CN101318848A - Method for preparing methyl hydride and hydrogen gas with mineralized garbage, leachate, kitchen garbage and sewage sludge - Google Patents
Method for preparing methyl hydride and hydrogen gas with mineralized garbage, leachate, kitchen garbage and sewage sludge Download PDFInfo
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- CN101318848A CN101318848A CNA200810040591XA CN200810040591A CN101318848A CN 101318848 A CN101318848 A CN 101318848A CN A200810040591X A CNA200810040591X A CN A200810040591XA CN 200810040591 A CN200810040591 A CN 200810040591A CN 101318848 A CN101318848 A CN 101318848A
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
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Abstract
The invention relates to a method for producing methane and hydrogen by aged refuse, leachate, kitchen wastes and mud, comprising the following steps that: the kitchen wastes are crushed, the mud passes through a sieve with 1.25mm, the water contents of the mud and the kitchen wastes are adjusted to 90 weight percent; then the mud, the kitchen wastes and the leachate are taken according to the ratio of (10-90 percent) to (5-45 percent) to (5-45 percent), the aged refuse accounting for 5 percent of the total weight of the mud, the kitchen wastes and the leachate are added, and the C/N is between 7.0 and 7.5, the pH is between 5.8 and 6.2; the materials are pumped into an anaerobic fermentation tank, nitrogen passes through to expel oxygen in the tank, the reaction is carried out for 15 days at a temperature of between 20 and 55 DEG C, and gas mixture of CH4 and H2, with H2 concentration between 4 and 10 volume percent and CH4 concentration between 55 and 57 volume percent, is produced. The method has easy operation, low cost and precious economic and social benefits. The gas mixture produced by the method improves generating efficiency of the methane by 10 to 15 percent, and well solves the problem of difficult ignition in the process of methane power generation.
Description
Technical field
The present invention relates to the method for a kind of mineralized waste, percolate, changing food waste and producing methane by sludge and hydrogen.Specifically be above-mentioned abandoned biomass anaerobic fermentation, obtain the technology of methane and hydrogen simultaneously.Belong to the recycling organic waste technical field.
Background technology
Fossil oil is just day by day exhausted as the disposable energy, and its a large amount of uses also cause the serious environmental pollution problem, is replaced by other energy the most at last with the primary energy source by representative such as oil.The biomass energy Study on Technology has become one of great heat subject in the world with exploitation, but since pell-mell development biomass fuel in recent years occur striving ground with grain, thereby may secondary grain be hard up, ecological damage.States such as Holland begin to halt one after another biofuel, and therefore abandoned biomass can more gain great popularity.Wherein the anaerobically fermenting of biomass is handled because energy consumption is low, and can reclaim biogas and utilize and become the research focus.
Utilize abandoned biomass to produce hydrogen, the research that reduces greenhouse gas emission is more.200610027750.3) and " a kind of method and apparatus that utilizes the hydrogen manufacturing of sewage plant excess sludge anaerobically fermenting " (application number: 200310116142.6) disclose the method for anaerobically fermenting generation hydrogen Chinese patent application " collaborative hogwash refuse of a kind of mineralized waste and mud are united the method for producing hydrogen " (application number:, but the concentration of hydrogen mostly is 50-60% usually most, can't directly be used.
The biogas main component that traditional anaerobic digestion reaction produces is methane (CH
4) and carbonic acid gas (CO
2).Methane accounts for 55%-65%, and carbonic acid gas accounts for 35%-45%, also has gases such as a small amount of hydrogen, carbon monoxide, hydrogen sulfide, oxygen and nitrogen, and wherein the content of hydrogen generally has only 0.5%.Marsh gas power generation can be divided into double fuel formula and clean burn formula dual mode.Self-igniton engine adopts diesel oil-biogas double fuel, carries out work by combustion by a small amount of diesel oil of compression ignite to light biogas.The characteristics of this engine are to regulate diesel oil/biogas fuel ratio, and are not enough even when stopping the supple of gas or steam when biogas, and engine still can works better, and shortcoming is system complex, and must use oil fuel, does not meet environmental protection policy.Some developed countries of west have put into effect the development of corresponding policy restriction double fuel formula generator, for example German Government 2004 to the revised provision of " renewable energy source method " in clear and definite regulation: the marsh gas power generation engineering of being built after on January 1st, 2007, if use the fossil fuel oil can not enjoy relevant preferential policy.The spark ignition type methane fuelled engine also claims clean burn formula methane fuelled engine, is characterized in simple in structure, and is easy to operate, and need not auxiliary fuel, be adapted at working under the large and medium-sized biogas engineering condition, this engine has become the main flow unit in the biogas power generation technology enforcement, but because the combustionvelocity of biogas is slow, make the combustion duration in the clean burn marsh gas power generation elongate, cause efficiency of combustion to reduce, after-burning is serious, row Wen Taigao, reliability does not pass a test, and economy is also bad.Improve hydrogen content (about 5-10%) in the biogas if under the condition that does not reduce methane content, (be not less than 50%), just can improve the biogas combustionvelocity, not only can improve the methane capacity factor greatly, and can solve the difficult problem of generating igniting.Therefore how to change traditional anaerobic ferment process, improve hydrogen content in the biogas, become the focus that the research worker makes great efforts to explore.
Anaerobic digestion is generally carried out under middle temperature or high temperature, and the optimum temps of middle temperature is about 35 degree, and high temperature is about 55 degree.Mesophilic digestion equipment is simple, and cost is lower, but processing efficiency is not as thermophilic fermentation.PH value aspect, discoveries such as Lay are within 6.6 to 7.8 scopes in the pH value, and the product methane speed when moisture content is 90%-96% is higher, and the pH value is lower than 6.1 or be higher than at 8.3 o'clock, and producing methane may stop.Robles Martinez has studied the biological degradation of pH value for household garbage.When the rubbish water saturation, after the pH value was adjusted to more than 6.5, degraded obviously improved.Aspect anaerobic digestion, in general acidifying will remain on slightly slant acidity, produces methane outline meta-alkalescence.At the beginning of the seventies, S.Ghosh and F.G.PHoland have at first proposed the notion of TPAD according to the theory of anaerobe decomposition mechanism and microbe groups; Acid-producing bacteria and methanogen are placed two placed in-line reactors respectively and required separately top condition is provided, make this two bacterioids group can both bring into play maximum activity, improve the processing efficiency of reactor.Schere has reached 98% of theoretical gas production rate with Anaerobic Digestion organic waste gas production rate.B.G.Yeoh has carried out contrast experiment's research to TPAD technology and single-phase anaerobic digestion process, and the result shows that the methanogenesis activity of two-phase anaerobic digestion system is apparently higher than single-phase anaerobic digester system.But hydrolysis mainly is to produce acid mutually in traditional two-phase reactor, removes CO
2Substantially not having other gas outward generates.But in present industrial practical application, the homogeneous reaction device has overwhelming superiority, and this mainly is because traditional two-phase reactor is compared homogeneous reaction device cost height and is difficult for operation and maintenance.
Summary of the invention
The objective of the invention is to disclose a kind of technology utilize percolate, changing food waste and mud and mineralized waste abandoned biomass simple, with low cost and carry out anaerobically fermenting for matrix, can obtain the method for methane and hydrogen simultaneously, the methane and the hydrogen that obtain with the present invention can improve the marsh gas power generation utilization ratio, and solve the difficult problem of generating igniting.
In order to achieve the above object, the present invention adopts the reactor (patent No.: 200710047071.7), but infiltrate the theory (the reactor front end is the acidication phase, produces the methane phase along with the propelling of reactor then enters) of two-phase reactor of integral type.Satisfying initial pH by the proportioning of regulating mud, percolate and changing food waste etc. is 5.8-6.2, initial C/N is 7.0-7.5, then these abandoned biomass through certain proportioning are carried out anaerobic fermentation, also obtain a certain amount of hydrogen (volume percent 4-10%) simultaneously thereby make matrix such as mud, percolate and changing food waste generate a large amount of volatile acids in the acidication phase.Producing the methane phase, on the one hand owing to main component in mud and the percolate is a protein, these proteinic degradeds make system pH be increased to the scope that methanobacteria is fit to growth, thereby the short chain fatty acid of acidication generation is utilized generation methane by methanobacteria on the other hand.
The present invention realizes by following steps:
The first step, the pre-treatment of changing food waste and mud
Earlier changing food waste is carried out fragmentation, broken particle diameter is 5-10mm.Then with mud by the 1.25mm processing of sieving.Then measure their pH, water ratio and C/N respectively, and add tap water, make water ratio be 90%;
In second step, adjust mud, percolate, changing food waste and mineralized waste proportioning
The water ratio of getting the first step is 90% mud and changing food waste, by mud: changing food waste: percolate=(10%-90%): (5%-45%): (5%-45%) weight percent is measured, the amount of measuring mineralized waste again is 5% of changing food waste, percolate and a mud gross weight, then they are mixed, fully stir evenly, this moment, the pH of mixture was 5.8-6.2, and C/N is 7.0-7.5;
The 3rd step, combined ferment
Percolate, changing food waste, mud and mineralized waste mixture that pH that the second step proportioning is good and C/N meet above-mentioned requirements place encloses container, charge into nitrogen to drive away the oxygen in the container, under 20-55 ℃, adopt 100～130 rev/mins of speed concussions or alr mode to begin anaerobic digestion, reaction times continues 15 days, obtains containing 55-57% volume CH
4With 4-10% volume H
2CH
4And H
2Gas mixture.This gas mixture makes marsh gas power generation efficient improve 10-15%, and solves the problem of marsh gas power generation ignition difficulties.
Above-mentioned mud is the press filtration mud of biochemical sewage work.
Above-mentioned percolate is the fresh percolate of incineration plant.
Above-mentioned mineralized waste is landfill mineralized waste more than 8 years.
The present invention has following advantage:
1. the present invention's acidifying theory of anaerobically fermenting that breaks traditions, by adjusting mud, percolate, changing food waste and mineralized waste proportioning, satisfy the initial pH and the C/N requirement of anaerobic fermentation methane and hydrogen, in the reactor of integral type, obtain 55% left and right sides volume percent CH simultaneously
4With 5% left and right sides volume percent H
2, realized CH
4And H
2Concentration is combination preferably, makes the methane generating efficiency improve 10-15%, and has solved the problem of marsh gas power generation ignition difficulties well.
2. because the present invention passes through to adjust mud, percolate, changing food waste and mineralized waste proportioning, satisfying initial pH is 5.8-6.2, C/N is 7.0-7.5, need not add C source or N source in addition, also need not add soda acid in addition and carry out pH regulator, therefore, simple to operate, with low cost, have valuable economic benefit.
3. because mud of the present invention, percolate, changing food waste and mineralized waste all belong to waste, therefore has the valuable social benefit of changing rejected material to useful resource.
Description of drawings
Fig. 1 is a process flow sheet of the present invention
Fig. 2 is the content graphic representation of institute's hydrogen producing in gas mixture of embodiments of the invention 1
Fig. 3 by embodiments of the invention 1 the content graphic representation of product methane in gas mixture
Embodiment
Embodiment 1
See also accompanying drawing 1.Changing food waste and mud are carried out pre-treatment: earlier the chopsticks in the changing food waste, os osseum etc. are sorted out in order to avoid damage crusher, being crushed to particle diameter then is 5-10mm; Mud is crossed the 1.25mm sieve; Measure their pH, water ratio and C/N again, the tap water that adds respective quality according to the measurement of water-content coefficient result is adjusted to 90% weight percent with water ratio then.Measure mud, changing food waste, percolate and the mineralized waste (system 1-3 is an experimental group in the table 1, and system 4 is a control group) of the listed weight of table 1.Then it is mixed, place 250ml serum bottle (300 milliliters of actual useful volumes), inflated with nitrogen 1min is to drive away the oxygen in the container, sealing rapidly, under 20-55 ℃, adopting speed is that concussion or alr mode begin anaerobic digestion under 100～130 rev/mins of conditions, and the reaction times continues 15 days.Hydrogen is produced in the C/N of the system of 1-4 shown in the table 1 and the initial index of pH and accumulation and methane content sees Table 2.The corresponding volume percent content of institute's hydrogen producing in gas mixture seen Fig. 2, the volume percent content of the methane that produces in gas mixture see Fig. 3.Control group is that system 4 hydrogen do not detect, and methane content is up to 3500ml.Though system 1 has hydrogen to generate, concentration is very low, and major cause is that initial pH is higher; System 3 hydrogen generate in a large number, and the concentration maximum reaches 52% volume percent, but do not have methane to detect, and major cause is that C/N is higher; System 2 has certain amounts of hydrogen to generate again in a large amount of generation methane, and major cause is that the initial pH and the C/N of this two individual system is controlled at comparatively ideal scope.
Table 1 is mud, changing food waste, percolate and mineralized waste proportioning
| System | 1 | 2 | 3 | 4 |
| Mud (g) | 80 | 60 | 50 | 100 |
| Changing food waste (g) | 0 | 10 | 25 | 0 |
| Percolate (g) | 20 | 30 | 25 | 0 |
| Mineralized waste (g) | 5 | 5 | 5 | 0 |
Table 2 is that methane content is produced in initial index of each experimental system and accumulation
| System | 1 | 2 | 3 | 4 |
| Initial C/N | 6.4 | 7.0 | 9.1 | 5.6 |
| Initial pH | 6.6 | 6.0 | 6 | 7.0 |
| Methane content (ml) is produced in accumulation | 3800 | 4500 | 0 | 3500 |
| Accumulation hydrogen output (ml) | 9.63 | 29.64 | 800 | 0 |
The anaerobic fermentation tank that this example is implemented is that (patent No.: 200710047071.7), the reactor front end is the acidication phase, produces the methane phase along with the propelling of reactor then enters for two-phase integrated reactor.Concrete implementation step is as follows:
Os osseum is removed in the changing food waste letter sorting, and it is 5-10mm that foreign material such as chopsticks are crushed to particle diameter again, measures pH, water ratio and C/N, the results are shown in Table 3.The tap water that adds respective quality according to the measurement of water-content coefficient result is adjusted to 90% weight percent with the water ratio of mud and changing food waste then.
Mud, changing food waste and percolate is even by 60%: 10%: 30% weight percent mixed, the addition of mineralized waste is a 5g/100g associating matrix (mud, changing food waste and percolate weight in wet base), mineralized waste and the substrate composed mixed-matrix of associating are continuously pumped in the anaerobic fermentation tank, and charging into nitrogen to drive away oxygen wherein, temperature of reactor is 20-55 ℃.Average methane production 50L/kg mixed-matrix in 15 days, density of hydrogen is in the fluctuation of 5-8% volume percent, and methane concentration is the 52-57% volume percent.
Table 3 is the basic initial index of mud, changing food waste, percolate and mixed-matrix
| System | Mud | Changing food waste | Percolate | Mixed-matrix |
| Water ratio (%) | 83％ | 75％ | 97％ | 90％ |
| pH | 7.0 | 5.0 | 5.0 | 6.2 |
| C(％) | 33.7 | 49.6 | 33.2 | 35.1 |
| N(％) | 6.0 | 2.2 | 2.4 | 4.5 |
| C/N | 5.6 | 23.0 | 13.6 | 7.7 |
Claims (4)
1. the method for mineralized waste, percolate, changing food waste and producing methane by sludge and hydrogen is characterized in that:
The first step, the pre-treatment of changing food waste and mud
Earlier changing food waste being crushed to particle diameter is 5-10mm, then with mud by 1.25mm processings of sieving, then measure their pH, water ratio and C/N respectively, and the interpolation tap water, make water ratio be 90%;
In second step, adjust mud, percolate, changing food waste and mineralized waste proportioning
The water ratio of getting the first step is 90% mud and changing food waste, by mud: changing food waste: percolate=(10%-90%): (5%-45%): (5%-45%) weight percent is measured, measure 5% mineralized waste of changing food waste, percolate and mud gross weight again, then they are mixed, fully stir evenly, this moment, the pH of mixture was 5.8-6.2, and C/N is 7.0-7.5;
The 3rd step, combined ferment
Percolate, changing food waste, mud and the mineralized waste mixture in second step are placed encloses container, charge into nitrogen to drive away the oxygen in the container, under 20-55 ℃, adopt 100～130 rev/mins of speed concussions or alr mode to begin anaerobic digestion, reaction times continues 15 days, obtains containing 55-57% volume CH
4With 4-10% volume H
2CH
4And H
2Gas mixture.
2. the method for mineralized waste according to claim 1, percolate, changing food waste and producing methane by sludge and hydrogen is characterized in that: described mud is the press filtration mud of biochemical sewage work.
3. the method for mineralized waste according to claim 1, percolate, changing food waste and producing methane by sludge and hydrogen is characterized in that: described percolate is the fresh percolate of incineration plant.
4. the method for mineralized waste according to claim 1, percolate, changing food waste and producing methane by sludge and hydrogen is characterized in that: described mineralized waste is landfill mineralized waste more than 8 years.
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| CN101786771A (en) * | 2010-03-19 | 2010-07-28 | 中国科学院广州能源研究所 | Equipped device for enhanced hydrolysis and anaerobic digestion of urban living organic garbage for producing biological fuel gas |
| CN101792246A (en) * | 2010-03-19 | 2010-08-04 | 中国科学院广州能源研究所 | Method for generating biogas through intensified hydrolysis and anaerobic digestion of municipal domestic organic refuse |
| CN102030456A (en) * | 2010-11-09 | 2011-04-27 | 同济大学 | Method for enhancing dry-process fermentation stability of sludge by adding kitchen waste |
| CN102115256A (en) * | 2010-12-14 | 2011-07-06 | 华中科技大学 | Anaerobic treatment method for landfill leachate |
| CN102492726A (en) * | 2011-11-21 | 2012-06-13 | 浙江大学 | Method and device for producing hydrogen and methane through fermentation of residual sludge |
| CN102674960A (en) * | 2012-05-06 | 2012-09-19 | 冷登书 | Liquid fertilizer utilizing city life garbage landfill leachate and preparation method thereof |
| CN103387936A (en) * | 2013-07-31 | 2013-11-13 | 河海大学 | Device for improving yield of methane produced from kitchen waste through anaerobic digestion and method for producing methane |
| CN103981875A (en) * | 2013-12-05 | 2014-08-13 | 青岛理工大学 | Landfill method capable of synchronously stabilizing chromium slag and household garbage |
| CN104651411A (en) * | 2013-11-18 | 2015-05-27 | 李进凯 | Method for producing methane from domestic garbage |
| CN106755124A (en) * | 2016-12-20 | 2017-05-31 | 天津凯英科技发展股份有限公司 | Consumer waste infiltration liquid cooperates with anaerobic treatment method with general solid waste |
| CN111424056A (en) * | 2020-02-28 | 2020-07-17 | 长沙凯天工研院环保服务有限公司 | Method for improving efficiency of anaerobic digestion biogas production of kitchen waste |
| CN113546951A (en) * | 2021-07-13 | 2021-10-26 | 东方电气集团东方锅炉股份有限公司 | Landfill treatment and recycling method and system suitable for hydrogen energy development and utilization |
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| CN1273373C (en) * | 2003-11-17 | 2006-09-06 | 中国科学院生态环境研究中心 | Method and device for making hydrogen using sewage plant residual mud to produce anaerobic fermentation |
| CN100532564C (en) * | 2006-06-19 | 2009-08-26 | 同济大学 | Combined hydrogen production method for combining mineralize refuse, swill waste and sludge |
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| CN101792246A (en) * | 2010-03-19 | 2010-08-04 | 中国科学院广州能源研究所 | Method for generating biogas through intensified hydrolysis and anaerobic digestion of municipal domestic organic refuse |
| CN101792246B (en) * | 2010-03-19 | 2011-05-11 | 中国科学院广州能源研究所 | Method for generating biogas through intensified hydrolysis and anaerobic digestion of municipal domestic organic refuse |
| CN101786771B (en) * | 2010-03-19 | 2011-07-20 | 中国科学院广州能源研究所 | Equipped device for enhanced hydrolysis and anaerobic digestion of urban living organic garbage for producing biological fuel gas |
| CN101786771A (en) * | 2010-03-19 | 2010-07-28 | 中国科学院广州能源研究所 | Equipped device for enhanced hydrolysis and anaerobic digestion of urban living organic garbage for producing biological fuel gas |
| CN102030456A (en) * | 2010-11-09 | 2011-04-27 | 同济大学 | Method for enhancing dry-process fermentation stability of sludge by adding kitchen waste |
| CN102115256A (en) * | 2010-12-14 | 2011-07-06 | 华中科技大学 | Anaerobic treatment method for landfill leachate |
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| CN102674960A (en) * | 2012-05-06 | 2012-09-19 | 冷登书 | Liquid fertilizer utilizing city life garbage landfill leachate and preparation method thereof |
| CN103387936A (en) * | 2013-07-31 | 2013-11-13 | 河海大学 | Device for improving yield of methane produced from kitchen waste through anaerobic digestion and method for producing methane |
| CN104651411A (en) * | 2013-11-18 | 2015-05-27 | 李进凯 | Method for producing methane from domestic garbage |
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| CN106755124A (en) * | 2016-12-20 | 2017-05-31 | 天津凯英科技发展股份有限公司 | Consumer waste infiltration liquid cooperates with anaerobic treatment method with general solid waste |
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| CN111424056A (en) * | 2020-02-28 | 2020-07-17 | 长沙凯天工研院环保服务有限公司 | Method for improving efficiency of anaerobic digestion biogas production of kitchen waste |
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| CN114804565A (en) * | 2022-04-29 | 2022-07-29 | 青岛理工大学 | Low-temperature anaerobic fermentation method for high-solid-content sludge |
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