CN1242943A - Air-purifying and antibiotic functional material activated by rare-earth to generate anions, and production method thereof - Google Patents

Air-purifying and antibiotic functional material activated by rare-earth to generate anions, and production method thereof Download PDF

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Publication number
CN1242943A
CN1242943A CN 99111380 CN99111380A CN1242943A CN 1242943 A CN1242943 A CN 1242943A CN 99111380 CN99111380 CN 99111380 CN 99111380 A CN99111380 A CN 99111380A CN 1242943 A CN1242943 A CN 1242943A
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rare
zno
air
purifying
rare earth
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CN 99111380
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CN1086109C (en
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金宗哲
梁金生
王静
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China Building Materials Academy CBMA
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China Building Materials Academy CBMA
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Abstract

The present invention relates to an air-purifying and antimicrobial material which can be activated by rare earth to produce negative ion. Its formula comprises AgNO3 0-1.6%, CaCO3 25%-35%, Al(OH)3 20%-25%, ZnO 20%-28%, Re(NO3)3 0.3%-1.6% and H3PO4 34.7%-8.8%, and its production process includes the procedures of mixing materials, acid-dissolving reaction, grinding, cleaning, filtering, drying, grinding and classifying. Said invention can be used for purifying air, antibiosis and producing negative ion, can be extensively used in the fields of ceramic, coating and plastic industries.

Description

The air cleaning of rare-earth activated generation anion and antibiotic functional material and manufacture method thereof
The present invention relates to a kind of air cleaning and anti-biotic material that utilizes rare-earth activated generation anion.
Nationwide coli-infection incident took place in Japan in 1996, once causing world's fear, caused " the anti-biotic material heat " of Japan thus, be not only at hospital, public place and dwelling house, even the daily necessities and the tool of production also progressively adopt anti-biotic material.The Japanese market of anti-biotic material in 1997 has surpassed 1,000,000,000 dollars, about 3,000,000,000 dollars of world market.These anti-biotic materials mainly are the inorganic antiseptics with metal ion such as silver, copper, zinc or its oxide.
The photocatalysis antibacterial scavenging material of people's researchs such as Japan Fyjishima is with TiO 2It is main antibacterial purifying agent.This material mainly is used to decompose airborne pernicious gas except that antibacterial effect.But anti-microbial property and air purification function only could realize that application is restricted under ultraviolet ray participates in.(Japan at first developed the material of the pernicious gases such as NOx that are used for the road surface purifying atmosphere in 1998, was 120 dollars/m with every square metre of photocatalysis pavior brick price 2Meter predicts that its market is 9,000,000 m 2/ year, then annual earnings are about 1,000,000,000 dollars).
Antibiotic and the clean-up effect of above-mentioned inorganic antiseptic and light catalytic purifying agent is undesirable, and cost is also higher, about 100,000 dollars/ton.The present invention has improved the antibiotic property and the purification function of material by rare-earth activated effect for this reason, and the output that improves the anion that helps healthy functions, has reduced cost significantly simultaneously, and price per ton is less than 100,000 yuan/ton.
The objective of the invention is to invent a kind of material, it utilizes rare-earth activated technology to improve the antibiotic and air-cleaning function of material.
1. material of the present invention is to have fully utilized metal ion and oxide antimicrobial technology and light catalytic purifying technology and rare-earth activated technology, and the comprehensive functions such as antibiotic property, air-cleaning function and health care of material are further improved.
TiO is adopted in photocatalysis 2Or ZnO
Antibacterial action adopts Ag, Cu, Zn and oxide thereof
Infrared composition adopts Zr, Co, Mn, Al, Ca, Zn and oxide thereof
Activation adopts rare earth (La, Ce, Nd)
2. find first and utilize rare-earth activated increase active oxygen radical rule, and the exploitation of the antibacterial purifying material that successfully this technology is used to keep healthy.
The atomic structure characteristics of rare earth element are: the outermost electron structure of atom identical (all being 2 electronics), inferior outer electronic structure is similar, and on the layer 4f track third from the bottom unpaired electron is arranged.Just because of the atomic structure of this uniqueness of rare earth element, it all is widely used at industry-by-industry.Especially in the catalytic field application of having succeedd.The research of this project utilizes the catalytic action of rare earth just, and the system generation catalytic reaction that antibacterial agent and water, air are formed produces O - 2With the OH active oxygen radical.Then active oxygen radical further with the bacterial cell membrane interaction, reach the purpose of kill bacteria.Active oxygen radical also can reach the purpose that purifies air with VOC in the air and NOx effect simultaneously.
The photocatalysis effect of rare earth element strengthening material increases OH free radical output, by our ESR experiment confirm.
3. find and record the rule of material surface generation anion of the present invention under daylight or the light effect.
4. material prescription of the present invention and the index that finally reaches
Prescription:
AgNO 3：?????0～1.6％
CaCO 3：?????25～35％
Al(OH) 3：???20～25％
ZnO：???????20～28％
Re(NO 3) 3：0.3～1.6％
H 3PO 4：???34.7～8.8％
Final index:
AgO：???0～1.72％
CaO：???14～18.9％
ZnO：???19.3～27.4％
Al 2O 3：26.4～32.1％
Re 2O 3：0.2～1.2％
Surplus: phosphate radical and inevitable impurity
In the described silver nitrate silver content be 0～1.5%, described phosphoric acid concentration is 85%, described rare earth Re for contain La, Nd, Ce is at least a, total content is 0.1～0.5%.
5. the manufacturing process of material of the present invention
1. with ZnO, CaCO 3And Al (OH) 3Fully mix in batch mixer Deng powder;
2. the powder that mixes being joined slowly temperature and be 40-60 ℃, concentration is in the phosphate aqueous solution of the 35-45% left and right sides, stirs while feeding in raw material;
3. after question response finished, bubble disappeared substantially in the solution, the slurry that makes is cooled to about 30 ℃ naturally, in the ball mill of packing into;
4. in ball mill, add silver nitrate and rare earth aqueous solution, ball milling 4-6 hour, go out grinding rate and cross 100 mesh sieves;
5. with 4-6 hour, clean, filter in, remove the acid ion in the solution;
6. 150 ℃ of-250 ℃ of dryings are sloughed slurry moisture;
7. in ultra-fine grinding mill, grind final fineness≤5 μ m;
8. classification detects packing.
6. example and explanation
(1) raw material and prescription (producing 1 ton) example one:
CaCO 3：?????300Kg???Al(OH) 3：200Kg????ZnO：274Kg
Ce (NO 3) 3: 15.5Kg H 3PO 4: 139ml example two:
CaCO 3：??300Kg??????Al(OH) 3：231Kg????ZnO：230.5Kg
AgNO 3: 7.9Kg Ce (NO 3) 3: 9.3Kg H 3PO 4: 118ml example three:
CaCO 3：??337.5Kg????Al(OH) 3：246Kg????ZnO：193.2Kg
AgNO 3：??15.7Kg?????Ce(NO 3) 3：3.1Kg??H 3PO 4：109ml
(2) production technology
1. with ZnO, CaCO 3And Al (OH) 3Fully mix in batch mixer Deng powder;
2. the powder that mixes being joined slowly temperature and be 40-60 ℃, concentration is in 40% left and right sides phosphate aqueous solution, stirs while feeding in raw material;
3. after question response finished, bubble disappeared substantially in the solution, the slurry that makes is cooled to 30 ℃ naturally, in the ball mill of packing into;
4. add the silver nitrate and the cerous nitrate aqueous solution in ball mill, ball milling 5 hours goes out grinding rate and crosses 100 mesh sieves;
5. with 5 hours, clean, filter in, remove the acid ion in the solution;
6. 200 ℃ of dryings are sloughed slurry moisture;
7. in ultra-fine grinding mill, grind final fineness≤5 μ m;
8. classification detects packing.
(3) performance indications
1. the anti-microbial property of rare earth activated inorganic health care antibacterial agent
[1] test method
Take by weighing antibacterial agent 0.5 gram with sterile working, put into the empty plate of sterilization, through ultraviolet disinfection 5 minutes, each plate added staphylococcus aureus (No. 25923) and contains 2000/ml bacterium, altogether 10ml; Establish control group simultaneously, in control group, only add 2000/ml bacterium, altogether 10ml.After mixing, sample thief and control group are inoculated each 3 of nutrient agar plates, each plating 0.1ml respectively immediately.At irradiation laboratory sample and control group under the 15W fluorescent lamp after 6 hours, after sample and control group fully mixed respectively, inoculate each 3 of nutrient agar plates more respectively, each plating 0.1ml cultivated 24 hours in 30-35 ℃, observed the growth number of bacterium.[2] result of the test
Laboratory sample Example one Example two Example three Blank
Total number of bacteria (10ml) ??2.0×10 4 ??2.0×10 4 ??2.0×10 4 ??2.0×10 4
Viable count after 6 hours (individual) ??8.7×10 2 ??2.4×10 4 ????0 ??3.0×10 3
Sterilizing rate (%) ????71 ????92 ????100 ?????-
2. the purifying property of rare earth activated inorganic health care antibacterial agent
[1] test method
To mix respectively in generic latex lacquer coating by the rare earth activated inorganic health care antibacterial agent that example one, example two, example three prescriptions are done, brush three rooms that size is similar, ventilation and lighting is similar respectively, and be made as contrast with the room of generic latex lacquer brushing that does not add antibacterial agent.The VOC amount is three days in each room of continuous measurement, and the harmful Volatile Gas scale of construction VOC value of contrast changes.
[2] result of the test
1 #(contrast room) 2 #(example one) 3 #(example two) 4 #(example three)
∑VOCppm ?545.6 ?434.6 ?387.2 ?326.2
Space factor * ?1 ?1.04 ?1.12 ?1.2
Relative VOC * ?1 ?0.77 ?0.63 ?0.50
*With the 1# room is benchmark
3. rare earth activated inorganic health care antibacterial agent produces the performance of anion
Be of the influence of test rare earth activated inorganic health care antibacterial agent to indoor negative ion concentration, engaged Shanghai City Bureau of Technical Supervision air monitoring chamber that the negative ion concentration in four rooms is measured, instrument is the SD9207 air ion concentration measuring apparatus that Shanghai Electric Tool Research Institute produces.The result is as follows:
The room Ion concentration is (individual/cm 3) Ion is electrical Remarks
??1 #(contrast room) ????150 ????+
??2 #(example one) ????130 ????-
??3 #(example two) ????130 ????-
??4 #(example three) ????130 ????- Back of the body sun, light difference
7. advantage and good effect
(1) material of the present invention is the new material with air cleaning and antibacterial functions of using the manufacturing of rare-earth activated increase active oxygen principle. Because the application of rare earth element, this material has overcome TiO2The deficiency that catalysis material needs ultraviolet light to participate in, and under the room light condition, also can produce anion, show preferably air cleaning and antibacterial effect.
(2) good anti-bacterial effect, sterilizing rate was 100% to the maximum in 6 hours,
Good purification, the VOC purifying rate is up to 50%.
(3) the about 100/cm of the generation of anion3
(4) be widely used in the fields such as coating, architectural pottery and plastics.

Claims (2)

1. the air cleaning of a rare-earth activated generation anion and anti-biotic material, it is characterized in that: described material prescription is:
AgNO 3：????0～1.6％
CaCO 3：????25～35％
Al(OH) 3：??20～25％
ZnO：??????20～28％
Re(NO 3) 3：0.3～1.6％
H 3PO 4: 34.7～8.8% wherein: AgO:0～1.72%, CaO:14～18.9%, ZnO:19.3～27.4%, Al 2O 3: 26.4～32.1%, Re 2O 3: 0.2～1.2%, in the described silver nitrate silver content be 0～1.5%, described phosphoric acid concentration is 85%, described rare earth Re for contain La, Nd, Ce is at least a, total content is 0.1～0.5%.
2. the manufacture method of the described material of claim 1 is characterized in that:
1. with ZnO, CaCO 3And Al (OH) 3Powder fully mixes in batch mixer,
2. the powder that mixes being joined slowly temperature and be 40-60 ℃, concentration is in the phosphate aqueous solution of the 35-45% left and right sides, stir while feeding in raw material,
3. after question response finished, bubble disappeared substantially in the solution, the slurry that makes is cooled to about 30 ℃ naturally, and in the ball mill of packing into,
4. in ball mill, add silver nitrate and rare earth aqueous solution, ball milling 4-6 hour, go out grinding rate and cross 100 mesh sieves,
5. with 4-6 hour, clean, filter in, remove the acid ion in the solution,
6. 150 ℃ of-250 ℃ of dryings are sloughed slurry moisture,
7. in ultra-fine grinding mill, grind, final fineness≤5 μ m,
8. classification detects packing.
CN99111380A 1999-08-12 1999-08-12 Air-purifying and antibiotic functional material activated by rare-earth to generate anions, and production method thereof Expired - Fee Related CN1086109C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104577726A (en) * 2015-01-30 2015-04-29 济南新活电器有限公司 Superconductive anion release electrode
CN106621761A (en) * 2016-12-08 2017-05-10 广东爱车小屋实业发展股份有限公司 Gel air freshener and preparation method thereof
CN106752950A (en) * 2016-11-28 2017-05-31 杭州金知科技有限公司 A kind of architectural paints
CN110876386A (en) * 2019-11-20 2020-03-13 厦门稀土材料研究所 Rare earth oxide and nano-silver synergistic antibacterial agent and preparation method thereof
CN111925740A (en) * 2020-06-04 2020-11-13 深圳昌茂粘胶新材料有限公司 Nano-silver antibacterial mildew-proof polyethylene label material and preparation method thereof
CN113122084A (en) * 2020-01-11 2021-07-16 中科(深圳)微能量科学技术研究院有限公司 Water-based air purification paint and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0737363B2 (en) * 1992-08-19 1995-04-26 工業技術院長 Antibacterial and antifungal ceramics and method for producing the same
JP3077486B2 (en) * 1993-12-24 2000-08-14 東洋インキ製造株式会社 Antibacterial agent
JPH08231324A (en) * 1995-02-28 1996-09-10 Teika Corp Antimicrobial composition and its blend

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104577726A (en) * 2015-01-30 2015-04-29 济南新活电器有限公司 Superconductive anion release electrode
CN106752950A (en) * 2016-11-28 2017-05-31 杭州金知科技有限公司 A kind of architectural paints
CN106621761A (en) * 2016-12-08 2017-05-10 广东爱车小屋实业发展股份有限公司 Gel air freshener and preparation method thereof
CN106621761B (en) * 2016-12-08 2019-11-08 广东爱车小屋电子商务科技有限公司 The preparation method of gel air fresher
CN110876386A (en) * 2019-11-20 2020-03-13 厦门稀土材料研究所 Rare earth oxide and nano-silver synergistic antibacterial agent and preparation method thereof
CN113122084A (en) * 2020-01-11 2021-07-16 中科(深圳)微能量科学技术研究院有限公司 Water-based air purification paint and preparation method thereof
CN111925740A (en) * 2020-06-04 2020-11-13 深圳昌茂粘胶新材料有限公司 Nano-silver antibacterial mildew-proof polyethylene label material and preparation method thereof

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