CN104892357A - Methanol and aluminum-silicon alloy synchronous production method utilizing industrial waste gas - Google Patents
Methanol and aluminum-silicon alloy synchronous production method utilizing industrial waste gas Download PDFInfo
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- CN104892357A CN104892357A CN201510105989.7A CN201510105989A CN104892357A CN 104892357 A CN104892357 A CN 104892357A CN 201510105989 A CN201510105989 A CN 201510105989A CN 104892357 A CN104892357 A CN 104892357A
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- China
- Prior art keywords
- gas
- raw material
- methanol
- methyl alcohol
- carbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
Abstract
A method for preparing methanol and metahnol derivatives by utilizing industrial waste gas as unique CO2 source is provided. According to the method, CO is produced by partially reducing CO2 in industrial waste gas as a production raw material (also a unique oxidizing agent), a reducing agent adopts a carbon raw material, and purified (or unpurified) CO enters a methanol production line and is transformed into methanol and methanol derivatives after hydrogen is added. Methanol and methanol derivatives can be used for producing liquid fuel or further transformed into synthetic hydrocarbons and products thereof. At the same time, the final product of the carbon raw material contains a large amount of aluminum-silicon alloy.
Description
Technical field
The present invention relates to the exhaust gas conversion of industrial discharge is the method for methyl alcohol and aluminum silicon alloy, belongs to energy and environment systems engineering and recycling waste technical field.
Background technology
Pertinent literature investigation finds, existing research only concentrates on separately the environmental protection of carbon emission reduction and the standby method of Methanol.Power plant aspect is only by CO
2trap and seal up for safekeeping, failing effectively to utilize CO
2, this results in the high cost of carbon trapping, the high running cost that domestic several carbon trapping pilot project faces is verified, and the road that present stage is walked " carbon traps+seal up for safekeeping " is difficult to possible economically.In fact, this research discloses CO
2also be a kind of carbon resource of preciousness, and Chemical Manufacture aspect only consider independent Methanol for production process, CO
2utilization be also only limitted to the high concentration CO of metallurgy, chemical enterprise
2flue gas, and have ignored this maximum carbon source of coal-burning power plant, or according to the traditional concept of chemical industry aspect, thinks thermal power plant lower concentration CO
2be difficult to prepare methyl alcohol.
In carbon trapping technique, Chinese patent CN101314102
[1]propose " CO in a kind of coal-fired plant flue gas
2capture method and device "; it is made up of flue gas pretreatment system, absorption tower, regenerator column, vent scrub system, solution heating recovery device, gas product treatment system (comprising condenser, gas-liquid separator, compressor), but this patent is only applicable to the trapping of simple carbon.Chinese patent CN201603511U
[2]propose " a kind of trapping carbon dioxide in flue gas system ", it comprises absorption tower and regenerator column, also comprises resurgent gases condenser, poor rich liquid heat exchanger, CO
2separator and CO
2compressor, this patent is only applicable to the engineering separately for the purpose of carbon emission reduction, and use thanomin is absorption liquid, and follow-up chemical industry operation uses the process for producing chloride of soda and sociation center.
Preparing methyl alcohol technical elements, United States Patent (USP) 5928806
[3]carbonic acid gas in employing air as the raw-material alternative source of methyl alcohol, but needs to capture CO economically from air
2gas, and in air, content is extremely rare, only ten thousand/several.
Reference
[1] Xu Shisen, Liu practices ripple, trapping carbon dioxide in flue gas method and apparatus, CN101314102 [P], 2008.05.30;
[2] Du Yungui, trapping carbon dioxide in flue gas system, CN201603511U [P], 2010.01.14
[3] Olah, George A.,Prakash, G. K. Surya，Recycling of carbon dioxide into methyl alcohol and related oxygenates for hydrocarbons，5,928,806 [P]，July 27, 1999。
Summary of the invention
The present invention adopts industrial gaseous waste as the important source material of methanol and derivative thereof, produces the fossil oil substitute products day by day reduced; The present invention also helps and slows down atmospheric greenhouse gas purging, relaxes global warming trend thus.Because thermal power plant's discharge amount of exhaust gas is very huge, coal combustion generates CO
2, burn 1kg coal and produce 3.67kgCO
2, China's coal causes CO more
2discharge is many, and as 2009, CO mainly arranged in the world
2country in, China the first, accounts for 24.2% of total release, China's power industry be row CO
2the first rich and influential family, power industry CO in 2010
2discharge accounts for 49.3% of China's total release, amounts to discharge 35.59 hundred million tons, produces primarily of thermal power plant.
The present invention relates to and use industrial gaseous waste as the sole oxidizing agent source material preparing methyl alcohol and derivative thereof, described methyl alcohol and compound thereof may be used for energy storage, transport, the preparation of liquid fuel and derivative synthesis hydrocarbon goods.Methyl alcohol prepared in accordance with the present invention can be processed into other derivative or derivative compound further.Such as, methanol dehydration is produced dme, both can prepare the liquid fuel of oil engine, the current more existing motor vehicle of China uses methanol fuel; Methyl alcohol can also form ethene and propen compounds, and changes into higher alkene, synthesis hydrocarbon, aromatic substance and goods thereof further.According to the present invention by the CO in industrial gaseous waste
2with electrolysis H
2methyl alcohol prepared by O and dme are convenient to store and transport, and methyl alcohol easily can process and produce synthesis hydrocarbons and their derivates, can also prepare methylcarbonate by the oxidative carbonylation of methyl alcohol.Methyl alcohol, dme and derivative thereof synthesis hydrocarbon and the fuel prepared of compound can facilitate and the storage of safety; Methyl alcohol, dme change into ethene or propylene by acidic-basic or zeolite catalyst, and they form ethanol and propyl alcohol with hydration respectively, and can change into polyolefine, multiple synthesis hydrocarbon, higher alkene or aromatic substance further.These reactions all have maturation process above, and employing CO has been described in technique
2condition needed for raw material production methyl alcohol.
Utilize the CO in industrial gaseous waste
2the first step of methanol technics processed is first by CO
2be reduced into CO:
CO
2+C=2CO …………………△H
298k= -41.66kcal/mol （1）
Use H again
2with CO methanol:
CO+2H
2=CH
3OH ………………△H
298k= -21.7kcal/mol （2）
Reaction (1) is an increase-volume, thermo-negative reaction, and in the reactor of an in-built lumped coal, electricity consumption is heated to 1000 DEG C, the CO passed into
2react with the coal of red heat, namely generate CO.
Quality, the energy relationship of reactant and resultant in table 1. CO reactor
I.e. 1g CO
2add 0.273g C and generate 1.273g CO, heat supply electricity consumption 0.0011kWh.
Reaction (2) is have in the methanol reactor of catalyzer (Cu, Zn compound) at one, the reaction occurred under certain temperature, pressure, and this reaction, for subtracting appearance, heat release, is pressurizeed, favourable reaction of dispelling the heat carried out.
The typical industry waste gas that the present invention relates to is thermal power plant's waste gas, and below introduce the method preparing methyl alcohol for thermal power plant's waste gas, the method comprises: adopt oxygen rich gas as the combustion-supporting gas of thermal power plant, O
2gas content>=21wt%, improves the CO in power plant flue gas
2content; The waste gas got rid of from power plant boiler combustion chamber directly enters CO reactor, can clipped heat exchange or dust collecting process, or simplifies part heat exchange or dust collecting process; The CO gas produced from CO reactor needs, through heat exchange, sulphur removal, denitration or dust collecting process, to reach the processing requirement of methanol; Through the pure H of CO gas and vapor permeation of purification
2gas prepares synthesis gas, and adding mass ratio and determine according to the ratio of the molecular weight of methyl alcohol, is CO:H
2=1:0.1-0.2.In the method, described CO
2gas all from thermal power plant's waste gas, H
2gas uses the form of energy of any necessity to produce.
Enter the CO in reaction vessel
2gas is carried out partial reduction by carbon raw material and obtains the synthesis gas that CO is master, and the oxygen that reaction vessel passes into and the heat that carbon raw material reaction produces add that the heat that hot power plant exhaust is brought into is enough to maintain reaction institute heat requirement, formation autothermal reactor; Reaction vessel passes into a small amount of oxygen and does not even pass into oxygen, needs to maintain reaction institute heat requirement by indirect heating, forms external-heat reactor.
CO
2the method transforming into methyl alcohol adopts Canizzaro-Tishenko type chemical process, methyl-formiate shortening.Produce required hydrogen and can pass through any suitable source, comprise pure water electrolysis.Electric power can from nuclear energy, fossil oil, water conservancy, sun power, wind energy, Geothermal energy etc.
In one embodiment, the combustion-supporting gas needed for thermal power plant is oxygen rich gas, prepares methyl alcohol by the shortening of carbon monoxide, and the hydrogen wherein for hydrogenation is obtained by the electrolysis of pure water, and required electric energy is that thermal power plant self produces.In another embodiment, the combustion-supporting gas needed for thermal power plant is air, and prepare methyl alcohol by the hydrogenation cooling supercharging of carbon monoxide, wherein required hydrogen is bought from other unit, such as: the hydrogen that power station surplus electricity electrolyzing pure water is produced.
In another embodiment, the present invention relates to and use thermal power plant's waste gas as the sole source material preparing methyl alcohol and derivative thereof, described waste gas comprises the higher carbonic acid gas of concentration and part nitrogen, oxynitrides and sulfide, from the carbon monoxide of reactor output too containing above-mentioned impurity, may be used for the present invention for capturing from this mixed gas with any method of separation of C O (no matter be catalytic absorption, adsorbent, membrane sepn or other technology).
Embodiment is only illustrative and should not be construed as the restriction scope of application of the present invention below.
embodiment:
The present invention mainly contains two steps and forms: the first, and utilize thermal power plant's waste gas to produce CO, the second, Hydrogenation is for methyl alcohol.According to different power plant exhaust and methyl alcohol preparation technology, different technical schemes should be designed:
embodiment 1:
Thermal power plant does not have oxygen generating station, directly adopts atmospheric air as combustion-supporting gas, containing a large amount of nitrogen and oxynitrides in combustion exhaust, and carbon dioxide content < 20wt%.Such waste gas needs to adopt polyethyleneimine polymers (or the polymkeric substance of other polyaminos, be supported on pyrolytic silicon dioxide, aluminum oxide or there is surfactivity, to improve activity on the carrier of nano-structured nature) absorbing carbon dioxide, then by heating, step-down is by absorbed carbonic acid gas desorb, gained carbonic acid gas enters reaction of carbon monoxide device again, the CO (carbon monoxide converter) gas produced also will deviate from the impurity such as sulfurous gas and dust further, only have the carbon monoxide after purification just can add hydrogen, be converted under the effect of catalyzer containing formic acid, the mixture of formaldehyde and methyl alcohol, Canizzaro-Tishenko type chemical process is used to convert formaldehyde to methyl alcohol, formic acid and methyl alcohol react and generate methyl-formiate, the methyl alcohol of twice can be produced again by shortening.The dump energy electrolyzing pure water that thermal power plant utilizes self to produce prepares hydrogen, as one of the raw material of above-mentioned methanol production.
Control the carbonic acid gas tolerance entering reaction of carbon monoxide device, guarantee that reaction of carbon monoxide device inside keeps reducing atmosphere, oxide containing silicon in carbon raw material and being reduced gradually in reducing atmosphere containing aluminum oxide, generates aluminum silicon alloy and gets rid of reaction of carbon monoxide device.
embodiment 2:
Thermal power plant is provided with oxygen station, adopts combustion-supporting gas is oxygen-rich air, O
2content > 70%, combustion exhaust is mainly carbonic acid gas, CO
2content > 80%, directly can enter reaction of carbon monoxide device and complete partial reduction, the Co mixed gas generated does not need the purifying treatment such as desulphurization and denitration, dedusting, directly add hydrogen and form mixed gas by reducing temperature and increasing pressure, can methyl alcohol be converted into.As the hydrogen of one of important raw materials for production from other producer, the hydrogen that such as power station utilizes the electricity more than needed in generating busy season to produce.
Control the carbonic acid gas tolerance entering reaction of carbon monoxide device, guarantee that reaction of carbon monoxide device inside keeps reducing atmosphere, silicon-containing compound in carbon raw material, aluminum contained compound and iron containing compounds are reduced gradually in reducing atmosphere, generate AL-Si-Fe alloy and flow out reaction of carbon monoxide device.
accompanying drawing explanation:
Fig. 1. the operational path of industrial gaseous waste methanol and aluminum silicon alloy.
Claims (10)
1., in this patent, prepare the CO needed for methyl alcohol
2raw material, all from industrial gaseous waste, utilizes the CO that industrial production gives off
2prepare the method for methyl alcohol as main raw material, completed by following steps:
A) will containing CO
2the industrial gaseous waste supply reaction of carbon monoxide container of 15wt%-100wt%, as required can through heat exchange, except sulfurous gas, except the step such as oxynitrides and dedusting;
B) CO in reaction vessel is entered
2gas is carried out partial reduction by carbon raw material and obtains the mixed gas that CO is master, and CO content is 20wt%-100wt%, and the mass ratio of required carbon raw material is C:CO
2=0.25-0.35;
C) mixed gas obtains pure CO after deviating from impurity and purification;
D) the pure CO gas that step c) obtains adds pure H
2gas prepares synthesis gas, and interpolation mass ratio is H
2: CO=0.1-0.2;
E) synthesis gas prepared of step d) obtains containing methyl alcohol and derivative thereof through overdraft, cooling or catalytic conversion mix products;
F) the last solid of the carbon raw material of step b) or product liquid are containing aluminum silicon alloy or AL-Si-Fe alloy.
2. for improving the CO in waste gas
2concentration, is replaced by oxygen rich gas by the combustion-supporting gas in industry by air, O
2gas content>=21wt%.
3. the process of claim 1 wherein a) step from industrial production line get rid of containing CO
2waste gas at least omits heat exchange, removes sulfide, of removing in nitride or dust collecting process.
4. the process of claim 1 wherein and b) carbon raw material is housed in reactor that step relates to, reactor adopts self-heating or external heat form, CO
2be C:CO with the mass ratio of required carbon amounts
2=0.25-0.35.
5. the process of claim 1 wherein obtain from b) step go out sulfide, carbonic acid gas, nitrogen compound and other possible impurity to obtain the CO gas through purification containing CO gas delivery.
6. the process of claim 1 wherein obtain from b) step containing CO gas not separating impurity directly add containing H
2gas generation goes out synthesis gas, and interpolation mass ratio is H
2: CO=0.1-0.2.
7. the impure synthesis gas produced in claim 6 obtains the mix products containing methyl alcohol and derivative thereof through overdraft, cooling or catalytic conversion.
8. the method for claim 1, controls to enter CO in the reactor of b) step
2tolerance, maintenance inside reactor is reducing atmosphere.
9., in claim 1 step b), the silicon-containing compound in carbon raw material, aluminum contained compound and iron containing compounds, by the step in claim 8, generate aluminum silicon alloy or AL-Si-Fe alloy after carbon raw material reduction.
10. reaction required origin of heat resistance, arc plasma, solid fuel, geseous fuel, microwave, sun power, heat pump or several array mode in claim 1 step b).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510105989.7A CN104892357A (en) | 2015-03-12 | 2015-03-12 | Methanol and aluminum-silicon alloy synchronous production method utilizing industrial waste gas |
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| CN201510105989.7A CN104892357A (en) | 2015-03-12 | 2015-03-12 | Methanol and aluminum-silicon alloy synchronous production method utilizing industrial waste gas |
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| CN104892357A true CN104892357A (en) | 2015-09-09 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1157281A (en) * | 1996-12-30 | 1997-08-20 | 王国良 | Preparation of methyl alcohol by using CO2 waste gas |
| CN104004547A (en) * | 2014-05-29 | 2014-08-27 | 华南理工大学 | Coal gasification and coal coking co-supply and cogeneration system and method |
-
2015
- 2015-03-12 CN CN201510105989.7A patent/CN104892357A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1157281A (en) * | 1996-12-30 | 1997-08-20 | 王国良 | Preparation of methyl alcohol by using CO2 waste gas |
| CN104004547A (en) * | 2014-05-29 | 2014-08-27 | 华南理工大学 | Coal gasification and coal coking co-supply and cogeneration system and method |
Non-Patent Citations (2)
| Title |
|---|
| 尚会建等: "煤焦二氧化碳气化反应活性影响因素研究现状", 《现代化工》 * |
| 李淑芬等: "五台型煤焦CO2催化气化的补偿效应", 《天津大学学报》 * |
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Application publication date: 20150909 |
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