CN101033427B - Dimethyl ether prepared from marsh gas and preparing method for the same - Google Patents
Dimethyl ether prepared from marsh gas and preparing method for the same Download PDFInfo
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- CN101033427B CN101033427B CN2007100108321A CN200710010832A CN101033427B CN 101033427 B CN101033427 B CN 101033427B CN 2007100108321 A CN2007100108321 A CN 2007100108321A CN 200710010832 A CN200710010832 A CN 200710010832A CN 101033427 B CN101033427 B CN 101033427B
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- biogas
- gas
- dme
- water
- desulfurization
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Abstract
This invention relates to dimethyl ether fuel prepared with biogas and a method characterizing that after biogas is compressed, desufurized (H2S) and part of CO2 in it is taken off, a transforming device is used to transform it into a synthesized gas composed of H2, CO and CO2, which is pressed by a compressor to form methyl alcohol first under the action of a catalyst with methyl alcohol composition and dewater functions then to be dewatered immediately to get the fuel used as the power fuel of cars instead of diesel, gas and liquefied gas or as the aerosol and vesicant instead of Freon.
Description
Technical field
The present invention relates to a kind of reproducible biomass new forms of energy, development and use that fresh fuel is new and technology thereof, particularly a kind of with biogas preparing dimethy ether (DME) fuel and production method thereof.
Background technology
Biogas is a kind of reproducible biomass new forms of energy, fresh fuel.Be organism under anaerobic, through the decomposing and fermenting of microorganism and a kind of inflammable gas that produces, its composition mainly is about 70% methane (CH
4) and about 30% carbonic acid gas (CO
2).The raw material of producing biogas is very extensive, resource is huge, as the settling of waste residue, sewage, tankage and the urbanization manure pit of people, animal ight soil, domestic refuse, agricultural crop straw, weeds leaf, various plantation, breed, various food, the meat product course of processing and sanitary sewage or the like, all be the good raw material of producing biogas.And the accumulation of these things and rot, not still dirty, random, the performance that differs from of city and rural area, family and social production living environment causes the important source of pollution of environmental pollution especially.If these things are removed to produce biogas as resource, not only can turn waste into wealth, solve the energy shortage problem, also can make people's productive life environment effectively be administered and improve simultaneously, this really is resources conservation, environmental friendliness.Though yet produce at present the raw material of biogas and resource many be the production of biogas and to use be very limited everywhere.From producing the noncommodity production that mostly is the self-sufficient formula of rural area single household, small scale yields poorly, and can directly use for heating up water to cook with the form of gas from only using, biogas can't be processed into and be easy to store the liquid power fuel that transportation and steam supply car use.Production and development that this has just limited biogas are abandoned and useless a large amount of resources that can produce biogas, and this is a kind of huge waste from resource; This is unfavorable for human existence very much from environment.Therefore by biogas being carried out on a large scale, many-sided development and use make it to become society's urgent need, both convenient storage, transportation, the commercialization liquid fuel that conveniently uses again and exchange is fundamentally to promote the big production of biogas, the great development problem is demanded urgently being resolved from technological innovation.
Summary of the invention
Purpose of the present invention, providing a kind of is raw material with biogas, with the form of liquid store, transportation, with the use of burning of the mode of gas, heat is big, efficient is high, save energy does not discharge harmful flue dust, dme free from environmental pollution (DME) fresh fuel.
Another purpose of the present invention provides a kind of method with biogas preparing dimethy ether (DME) fuel.
The technical scheme that adopts is:
Dme (DME) fuel is compressed to 1.6MPa-6.0MPa by biogas, adopts known process of desulfurizing gases desulfurization (H
2S), adopt known gas decarbonation device to remove partial CO 2 (CO
2), make the carbonic acid gas that keeps in the biogas account for 6-20% after, with known tubular type steam reforming stove through water vapor (H
2O) at temperature 700-920 ℃, pressure 1.6MPa-6.0MPa, steam/hydrocarbons ratio are 3.5, and are converted into hydrogen (H under the nickel-base catalyst effect
2), carbon monoxide (CO) and carbonic acid gas (CO
2) synthetic gas formed.The compressed machine of synthetic gas is pressed into catalyticreactor, at 130-300 ℃, under the pressure 2-6MPa condition, methyl alcohol synthesizes and the catalyzer such as the composite catalyst of two kinds of functions of methanol dehydration having, perhaps under the effect of bifunctional catalyzer, elder generation's synthesizing methanol, methyl alcohol dewaters and makes once synthetic at once.
Nickel-base catalyst can adopt Ni/Al
2O
3Or 10%Ni/ZrO
2Composite catalyst can adopt known industrialized methanol synthesis catalyst C301 and dehydration catalyst γ-Al
2O
3, two kinds of catalyzer are milled to respectively below the 0.053mm, by a certain percentage, as 1: get composite catalyst (catalyst loading is in the conversion tube of converter) after the 4-5 mechanically mixing.
The bifunctional catalyzer can adopt the bifunctional Catalysts Cu O-ZnO-Al of Dalian Inst of Chemicophysics, Chinese Academy of Sciences's exploitation
2O
3-HZSM-5 and CuO-ZnO-Al
2O
3-HSY.
The present invention utilizes the dme of biogas system, is the very good fuel of a kind of performance.Because oxygen level is up to 34.78% in its molecule, so it does not produce black smoke when burning.The boiling point of this fuel is-25 ℃ under normal pressure, than high about 20 ℃ of liquefied petroleum gas (LPG), just makes its liquefaction when being pressurized to 0.54MPa at normal temperatures, and the conventional liquefied gas of pressure ratio is low, helps storing, transports and uses.The automobile usage quantity of China growth that can double from now on, the air-polluting problem of motor vehicle exhaust can be more and more serious, what China's motor vehicle exhaust was adopted at present is Europe I or Europe II standard, and the present invention all is lower than the strictest EUROIII Emission Standard with every discharge index of dme (DME) fuel of biogas system, alternative diesel oil, gasoline and liquefied gas are as the cleaning power fuel of automobile, cause the air-polluting problem to solve motor vehicle exhaust, satisfy harsh at present environmental requirement.In addition, the present invention does aerosol and whipping agent with the also alternative fluorine of dme (DME) Lyons of biogas system, and market outlook are very wide.The more important thing is the present invention's biogas preparing dimethy ether, promote the production and the development of biogas greatly, this is to economizing on resources, and the development energy is protected environment, and particularly to the solution of China's agriculture, rural areas and farmers problem, building a New Socialist Countryside has very significant meaning.
Description of drawings
Fig. 1 is the biogas production process flow sheet.
Fig. 2 prepares H with biogas
2, CO and CO
2The synthesis gas process schema.
Fig. 3 is to be raw material process for synthesis of dimethyl ether schema with biogas.
Embodiment
Utilizing biogas preparing dimethy ether fuel, is after the compressed machine of a certain amount of biogas is compressed to 3.0-3.6MPa, to adopt known wet desulfurizing process to carry out thick desulfurization, adopts known dry desulfurizing process to carry out smart desulfurization then, and desulfurization reaches sulphur content less than 10
-8Adopt known ammoniacal liquor method decarbonation technology to remove that partial CO 2 makes the carbon dioxide content of staying in the biogas account for the 6-20% of cumulative volume in the biogas, by known tubular type steam reforming stove, transform through water vapor and under the nickel-base catalyst effect, catalyzer adopts Ni/Al
2O
3, known converting furnace pipe surface temperature is controlled at 700-920 ℃, and gas medium temperature is 680-820 ℃, and the converter working pressure is 1.6-4.0MPa, and steam/hydrocarbons ratio is 3.5, gas flow rate is 500-3000h
-1, be converted into H
2, CO and CO
2Synthesis gas, hydrogen-carbon ratio is f=(H
2-CO
2)/(CO+CO
2)=2.05-2.3 with the synthesis gas compressor pressurizes that generates, compresses into catalyticreactor through water-and-oil separator again, under temperature 130-300 ℃, the condition of pressure 2-4MPa, at bifunctional Catalysts Cu O-ZnO-Al
2O
3The effect of-HZSM-5 generates dme (DME) reaction product down.Reaction product enters the water absorption tower, wherein dme (DME) is absorbed by water, the water-fast component of part is separated, water-soluble dme (DME) enters rectifying tower again, at temperature 120-140 ℃, carry out product separation under the condition of pressure 0.5-0.6MPa, dme (DME) obtains through cooling and after separating at cat head.
Utilize the production method of biogas preparing dimethy ether fuel:
Utilize the production method of biogas preparing dimethy ether fuel to comprise that unstripped gas is the production method of biogas, biogas prepares the production method of synthetic gas and the production method of directed preparing dimethyl ether by synthetic gas (DME) fuel.
Utilize the production method of biogas preparing dimethy ether fuel:
The raw material that can produce biogas is very extensive, and resource is huge, says above, repeats no more here.Describe below in conjunction with the production method and the production process of accompanying drawing biogas:
At first carry out raw material and prepare, getting the raw materials ready in the accompanying drawing is first link in the biogas production, the requested number abundance, the raw material of preparation biogas very abundant as, people, animal, poultry manure, straw and root, stem, leaf, rubbish etc.The raw material type collocation of preparation biogas does not rationally allow to be mixed with poisonous and hazardous materials such as heavy metal and various agricultural chemicals, particularly some highly toxic pesticide such as a large amount of inorganic substance and lead, mercury, zinc, silver, copper in the raw material.The running repair of old pond is checked in new pond in the accompanying drawing 1, is the important environment in the biogas production, because methane-generating pit is the nucleus equipment of biogas production, if methane-generating pit has problem, defective, will fundamentally destroy the production of biogas, therefore requirement in this link, before feeding intake, no matter be the pond of newly repairing, still strict check maintenance all must be carried out in existing old pond, must accomplish to guarantee air tight, water-tight.The method of inspection can adopt and add water and suppress method and test, suppress pressure generally under 8000-10000Pa, do not have the gas leak phenomenon that leaks be qualified.Compounding links in the accompanying drawing one mainly is to solve the carbon element of raw material and the ratio problems of nitrogen.Requirement is low with carbon containing height and carbon containing, and nitrogenous height and nitrogenous low raw material carry out reasonably combined, and the carbon, the nitrogen that reach raw material compare at (20-30): 1 for qualified.Stirring in the accompanying drawing one inoculation link requires the raw material that will prepare and is rich in the active sludge of methanogen, the mud bottom the perhaps old methane-generating pit, and perhaps inoculum such as fermented feed liquid stirs together, prepares to feed intake.The 10-15% that the amount of inoculum should account for the fermented feed liquid total amount is advisable.The pond stack retting link of going in the accompanying drawing 1 is meant and will stirs, and the raw material of some amount is put into and has been up to the standards, has in certain volumetrical methane-generating pit.The input amount of raw material should meet the feed concentration requirement that adds behind the water, and the concentration requirement of general feed liquid is: the 6-15% that the quality of the total solids of raw material (or dry-matter) accounts for the fermented feed liquid total mass is advisable.After raw material is put in the methane-generating pit, track tramping compacting and in the pond, carry out stack retting.Add the requirement of water seal tank link in the accompanying drawing one, when the temperature of the raw material of stack retting in the pond rises to 40-60 ℃, will be timely in the pond, add water from the opening for feed of methane-generating pit.Amount of water must surpass more than the 300mm of discharge port upper edge in pond, but can not surpass 85% of methane-generating pit cubic capacity, and 15% the space that stays is as the biogas volume behind the aerogenesis.To check the potential of hydrogen of fermented feed liquid in the pond after water injection with special pH test paper,, just can cover removable cover, the sealing methane-generating pit when pH value is between the 6.8-7.6 time.If find that pH value is lower than at 6 o'clock, can in the pond, add vegetation matter, ammoniacal liquor or clarifying liming the pH value of fermented feed liquid is adjusted to about 7, and then methane-generating pit is sealed.Feng Chihou should in time install pneumatic tube and be communicated with by valve with accumulator unit.Fermentation gas link in the accompanying drawing is last link in the biogas production, generally seals after pond 2-3 days fermentation gas normally, and normal fermentation gas whether should if can be lighted and can use normally by the stove and accessory gas testing of lighting a fire.Do not fire fire as point, just should bleed off the waste gas in the pond, the gas testing of lighting a fire again next day is till lighting and enter normal use.Whether behind the normal gas producing, the pH value of fermented feed liquid in the running check pond normal, want regularly irregular reinforced simultaneously, discharging and stirring could guarantee the stable, efficient of biogas production like this.
Biogas production is except will guaranteeing above-mentioned working condition, and another important condition is exactly to produce required temperature condition, because only under certain temperature condition, methane fermentating microorganism could growth and breeding, could produce biogas.Methane fermentating microorganism is in 8-65 ℃ temperature range in general, can both carry out normal vegetative activity, produce biogas, but in certain temperature range with interior (as 15-40 ℃) increasing along with temperature, the metabolism of microorganism is accelerated, decompose the also corresponding raising of speed of raw material, gas production rate and factor of created gase also all correspondingly increase as a result.Therefore in order to stablize, carry out efficiently biogas production, the temperature in the methane-generating pit preferably is stabilized in 20-40 ℃, and biogas will be endlessly like this, and a large amount of is produced.According to check with measure, if when the temperature in the methane-generating pit is lower than 8 ℃, aerogenesis not basically.If the temperature in the methane-generating pit is in the time of 8-20 ℃, every cubic metre of pond holds can produce biogas 0.1-0.2 cubic meter every day.If the temperature in the methane-generating pit is in the time of 20-40 ℃, every cubic metre of pond holds can produce biogas 0.5-1.2 cubic meter every day.Measure in addition, the total solids of every kilogram of fermentation raw material (or dry-matter) can produce biogas 0.4-0.45 cubic meter, and its aerogenesis speed is different with the difference of temperature.
Biogas prepares the production method and the production process of synthetic gas:
The task that biogas prepares synthetic gas is that biogas is converted into carbon monoxide (CO), carbonic acid gas (CO
2) and hydrogen (H
2) synthetic gas formed.Below in conjunction with accompanying drawing production method and the production process that biogas prepares synthetic gas described:
Compression in the accompanying drawing two is first production link that biogas prepares synthetic gas, purpose is to solve biogas to produce the lower problem of pressure ratio from methane-generating pit, therefore require it to be compressed by pressurization with compressor, the pressure of pressurization should be decided on the device and the needed pressure of equipment that are adopted in the processing.Desulfurization in the accompanying drawing two is that requirement is taken off sulphur contained in the biogas totally by equipment.Why will carry out desulfurizing and purifying to biogas and handle, be that the hydrogen sulfide content of testing factually and testing in the urban night soil treatment plant biogas is 7.56-7.59mg/L because all contain certain sulphur in the general biogas; Hydrogen sulfide content in the biogas of slaughterhouse is: 1.7-1.96mg/L; Hydrogen sulfide content in the fowl poultry factory biogas is 1.22-1.79mg/L; Hydrogen sulfide content in brewery's biogas is 0.96-1.15mg/L; Hydrogen sulfide content in the garbage category sludge gas is: 1.00-1.15mg/L.And the existence of sulphur in the biogas, this is synthetic all very unfavorable for processing unit (plant) and equipment and synthetic gas, therefore it must be removed clean.Biogas desulfurization can adopt wet method to carry out thick desulfurization earlier, and then carries out smart desulfurization with dry method, reaches sulphur content 10
-8Below.The partial CO 2 that takes off in the accompanying drawing two is meant contained about 30% carbonic acid gas in the biogas, removes 10-24% by the ammoniacal liquor method.Staying 6%-20%, to participate in conversion as the carbon source of necessity synthetic, this also just equal before conversion to necessity of carbonic acid gas mend into, its amount of leaving promptly is that the benefit before transforming is gone into amount, specifically amount should guarantee the hydrogen-carbon ratio f=(H of synthesis gas
2-CO
2)/(CO+CO
2)=2.05-2.3 is advisable.Steam reforming in the accompanying drawing two is that biogas prepares the most crucial production link of synthetic gas, and its conversion process is by converter, finishes under the effect of certain temperature, pressure, steam/hydrocarbons ratio, air speed and catalyzer.Temperature requirement boiler tube pipe surface temperature is at 700-920 ℃, and medium temperature correspondingly is at 680-820 ℃.Working pressure is at 1.6-6.0MP
2Steam/hydrocarbons ratio is about 3.0-3.5.Air speed is selected and will be taken all factors into consideration from the reaction and two aspects of conducting heat.Synthetic gas in the accompanying drawing two is a biogas after a series of production technique are handled, the production results that is obtained, also be biogas prepare synthetic gas the production task that must finish.Its composition is:
Hydrogen (H
2), carbon monoxide (CO) and carbonic acid gas (CO
2), its hydrogen-carbon ratio should be f=(H
2-CO
2)/(CO+CO
2)=2.05-2.3 is advisable.
The production method and the production process of directed preparing dimethyl ether by synthetic gas (DME):
The production task of directed preparing dimethyl ether by synthetic gas (DME) is that the synthetic gas that biogas transforms is directly made dme (DME) fuel.Below in conjunction with accompanying drawing its production method and production process are described:
Accompanying drawing three is to be raw material with biogas, the process flow sheet of dimethyl ether synthesis (DME).
With biogas be that the technical process of raw material dimethyl ether synthesis (DME) comprises that biogas transforms, synthetic gas compression, dme are synthetic, reaction product absorbs steps such as rectifying separation.Its production process is: with sulphur content less than 10
-8The pressurization of the compressed machine of synthetic gas after, enter catalyticreactor through water-and-oil separator, under temperature 230-300 ℃, the condition of pressure 2-4MPa, under the effect of catalyzer, carry out catalyzed reaction, generate dme (DME) reaction product, the reflection product enters the water absorption tower, wherein dme (DME) is absorbed by water, the water-fast component of part is separated, water and dissolved dme (DME) enter rectifying tower again, under 120-140 ℃, the condition of 0.5-0.6MPa pressure, carry out product separation, dme (DME) at cat head through cooling and separate the back acquisition.
Claims (1)
1. utilize the method for biogas preparing dimethy ether fuel, it is characterized in that the biogas of preparation is compressed with compressor, be compressed to 1.6-6MPa; Again biogas is carried out desulfurization and handle, biogas desulfurization adopts known wet desulfurizing process to carry out thick desulfurization, and then adopts known dry desulfurizing process to carry out smart desulfurization, and the biogas sulphur content after the process desulfurization is 10
-8Below; Remove partial CO 2 in the biogas by known ammoniacal liquor method decarbonation technology, make the carbonic acid gas that keeps 6-20% in the biogas; Through desulfurization and the biogas of removing partial CO 2 by the conversion of tubular type steam reforming stove, the converting furnace pipe surface temperature is controlled at 700-920 ℃, and gas medium temperature is 680-820 ℃, and the converter working pressure is 1.6-4.0MPa, steam/hydrocarbons ratio is 3.5, and gas flow rate is 500-3000h
-1, and at nickel-base catalyst Ni/Al
2O
3Or 10%Ni/ZrO
2Effect under be converted into H
2, CO and CO
2Synthesis gas, hydrogen-carbon ratio is f=(H
2-CO
2)/(CO+CO
2)=2.05-2.3, again with the synthesis gas compressor pressurizes that generates, in water-and-oil separator is pressed into catalyticreactor, at temperature 130-300 ℃, carry out catalyzed reaction under the condition of pressure 2-4MPa, catalyzer is selected the catalyzer with synthesizing methanol and two kinds of functions of methanol dehydration for use, resultant of reaction enters the water absorption tower, wherein dme is absorbed by water, water-fast separating substances is removed, water and dme soluble in water enter rectifying tower again, at 120-140 ℃, carry out product separation under the 0.5-0.6MPa pressure condition, dme at cat head through cooling, and after separating promptly; Described catalyzer with synthesizing methanol and two kinds of functions of methanol dehydration is composite catalyst or bifunctional catalyzer; Composite catalyst adopts methanol synthesis catalyst C301 and dehydration catalyst γ-Al
2O
3, two kinds of catalyzer are milled to respectively below the 0.053mm, by 1: the mixed of 4-5 is made; The bifunctional catalyzer is selected CuO-ZnO-Al for use
2O
3-HZSM-5 or CuO-ZnO-Al
2O
3-HSY.
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|---|---|---|---|
| CN2007100108321A CN101033427B (en) | 2007-04-04 | 2007-04-04 | Dimethyl ether prepared from marsh gas and preparing method for the same |
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| CN101033427B true CN101033427B (en) | 2010-06-23 |
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| DE102015215939B4 (en) * | 2015-08-20 | 2021-02-04 | Mtu Friedrichshafen Gmbh | Method for generating a fuel composition and for operating an internal combustion engine |
| CN108047005A (en) * | 2017-12-26 | 2018-05-18 | 安徽昊源化工集团有限公司 | A kind of energy-saving dimethyl ether production system |
| CN108557762A (en) * | 2018-06-13 | 2018-09-21 | 四川英资新能源有限公司 | A kind of environment-friendly type synthetic method of hydrogen power fuel |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315315A (en) * | 2000-03-29 | 2001-10-03 | 中国科学院大连化学物理研究所 | Process for preparing dimethylether from natural gas via partial oxidation by air or oxygen-enriched air to make gas |
| JP2001342161A (en) * | 2000-06-01 | 2001-12-11 | Nkk Corp | Method for producing dimethyl ether from coal mine gas |
| CN1477090A (en) * | 2003-05-16 | 2004-02-25 | 中国科学院广州能源研究所 | Method for synthesizing dimethyl ether by adopting biomass indirect liquification one-step process |
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2007
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315315A (en) * | 2000-03-29 | 2001-10-03 | 中国科学院大连化学物理研究所 | Process for preparing dimethylether from natural gas via partial oxidation by air or oxygen-enriched air to make gas |
| JP2001342161A (en) * | 2000-06-01 | 2001-12-11 | Nkk Corp | Method for producing dimethyl ether from coal mine gas |
| CN1477090A (en) * | 2003-05-16 | 2004-02-25 | 中国科学院广州能源研究所 | Method for synthesizing dimethyl ether by adopting biomass indirect liquification one-step process |
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