CN113773814A - Preparation method of bio-based anti-freezing agent - Google Patents
Preparation method of bio-based anti-freezing agent Download PDFInfo
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- CN113773814A CN113773814A CN202111118420.6A CN202111118420A CN113773814A CN 113773814 A CN113773814 A CN 113773814A CN 202111118420 A CN202111118420 A CN 202111118420A CN 113773814 A CN113773814 A CN 113773814A
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- 238000007710 freezing Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000002028 Biomass Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 230000002528 anti-freeze Effects 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 235000019253 formic acid Nutrition 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012263 liquid product Substances 0.000 claims abstract description 3
- 238000002844 melting Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000010902 straw Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002826 coolant Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 230000008014 freezing Effects 0.000 abstract description 6
- 238000009835 boiling Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000002154 agricultural waste Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract 1
- 239000007769 metal material Substances 0.000 abstract 1
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000007798 antifreeze agent Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a preparation method of a bio-based antifreeze, which adopts an efficient catalytic liquefaction technology to catalytically liquefy biomass raw materials to prepare an environment-friendly antifreeze medium, and belongs to the technical field of efficient utilization of chemical material biomass. The method comprises the steps of taking agricultural wastes as raw materials, deionized water as a liquefying agent and formic acid as a catalyst, carrying out catalytic liquefaction reaction for a certain time, cooling, adding potassium hydroxide for neutralization until the pH value is 7.0-8.0, and filtering to obtain a liquid product, namely the bio-based antifreeze. The freezing point of the obtained antifreezing medium is-40 ℃, the boiling point is 118-120 ℃, and the product yield is more than 95%. The obtained medium is nontoxic and harmless, has no corrosion effect on various metal materials and high polymer materials, and can be applied to industrial cooling media, antifreezing media, road snow melting agents and the like.
Description
Technical Field
The invention relates to the technical field of high-quality utilization of new chemical materials and biomass, in particular to a preparation method and application of a biomass-based antifreezing medium.
Background
The glycol type antifreezing solution is an antifreezing product widely used in industry, but because glycol has higher cost and certain biotoxicity and does not conform to the concept of green products, the application field of the product is continuously limited, and under the condition, the environment-friendly antifreezing medium obtains more and more attention in industry. At present, the types of the antifreezing media include glycerol type antifreezing solution, polyethylene glycol type antifreezing solution and the like.
The biomass-based antifreezing medium mainly comprises biomass components such as polyhydric alcohol and the like, is non-toxic and harmless, has no negative effect on the environment after subsequent treatment, and does not corrode metal and organic high polymer materials. Therefore, the product is not only environment-friendly, but also reduces the subsequent treatment cost, so the antifreezing medium has more practical application value.
Disclosure of Invention
Aiming at the problems, the invention provides a method for preparing an antifreezing medium by catalytic liquefaction of agricultural wastes, which has the characteristics of low freezing point and high boiling point, has good corrosion resistance, does not need to add any corrosion inhibitor, and has the advantages of simple process operation, low price, environmental protection and the like. In order to achieve the above object, the present invention adopts the following technical solutions:
a preparation method of a bio-based antifreeze agent adopts an efficient catalytic liquefaction technology, agricultural and forestry waste raw materials, a liquefying agent and a catalyst are sequentially added into a reaction device according to a certain proportion, after uniform mixing, reaction is carried out for 6-12h under the condition of 110-140 ℃, after cooling, potassium hydroxide is added to adjust the pH value to 7.5-8.0, and filtration is carried out, so that the obtained liquid product is the bio-based antifreeze agent.
The raw materials are various straw powders with the granularity of 80-100 meshes.
The mass ratio of the raw material to the liquefying agent is 1-1.5: 1.
The reaction temperature is 110-140 ℃, and the preferable temperature is 120-130 ℃.
The reaction time is 6-12h, preferably 7-10 h.
The catalyst is formic acid, and the addition amount of the catalyst is 5.0-15.0% of the total mass of the liquefying agent and the raw materials. Preferably 8.0% to 12.0%.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
(1) the invention adopts the high-efficiency catalytic liquefaction technology, compared with the common liquefaction technology, the high-efficiency liquefaction of the raw materials can be realized, the liquefaction product obtained by optimizing the components of the formula has low freezing point and weak corrosivity on metals, the technological process is simple to operate, and the cost is greatly reduced. (2) The liquefied product of the invention mainly takes biomasses such as polyalcohol and the like as main components, is environment-friendly and nontoxic, and compared with the traditional glycol type antifreezing medium, the cost of the treatment of the waste antifreezing medium is reduced, and the harm to the environment of an ecosystem is greatly reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
Example 1.
Sequentially adding 2.0Kg of corn straw powder, 2.0Kg of deionized water and 0.62Kg of formic acid into a 10L stainless steel reactor provided with a stirring device and a temperature control device, uniformly stirring, controlling the temperature of the reactor to 120 ℃, reacting for 5 hours, rapidly cooling to room temperature, centrifuging, adding 0.75Kg of potassium hydroxide into the obtained liquefied product, adjusting the pH to 7.7, and obtaining the biomass-based antifreezing medium, wherein the product yield is 92.3%, the freezing point is-41 ℃, and the boiling point is 120 ℃.
Example 2.
2.0Kg of wheat straw powder, and,
3.0Kg of deionized water and 0.5Kg of formic acid are uniformly stirred, the temperature of the reactor is controlled to 140 ℃ for 8 hours of reaction, the reactor is cooled to room temperature and then centrifuged, the liquefied product is adjusted to pH 7.7 by potassium hydroxide to obtain the biomass-based antifreezing medium, and the yield of the product is 93.4 percent, the freezing point is-40 ℃ and the boiling point is 118 ℃ through determination.
Example 3.
Adding 5.0kg of straw powder, 5.0kg of deionized water and 1.55kg of formic acid into a 10L stainless steel reaction kettle provided with a stirring device and a temperature control device in sequence, stirring uniformly, reacting at 130 ℃ for 10h, cooling to room temperature, centrifuging, adjusting the pH of the obtained liquefied product to 7.9 by using potassium hydroxide to obtain a biomass-based antifreezing medium, and determining that the yield of the product is 90.2%, the freezing point is-41 ℃ and the boiling point is 118 ℃.
EXAMPLE 4 preparation of antifreeze media from liquefied products
Note: the indexes are all superior to the national standard (GB 29743-
EXAMPLE 5 preparation of snow-melting Agents from liquefied products
Note: the indexes are all superior to the national standard (GB 29743-
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing examples can be modified, or some technical features can be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (6)
1. A preparation method of a bio-based antifreeze comprises the following steps: adding a certain mass of biomass raw material into a 10L stainless steel reaction kettle provided with a stirring device and a temperature control device, then adding 1-2 times of liquefying agent and catalyst which accounts for 5.0-15.0% of the total mass of the liquefying raw material and the liquefying agent into the reaction kettle, uniformly mixing, reacting for 6-12h at the temperature of 110 plus 140 ℃, cooling the liquefied product to room temperature, performing centrifugal separation, and adding potassium hydroxide into the liquid product to adjust the pH value to 7.0-8.0, thus obtaining the bio-based antifreeze.
2. The method for preparing a bio-based anti-freezing agent according to claim, wherein the method comprises the following steps: the method adopts an efficient catalytic liquefaction technology, and the raw materials are various plant straw powder with the granularity of 80-100 meshes.
3. The method for preparing a bio-based anti-freezing agent according to claim, wherein the method comprises the following steps: the liquefying agent is deionized water, and the mass ratio of the liquefying agent to the raw materials is 1-2: 1.
4. The method for preparing a bio-based anti-freezing agent according to claim, wherein the method comprises the following steps: the catalyst is formic acid, and the mass of the added catalyst is 5.0-15.0% of the total mass of the liquefaction raw material and the liquefaction agent.
5. The method for preparing a bio-based anti-freezing agent according to claim, wherein the method comprises the following steps: the catalytic liquefaction reaction temperature is 110-140 ℃, and the reaction time is 6-12 h.
6. The method for preparing a bio-based antifreeze according to any one of claims 1 to 5, which comprises the steps of: it is suitable for industrial antifreezing medium, cooling medium and road snow-melting agent.
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CN202111118420.6A CN113773814A (en) | 2021-09-24 | 2021-09-24 | Preparation method of bio-based anti-freezing agent |
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CN202111118420.6A CN113773814A (en) | 2021-09-24 | 2021-09-24 | Preparation method of bio-based anti-freezing agent |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080103340A1 (en) * | 2006-10-27 | 2008-05-01 | Archer-Daniels-Midland Company | Applications of biobased glycol compositions |
DE102008059943A1 (en) * | 2008-12-02 | 2010-06-10 | Daimler Ag | Coolant for cooling a battery, where the coolant is completely free of water and polar hydroxyl bonds, and is hydrophobic, and silicone oil, mineral oil distillate, mineral oil raffinate, synthetic oil or biological oil |
CN102352222A (en) * | 2011-08-12 | 2012-02-15 | 齐中兴 | Preparation method of biomass based antifreeze fluid mother liquor |
CN106543982A (en) * | 2016-10-20 | 2017-03-29 | 华东师范大学 | A kind of method for preparing propylene glycol anti-icing fluid from natural wooden fiber's element raw material |
CN106590532A (en) * | 2016-12-15 | 2017-04-26 | 陕西易阳科技有限公司 | Preparation method of snow melting agent |
CN110951461A (en) * | 2019-12-10 | 2020-04-03 | 辽宁大学 | Environment-friendly snow-melting agent taking acetic acid waste liquid and straw ash as raw materials and preparation method and application thereof |
CN111499861A (en) * | 2020-06-23 | 2020-08-07 | 长春工业大学 | Method for preparing polyether polyol by liquefying agricultural wastes |
-
2021
- 2021-09-24 CN CN202111118420.6A patent/CN113773814A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080103340A1 (en) * | 2006-10-27 | 2008-05-01 | Archer-Daniels-Midland Company | Applications of biobased glycol compositions |
DE102008059943A1 (en) * | 2008-12-02 | 2010-06-10 | Daimler Ag | Coolant for cooling a battery, where the coolant is completely free of water and polar hydroxyl bonds, and is hydrophobic, and silicone oil, mineral oil distillate, mineral oil raffinate, synthetic oil or biological oil |
CN102352222A (en) * | 2011-08-12 | 2012-02-15 | 齐中兴 | Preparation method of biomass based antifreeze fluid mother liquor |
CN106543982A (en) * | 2016-10-20 | 2017-03-29 | 华东师范大学 | A kind of method for preparing propylene glycol anti-icing fluid from natural wooden fiber's element raw material |
CN106590532A (en) * | 2016-12-15 | 2017-04-26 | 陕西易阳科技有限公司 | Preparation method of snow melting agent |
CN110951461A (en) * | 2019-12-10 | 2020-04-03 | 辽宁大学 | Environment-friendly snow-melting agent taking acetic acid waste liquid and straw ash as raw materials and preparation method and application thereof |
CN111499861A (en) * | 2020-06-23 | 2020-08-07 | 长春工业大学 | Method for preparing polyether polyol by liquefying agricultural wastes |
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