CN103755548A - Method for hydrothermally converting CO2 into formic acid by hydrazine hydrate - Google Patents

Method for hydrothermally converting CO2 into formic acid by hydrazine hydrate Download PDF

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CN103755548A
CN103755548A CN201310746700.0A CN201310746700A CN103755548A CN 103755548 A CN103755548 A CN 103755548A CN 201310746700 A CN201310746700 A CN 201310746700A CN 103755548 A CN103755548 A CN 103755548A
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hydrazine hydrate
formic acid
hydrothermal
reaction
reactor
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CN103755548B (en
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金放鸣
陈飞燕
姚国栋
曾旭
霍志保
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Shanghai Jiaotong University
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides

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Abstract

The invention discloses a method for hydrothermally converting CO2 into formic acid by hydrazine hydrate. The method comprises the following steps: adding a CO2 reagent (CO2 gas, dry ice, Na2CO3, NaHCO3 and KHCO3) or automobile tail gas or industrial waste gas and the hydrazine hydrate into a hydrothermal reactor; and reacting under certain temperature and pressure to obtain the product formic acid. According to the method, under the condition that a catalyst is added, the CO2 conversion rate can be up to 23% to the maximum; under the condition that Ni is added to be used as the catalyst, the CO2 conversion rate can be up to 37% to the maximum. The hydrazine hydrate is a good hydrogen source and the problems that hydrogen is difficult to transport, is not easy to store, is flammable and combustible and is not safe and the like can be avoided. The process is simple in process and convenient to operate; the CO2 can be efficiently converted into a chemical product with a high addition value by low consumption.

Description

Hydrazine hydrate hydrothermal conversion CO 2for the method for formic acid
Technical field
The invention belongs to field of environment engineering technology and changing waste into resources utilizes field, be specifically related to a kind of hydrazine hydrate hydrothermal conversion CO 2for the method for formic acid.
Background technology
Along with consumption and the CO of fossil energy fuel 2the sustainable growth of quantity discharged, the Greenhouse effect that bring thus and energy shortage problem will be day by day serious.Since the Industrial Revolution, CO in atmosphere 2content has increased by 25%.In world wide, think CO in atmosphere 2quantity discharged increase is the root that causes terrestrial climate to warm.The consequence of Global warming, can make that Global Precipitation amount is redistributed, glacier and frozen soil melts, sea level rise etc., has both endangered the balance of natural ecosystems, more threaten the mankind's provand and living environment.According to the statistics of International Energy Agency (IEA), from 2006, the mankind discharged CO every year in atmosphere 2about 30,000,000,000 t, expect global CO in 2035 2quantity discharged will reach 35,400,000,000 t.CO 2itself is as abundant, cheap, clean, safe carbon resource, if can be reduced into other resources and make it recycle, this will be from solving the problem of Greenhouse effect and resource exhaustion in essence so.
At present, CO 2the main method of recycling has electrochemical reducing, photoreduction method and catalytic hydrogenating reduction method.Wherein catalytic hydrogenating reduction method is comparatively ripe effective means, but the additional H of this Technology Need 2as hydrogen source, H 2be a kind of stable, inflammable gas, transportation and storage are all inconvenient; Precious metals pd, Rh, Ir and Ru etc. are as catalyzer, high as catalyzer cost using precious metal.
Hydro-thermal reaction method is rise over nearly twenty or thirty year and become rapidly one of study hotspot of applied chemistry, hydro-thermal reaction (hydrothermal reaction) refers under high temperature (150 ℃～600 ℃) high pressure (2MPa～50MPa), the reaction process take water as solvent.According to (374 ℃ of the critical temperatures of water, 22MPa), hydro-thermal reaction can be divided into hypercritical hydrothermal reaction (supercritical water reaction) and subcritical water thermal response (subcritical water reaction).Compared with ortho-water, the reduced dielectric constant of high-temperature high pressure water, intermolecular hydrogen bond weakens, and isothermal compressibility improves, ion constant (K w) than normal-temperature water, almost increased by 10 3doubly.H in high-temperature water +and OH -ionic concn increases, and number acid base catalyzed reactions also can be carried out smoothly without acid base catalysator in the situation that.
Up to now, comprise that this research department utilizes hydrothermal technique to transform CO both at home and abroad 2for high added value organism all adopts Zn, the metals such as Fe are as reductive agent, but metallic reducing agent consumption is large and be difficult to recycle and reuse, and finding new reductive agent is a problem demanding prompt solution.
Summary of the invention
The object of the invention is to overcome the deficiency that above-mentioned prior art exists, a kind of hydrazine hydrate hydrothermal conversion CO is provided 2for the method for formic acid.Particularly, be under hydrothermal condition, utilize hydrazine hydrate as hydrogen source and reductive agent direct-reduction CO 2formic acid, reacted by product ammonia can be used as other purposes by Distillation recovery; Method of the present invention has realized CO 2resource utilization, there is the advantages such as technique is simple, easy to operate, non-secondary pollution.
The object of the invention is to be achieved through the following technical solutions:
The present invention relates to a kind of hydrazine hydrate hydrothermal conversion CO 2for the method for formic acid, using hydrazine hydrate as reductive agent, under hydrothermal reaction condition, by CO 2raw material direct-reduction formic acid.
Preferably, described CO 2raw material is CO 2reagent, vehicle exhaust or the discharge of highly energy-consuming factory containing high concentration CO 2waste gas.Highly energy-consuming factory refers to coal-burning power plant, steelworks etc.
Preferably, described CO 2reagent is CO 2gas, dry ice, Na 2cO 3, NaHCO 3or KHCO 3.
Preferably, described method specifically comprises the steps:
A, by CO 2raw material and hydrazine hydrate in molar ratio 1: (2～10) are placed in hydrothermal reactor, adding the liquid filling rate that water makes reactor is 25%～55%;
The temperature of B, control reactor is 250 ℃～350 ℃, and regulating the pressure of reactor is 2MPa～20MPa, and the reaction times is 2min～150min, can obtain reaction product formic acid.
Preferably, described hydrazine hydrate is liquid, and hydrazine hydrate volume percent content is 40%～85%.
Preferably, described CO 2the mol ratio of raw material and hydrazine hydrate is 1: (2～6).
Preferably, the temperature of described reactor is 250 ℃～325 ℃, and pressure is 2MPa～15MPa, and the reaction times is 30min～150min.
Preferably, described method also comprises using Powdered or block metal Ni as catalyzer.
Preferably, described Ni and CO 2the mol ratio of raw material is 1: (1～10).
Preferably, described Ni and CO 2the mol ratio of raw material is 1: (2～4).
Compared with prior art, tool of the present invention has the following advantages:
1, the present invention is by pure CO 2or the CO in waste gas 2change into useful industrial raw material formic acid, realized CO 2resource utilization, whole reaction process technique is simple, easy to operate, non-secondary pollution.
2, the present invention adopts liquid hydrazine hydrate as hydrogen source and reductive agent, has avoided hydrogen to be difficult for transportation and storage and the congruent problem of inflammable and explosive uneasiness.Meanwhile, reaction, without extra catalyst, has been avoided reuse and the sepn process of catalyzer, has reduced production cost, has considerable economic benefit.
3, the by product ammoniacal liquor obtaining in the present invention can pass through Distillation recovery, as other purposes.
Accompanying drawing explanation
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that other features, objects and advantages of the present invention will become:
Fig. 1 is that the present invention utilizes hydrazine hydrate to make the HPLC analysis of spectra of formic acid product;
Fig. 2 is the XRD analysis spectrogram of metal Ni after as catalyst reaction.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
embodiment 1
CO 2the CO collecting from coal-burning power plant 2.At present, the annual CO of China 2quantity discharged has reached 3,000,000,000 t and has accounted for 10% of global total amount, is only second to the U.S., occupies the 2nd, the whole world.It will be the main body of China's power supply that the primary energy source structure of China take coal as main body causes coal within one period quite growing future, and coal occupies more than 60% ratio all the time in primary energy source consumption, causes coal-burning power plant to become CO 2maximum emission source.The present invention is applied to power department, can be by the CO of its discharge 2passing into hydrothermal reactor processes.And a large amount of used heat of coal-burning power plant can provide reaction needed portion temperature, reduce hydrothermal treatment consists CO 2energy consumption, realize CO 2low consumption resource utilization.
In lab scale experiment, adopt the tubular type intermittent type hydrothermal reactor of SUS316 stainless pipe to test, by CO 2within 1: 4 in molar ratio, add in reactor with hydrazine hydrate, adding the filling ratio that water makes reactor is 35%, sealed reactor.Controlling temperature of reaction is 300 ℃, reaction pressure 12MPa, and reaction times 100min, carries out HPLC qualitative and quantitative analysis to product liquid after reaction, as shown in Figure 1.Analytical results shows, formic acid is primary product, and productive rate can reach 18%, and product is attended by a small amount of acetic acid.
Coal-burning power plant can select suitable hydrothermal reactor according to demand, can control temperature of reaction at 250 ℃～350 ℃, and reaction pressure is at 2MPa～20MPa, and the addition of hydrazine hydrate is for entering the total CO of conversion unit 22～10 times (with molar ratio notes) of content, reaction 30min～180min.After reaction finishes, product is mainly formic acid, and follows a small amount of acetic acid, and remaining ammoniacal liquor can be used as other purposes by Distillation recovery.
By above-mentioned reaction, CO 2can be converted in a large number formic acid, meanwhile, the obnoxious flavour SO in coal-burning power plant's waste gas x, NO xcan be soluble in water under hydrothermal condition, reduced the harm that obnoxious flavour causes atmosphere, and SO soluble in water x, NO xcan not affect CO 2reduction effect.Effectively utilize the waste gas CO of coal-burning power plant 2and used heat, under hydrothermal condition, realize CO 2recycling, not only can obtain the new energy, can also reduce greenhouse gases CO 2discharge, can make certain contribution to slowing down lack of energy and Global warming.
embodiment 2
CO 2the CO collecting from coal-burned industrial boiler 2.According to measuring and calculating, the existing coal-burned industrial boiler of China approximately has 480,000, total evaporation approximately 2,500,000 t/h.Industrial Boiler is the coal user of national the second maximum, and the annual coal consuming reaches 6.4 hundred million tons of left and right.Coal-burned industrial boiler evenly heat efficiency only has an appointment 60%～65%, the CO of annual Industrial Boiler discharge 2there are 700,000,000 5,000 ten thousand tons, SO 2there is 6,000,000 tons, 6,300,000 tons and dust.The applying unit of coal-burned industrial boiler is different from power plant, and one scale is all smaller.For this present situation, can, at each coal-burning power plant's configuration hydro-thermal reaction device, collect the waste gas of its discharge and process.
In lab scale experiment, adopt the tubular type intermittent type hydrothermal reactor of SUS316 stainless pipe to test, by CO 2within 1: 4 in molar ratio, add in reactor with hydrazine hydrate, Ni powder adds in reactor together as catalyzer, makes CO 2with the mol ratio of Ni powder be 1: 2, then to add the filling ratio that water makes reactor be 35%, sealed reactor.Controlling temperature of reaction is 300 ℃, reaction pressure 12MPa, reaction times 30min.After reaction, product liquid is carried out to HPLC qualitative and quantitative analysis, analytical results shows, formic acid is primary product, and product is attended by a small amount of acetic acid.Meanwhile, collect that reacted solid sample is washed and ethanol is washed, carry out XRD qualitative analysis after oven dry, as shown in Figure 2, after metal Ni reaction, form does not change analytical results, shows that Ni participates in reaction as catalyzer.
Coal-burned industrial boiler can be selected suitable hydrothermal reactor according to demand, can control temperature of reaction at 250 ℃～325 ℃, and reaction pressure is at 2MPa～15MPa, and the addition of hydrazine hydrate is for entering the total CO of conversion unit 21～8 times of content (with molar ratio note), metal Ni as the addition of catalyzer for entering the total CO of conversion unit 21～4 times (with molar ratio note) of content, reaction 5min～150min.After reaction finishes, product is mainly formic acid, and follows a small amount of acetic acid, and remaining ammoniacal liquor can be used as other purposes by Distillation recovery, and catalyzer can recycling use.
Through above-mentioned reaction, CO 2can be converted in a large number formic acid, meanwhile, the obnoxious flavour SO in coal-burned industrial boiler waste gas 2can be soluble in water under hydrothermal condition, reduced the harm that obnoxious flavour causes atmosphere, and SO soluble in water 2can be to CO 2reduction effect exert an influence.Coal-burned industrial boiler quantity is large, small scale, CO 2be difficult to focus on, can use present method according to the specification of coal-burned industrial boiler, independent hydro-thermal reaction treater is set, not only can obtain the new energy, can also reduce CO 2and the discharge of obnoxious flavour.
embodiment 3
CO 2the CO collecting from garbage burning factory 2.At present, burning city domestic garbage is one of important method of rubbish processing to be harmless, have the remarkable advantages such as the appearance of subtracting, decrement and energy recovery, but a large amount of CO is discharged in waste incineration meeting 2isothermal chamber gas.According to calculating, the CO of the annual discharge of most of garbage burning factories 2also more than power plant.For this present situation, can, at each garbage burning factory configuration hydro-thermal reaction device, collect the waste gas of its discharge as CO 2raw material carries out hydrothermal conversion, and meanwhile, a large amount of heat energy that waste incineration produces can be hydrothermal conversion provides reaction required temperature, has reduced CO 2the running cost of hydrothermal conversion.
In lab scale experiment, adopt the tubular type intermittent type hydrothermal reactor of SUS316 stainless pipe to test, by CO 2within 1: 6 in molar ratio, add in reactor with hydrazine hydrate, adding the filling ratio that water makes reactor is 35%, sealed reactor.Controlling temperature of reaction is 325 ℃, reaction pressure 18MPa, reaction times 90min.After reaction, product liquid is carried out to HPLC qualitative and quantitative analysis.Analytical results shows, formic acid is primary product, and product is attended by a small amount of acetic acid.
Garbage burning factory can be selected suitable hydrothermal reactor according to demand, can control temperature of reaction at 250 ℃～350 ℃, and reaction pressure is at 2MPa～20MPa, and the addition of hydrazine hydrate is for entering the total CO of conversion unit 21～10 times (with molar ratio note) of content, reaction 60min～180min.After reaction finishes, product is mainly formic acid, and follows a small amount of acetic acid, and remaining ammoniacal liquor can be used as other purposes by Distillation recovery.
By above-mentioned reaction, CO 2can be converted in a large number formic acid.Meanwhile, a large amount of heat energy that waste incineration produces can be CO 2hydrothermal conversion provide reaction required temperature.Therefore, present method not only can reduce CO 2discharge, obtain the new energy, can also effectively utilize the heat energy of garbage burning factory.
embodiment 4
CO 2the CO collecting from Steel Plant 2.The continuous more than ten years of China's iron and steel output occupy the first in the world, have also consumed a large amount of fossil oils simultaneously, give off a large amount of greenhouse gases CO 2.According to calculating, Iron And Steel Industry CO 2quantity discharged accounts for CO 214% of total release.Therefore, Iron And Steel Industry is China CO 2the key industry reducing discharging, and collect the CO of its discharge 2carrying out hydrothermal resources processing is a kind of effectively reduction of discharging approach.
In lab scale experiment, adopt the tubular type intermittent type hydrothermal reactor of SUS316 stainless pipe to test, by CO 2within 1: 2 in molar ratio, add in reactor with hydrazine hydrate, simultaneously by CO 2be to add reactor at 1: 4 in molar ratio with Ni powder, then to add the filling ratio that water makes reactor be 25%, sealed reactor.Controlling temperature of reaction is 275 ℃, reaction pressure 10MPa, reaction times 60min.After reaction, product liquid is carried out to HPLC qualitative and quantitative analysis, analytical results shows, formic acid is primary product, and product is attended by a small amount of acetic acid.Meanwhile, collect that reacted solid sample is washed and ethanol is washed, carry out XRD qualitative analysis after oven dry, analytical results shows, after metal Ni reaction, form does not change, and shows that Ni participates in reaction as catalyzer.
Steel Plant can select suitable hydrothermal reactor according to our factory's demand, can control temperature of reaction at 250 ℃～350 ℃, and reaction pressure is at 2MPa～20MPa, and the addition of hydrazine hydrate is for entering the total CO of conversion unit 21～6 times of content (with molar ratio note), metal Ni as the addition of catalyzer for entering the total CO of conversion unit 21～10 times (with molar ratio note) of content, reaction 10min～150min.After reaction finishes, product is mainly formic acid, and follows a small amount of acetic acid, and remaining ammoniacal liquor can be used as other purposes by Distillation recovery, and catalyzer can recycling use.
Through above-mentioned reaction, CO 2can be converted in a large number formic acid.Meanwhile, the obnoxious flavour in discarding can be soluble in water under hydrothermal condition, do not affect CO 2hydrothermal conversion effect.In addition, the used heat that Steel Plant produce can be CO 2hydrothermal conversion provides portion temperature, has reduced the running cost of reaction.Therefore, present method not only can be by CO 2be converted into the energy, reduce CO 2discharge, can also reduce obnoxious flavour and enter atmosphere, effectively utilize used heat, be the method for killing three birds with one stone.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.

Claims (10)

1. a hydrazine hydrate hydrothermal conversion CO 2for the method for formic acid, it is characterized in that, using hydrazine hydrate as reductive agent, under hydrothermal reaction condition, by CO 2raw material direct-reduction formic acid.
2. hydrazine hydrate hydrothermal conversion CO as claimed in claim 1 2for the method for formic acid, it is characterized in that described CO 2raw material is CO 2reagent, vehicle exhaust or the discharge of highly energy-consuming factory containing high concentration CO 2waste gas.
3. hydrazine hydrate hydrothermal conversion CO as claimed in claim 2 2for the method for formic acid, it is characterized in that described CO 2reagent is CO 2gas, dry ice, Na 2cO 3, NaHCO 3or KHCO 3.
4. the hydrazine hydrate hydrothermal conversion CO as described in any one in claim 1～3 2for the method for formic acid, it is characterized in that, described method specifically comprises the steps:
A, by CO 2raw material and hydrazine hydrate in molar ratio 1: (2～10) are placed in hydrothermal reactor, adding the liquid filling rate that water makes reactor is 25%～55%;
The temperature of B, control reactor is 250 ℃～350 ℃, and regulating the pressure of reactor is 2MPa～20MPa, and the reaction times is 2min～150min, can obtain reaction product formic acid.
5. hydrazine hydrate hydrothermal conversion CO as claimed in claim 4 2for the method for formic acid, it is characterized in that, described hydrazine hydrate is liquid, hydrazine hydrate volume percent content is 40%～85%.
6. hydrazine hydrate hydrothermal conversion CO as claimed in claim 4 2for the method for formic acid, it is characterized in that described CO 2the mol ratio of raw material and hydrazine hydrate is 1: (2～6).
7. hydrazine hydrate hydrothermal conversion CO as claimed in claim 4 2for the method for formic acid, it is characterized in that, the temperature of described reactor is 250 ℃～325 ℃, and pressure is 2MPa～15MPa, and the reaction times is 30min～150min.
8. hydrazine hydrate hydrothermal conversion CO as claimed in claim 4 2for the method for formic acid, it is characterized in that, described method also comprises using Powdered or block metal Ni as catalyzer.
9. hydrazine hydrate hydrothermal conversion CO as claimed in claim 8 2for the method for formic acid, it is characterized in that described Ni and CO 2the mol ratio of raw material is 1: (1～10).
10. hydrazine hydrate hydrothermal conversion CO as claimed in claim 9 2for the method for formic acid, it is characterized in that described Ni and CO 2the mol ratio of raw material is 1: (2～4).
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