CN106433562B - A kind of environment-friendly snowmelt agent and the method that the Snow Agent is prepared using amino acid zymotic fluid - Google Patents
A kind of environment-friendly snowmelt agent and the method that the Snow Agent is prepared using amino acid zymotic fluid Download PDFInfo
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- CN106433562B CN106433562B CN201610853026.XA CN201610853026A CN106433562B CN 106433562 B CN106433562 B CN 106433562B CN 201610853026 A CN201610853026 A CN 201610853026A CN 106433562 B CN106433562 B CN 106433562B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
- C09K3/185—Thawing materials
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
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Abstract
A kind of method that the Snow Agent is prepared the present invention relates to environment-friendly snowmelt agent and using amino acid zymotic fluid, its main component are：Ammonium salt organic acid, amphoteric amino acids sulfuric acid amine salt, ammonium sulfate and urea.Using the raffinate after amino acid zymotic fluid or newborn hairless protein hydrolyzate extraction amino acid as raw material, first concentrate, then concentrate is decolourized, filtered；Urea is added into obtained filtrate, product is neutralized to pH value 7~8 with ammoniacal liquor, obtains thick fluid；Then fluidized bed for spraying, granulating, that is, Snow Agent is obtained.Snow Agent snow melt temperature of the present invention is low, is easy to dissolve, complete biodegradable, and environment zero is endangered, and can avoid the salinization of soil problem caused by general inorganic Snow Agent of applying；Preparation method is simple and easy, cost is low.
Description
Technical field
The present invention relates to a kind of Snow Agent, the degradable type of particularly a kind of biology, ready dissolution amino acids Snow Agent and
Its preparation method, it is also the organic fertilizer of green plants after snow melt, belongs to environmental protection technical field.
Background technology
Many national extremely frigid zones, winter ice and snow turn into serious public hazards, deep accumulated snow in China and in the world
With smooth road surface, triggered traffic jam, accident repeatedly, highway stop transport, the serious consequence such as socked-in.It is general to use
The mode of surface sprinkling deicing or snow melting agent after snow reaches deicing or snow melting effect.The exploitation of deicing or snow melting agent experienced single
Salt type, inorganic chlorine salt form to organic type, the process of anticorrosion type.But the Snow Agent of the above-mentioned type, can not be degradable,
Also there is certain harm to environment.
Winter snowy day ensure highway it is unimpeded be a major issue in highway maintenance, Snow Agent is then the side of the most frequently usedization ice and snow
Method.Such as night Beijing snowstorm on November 4th, 2012, only early morning on the same day, Beijing just dissipated the t of Snow Agent more than 1200, Snow Agent all through the night
The t of liquid more than 3000.
Snow Agent be divided into it is non-containing chlorine type and containing two kinds of chlorine type, the non-effect of Snow Agent containing chlorine type is preferable, no corrosion damages,
But price is higher；Snow Agent containing chlorine type (including sodium chloride, calcium chloride, magnesium chloride etc.) is quite big due to cheap dosage.But
The use of the Snow Agent containing chlorine type can produce very big harm, including promote concrete expansion cracking, cause concrete cover to come off,
Reinforcing steel bars exposed corrosion, with the biochemical reaction of Asphalt Production asphalt surface can be caused to come off and road surface breakage, will also result in soil in addition
Salinization of soil, the growth of serious threat green plants.It has been reported that when concentration 2%-3% Snow Agent salt solution immerses greenery patches, plant is
Growth retardation can be caused because of physiological water shortage, leaf is withered or dead：Winter in 2004, Beijing was using Snow Agent 8000t, 2005
Spring about 1.1 ten thousand plants of shade trees, 200,000 m2The shrub such as lawn and more than 1,490,000 strain hedgerows suffers severe salt damage or death, direct economy
Loss is more than 30,000,000 yuan.Simultaneously snow-broth containing Snow Agent enter soil will also result in roadside soil salination, hardening, it is hardened,
It is barren.According to the statistics made by the departments concerned, 2011 end of the year China's highway total kilometrages are up to 8.5 ten thousand km, as highway is quickly sent out
Exhibition, Snow Agent bring a series of problems to turn into one of major issue of expressway greening and maintenance.According to statistics, Beijing is because making
With Snow Agent nearly ten thousand trees in heaven, especially greenbelt plant injury in expressway is very big, causes 120,000-15 ten thousand/Km greening warps every year
Ji loss.
To ensure the actively research environment-friendly snowmelt agent such as the facility such as ecological environment and road, the U.S., Canada, Northern Europe.Vinegar
Sour calcium and magnesium salt (CMA) be the 1980s U.S. to substitute a kind of environment-friendly snowmelt ice chemistry for developing of salt
Product, compared with NaCl, CMA have fusing point it is low, it is biodegradable, corrosion-free to road and bridge facility and concrete component, to soil
Earth and water source do not pollute.But it is higher to prepare one of CMA raw material glacial acetic acid price so that CMA is higher by than NaCl price
More than 30 times, thus constrain the generally use of CMA Snow Agents.In addition, there are research and development, use potassium acetate, ethylene glycol, propane diols
(price is above CMA).At present, the Snow Agent that also prepared by useful pyrolkigneous liquid, so a kind of low-cost environment-friendly such as English plum melts
Preparation and the performance study of agent are avenged, Liaoning chemical industry, the 1st phase of volume 36, is illustrated in the document that in January, 2007 delivers：Take and quantify
Know the pyrolkigneous liquid of acid content, add excessive dolomite dust, stir, react 30~50min at room temperature；Filtering, obtain black or
Dark brown filtrate；By filtrate activated carbon decolorizing, liquid CMA class Snow Agents are filtered to obtain.Filtrate evaporative crystallization or underflow are sprayed
Dry solid CMA class Snow Agents.But cost is higher, it is unfavorable for promoting.
The content of the invention
The purpose of the present invention is the defects of presence for prior art, there is provided a kind of environment-friendly snowmelt agent and utilizes amino acid
The method that zymotic fluid prepares the Snow Agent, Snow Agent snow melt temperature of the present invention is low, is easy to dissolve, complete biodegradable, to environment
Zero harm, can avoid the salinization of soil problem caused by general inorganic Snow Agent of applying；Preparation method is simple and easy, cost is low.
The technical scheme that the present invention takes is：
A kind of environment-friendly snowmelt agent, its main component are：Ammonium salt organic acid, amphoteric amino acids sulfuric acid amine salt, ammonium sulfate and
Urea.
Described environment-friendly snowmelt agent, its main component ammonium salt organic acid, amphoteric amino acids sulfuric acid amine salt, ammonium sulfate and urine
The weight ratio of element is preferably 1-20：1-50：0.5-30：1-25.Further preferred urea accounts for the 1-25% of Snow Agent dry weight.
Described ammonium salt organic acid, amphoteric amino acids sulfuric acid amine salt be amino acid and micromolecule polypeptide compound and sulfuric acid and
Ammoniacal liquor reaction generation.
A kind of method that environment-friendly snowmelt agent is prepared using amino acid zymotic fluid, including step are as follows：
(1) concentration-decolouring：During fermentation method production amino acid, the hair after ion exchange resin extracts amino acid
During containing substantial amounts of ammonium sulfate and ammonium salt organic acid, or feather hydrolysis method production amino acid in zymotic fluid, first have to use
Sulfuric acid substitutes traditional hydrochloric acid hydrolysis, substitutes traditional caustic soda neutralization using ammoniacal liquor in N-process, then uses ion exchange column
The amino acid needed for extraction is exchanged, the remaining raffinate after extraction also contains substantial amounts of ammonium sulfate and amino acid ammonium sulfate, by this
Then concentrate is decolourized, filtered using multi-effect evaporator evaporation further concentration by a little zymotic fluids or remaining raffinate；
(2) allotment-slurry-spraying pelletizing：Urea is added into the filtrate after concentration, product adjusts pH value 7~8 with ammoniacal liquor, obtained
Thick fluid；Then fluidized bed for spraying, granulating, that is, Compositional type Snow Agent particle is obtained.
In above-mentioned preparation method, the concentration step described in step (1) is concentrated into the 1/4~1/5 of original volume.Described is de-
Color is passed through steam and maintains in agitator tank temperature to more than 40 DEG C (preferably 50~70 DEG C) for concentrate is pumped into agitator tank,
Concentrate quality 1%-5% atlapulgite or activated carbon decolorizing is added, bleaching time is not less than 1 hour.Described is filtered into
Press filtration.
600-800 DEG C of fluidized bed for spraying, granulating temperature described in step (2), discharged gas fume temperature are not less than 600 DEG C, fluidisation
Bed granulation time control is in 1-60S.The addition of described urea accounts for the 1-25% of Snow Agent dry weight.
Snow Agent prepared by above-mentioned preparation method.
Beneficial effects of the present invention have：
(1) production cost is low, makees raw material using amino acid zymotic fluid or protein hydrolyzate, not only can zymotic fluid or extraction
The comprehensive utilization of liquid, added value is obviously improved, and raw material sources enrich, and method simple possible, overcome organic environment-friendly type
Snow Agent is because valency is high, prevents the defects of it is from popularizing use.
(2) Snow Agent is combined formula using organic and inorganic, contains ammonium salt organic acid, amphoteric amino acids sulfuric acid amine salt, sulphur
Sour ammonium and urea etc., organic ammonium sulfate of formation, ammonium sulfate etc. make it that Snow Agent is water-soluble very well, and water-soluble speed is fast；With urine
The compound of element makes its freezing point reach less than -40 DEG C, and snow melt temperature is lower, and Rateof snowmelt is higher.
(3) Snow Agent complete biodegradable, environment zero is endangered, can avoids applying soil caused by general inorganic Snow Agent
Salinization of soil problem, moreover it is possible to be obviously improved soil texture, strengthen water retention, reduce soil Na+, Cl- ion concentration, reduce soil
Earth sodium adsorption ratio SAR, can effectively solve the problems, such as the salinization of soil that expressway central partition soil is brought by Snow Agent, favorably
In the growth and maintenance of expressway greening plant.
(4) plus in the snow-broth after Snow Agent dissolving, containing the composition to greenbelt plant with good weight-improving effect, have
Beneficial to plant growth, while greenbelt dose is reduced, reduce greening fertilising spending.
Embodiment
Further illustrated with reference to specific embodiment, but the implementation of the present invention is not limited to this.
Embodiment 1
Glutami acid fermentation liquor is exchanged to the parts by weight of the liquid 100 suction multiple-effect evaporation after extraction amino acid with ion exchange column
In device, steam, circulating pump and vacuum are opened, the 1/5 of original volume is concentrated into, concentrated mother liquor is pumped into agitator tank, be passed through and add
Entering atlapulgite/activated carbon decolorizing of concentrated mother liquor quality 1%, bleaching temperature control is at 50 DEG C, bleaching time 1 hour, press filtration,
To another hybrid reactor, addition urea (addition is the 1% of Snow Agent dry weight), product is neutralized to pH value 7~8 with ammoniacal liquor,
Obtain thick fluid；Then fluidized bed for spraying, granulating, 600-800 DEG C of fluidized bed prilling temperature, discharged gas fume temperature are not less than
600 DEG C, the spherical particle being collected into is sieved, that is, obtains Snow Agent in 20S by fluidized bed prilling time control.Test condition：
Below -25 DEG C of snow melt temperature, snow-broth shows slightly light yellow after snow melt.
Embodiment 2
Glutami acid fermentation liquor is exchanged in the parts by weight of the liquid 100 suction multi-effect evaporator after extraction with ion exchange column,
Steam, circulating pump and vacuum are opened, the 1/5 of original volume is concentrated into, concentrated mother liquor is pumped into agitator tank, is passed through addition concentration
Liquid quality 5wt% atlapulgite/activated carbon decolorizing, bleaching temperature is to 70 DEG C, bleaching time 1 hour, press filtration, to another mixing
Reactor, addition urea (addition is the 5% of Snow Agent dry weight), product is neutralized to pH value 7~8 with ammoniacal liquor, obtains thick
Fluid；Then fluidized bed for spraying, granulating, 600-800 DEG C of fluidized bed prilling temperature, discharged gas fume temperature are not less than 600 DEG C, fluidisation
Bed granulation time is controlled in 60S, and the spherical particle being collected into is sieved, that is, obtains Snow Agent.Test condition：Snow melt temperature-
Less than 35 DEG C, snow-broth is colourless after snow melt.
Embodiment 3
The parts by weight of liquid 100 suck multi-effect evaporator after xanthan gum fermentation broth is exchanged into extraction amino acid with ion exchange column
In, steam, circulating pump and vacuum are opened, the 1/5 of original volume is concentrated into, concentrated mother liquor is pumped into agitator tank, be passed through addition
Concentrate quality 5wt% atlapulgite/activated carbon decolorizing, bleaching temperature is to 70 DEG C, bleaching time 1 hour, press filtration, to another
Hybrid reactor, addition urea (addition is the 20% of Snow Agent dry weight), product is neutralized to pH value 7~8 with ammoniacal liquor, is glued
Thick shape fluid；Then fluidized bed for spraying, granulating, 600-800 DEG C of fluidized bed prilling temperature, discharged gas fume temperature are not less than 600 DEG C,
The spherical particle being collected into is sieved, that is, obtains Snow Agent in 60S by fluidized bed prilling time control.Test condition：Snow melt temperature
Less than -40 DEG C of degree, it is colourless after snow melt.
Embodiment 4
After feather acid hydrolysis solution (using sulphuric acid hydrolysis, ammoniacal liquor neutralizes) is exchanged into amino acid needed for extraction with ion exchange column
In the parts by weight of raffinate 100 suction multi-effect evaporator, steam, circulating pump and vacuum are opened, is concentrated into the 1/5 of original volume, will be dense
Contracting mother liquor is pumped into agitator tank, is passed through the atlapulgite/activated carbon decolorizing for adding concentrate quality 5wt%, bleaching temperature to 70
DEG C, bleaching time 1 hour, press filtration, to another hybrid reactor, addition urea (addition is the 10% of Snow Agent dry weight), production
Thing is neutralized to pH value 7~8 with ammoniacal liquor, obtains thick fluid；Then fluidized bed for spraying, granulating, fluidized bed prilling temperature 600-
800 DEG C, discharged gas fume temperature is not less than 600 DEG C, and fluidized bed prilling time control is in 50S, the spherical particle mistake that will be collected into
Sieve, that is, obtain Snow Agent.Test condition：It is colourless after snow melt below -40 DEG C of snow melt temperature.
Application examples performance analysis
Production performance analysis：Production cost (by taking the product of embodiment 2 as an example, including slurry-spraying pelletizing process, artificial, energy
Source) it is total：700 yuan/ton, product price：3500 yuan/ton, 2800 yuan/ton of products of profit.
Applied D emonstration performance analysis：During experiment and demonstration, cost is calculated with the prices of raw materials plus 20% processing charges,
It is 2800 yuan/t to obtain input-output analysis.Economic benefit includes two aspects, first, the application of amino acids Snow Agent directly reduces
Greening sapling is filled the gaps with seedlings spending caused by Snow Agent, second, the benefit of composite water conservation fertilizer application reduction greenbelt dose.According to north
The starting group's virescence maintenance Csr Practice in capital, with 2010-2011, the spending of greening seedling after-culture engineering is the back of the body caused by Snow Agent
Scape, every kilometer of application amino acids Snow Agent cost is 2499 yuan, applies after-culture rate drop 1/2 after amino acids Snow Agent, by every
Yuan/plant of strain juniper after-culture cost 170.8, removes cost, then 6553 yuan/km of greening sapling after-culture expense is directly reduced using SFO.Press
Beijing's highway 739km greenbelt application amino acids Snow Agents, can directly it save every year green caused by Snow Agent is answered
Change 4,840,000 yuan of the spending that after-culture is carried out with Plant death.
Apply amino acids Snow Agent and reduce the annual dose of greenbelt, high speed greenbelt green plants juniper is held according to capital
414 yuan/the km of spending that applies fertilizer in year is calculated, and Beijing's highway greenbelt application composite water conservation fertilizer year reduction greenbelt, which applies fertilizer, pays wages
30.5 ten thousand yuan.
The above two is total, and Beijing highway 739km applies amino acids Snow Agent, directly passes through in the year for removing cost
514.5 ten thousand yuan of benefit of Ji.
Above is the present invention is discussed in detail in conjunction with specific embodiments, protection scope of the present invention not limited to this.
Claims (7)
1. a kind of environment-friendly snowmelt agent, its main component are：Ammonium salt organic acid, amphoteric amino acids sulfuric acid amine salt, ammonium sulfate and urine
Element；Ammonium salt organic acid, amphoteric amino acids sulfuric acid amine salt, the weight ratio of ammonium sulfate and urea are 1-20：1-50：0.5-30：
1-25；Described ammonium salt organic acid, amphoteric amino acids sulfuric acid amine salt are amino acid and micromolecule polypeptide compound and sulfuric acid and ammonia
Water reaction generation.
2. a kind of method that environment-friendly snowmelt agent is prepared using amino acid zymotic fluid, it is characterized in that, including step is as follows：
(1) during fermentation method production amino acid, containing a large amount of in the zymotic fluid after ion exchange resin extracts amino acid
Ammonium sulfate and ammonium salt organic acid, or feather hydrolysis method production amino acid during, first have to using sulfuric acid substitute it is traditional
Hydrochloric acid hydrolyzes, and substitutes traditional caustic soda to neutralize using ammoniacal liquor in N-process, is then exchanged with ion exchange column needed for extraction
Amino acid, the remaining raffinate after extraction also contains substantial amounts of ammonium sulfate and amino acid ammonium sulfate, by these zymotic fluids or residue
Raffinate is concentrated by evaporation, and then concentrate decolourizes, filtered；
(2) urea is added into the filtrate after concentration, product is neutralized to pH value 7~8 with ammoniacal liquor, obtains thick fluid；Then
Fluidized bed for spraying, granulating, that is, obtain Snow Agent granular product.
3. a kind of method that environment-friendly snowmelt agent is prepared using amino acid zymotic fluid according to claim 2, it is characterized in that,
Be concentrated into original volume 1/4~1/5 described in step (1).
4. a kind of method that environment-friendly snowmelt agent is prepared using amino acid zymotic fluid according to claim 2, it is characterized in that,
Described decolouring is passed through steam and maintains temperature in agitator tank to more than 40 DEG C, to add concentration for concentrate is pumped into agitator tank
Liquid quality 1%-5% atlapulgite or activated carbon decolorizing, bleaching time are not less than 1 hour.
5. a kind of method that environment-friendly snowmelt agent is prepared using amino acid zymotic fluid according to claim 4, it is characterized in that,
Described bleaching temperature is 50~70 DEG C.
6. a kind of method that environment-friendly snowmelt agent is prepared using amino acid zymotic fluid according to claim 2, it is characterized in that,
600-800 DEG C of fluidized bed for spraying, granulating temperature described in step (2), discharged gas fume temperature are not less than 600 DEG C, during fluidized bed prilling
Between control in 10-60S.
7. a kind of method that environment-friendly snowmelt agent is prepared using amino acid zymotic fluid according to claim 2, it is characterized in that,
The addition of described urea accounts for the 1-25% of Snow Agent dry weight.
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| CN110504362B (en) * | 2019-07-17 | 2023-06-16 | 浙江浙能技术研究院有限公司 | SnO (tin oxide) 2 Modification method of electron selective transport layer |
| CN111363521A (en) * | 2020-05-06 | 2020-07-03 | 延安市公路局 | Preparation method of environment-friendly snow-melting deicing fluid |
| CN111763496A (en) * | 2020-07-24 | 2020-10-13 | 中南安全环境技术研究院股份有限公司 | Environment-friendly novel chlorine-free liquid snow-melting agent and preparation method thereof |
| CN115260991A (en) * | 2022-07-27 | 2022-11-01 | 胡勇 | Coated snow-melting agent and preparation method and application thereof |
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Effective date of registration: 20190620 Address after: 211135 300 Chi Hui Road, Qilin science and Technology Innovation Park, Jiangning District, Nanjing, Jiangsu Patentee after: Nanjing Environmental Protection Technology Co., Ltd. Address before: 276000 Shuangyueyuan Road Science and Technology Pioneer Park A307, Linyi High-tech Zone, Shandong Province Patentee before: Shandong Boyang Environment Resource Co.,Ltd. |