CN100392040C - Environmental protection snow melt agent and preparation method thereof - Google Patents
Environmental protection snow melt agent and preparation method thereof Download PDFInfo
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- CN100392040C CN100392040C CNB2005100549645A CN200510054964A CN100392040C CN 100392040 C CN100392040 C CN 100392040C CN B2005100549645 A CNB2005100549645 A CN B2005100549645A CN 200510054964 A CN200510054964 A CN 200510054964A CN 100392040 C CN100392040 C CN 100392040C
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Abstract
The present invention provides an environmental protection type snow melt agent which is prepared from waste liquor and has no corrosion, low cost and low snow melt temperature. The environmental protection type snow melt agent is converted from waste liquor generated in the process of making gas from waste wood dust. The present invention as a good substitute of NaCl can be used for removing snow on northern freeways in winter, on one hand, the corrosiveness of snow melt agents of chlorine salts is overcome, and on the other hand, the cost of snow melt agents of acetic acid salts is lowered. Therefore, the environmental protection type snow melt agent is possible to substitute chlorine salts in economy, and roads can obtain better snow melt effect.
Description
Technical field
The present invention relates to a kind of in the Green Chemistry field does not have the low environment-friendly type snow-melting agent of burn into snow melt temperature.A kind of low-cost environment-friendly snow-melting agent that particularly utilizes wood vinegar to make.
Background technology
The method of domestic and international chemical deicing at present mainly is to use villaumite (NaCl, CaCl
2Deng) make ice and snow remover.As everyone knows, the villaumite snow-melting agent is effective, low price, but its main shortcoming is a contaminate environment, and the both sides greening of harm road, farmland and river, and corrode road surface and corrosion bridge reinforcement influence road work-ing life.In order to reduce the loss that villaumite harm causes, some developed country's test thermals source thaw ice and snow, but are subjected to energy condition restriction not seen widespread use.The country that also has adopts liquid (NaCl solution, CaCl
2Solution) snow-melting agent though can receive the effect of quick thawing and minimizing consumption, can not be eradicated the chlorine evil.If fundamentally eliminate the alternative villaumite of environment-friendly type snow-melting agent that chlorine evil problem must be researched and developed harmless and low evil, this is the development in future direction.Publication number be CN1537915A public announcement of a patent application a kind of environment-friendly type snow-melting agent, by in the Sodium orthomolybdate of two or three and 0.1%-10% in Potassium ethanoate (0-98%), calcium chloride (0-85%), magnesium chloride (0-85%), sodium-chlor (0-85%), the magnesium nitrate (0-50%), Sodium Benzoate, Sodium Nitrite, Starso, benzotriazole, the trolamine one or both, three kinds mix composite forming.Still there is following deficiency in this Snow Agent: (1) does not eradicate the chlorine evil fully.(2) cost is too high.Other component prices in the prescription except that sodium-chlor all will be higher than sodium-chlor, and price such as Potassium ethanoate, magnesium nitrate, Sodium orthomolybdate, Sodium Benzoate, trolamine, benzotriazole on average will exceed more than 10 times, and economic feasibility is relatively poor.Publication number be CN1381537A public announcement of a patent application a kind of environment-friendly type snow-melting agent that has utilized the soak solution in the grain deep-processing process, its method is in wet method corn deep processing process, corn is soaked, remove after the immersion corn remaining liquid be corn steep liquor, again corn steep liquor and muriate (sodium-chlor or magnesium chloride or calcium chloride) are mixed and make.This novel environment-friendly snow-melting agent cost is not high, has the certain economic feasibility, has reduced the chlorine evil to a certain extent yet, but can not eradicate the chlorine evil equally.The U.S. at first develops the favorable substitutes of a kind of calcium magnesium acetate (CMA) as villaumite in the eighties in 20th century, and it forms a certain proportion of mixture by calcium acetate and magnesium acetate.This novel snow-melting agent is compared with villaumite, and its snow melt ability is stronger, and the snow melt ultimate temperature is lower, and is particularly lower to metal protection, and the bridge rusting rate can reduce by 80% or lower.Acetic acid is biodegradable, and is minimum to biology in the water and plant influence simultaneously.The research checking of many countries, CMA is a kind of green chemical, a kind of efficient and environment-friendly type snow-melting agent.But problem is that the method for preparing CMA at present is by rhombspar (Ca/MgO) or Wingdale (Ca/MgCO
3) get with the chemical reaction of Glacial acetic acid, the price height reaches 1000 dollars/ton (villaumite has only 40～50 dollars/ton), therefore hampers this product applying in the snow removing field.Analyze the CMA cost structure and find, acetic acid is to influence the principal element of cost and calcium magnesium is cheap.Therefore using cheap acetic acid raw material production CMA is valid approach.Wood vinegar waste water claims wood vinegar again, and agricultural residue (wheat straw bar etc.) and wood working resistates (wood chip etc.) produce a large amount of wood vinegar when destructive distillation prepares charcoal, and acetic acid content can reach 5%-13% in the wood vinegar.Past people is discarded wood vinegar as waste water, not only cause environmental pollution, and causes the waste of resource.Originate as low-cost acetic acid with wood vinegar, produce environment-friendly type snow-melting agent CMA, not only opened up and reduced the new way of CMA production cost, and be a novel method that turns waste into wealth.
Summary of the invention
The present invention is used for preparing Snow Agent cheaply with traditional waste wood vinegar, reaches the purpose that makes full use of resource, reduces environmental pollution.
The technical solution adopted for the present invention to solve the technical problems is: a kind of environment-friendly snowmelt agent is provided, and is formic acid, acetate and the propionic acid mixing low-carbon (LC) calcium carboxylates magnesium salts that is made by wood vinegar and calcium magnesium oxide, oxyhydroxide or carbonate reaction; Its weight percent consists of:
CaAc
2 1～70
MgAc
2 28～99
Water 0～66
Wherein, Ac represents the acid group of formic acid, acetate and propionic acid mixing acid, and the weight percent of mixing acid consists of:
Formic acid 5～20
Acetate 70～90
Propionic acid 3～10.
The preparation method of this environment-friendly snowmelt agent is to be raw material with the wood vinegar, makes formic acid, acetate and propionic acid mixing low-carbon (LC) calcium carboxylates magnesium salts with calcium magnesium oxide, oxyhydroxide or carbonate reaction; May further comprise the steps:
A, get 1000 parts in the wood vinegar that acidity value is 40-120mgKOH/g, in 1/2nd of contained acid group mole number wherein, add excessive 5% mole calcium magnesium oxide, oxyhydroxide or carbonate, stirring and evenly mixing at room temperature reacted 20-50 minute;
B, remove by filter insolubles, obtain black or auburn filtrate;
C, add 100 parts of gacs in filtrate, concussion decolouring at room temperature 20～50 minutes is filtered and is obtained colourless or light filtrate;
D, filtrate evaporation concentration to solid content is 34～36% (weight) after, be liquid Snow Agent product; Perhaps the filtrate evaporation drying is obtained the faint yellow solid powder, be solid Snow Agent product.
Wherein, calcium magnesium oxide, oxyhydroxide or the carbonate with the wood vinegar reaction is that solid content is calcium magnesium oxide, oxyhydroxide or the carbonate water suspension of 3～10% (weight).Wood vinegar also is vegetable acid, a kind of foxy liquid mixture that reclaims when being the material destructive distillation of cellulose such as timber and hemicellulose, have the tart flavour of acetic acid and the smell of pungency charcoal fire, contain in the crude pyroligneous acid the deleterious composition methyl alcohol of organism, formaldehyde, 3,4 benzopyrenes etc. must carry out purifying treatment.Present treatment process mainly is to leave standstill heavy heat-clearing method: crude pyroligneous acid is placed on leaves standstill more than the 30d in the container, will isolate 3 layers, remove the impurity parts such as tar of upper strata 10% light oil and lower floor 30%, middle portion is wood vinegar composition safely and effectively, contains 6～14%C
3Following low-carbon (LC) carboxylic acid.
When using liquid Snow Agent product, liquid Snow Agent product can be sprayed directly on the ice and snow face and thaw ice and snow; When using solid Snow Agent product, its powder evenly is spread on snow melt on the snow face.Use the ice-melt snow effect of product of the present invention to show, the ice-melt snow effect of product mixing acid tachydrite of the present invention and mixing acid magnesium salts is not only effective than traditional villaumite Snow Agent, as table 1; And because the synergistic blend effect of calcium formiate magnesium salts, lime acetate magnesium salts, calcium propionate magnesium salts, what their snow melt effect will be good than the simple Snow Agent made from formic acid, acetate or propionic acid is many, as table 2.
Table 1. Snow Agent of the present invention and NaCl snow melt effect comparison
Table 2. Snow Agent of the present invention and formate, acetate and propionic salt snow melt effect comparison
It is raw material that the present invention utilizes the acetic acid waste liquid-wood vinegar in local biomass (wheat straw bar, wood chip etc.) the gasification conversion process, prepare environment-friendly snowmelt agent cheaply, and the realization suitability for industrialized production, both guaranteed the feature of environmental protection and the raw-material biological Sustainable development of snow-melting agent; Simultaneously main is to have reduced cost, as 1000 dollars/ton of the tachydrite Snow Agent (CMA) made with Glacial acetic acid; And 200 dollars/ton of mixing acid tachydrite Snow Agent made from wood vinegar (MC).The ice and snow of removing 1 ton with CMA approximately needs 800 yuan of RMB; The ice and snow of removing 1 ton with MC approximately needs 160 yuan of RMB.Snow Agent particularly of the present invention is compared with other Snow Agent, given full play to the snow melt effect of various low-carbon (LC) carboxylate salt synergistic blends, have advantages such as consumption is few, remarkably productive, snow melt fast, the snow melt temperature is low, not only provide a high-efficiency environment friendly low cost production technological line for road deicing snow, also, it is turned waste into wealth opened up a new way for administering the acetic acid waste liquid.To the northern area that snows winter frequently, the prosperity of high-grade highway net, city are concentrated, has the important meaning of fast and low-cost snow removing; Simultaneously, adopt environment-friendly type snow-melting agent of the present invention to greatly reduce corrodibility, can prolong the work-ing life of bridge, road steel bridge.Flowers, plants and trees is not had harm yet, meet people's enhanced environmental consciousness gradually, help the objective of the struggle of garden type urban construction.
The present invention will be further described below in conjunction with embodiment.
Embodiment
Embodiment 1: preparation magnesium calcium Snow Agent.
A, get 1000 kilograms in the wood vinegar that acidity value is 84mg KOH/g, add excessive 5% mole magnesium oxide and calcium oxide (mol ratio of magnesium and calcium is 7: 3), wherein, calcium oxide and magnesium oxide are the pigment suspension of ready-made solid content 6% (Wt), stirring and evenly mixing at room temperature reacted 20-50 minute;
B, remove by filter insolubles, obtain black or auburn filtrate;
C, add 100 parts of gacs in filtrate, concussion decolouring at room temperature 20～50 minutes is filtered and is obtained colourless or light filtrate;
D, filtrate evaporation concentration to solid content is 36% (weight) after, be liquid Snow Agent product; Perhaps the filtrate evaporation drying is obtained the faint yellow solid powder, be solid Snow Agent product.
Analyze in the liquid Snow Agent and respectively consist of: water 64%, CaAc
212%, MgAc
224%.
Analyze in the solid Snow Agent and respectively consist of: CaAc
233%, MgAc
267%.
Embodiment 2: preparation magnesium calcium Snow Agent.
Get acidity value and be 1000 kilograms in the wood vinegar of 120mg KOH/g, adopting magnesium hydroxide and calcium hydroxide is raw material, makes filtrate by embodiment 1 step a, b, c, d, filtrate evaporation concentration to solid content is 35% (weight) after, be liquid Snow Agent product; Perhaps the filtrate evaporation drying is obtained the faint yellow solid powder, be solid Snow Agent product.
Analyze in the liquid Snow Agent and respectively consist of: water 65%, CaAc
29%, MgAc
226%.
Analyze in the solid Snow Agent and respectively consist of: CaAc
226%, MgAc
274%.
Embodiment 3: preparation magnesium salts Snow Agent.
Get acidity value and be 1000 kilograms in the wood vinegar of 120mg KOH/g, add excessive 5% mole magnesium oxide, wherein, magnesium oxide is the magnesia powder aqeous suspension of ready-made solid content 10%, stirring and evenly mixing at room temperature reacted 20-50 minute, made filtrate by embodiment 1 step b, c, d, filtrate evaporation concentration to solid content is 36% (weight) after, be liquid Snow Agent product; Perhaps the filtrate evaporation drying is obtained the faint yellow solid powder, be solid Snow Agent product.
Analyze in the liquid Snow Agent and respectively consist of: water 64%, CaAc
20.4%, MgAc
235.6%.
Analyze in the solid Snow Agent and respectively consist of: CaAc
21.0%, MgAc
299.0%.
Embodiment 4: preparation magnesium calcium Snow Agent.
Get acidity value and be 1000 kilograms in the wood vinegar of 40mg KOH/g, add in magnesium calcium, excessive 5% mole of ground dolomite, wherein, ground dolomite is ready-made solid content 3% aqeous suspension, stirring and evenly mixing at room temperature reacted 20-50 minute;
B, remove by filter insolubles, obtain black or auburn filtrate;
C, add 100 parts of gacs in filtrate, concussion decolouring at room temperature 20～50 minutes is filtered and is obtained colourless or light filtrate;
D, filtrate evaporation concentration to solid content is 34% (weight) after, be liquid Snow Agent product; Perhaps the filtrate evaporation drying is obtained the faint yellow solid powder, be solid Snow Agent product.
Analyze in the liquid Snow Agent and respectively consist of: water 66%, CaAc
214%, MgAc
220%.
Analyze in the solid Snow Agent and respectively consist of: CaAc
241%, MgAc
259%.
Claims (3)
1. an environment-friendly snowmelt agent is characterized in that it being the low-carbon (LC) calcium carboxylates magnesium salts that is made by wood vinegar and calcium magnesium oxide, oxyhydroxide or carbonate reaction; Its weight percent consists of:
CaAc
2 1～70
MgAc
2 28～99
Water 0～66
Wherein, Ac represents the acid group of formic acid, acetate and propionic acid mixing acid, and the weight percent of mixing acid consists of:
Formic acid 5～20
Acetate 70～90
Propionic acid 3～10.
2. a method for preparing the environment-friendly snowmelt agent of claim 1 is characterized in that being is raw material with the wood vinegar, makes formic acid, acetate and propionic acid mixing low-carbon (LC) calcium carboxylates magnesium salts with calcium magnesium oxide, oxyhydroxide or carbonate reaction; May further comprise the steps:
A, get 1000 parts in the wood vinegar that acidity value is 40～120mgKOH/g, in 1/2nd of contained acid group mole number wherein, add excessive 5% mole calcium magnesium oxide, oxyhydroxide or carbonate, stirring and evenly mixing at room temperature reacted 20-50 minute;
B, remove by filter insolubles, obtain black or auburn filtrate;
C, add 100 parts of gacs in filtrate, concussion decolouring at room temperature 20～50 minutes is filtered and is obtained colourless or light filtrate;
D, filtrate evaporation concentration to solid content is 34～36% (weight) after, be liquid Snow Agent product; Perhaps the filtrate evaporation drying is obtained the faint yellow solid powder, be solid Snow Agent product.
3. method as claimed in claim 2 is characterized in that the calcium magnesium oxide, oxyhydroxide or the carbonate that react with wood vinegar are that solid content is calcium magnesium oxide, oxyhydroxide or the carbonate water suspension of 3～10% (weight).
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| CNB2005100549645A CN100392040C (en) | 2005-03-18 | 2005-03-18 | Environmental protection snow melt agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100549645A CN100392040C (en) | 2005-03-18 | 2005-03-18 | Environmental protection snow melt agent and preparation method thereof |
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| CN100392040C true CN100392040C (en) | 2008-06-04 |
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Cited By (1)
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|---|---|---|---|---|
| CN101787216B (en) * | 2010-01-25 | 2012-07-11 | 重庆鹏方路面工程技术研究院有限公司 | Anticoagulant icer for asphalt concrete crushed stone sealing layer and preparation method thereof |
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| CN102690632B (en) * | 2012-06-15 | 2014-05-14 | 天津喜研科技有限公司 | Method for preparing environment-friendly snow melting agent by using pyroligneous liquid |
| CN102775959A (en) * | 2012-07-16 | 2012-11-14 | 深圳市科中大交通建材有限公司 | Novel environment-friendly snow-melting agent and preparation method thereof |
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| CN103387817B (en) * | 2013-07-02 | 2015-04-15 | 长安大学 | Environment-friendly salt for ice and snow melting and preparation method thereof |
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| CN109337650B (en) * | 2018-12-13 | 2023-05-23 | 湖南利农五倍子产业发展有限公司 | Low-corrosiveness snow melt liquid and preparation method thereof |
| CN109943287A (en) * | 2018-12-15 | 2019-06-28 | 杭州银帆环境科技有限公司 | A kind of glass demisting frost fresh snow preparation manufacturing method of the vinegar liquid containing biomass pyrolytic |
| CN110386870A (en) * | 2019-07-26 | 2019-10-29 | 大连海洋大学 | A kind of mixture and its method and the application of the nacre and acetic acid calcium salt and acetic acid magnesium salts separating preparation simultaneously using oyster shell |
| CN110939035A (en) * | 2019-10-22 | 2020-03-31 | 重庆市市政设计研究院 | Asphalt concrete snow melting and ice suppression pavement structure |
| CN114806504B (en) * | 2022-04-19 | 2023-05-23 | 华能伊敏煤电有限责任公司 | Outdoor conveying adhesive tape anti-freezing adhesive agent for alpine regions and preparation method thereof |
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| CN101787216B (en) * | 2010-01-25 | 2012-07-11 | 重庆鹏方路面工程技术研究院有限公司 | Anticoagulant icer for asphalt concrete crushed stone sealing layer and preparation method thereof |
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| CN1657586A (en) | 2005-08-24 |
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Effective date of registration: 20220121 Address after: 239000 ganliu Houshan, Liji village, Shiji Town, Nanqiao District, Chuzhou City, Anhui Province Patentee after: Chuzhou Changchun charcoal professional cooperative Patentee after: Dalian Chengjun Environmental Protection Technology Co., Ltd Address before: 116600 No. 18 West Liaohe Road, Dalian Development Zone, Liaoning, Dalian Patentee before: DALIAN NATIONALITIES University |
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