and a carbon atom having only two bonds to hetero atoms with at the most one bond to halogen, e.g. keto-carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/70—Non-metallic catalysts, additives or dopants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/91—Bacteria; Microorganisms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/06—Polluted air

Abstract

The invention relates to an application of anthraquinone salt in the preparation of a disinfectant for sterilization or for removing formaldehyde and provides a sterilization disinfection system which takes oxygen in air as an oxidant, kills microorganisms by catalytic oxidation and is particularly suitable for an air purification system. The disinfectant can be used for a long time under a condition that the air continuously enters a room; medicaments such as an antiviral medicament are not required, and peroxides with potential safety hazards are not required; stimulating substances containing halogen, alcohol with the probability of explosion hazards and the like are not used. The disinfectant system in which no noble metal is used is easy to prepare and low in use cost, does not cause the secondary pollution and has a good application prospect.

Description

The application of anthraquinone salt in the disinfectant for the preparation of sterilization or removal formaldehyde
(1) technical field
The present invention relates to anthraquinone salt for the preparation of sterilization or remove the application in the disinfectant of formaldehyde, it is oxidant that the airborne oxygen of a kind of use is provided, by catalytic oxidation killing microorganisms, be specially adapted to the sterilization system of air cleaning system.
(2) background technology
Along with the continuous increase of the density of population, industrializedly significantly promote, environmental pollution progressively aggravates, and particularly air pollution has a strong impact on the mankind's health.Air cleaning unit becomes the household products that current quilt is promoted rapidly, and the improvement of quality of life is played to certain impetus.
But there is larger deficiency in current air cleaning system.Known air cleaning system mainly contains two kinds, a kind of is to come the airborne microorganism of filtering and molecule (as pm2.5 particle) by adsorbent and filter membrane, because filtration system does not have efficient sterilizing function, cause the germ virus filtering out to be assembled in filtration system, the germ virus that these flock together can be by cutting one another's throats, only have the most powerful germ virus to survive, be actually cultivating superbug virus, people's health is existed to great potential danger.The second air cleaning system is to be hit and killed airborne microorganism by high-energy electric field, because its voltage is usually up to nearly 20,000 volts, in running, can causes the ionization of air, thereby produce a large amount of free radicals and ozone.Free radical and ozone have been generally acknowledged conclusions to the harm of health.
The method of killing pathogenic bacteria has a lot, and still, they are not all suitable for the air cleaning system of serialization operation.
Antibiotic and antiviral drugs cannot because they all have certain volatility, can produce secondary pollution for air cleaning system, and can cause pesticide resistance germ and viral generation.The disinfectant that contains halogen, for example clorox, cannot, for air purifier, because their excitant is large, damage skin and the respiratory system of human body, and a lot of things and air purifier itself in room, corrosivity be large.Peroxide (as peroxy acid, peroxide alcohol, hydrogen peroxide, etc.) also cannot be for air purifier, the one because their participate in, after Oxidative demage, no longer possessing sterilizing function, so their consumption is large, the 2nd, there is the potential safety hazard of blast in their.Traditional disinfectant such as ethanol also cannot be for air purifier, because their volatility is very high, flash-point is low, has larger hidden peril of explosion.Silver ion also cannot be for air purifier, because they are easy to inactivation under the condition of air purifier operation, regeneration difficulty, causes use cost high.
Air purifier needs a kind of can long continuous use, can not produce the secondary pollutants such as organic matter and free radical and ozone, can not cause pesticide resistance germ and viral generation, produce and use cost is lower, non-corrosiveness and safe disinfecting system.
(3) summary of the invention
The object of the invention is to provide the application of anthraquinone salt in the disinfectant for the preparation of sterilization or removal formaldehyde, and a kind of disinfectant system that can use in air purifier is provided.
The technical solution used in the present invention is:
The application of structure anthraquinone salt as shown in the formula (I) in preparing disinfectant:
Figure BDA0000378837000000021
In formula (I), R 1, R 2independent is separately the substituting group of sylvite, sodium salt, ammonium salt, calcium salt or magnesium salts that sulfonic group, formyl or hydroxyl are corresponding, and the position that they replace is respectively 1,2,3,4,5,6,7,8, it can be any combination of these positions, can be two replacements, three replace, four replace, five replace, six replace, seven replace, eight replace, include, but are not limited to, for example, 1, 5-bis-replaces, 1, 6-bis-replaces, 1, 7-bis-replaces, 1, 8-bis-replaces, 2, 5-bis-replaces, 2, 6-bis-replaces, 2, 7-bis-replaces, 2, 8-bis-replaces, 3, 5-bis-replaces, 3, 6-bis-replaces, 3, 7-bis-replaces, 3, 8-bis-replaces, 4, 5-bis-replaces, 4, 6-bis-replaces, 4, 7-bis-replaces, 4, 8-bis-replaces, 1, 2-bis-replaces, 1, 3-bis-replaces, 1, 4-bis-replaces, 2, 3-bis-replaces, 2, 4-bis-replaces, 3, 4-bis-replaces, etc..The disinfecting power of described anthraquinone salt shows under the condition of logical oxygen, and therefore, while using as disinfectant, need to constantly pass into air, its mechanism of action is referring to Fig. 1.Under normal air purifier service condition (more than 5 minutes, room temperature, a large amount of air passes through), effectively killing pathogenic bacteria and virus, reach sterilization target.
In order better further to set forth the structure of anthraquinone salt, below provide several concrete structures and be beneficial to understand, still, these examples are not to limit scope of the present invention, the scope that comprises of the present invention is by shown in formula (I) structure.Example anthraquinone salt structure is suc as formula shown in (I-1)～(I-9):
Figure BDA0000378837000000031
R wherein 1, R 2for corresponding sylvite, sodium salt, ammonium salt, calcium salt or the magnesium salts of hydroxyl (from left to right position is followed successively by 1,5-, bis-replacements, 1, and 8-bis-replaces and 1,2-bis-replaces);
Figure BDA0000378837000000032
R wherein 1, R 2for corresponding sylvite, sodium salt, ammonium salt, calcium salt or the magnesium salts of sulfonic group (from left to right position is followed successively by 1,5-, bis-replacements, 1, and 8-bis-replaces and 1,2-bis-replaces);
Figure BDA0000378837000000041
R wherein 1, R 2for corresponding sylvite, sodium salt, ammonium salt, calcium salt or the magnesium salts of formyl (from left to right position is followed successively by 1,5-, bis-replacements, 1, and 8-bis-replaces and 1,2-bis-replaces).
Be that in formula (I-1)～(I-9), M is Na, K, NH 4, Ca or Mg.
Concrete, described disinfectant is dispersed in and in solvent, is made base soln by described anthraquinone salt, pH be 8～12(lower than this interval, the effect of sterilization is poor; Higher than this interval, have certain corrosivity.), under the condition existing at oxygen, realize effective disinfective action; Described solvent is water, glycerine or its mixture; In described base soln, anthraquinone salt mass concentration is that the general consumption of 0.5%～20%(is no more than 10%, optimum is less than 5%, the too high cost that can affect use), this base soln can directly be used as disinfectant, also after can adding some common additives, as disinfectant, use, described additive, comprises essence, pigment etc. again, be not specifically limited, only otherwise goal of the invention of the present invention is produced to restriction.Described disinfectant can be made the formal products such as liquid, pulpous state lotion, solid.
Preferably, described disinfectant pH is 9.5～11, and in base soln, anthraquinone salt mass concentration is 1%～5%.
Described disinfectant is mainly used in being added in air purifier and (for example disinfectant solution is placed in to the inlet channel of air purifier), for sterilization or removal formaldehyde.
Beneficial effect of the present invention is mainly reflected in: disinfectant of the present invention is constantly entering under the condition of air, can use for a long time, do not need the antiviral medicine of Denging, do not need to exist the peroxide of potential safety hazard yet, do not use halogen-containing pungent, there is the alcohol of explosion danger etc. in use more.This disinfectant system of not using noble metal, prepares easyly, and use cost is low, there is no secondary pollution, has better application prospect.
(4) accompanying drawing explanation
Fig. 1 is the mechanism of action that utilizes airborne oxygen killing microorganisms;
Fig. 2 is Bryant-Bao Er diffusion measurement result;
Fig. 3 is the sterilizing ability of anthraquinone salt and the graph of a relation between acid-base value;
Fig. 4 is anthraquinone salt pair specific activity charcoal absorption effect of formaldehyde figure.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1: catalyst screening
It is microorganism that staphylococcus aureus is used in catalyst screening, and tryptic soy agar is medium.It is uniform mixture with pure water preparation that screened material powder be take 5% weight per volume proportioning (being 5g powder/100mL water), then with the neutral secondary filter filter paper of 5mm diameter, soak after approximately 10 seconds, be placed in Bryant-Bao Er (Kirby-Bauer) diffusion measurement ware.Bryant-Bao Er (Kirby-Bauer) diffusion measurement ware is placed in the cloche of sealing, and air feeds in cloche with the speed of 10 liters approximately per minute.The sterilizing ability of catalyzer, does not grow the area diameter of bacterium around and weighs with filter paper.Fig. 2 is a typical catalyst action effect Bryant-Bao Er (Kirby-Bauer) diffusion measurement ware photo (having 5 kinds of materials on this dish).
The results are shown in Figure in 2, Fig. 2 is No. 1 in the middle of lower end, is respectively clockwise 1,5-diphenol sodium anthraquinone, lignin, cellulose, fluorocarbon rubber, sodium silicate.As seen from the figure, the bactericidal effect of anthraquinone salt is (antibacterial circle diameter 13mm) very obviously, and other does not have substantially; And do not passing in air situation, anthraquinone salt does not have bactericidal effect (antibacterial circle diameter 0mm).
Embodiment 2:
It is 5% the aqueous solution that multiple anthraquinone salt is mixed with respectively mass concentration, controls pH=10.Sterilizing ability is still used staphylococcus aureus for microorganism, and Bryant-Bao Er (Kirby-Bauer) diffusion measurement method is measured, and logical oxygen condition is consistent, and temperature is room temperature (25 ℃) and 37 ℃.The results are shown in Table 1, display density 5% time, room temperature or slightly high-temperature, sterilizing ability does not have significant difference, shows that this disinfectant system is stable.
Table 1: the bactericidal effect under 5% concentration and different temperatures
Figure BDA0000378837000000061
Figure BDA0000378837000000071
Result demonstration, for the salt of anthraquinone, no matter where substituting group is, no matter is Na, NH 4, K, etc. the divalent salts such as monovalent salt or Ca, it is all fine that their catalytic activation oxygen reaches the ability of sterilization.
Embodiment 3:
The content of test is substantially identical with embodiment 2, and difference is, for what dissolve that the solvent of anthraquinone salt uses, is glycerine, and the result of test and embodiment 2 are basically identical.
Embodiment 4:
It is 0.5%, 1.0%, 2.0%, 5%, 10%, 15% and 20% the aqueous solution that 1,5-diphenol sodium anthraquinone is mixed with respectively mass concentration, controls pH=10.Sterilizing ability is still used staphylococcus aureus for microorganism, and Bryant-Bao Er (Kirby-Bauer) diffusion measurement method is measured, and logical oxygen condition is consistent, and temperature is room temperature (25 ℃) and 37 ℃.The results are shown in Table 2, display density is more than 5%, room temperature or slightly high-temperature, and sterilizing ability does not have significant difference.
Table 2: the bactericidal effect at variable concentrations and temperature
Figure BDA0000378837000000072
Embodiment 5: the relation between anthraquinone salt sterilizing ability and pH value
It is that 5%, pH value is 6,7,8,8.5,9,9.5,10,10.5,11,11.5,12 the aqueous solution that 1,5-diphenol sodium anthraquinone is configured to respectively concentration.Sterilizing ability is still used staphylococcus aureus for microorganism, and Bryant-Bao Er (Kirby-Bauer) diffusion measurement method is measured, and logical oxygen condition is consistent, and temperature is room temperature (25 ℃) and 37 ℃.The results are shown in Table 3 and Fig. 3, when display density is 5%, room temperature or slightly high-temperature, pH is that more than 8 sterilizing abilities is better, pH value is more than 10 best.
Table 3: the relation database table between anthraquinone salt bactericidal effect and acid-base value
Figure BDA0000378837000000081
Embodiment 6: disinfectant is removed the ability of formaldehyde
Test is used the stainless steel box (0.7m * 0.7m * 0.7m) of sealing as the mensuration space of formaldehyde, removes the ability contrast active carbon of formaldehyde.The box of two tests, 5% anthraquinone saline solution (pH=10), another the food stage active carbon of putting into 500 grams of putting into 500ml, use formaldehyde measurement instrument (PPM Formaldehydemeter400, resolution is 0.01ppm), measuring initial concentration is the variation of 10ppm formaldehyde air formaldehyde concentration, the results are shown in Table 4 and Fig. 4.
Table 4: air formaldehyde concentration reduces tables of data
Time (hour) Anthraquinone salt effect (ppm) Active carbon effect (ppm)
0 10 10
1 8.5 9.6
2 6.9 8.4
3 5.5 7.8
4 3.3 5.3
5 1.8 3.9
Result shows, the new disinfecting system disclosing in the present invention, and the ability of absorption formaldehyde is better than active carbon, points out disinfectant of the present invention to have good application prospect in air purification field.
The foregoing is only preferred embodiment of the present invention, not in order to limit essence technology contents scope of the present invention, essence technology contents of the present invention is to be broadly defined in the claim scope of application, any technology entity or method that other people complete, if defined identical with the claim scope of application, also or a kind of change of equivalence, all will be regarded as being covered by among this claim scope.

Claims (6)

1. the application of structure anthraquinone salt as shown in the formula (I) in preparing disinfectant:
Figure FDA0000378836990000011
In formula (I), R 1, R 2independent is separately the substituting group of sylvite, sodium salt, ammonium salt, calcium salt or magnesium salts that sulfonic group, formyl or hydroxyl are corresponding.
2. application as claimed in claim 1, is characterized in that described disinfectant is dispersed in solvent and is made base soln by described anthraquinone salt, and pH is 8～12, under the condition existing, realizes effective disinfective action at oxygen; Described solvent is water, glycerine or its mixture; In described base soln, anthraquinone salt mass concentration is 0.5%～20%.
3. application as claimed in claim 2, is characterized in that the pH of described disinfectant base soln is 9.5～11, and in base soln, anthraquinone salt mass concentration is 1%～5%.
4. application as claimed in claim 1 or 2, is characterized in that described disinfectant is added in air purifier, for sterilization or removal formaldehyde.
5. application as claimed in claim 1 or 2, is characterized in that also containing in described base soln additive.
6. application as claimed in claim 1 or 2, is characterized in that described disinfectant makes liquid, pulpous state lotion or solid product.
CN201310405625.1A 2013-09-07 2013-09-07 Application of anthraquinone salt in preparation of disinfectant for sterilization or for removing formaldehyde Pending CN103651349A (en)

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Application publication date: 20140326