Method for producing aminic acid by glycerin water thermal reduction of CO2

Abstract

The invention discloses a method for producing methanoic acid by glycerol to hydrothermally reduce CO2, which relates to a process that the glycerol is also transformed into lactic acid when the glycerol is utilized to reduce CO2 into the methanoic acid. Firstly, according to the mass proportion of 1 to (1-10) to (1-10), the glycerol, NaOH (or KOH) as well as CO2 are added into a hydro-thermal reactor, and then react for 20 to 300 minutes at a temperature of between 150 and 400 DEG C under the pressure of between 2 and 15Mpa to produce sodium (potassium) lactate and sodium (potassium) formate solution, and the solution is cooled to the room temperature to produce the sodium (potassium) lactate and sodium (potassium) formate crystals; then hydrochloric acid is used to neutralize the crystals to produce mixed solution of the methanoic acid and the lactic acid, and finally the mixed solution is subjected to the reduced pressure distillation and is separated according to different boiling points of the lactic acid and the methanoic acid to produce the lactic acid and the methanoic acid. Or the prior esterification separation technology is used to esterify the neutralized lactic acid and methanoic acid, and the reduced pressure distillation and the separation are performed according to the different boiling points to produce the lactic acid and the methanoic acid. In the invention, the glycerol can be byproduct glycerol of biodiesel, CO2 can be CO2 discharged by combustion, and the method has simple process, no secondary pollution, and valuable economic and social benefits.

Description

technical field

[0001] The invention relates to a hydrothermal reduction of CO using glycerol as a reducing agent 2 into formic acid, while glycerin itself is also converted into lactic acid. Specifically, under hydrothermal reaction conditions, glycerol is used to convert CO 2 The technology of reducing formic acid and converting glycerin itself into lactic acid at the same time belongs to the technical field of environmental engineering and the technical field of waste recycling. Background technique

[0002] by CO 2 The global warming effect caused by environmental pollution is one of the most concerned environmental problems in the world. If measures are not taken in time to reverse the trend of global warming, it will directly threaten the survival of human beings and the earth. but only through the CO 2 The emission reduction to control the greenhouse effect still cannot fully meet our requirements. CO 2 It is the final product of the combustion of all organic m...

Examples

Embodiment 1

[0022] With the increasing production of biodiesel (the annual production of biodiesel in my country is expected to reach 1 million tons in 2010 and 9 million tons in 2020), the by-product glycerin, which accounts for 10% of the total biodiesel production, is also increasing sharply. . Hydrothermal reduction of CO using biodiesel by-product glycerol as reductant 2 into formic acid, while glycerin itself is also converted into lactic acid process, not only can glycerin and CO 2 resources, and can reduce the production cost of biodiesel.

[0023] SUS316 stainless steel round tube tubular batch hydrothermal reactor was used for small-scale experiments. Glycerin comes from the by-product of biodiesel production plant, CO 2 for pure CO 2 , the filling rate of water in the hydrothermal reactor is 30-60%, and glycerol is added in proportion by mass: NaOH (or KOH): CO 2 =1:(1.9~4.9):(1~5) into the hydrothermal reactor. The temperature is 250~320℃, the reaction pressure is 5~14Mpa,...

Embodiment 2

[0025] CO 2 CO collected from coal chemical enterprises 2 , CO in coal-to-oil and coal-to-methanol industries 2 The emissions were 9.2 tons of CO 2 / ton of synthetic oil, 3.8 tons of CO 2 / ton of methanol, and CO in the exhaust gas 2 The purity is as high as 80-90%. The filling rate of glycerol source, equipment and water is the same as that of Example 1, and glycerin is added in proportion by mass: NaOH (or KOH): CO 2 =1:(2~5):(1~5) into the hydrothermal reactor. The temperature is 250~350℃, the reaction pressure is 5~5Mpa, the reaction time is 0.5~1.5h, and the product is used after the reaction 1 H-NMR qualitative and HPLC quantitative. Analysis results showed that the yield of formic acid was 30-65%, and the yield of lactic acid was 60-80%.

[0026] Industrial production can be used as figure 1 Process flow shown. The reaction conditions are controlled as follows: the temperature is 200°C to 400°C, the reaction pressure is 2 to 15Mpa, and glycerin: NaOH (or KOH)...

Embodiment 3

[0028] CO 2 CO captured from coal-fired power plants 2 . Currently, China's power sector emits 2.7 billion tons of CO2 per year 2 It ranks second in the world after the United States. Applying the present invention to the power sector, the waste CO emitted by it can be 2 The collection is passed into a hydrothermal reactor for treatment. Moreover, the waste heat of the power plant can provide the temperature required for some reactions, so that the energy consumption of hydrothermal treatment of carbon dioxide can be reduced. Glycerin source, equipment are identical with embodiment 1. The filling rate of water is 30-70%, adding glycerin: NaOH (or KOH): CO in proportion to mass 2 =1:(2~5):(2~5) into the hydrothermal reactor. The temperature is 250~350℃, the reaction pressure is 5~10Mpa, the reaction time is 0.5~2h, and the product is used after the reaction 1 H-NMR qualitative and HPLC quantitative. Analysis results showed that the yield of formic acid was 30-55%, and ...

technical field

[0001] The invention relates to a hydrothermal reduction of CO using glycerol as a reducing agent 2 into formic acid, while glycerin itself is also converted into lactic acid. Specifically, under hydrothermal reaction conditions, glycerol is used to convert CO 2 The technology of reducing formic acid and converting glycerin itself into lactic acid at the same time belongs to the technical field of environmental engineering and the technical field of waste recycling. Background technique

[0002] by CO 2 The global warming effect caused by environmental pollution is one of the most concerned environmental problems in the world. If measures are not taken in time to reverse the trend of global warming, it will directly threaten the survival of human beings and the earth. but only through the CO 2 The emission reduction to control the greenhouse effect still cannot fully meet our requirements. CO 2 It is the final product of the combustion of all organic m...

Examples

Embodiment 1

[0022] With the increasing production of biodiesel (the annual production of biodiesel in my country is expected to reach 1 million tons in 2010 and 9 million tons in 2020), the by-product glycerin, which accounts for 10% of the total biodiesel production, is also increasing sharply. . Hydrothermal reduction of CO using biodiesel by-product glycerol as reductant 2 into formic acid, while glycerin itself is also converted into lactic acid process, not only can glycerin and CO 2 resources, and can reduce the production cost of biodiesel.

[0023] SUS316 stainless steel round tube tubular batch hydrothermal reactor was used for small-scale experiments. Glycerin comes from the by-product of biodiesel production plant, CO 2 for pure CO 2 , the filling rate of water in the hydrothermal reactor is 30-60%, and glycerol is added in proportion by mass: NaOH (or KOH): CO 2 =1:(1.9~4.9):(1~5) into the hydrothermal reactor. The temperature is 250~320℃, the reaction pressure is 5~14Mpa,...

Embodiment 2

[0025] CO 2 CO collected from coal chemical enterprises 2 , CO in coal-to-oil and coal-to-methanol industries 2 The emissions were 9.2 tons of CO 2 / ton of synthetic oil, 3.8 tons of CO 2 / ton of methanol, and CO in the exhaust gas 2 The purity is as high as 80-90%. The filling rate of glycerol source, equipment and water is the same as that of Example 1, and glycerin is added in proportion by mass: NaOH (or KOH): CO 2 =1:(2~5):(1~5) into the hydrothermal reactor. The temperature is 250~350℃, the reaction pressure is 5~5Mpa, the reaction time is 0.5~1.5h, and the product is used after the reaction 1 H-NMR qualitative and HPLC quantitative. Analysis results showed that the yield of formic acid was 30-65%, and the yield of lactic acid was 60-80%.

[0026] Industrial production can be used as figure 1 Process flow shown. The reaction conditions are controlled as follows: the temperature is 200°C to 400°C, the reaction pressure is 2 to 15Mpa, and glycerin: NaOH (or KOH)...

Embodiment 3

[0028] CO 2 CO captured from coal-fired power plants 2 . Currently, China's power sector emits 2.7 billion tons of CO2 per year 2 It ranks second in the world after the United States. Applying the present invention to the power sector, the waste CO emitted by it can be 2 The collection is passed into a hydrothermal reactor for treatment. Moreover, the waste heat of the power plant can provide the temperature required for some reactions, so that the energy consumption of hydrothermal treatment of carbon dioxide can be reduced. Glycerin source, equipment are identical with embodiment 1. The filling rate of water is 30-70%, adding glycerin: NaOH (or KOH): CO in proportion to mass 2 =1:(2~5):(2~5) into the hydrothermal reactor. The temperature is 250~350℃, the reaction pressure is 5~10Mpa, the reaction time is 0.5~2h, and the product is used after the reaction 1 H-NMR qualitative and HPLC quantitative. Analysis results showed that the yield of formic acid was 30-55%, and ...

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