CN102614769A - Method for converting carbon dioxide in smoke into formic acid under normal pressure - Google Patents
Method for converting carbon dioxide in smoke into formic acid under normal pressure Download PDFInfo
- Publication number
- CN102614769A CN102614769A CN2012100551378A CN201210055137A CN102614769A CN 102614769 A CN102614769 A CN 102614769A CN 2012100551378 A CN2012100551378 A CN 2012100551378A CN 201210055137 A CN201210055137 A CN 201210055137A CN 102614769 A CN102614769 A CN 102614769A
- Authority
- CN
- China
- Prior art keywords
- absorbent
- carbon dioxide
- hydrogen donor
- reaction
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
A method for converting carbon dioxide in smoke into formic acid under normal pressure is used for resolving the problem of resource utilization of carbon dioxide. According to the method, an absorbent is sprayed downwards from a spray absorber so as to spray the smoke which is led to the inside of the absorber from the lower portion of the absorber and achieve full reaction of carbon dioxide and the absorbent. The reaction is produced under the pressure of 0.1-0.15Mpa, potential of hydrogen (pH) of the reaction ranges from 8-12, and reaction temperature ranges from 20-85 DEG C. The absorbent is composed of a hydrogen donor reagent, a solvent and a catalyst. The method has the advantages of being simple in equipment, easy to operate, stable in running, high in absorbent utilization ratio, easy in product disposal, convenient to popularize and apply and the like. The method is not only suitable for large boilers, but also suitable for middle and small boilers and other technical fields of carbon dioxide resource utilization, and has broad application prospects.
Description
Technical field
The present invention relates to a kind of carbon dioxide recovery and trans-utilization method, particularly under normal pressure with flue gas in carbon dioxide be converted into the method for formic acid.
Background technology
Greenhouse effects are the natural processes that earn a bare living and exist, and do not have greenhouse effects, and surface temperature will drop to-18 ℃ from present average 15 ℃, and the mankind can't live on earth.Yet; Frequent day by day mankind's activity especially increases gas concentration lwevel to the dependence of fossil fuel greatly; Carbon dioxide accounts for 55% of greenhouse gases; Wherein 80% carbon dioxide comes from the burning of fossil fuel (like coal, oil, natural gas); The carbon dioxide excessive emissions has increased the weight of greenhouse effects greatly, and Tab phenolphthaleinum causes that melt in glacier, the two poles of the earth, sea level rise and land is flooded, ocean current changes and the taking place frequently of natural calamity such as EI Nino thereafter, thus greenhouse gases especially carbon dioxide discharge-reduction and utilization seem particularly important.The measure of control CO2 emission mainly contains: select environment-friendly type, the renewable energy; Improve energy utilization rate; Collecting carbonic anhydride; Carbon dioxide recovery and trans-utilization.Wherein, the carbon dioxide recycling becomes the hot issue of research gradually.At present, the limiting factor of carbon dioxide recycling mainly comprises: higher collecting carbonic anhydride, separation, purification and freight; The energy demand that carbon dioxide transforms is like raw material and co-reactant; It is the shortage used of the chemical substance on basis etc. that the limited market demand, lower investment return and industry go up with the carbon dioxide.Traditional carbon dioxide trans-utilization technology is mostly carried out under HTHP, and energy consumption is higher, complicated operation, and the equipment safety in operation is lower; Catalyst that uses and material are also all expensive, and economy and operating cost are higher.Therefore, how reducing reaction and operating cost, cut down the consumption of energy, realize effective conversion of carbon dioxide under temperate condition, improve carbon dioxide conversion, is the emphasis and the difficult point of carbon dioxide trans-utilization problem.
Summary of the invention
Problem to be solved by this invention provide simple, the low operating cost of a kind of equipment low, easy to implement under normal pressure with flue gas in carbon dioxide be converted into the method for formic acid.
The alleged problem of the present invention is solved by following technical scheme:
Under a kind of normal pressure carbon dioxide in the flue gas is converted into the method for formic acid; Its special feature is: transform and in spray absorber, carry out; Absorbent is sprayed down from spraying top, absorption tower; Absorbent sprays the flue gas of being introduced in the tower by the tower bottom, realizes the abundant reaction of carbon dioxide and absorbent; Carry out under the said pressure that is reflected at 0.1～0.15Mpa, reaction pH scope is 8～12, and range of reaction temperature is 20 ℃～85 ℃; Said absorbent is made up of hydrogen donor reagent, solvent and catalyst, and said hydrogen donor reagent is one or more mixtures in lithium aluminium hydride reduction, sodium borohydride, isopropyl alcohol or the cyclohexanol, and the concentration of hydrogen donor reagent is 1.860～4.960mol/L in the absorbent; Said solvent is the mixed solution of one or both and high purity water of methyl alcohol, ethanol, and the volume ratio of methyl alcohol, ethanol and high purity water is 2:8～9:1 in the mixed solution; Said catalyst is titanium dichloride load platinum complex (Pt/TiO
2), lanthanum/strontium/di-iron trioxide complex (La/Sr/Fe
2O
3) and ruthenium/complex of iridium (Ru/Ir) in a kind of or its mixture, its amount with respect to hydrogen donor reagent is 0.01%～0.05% (wt).
Under the above-mentioned normal pressure carbon dioxide in the flue gas is converted into the method for formic acid: said absorbent preparation is carried out as follows: get hydrogen donor reagent, solvent and catalyst by proportioning; Earlier one or both and high purity water in methyl alcohol, the ethanol are mixed into homogeneous solution, with NaOH pH value of solution are adjusted between 8～12, more at ambient temperature; Add catalyst; Left standstill 3～5 minutes, and added hydrogen donor then in proportion, mix to add to and hold in the liquid bath.
Under the above-mentioned normal pressure carbon dioxide in the flue gas is converted into the method for formic acid; Said spray absorber bottom is provided with collecting tank; Outer with being arranged on tower successively reaction displacement pool, the filtering separation device of collecting tank is communicated with, and the reactant liquor of being collected by collecting tank obtains the formic acid product after reaction displacement, isolated by filtration.
The present invention is directed to problems such as traditional carbon dioxide trans-utilization technology energy consumption is higher, complicated operation, investment operating cost height; Proposed that a kind of (realize the technology of carbon dioxide recycling 0.1～0.15Mpa) time: the present invention is under condition of normal pressure at normal pressure; In spray absorber, add a certain amount of absorbent; Described absorbent can be realized effective conversion of carbon dioxide; For the carbon dioxide volume fraction is 10.6% ~ 18.1% simulated flue gas, and the carbon dioxide transformation efficiency can reach 57.96%.Experiment shows that the present invention has characteristics such as equipment is simple, easy and simple to handle, stable, and the absorbent utilization rate is high, and product is prone to handle, and is easy to utilize.The present invention is not only applicable to large-sized boiler, and is applicable to medium and small boiler and other carbon dioxide application technology as the second resource field, has broad application prospects.
Description of drawings
Fig. 1 is that Fig. 1 of the present invention is the process flow diagram of the inventive method.
The label implication is following among the figure: 1. spray absorber; 1-1. collecting tank; 2. booster fan; 3. chimney; 4. demister; 5. circulating pump; 6. slush pump; 7. hold liquid bath; 8. reaction displacement pool; 9. filtering separation device.
The specific embodiment
Referring to Fig. 1; The present invention utilizes spray absorber 1; Respectively the absorbent that tower bottom collecting tank 1-1 and tower are held in the liquid bath 7 is pumped into tower top outward by circulating pump 5, slush pump 6, to being sprayed by the flue gas of booster fan 2 in tower is introduced in the tower bottom, flue gas is in up process; Carbon dioxide and absorbent that it contains fully react; Realize that (0.1～0.15Mpa), the pH scope is 8～12, and reaction temperature is that 20 ℃～85 ℃ condition carbon dioxides and absorbent reaction conversion are the process of formic acid under the normal pressure.Flue gas through reaction purifies is discharged through demister 4, top of tower exhanst gas outlet, chimney 3.Above-mentioned course of reaction is guidance with Related Mechanism such as catalytic transfer hydrogenations, under the catalyst existence condition, realizes that absorbent reagent is the hydro-conversion of hydrogen donor to carbon dioxide, and finally generates product such as formic acid.Said hydrogen donor comprises lithium aluminium hydride reduction LiAlH
4, sodium borohydride NaBH
4, isopropyl alcohol CH
3-CHOH-CH
3And cyclohexanol, reaction mechanism is distinguished as follows:
CO
2+LiAlH
4+3H
2O→HCOOLi+Al(OH)
3+3H
2
2CO
2+2NaBH
4→2HCOONa+B
2H
6
CO
2+ CH
3-CHOH-CH
3→ HCOOH+CH
3-CO-CH
3(acetone)
CO
2+ C
6H
11OH (cyclohexanol) → HCOOH+C
6H
10O (cyclohexanone).
Regularly to the hydrops suction reaction displacement pool 8 among the collecting tank 1-1 of spray absorber bottom; Reclaim through filtering 9 pairs of product of separator again; Concrete grammar is following: when with isopropyl alcohol or ring ethanol during as hydrogen donor; Adopt centrifugal, filter plant that the product in the reaction displacement pool is carried out Separation of Solid and Liquid, in 56.05 ℃～100 ℃ scopes to liquid distill, purifying obtains sodium formate; When lithium aluminium hydride reduction or sodium borohydride during as hydrogen donor, centrifugal, the solid product that need be dissolved in water after filtering obtains organic acid sodium solid product at 100 ℃ through distillation, separation, drying.
Absorbent according to the invention is made up of hydrogen donor reagent, solvent and catalyst; Wherein hydrogen donor reagent is one or more mixtures in lithium aluminium hydride reduction, sodium borohydride, isopropyl alcohol or the cyclohexanol, and the concentration of hydrogen donor reagent is 1.860～4.960mol/L in the absorbent; Said solvent is the mixed solution of one or both and high purity water of methyl alcohol, ethanol, and the volume ratio of methyl alcohol, ethanol and high purity water is 2:8～9:1 in the mixed solution; Said catalyst is Pt/TiO
2, La/Sr/Fe
2O
3With one or more mixtures of Ru/Ir, catalyst is 0.01%～0.05% (wt) with respect to the amount of hydrogen donor reagent.Above-mentioned absorbent preparation is carried out as follows: get hydrogen donor reagent, solvent and catalyst by proportioning; Earlier one or both and high purity water in methyl alcohol, the ethanol are mixed into homogeneous solution, with NaOH pH value of solution are adjusted between 8～12, more at ambient temperature; Add catalyst; Left standstill 3～5 minutes, and added hydrogen donor reagent then in proportion, mix to add to and hold in the liquid bath.
Test shows that working as absorbent prepares according to following condition: be ethanol with the volume ratio: ultra-pure water=4:6 prepares solvent; With the sodium borohydride is hydrogen donor, and hydrogen donor mol/L is 3.053; With TiO
2+ Fe
2O
3+ Ir is catalyst, wherein TiO
2: Fe
2O
3: Ir is 2:4:4, and catalyst is 0.03%～0.05% (wt) with respect to the amount of hydrogen donor reagent, and absorbent can reach 57.96% to carbon dioxide transformation efficiency in the flue gas.
The carbon dioxide content relation is in absorbent consumption and the flue gas:
In the formula (1),
Be the mass concentration of hydrogen donor in the absorbent, g/L;
For the volume fraction of carbon dioxide in the flue gas, 10.6% ~ 18.1%;
Be flue gas volume, L/s;
For the moles of gas volume, reacting gas is regarded as perfect gas, get 22.4L/mol;
And
Be respectively hydrogen donor and CO in the chemical equation
2Stoichiometric number;
Be hydrogen donor molal weight, g/mol;
Be absorbent volume, L.
The embodiment of several preparation absorbents below is provided:
Embodiment 1: get methyl alcohol 0.03L, high purity water 0.12L, take by weighing hydrogen donor reagent lithium aluminium hydride reduction 10.588g, take by weighing catalyst Pt/TiO
2Be total to 0.0011g with two kinds of complexs of Ru/Ir, the catalyst mix ratio is 7:3.By above-mentioned absorbent configuration proportion, methyl alcohol and high purity water are mixed into homogeneous solution, with NaOH pH value of solution is adjusted to 8; Again at ambient temperature, add catalyst, left standstill 3～5 minutes; It is even to add the hydrogen donor reagent mix then; Promptly make absorbent, the concentration of hydrogen donor reagent is 1.860mol/L in the absorbent, the absorbent for preparing is added to hold (volume is 100L) in the liquid bath.
Embodiment 2: get methyl alcohol 0.06L, high purity water 0.09L, take by weighing hydrogen donor reagent sodium borohydride 14.136g, take by weighing catalyst Pt/TiO
2And La/Sr/Fe
2O
3Two kinds of complexs are total to 0.0028g, and mixed proportion is 6:4.By above-mentioned absorbent configuration proportion, methyl alcohol and high purity water are mixed into homogeneous solution, with NaOH pH value of solution is adjusted to 9; Again at ambient temperature, add catalyst, left standstill 3～5 minutes; It is even to add the hydrogen donor reagent mix then; Promptly make absorbent, the concentration of hydrogen donor reagent is 2.480mol/L in the absorbent, the absorbent for preparing is added to hold (volume is 100L) in the liquid bath.
Embodiment 3: get ethanol 0.06L, high purity water 0.09L, take by weighing hydrogen donor reagent sodium borohydride 17.402g, take by weighing catalyst Pt/TiO
2, La/Sr/Fe
2O
3Be total to 0.0087g with the Ru/Ir complex, mixed proportion is 2:4:4.By above-mentioned absorbent configuration proportion, ethanol and high purity water are mixed into homogeneous solution, with NaOH pH value of solution is adjusted to 10; Again at ambient temperature, add catalyst, left standstill 3～5 minutes; It is even to add the hydrogen donor reagent mix then; Promptly make absorbent, the concentration of hydrogen donor reagent is 3.053mol/L in the absorbent, the absorbent for preparing is added to hold (volume is 150L) in the liquid bath.
Embodiment 4: get ethanol 0.105L, high purity water 0.045L, measure hydrogen donor reagent cyclohexanol 53.980g, take by weighing catalyst La/Sr/Fe
2O
3Be total to 0.0216g with the Ru/Ir complex, mixed proportion is 8:2.By above-mentioned absorbent configuration proportion, ethanol and high purity water are mixed into homogeneous solution, with NaOH pH value of solution is adjusted to 11; Again at ambient temperature, add catalyst, left standstill 3～5 minutes; It is even to add the hydrogen donor reagent mix then; Promptly make absorbent, the concentration of hydrogen donor reagent is 3.593mol/L in the absorbent, the absorbent for preparing is added to hold (volume is 150L) in the liquid bath.
Embodiment 5: get ethanol 0.12L, high purity water 0.03L, measure hydrogen donor reagent isopropyl alcohol 39.420g, take by weighing catalyst Pt/TiO
2, La/Sr/Fe
2O
3Be total to 0.0197g with the Ru/Ir complex, mixed proportion is 4:4:2.By above-mentioned absorbent configuration proportion, ethanol and high purity water are mixed into homogeneous solution, with NaOH pH value of solution is adjusted to 9; Again at ambient temperature, add catalyst, left standstill 3～5 minutes; It is even to add the hydrogen donor reagent mix then; Promptly make absorbent, the concentration of hydrogen donor reagent is 4.380mol/L in the absorbent, the absorbent for preparing is added to hold (volume is 150L) in the liquid bath.
Embodiment 6: get methyl alcohol 0.045L, high purity water 0.105L, take by weighing hydrogen donor reagent lithium aluminium hydride reduction 12.142g, take by weighing catalyst Pt/TiO
2Be total to 0.0036g with the Ru/Ir complex, mixed proportion is 3:7.By above-mentioned absorbent configuration proportion, methyl alcohol and high purity water are mixed into homogeneous solution, with NaOH pH value of solution is adjusted to 12; Again at ambient temperature, add catalyst, left standstill 3～5 minutes; It is even to add the hydrogen donor reagent mix then; Promptly make absorbent, the concentration of hydrogen donor reagent is 2.133mol/L in the absorbent, the absorbent for preparing is added to hold (volume is 150L) in the liquid bath.
Claims (3)
1. under the normal pressure carbon dioxide in the flue gas is converted into the method for formic acid; It is characterized in that: said conversion is carried out in spray absorber, and from spraying the spray of top, absorption tower down, absorbent sprays the flue gas of being introduced in the tower by the tower bottom with absorbent; Realize the abundant reaction of carbon dioxide and absorbent; Carry out under the said pressure that is reflected at 0.1～0.15Mpa, reaction pH scope is 8～12, and range of reaction temperature is 20 ℃～85 ℃; Said absorbent is made up of hydrogen donor reagent, solvent and catalyst, and said hydrogen donor reagent is one or more mixtures in lithium aluminium hydride reduction, sodium borohydride, isopropyl alcohol or the cyclohexanol, and the concentration of hydrogen donor reagent is 1.860～4.960mol/L in the absorbent; Said solvent is the mixed solution of one or both and high purity water of methyl alcohol, ethanol, and the volume ratio of methyl alcohol, ethanol and high purity water is 2:8～9:1 in the mixed solution; Said catalyst is a kind of or its mixture in titanium dichloride load platinum complex, lanthanum/strontium/di-iron trioxide complex and the ruthenium/complex of iridium, and its amount with respect to hydrogen donor reagent is 0.01%～0.05% (wt).
2. under the normal pressure according to claim 1 carbon dioxide in the flue gas is converted into the method for formic acid; It is characterized in that: said absorbent preparation is carried out as follows: get hydrogen donor reagent, solvent and catalyst by proportioning; Earlier one or both and high purity water in methyl alcohol, the ethanol are mixed into homogeneous solution, with NaOH pH value of solution are adjusted between 8～12, more at ambient temperature; Add catalyst; Left standstill 3～5 minutes, and added hydrogen donor then in proportion, mix to add to and hold in the liquid bath.
3. under the normal pressure according to claim 2 carbon dioxide in the flue gas is converted into the method for formic acid; It is characterized in that: said spray absorber bottom is provided with collecting tank; Outer with being arranged on tower successively reaction displacement pool, the filtering separation device of collecting tank is communicated with, and the reactant liquor of being collected by collecting tank obtains the formic acid product after reaction displacement, isolated by filtration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210055137.8A CN102614769B (en) | 2012-03-05 | 2012-03-05 | Method for converting carbon dioxide in smoke into formic acid under normal pressure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210055137.8A CN102614769B (en) | 2012-03-05 | 2012-03-05 | Method for converting carbon dioxide in smoke into formic acid under normal pressure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102614769A true CN102614769A (en) | 2012-08-01 |
| CN102614769B CN102614769B (en) | 2014-04-16 |
Family
ID=46555186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210055137.8A Expired - Fee Related CN102614769B (en) | 2012-03-05 | 2012-03-05 | Method for converting carbon dioxide in smoke into formic acid under normal pressure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102614769B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2765430A1 (en) * | 2009-06-26 | 2010-12-29 | Basf Se | Method for producing formic acid |
| CN102010291A (en) * | 2010-11-30 | 2011-04-13 | 同济大学 | Method for producing formic acid and preparing acetone through hydrothermal reduction of CO2 by isopropanol |
| CA2774151A1 (en) * | 2010-06-29 | 2012-01-05 | Basf Se | Process for preparing formic acid by reaction of carbon dioxide with hydrogen |
-
2012
- 2012-03-05 CN CN201210055137.8A patent/CN102614769B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2765430A1 (en) * | 2009-06-26 | 2010-12-29 | Basf Se | Method for producing formic acid |
| CA2774151A1 (en) * | 2010-06-29 | 2012-01-05 | Basf Se | Process for preparing formic acid by reaction of carbon dioxide with hydrogen |
| CN102010291A (en) * | 2010-11-30 | 2011-04-13 | 同济大学 | Method for producing formic acid and preparing acetone through hydrothermal reduction of CO2 by isopropanol |
Non-Patent Citations (4)
| Title |
|---|
| SUMIT CHAKRABORTY等: "Catalytic properties of nickel bis(phosphinite) pincer complexes in the reduction", 《POLYHEDRON》 * |
| 尹传奇等: "过渡金属钌配合物催化氢化CO2生成甲酸的反应", 《武汉工程大学学报》 * |
| 尹传奇等: "钌配合物催化氢化CO2生成甲酸反应中的醇促进效应", 《化学学报》 * |
| 赵毅，张自丽: "催化氢化二氧化碳研究进展", 《华东电力》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102614769B (en) | 2014-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11668266B2 (en) | Total recycling system of capturing, conversion and utilization of flue gas from factory, power plant and refinery | |
| Liu et al. | Energy-saving pathway exploration of CCS integrated with solar energy: A review of innovative concepts | |
| CN104959158B (en) | Mo2C/CdS composite photocatalyst and preparation and application thereof | |
| CN104084228A (en) | Oxygen-doped carbon nitride/zinc oxide photo-catalyst as well as preparation method and application thereof | |
| CN102145287B (en) | Preparation method of catalyst for synthesizing methanol from hydrogenated carbon dioxide | |
| CA2958502A1 (en) | Hydrogen purification device protection system and method based on methanol-water mixture reforming hydrogen production system | |
| CN111547678B (en) | Method and system for preparing methanol by full-component thermal catalysis of marsh gas | |
| CN101757943B (en) | Catalyst for synthesizing methanol by hydrogenating carbon dioxide, preparation method and application thereof | |
| CN104232195A (en) | Method for jointly producing methanol and synthetic natural gas by utilizing coke oven gas | |
| CN111039258A (en) | Methanol-water reforming hydrogen production system based on solar fuel | |
| CN104725230A (en) | Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate | |
| CN105771974A (en) | Catalyst for producing hydrogen by catalyzing decomposition of formate at room temperature | |
| CN110183683A (en) | A kind of green technological process of novel degraded macromolecular amount lignin | |
| CN102600852B (en) | Catalyst for preparing dimethyl ether as well as preparation method and application thereof | |
| CN101857204B (en) | Process and device for purifying sulfuric acid phase in iodine and sulfur cycle under low pressure | |
| CN107777660B (en) | Aluminum water reaction continuous hydrogen production device and method | |
| CN105126821A (en) | Flower-like Bi2MoO6 preparation and applications of flower-like Bi2MoO6 in photocatalytic reduction of CO2 | |
| CN201510842U (en) | Double-loop hollow tower spray and tower body demisting air flue integrating device | |
| Sharma et al. | A comprehensive study on production of methanol from wind energy | |
| WO2015161676A1 (en) | Method for removing nitrogen oxides in flue gas and nano flue gas denitration system | |
| CN102614769B (en) | Method for converting carbon dioxide in smoke into formic acid under normal pressure | |
| CN102464544A (en) | Method for hydrothermally reducing CO2 or CO into methane by using porous nickel catalyst | |
| CN104028304A (en) | Catalyst for converting methyl isobutyl ketone into 2-methylpentane and preparation method of catalyst | |
| CN105194996B (en) | A kind of method of comprehensive utilization of yellow phosphoric tail gas | |
| CN106964380A (en) | A kind of three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst and preparation method and applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140416 Termination date: 20200305 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |