CN109652153A - A kind of processing method of agriculture and forestry organic waste material alkaline pretreatment coupling marsh gas purifying - Google Patents
A kind of processing method of agriculture and forestry organic waste material alkaline pretreatment coupling marsh gas purifying Download PDFInfo
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- CN109652153A CN109652153A CN201910011685.2A CN201910011685A CN109652153A CN 109652153 A CN109652153 A CN 109652153A CN 201910011685 A CN201910011685 A CN 201910011685A CN 109652153 A CN109652153 A CN 109652153A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 25
- 239000010815 organic waste Substances 0.000 title claims abstract description 24
- 230000008878 coupling Effects 0.000 title claims abstract description 19
- 238000010168 coupling process Methods 0.000 title claims abstract description 19
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 19
- 238000003672 processing method Methods 0.000 title claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 86
- 239000002699 waste material Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000000855 fermentation Methods 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 239000010802 sludge Substances 0.000 claims abstract description 10
- 239000006228 supernatant Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000012530 fluid Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000004151 fermentation Effects 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 238000007781 pre-processing Methods 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 description 37
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 239000010902 straw Substances 0.000 description 4
- 241000609240 Ambelania acida Species 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000010905 bagasse Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000006213 oxygenation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 240000000111 Saccharum officinarum Species 0.000 description 2
- 235000007201 Saccharum officinarum Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/02—Biological treatment
- C02F11/04—Anaerobic treatment; Production of methane by such processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/104—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M1/00—Apparatus for enzymology or microbiology
- C12M1/107—Apparatus for enzymology or microbiology with means for collecting fermentation gases, e.g. methane
-
- 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
-
- 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
- Y02W30/20—Waste processing or separation
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Abstract
The invention discloses a kind of processing methods of agriculture and forestry organic waste material alkaline pretreatment coupling marsh gas purifying, specifically include that step 1: Ca (OH) is added after agriculture and forestry organic waste material is crushed2Solution carries out alkalescence pretreatment, and after being sufficiently mixed, separation of solid and liquid obtains pretreatment residue and pre-processes waste liquid；Step 2: pretreatment residue is mixed with seed sludge, carries out anaerobic fermentation Biogas；Step 3: biogas is passed through pretreatment waste liquid by reflux unit；Step 4: will be passed through the pretreatment waste liquid after biogas and be separated by solid-liquid separation, and continue anaerobic fermentation Biogas after gained supernatant seed sludge, and gained biogas is reflowable to pretreatment waste liquid；Biogas after pre-processing waste liquid is purified biogas；Through the invention, the CO in biogas is made full use of2To Ca2+It is precipitated, it is easy to operate, it is low in cost, secondary pollution is not generated and introduces new foreign ion, solves the problems, such as fermentation inhibitory and marsh gas purifying.
Description
Technical field
The present invention relates to agricultural field more particularly to a kind of processing of agriculture and forestry organic waste material alkaline pretreatment coupling marsh gas purifying
Method.
Background technique
In the technical field of agriculture and forestry organic waste material fermentation Biogas, oxygenation pretreatment method can pass through alkali dissolved lignin
Effect removal raw material in lignin, and most of cellulose and hemicellulose are retained.And Ca (OH)2Price is relatively low
Honest and clean, pretreating effect is good, and economic serviceability is strong, is common oxygenation pretreatment method.But this preprocess method is there are still disadvantage,
Since alkalescence pretreatment liquid is a kind of akaline liquid, and the Ca containing higher concentration2+Ion, phenolic substances and carboxylic-acid substance
Equal fermentation inhibitors can not carry out biogas utilization without processing, deal with improperly and be also easy to cause secondary pollution, it is difficult to realize work
Industry metaplasia produces.Currently, common removal Ca2+There are ion-exchange, chemical method, absorption method, film point with the method for organic mortifier
From method etc..Above method comes with some shortcomings, and such as complicated for operation, higher cost is not suitable for highly concentrated solution, is also easy to produce two
Secondary pollution etc..
In addition, the CO in removal biogas2It is the research and development focus in biogas project field to promote the product grade of biogas.
Currently, CO in removal biogas2Conventional method mainly have chemical absorption method, physical method, alkali wash, membrane separation process, cryogenic separation
Method and ADSORPTION IN A FIXED BED method etc..Above-mentioned tradition biogas project CO2Although removal technology has been achieved with certain progress, still
Have the shortcomings that one it is common: be exactly removal CO2Waste liquid, the waste generated in the process can cause secondary pollution to environment.
Therefore, those skilled in the art is dedicated to developing a kind of efficiently removal Ca (OH)2Ca in pretreatment product2+And hair
Ferment mortifier, while coupling CO in alkali wash removal biogas2Method.The technical method is not using only Ca (OH)2Remove biogas
Middle CO2, but utilize Ca (OH)2It pre-processes remaining alkaline matter in waste liquid and realizes CO2Ca is reduced while removal2+Equal mortifiers
Limitation to pretreatment fluid biogas development.This method is to Ca (OH)2Pretreatment joint marsh gas fermentation process technology is changed
Into utilizing the CO in biogas2To Ca2+It is precipitated, solves the problems, such as fermentation inhibitory and marsh gas purifying, it is easy to operate,
Raw material is easy to get, low in cost, and removal effect is good and environmentally friendly, does not generate secondary pollution and introduces new foreign ion, and realizes
Biogas potentiality is promoted to the full extent；And byproduct CaCO can be obtained3, increase economic benefit.
Summary of the invention
In view of the above drawbacks of the prior art, the technical problem to be solved by the present invention is to existing agriculture and forestry organic waste material alkali
In property preprocess method, conventional Ca2+Removal will cause secondary pollution and operating cost is higher, complicated；And in removal biogas
CO2During product grade to promote biogas, CO is removed2Waste liquid, the scrap polymer film generated in the process may be to environment
The problem of causing secondary pollution.
To achieve the above object, the present invention provides a kind of processing of agriculture and forestry organic waste material alkaline pretreatment coupling marsh gas purifying
Method, steps are as follows:
Step 1: Ca (OH) is added after agriculture and forestry organic waste material is crushed2Solution carries out alkalescence pretreatment, after being sufficiently mixed, Gu
The isolated pretreatment residue of liquid and pretreatment waste liquid；
Step 2: the pretreatment residue is mixed with seed sludge, carries out anaerobic fermentation Biogas；
Step 3: biogas is passed through the pretreatment waste liquid by reflux unit；
Step 4: the pretreatment waste liquid after biogas will be passed through and be separated by solid-liquid separation, continued after gained supernatant seed sludge
Carry out anaerobic fermentation Biogas, the biogas pretreatment waste liquid.
Further, the agriculture and forestry organic waste material is bagasse.
Further, in step 1, the Ca (OH)2Ca (OH) in solution2Mass percent is 0.5%-10%.
Further, in step 1, the alkalescence pretreatment is aided with including but not limited to grinding, microwave treatment, Re Chu
Reason.
Further, in step 1, the separation of solid and liquid including but not limited to centrifugation, filtering.
Further, in step 3, CO in the biogas reflux2Concentration be 30%-60%, temperature be 20 DEG C -40 DEG C.
Further, in step 3, the rate that is passed through of the biogas is 10-100mL/mL pretreatment fluid/min, when being passed through
Between be 1-30min.
Further, in step 3, CO in the biogas2Intake is preferably 120mL, and temperature is preferably 30 DEG C.
Further, in step 3, the reflux unit includes conduit, connects the pretreatment waste liquid and the biogas produces
Generating apparatus, the conduit for connecting the pretreatment waste liquid go deep under the pretreatment waste liquid liquid level, and the conduit connects the biogas
The gas outlet of generation device.
Further, in step 4, the purified biogas pretreatment waste liquid is further removed
CO2。
Further, in step 4, the supernatant seed sludge device is provided with gas outlet, the gas outlet with it is described
Conduit connection.
This method is to Ca (OH)2Pretreatment coupling marsh gas fermentation process technology is improved, and the CO in biogas is utilized2
To Ca2+It is precipitated, solves the problems, such as fermentation inhibitory and marsh gas purifying, easy to operate, raw material is easy to get, and it is low in cost,
Removal effect is good and environmentally friendly, does not generate secondary pollution and introduces new foreign ion, realizes that biogas potentiality mentions to the full extent
It rises；And byproduct CaCO can be obtained3, increase economic benefit.
It is described further below with reference to technical effect of the attached drawing to design of the invention, specific structure and generation, with
It is fully understood from the purpose of the present invention, feature and effect.
Detailed description of the invention
Fig. 1 is the processing side of the agriculture and forestry organic waste material alkaline pretreatment coupling marsh gas purifying of a preferred embodiment of the invention
The schematic diagram of method；
Fig. 2 is the temperature and CO of a preferred embodiment of the invention2Influence of the intake to pretreatment waste liquid pH value is shown
It is intended to；
Fig. 3 is the temperature and CO of a preferred embodiment of the invention2Intake is to Ca in pretreatment waste liquid2+Removal rate
Influence schematic diagram；
Fig. 4 is influence schematic diagram of the time to pretreatment waste liquid pH value of a preferred embodiment of the invention；
Fig. 5 is the time of a preferred embodiment of the invention to Ca in pretreatment waste liquid2+Concentration influences schematic diagram；
Fig. 6 is the time of a preferred embodiment of the invention to Ca in pretreatment waste liquid2+Removal rate experiment value and fitting
Value variation schematic diagram；
Fig. 7 is the temperature and CO of a preferred embodiment of the invention2Intake is to total phenol removal rate in pretreatment waste liquid
Influence schematic diagram；
Fig. 8 is that influence of the time of a preferred embodiment of the invention to total phenol removal rate in pretreatment waste liquid is illustrated
Figure.
Specific embodiment
Multiple preferred embodiments of the invention are introduced below with reference to Figure of description, keep its technology contents more clear and just
In understanding.The present invention can be emerged from by many various forms of embodiments, and protection scope of the present invention not only limits
The embodiment that Yu Wenzhong is mentioned.
In the accompanying drawings, the identical component of structure is indicated with same numbers label, everywhere the similar component of structure or function with
Like numeral label indicates.The size and thickness of each component shown in the drawings are to be arbitrarily shown, and there is no limit by the present invention
The size and thickness of each component.Apparent in order to make to illustrate, some places suitably exaggerate the thickness of component in attached drawing.
Embodiment 1: as shown in Figure 1, a kind of processing method of agriculture and forestry organic waste material alkaline pretreatment coupling marsh gas purifying, specifically
Step includes:
Step 1: Ca (OH) is added after agriculture and forestry organic waste material is crushed2Solution, i.e. bottle 1 carry out alkalescence pretreatment, sufficiently mixed
After conjunction, separation of solid and liquid obtains pretreatment residue, i.e. bottle 3 and pretreatment waste liquid, i.e. bottle 2；The Ca (OH) being wherein added2Ca in solution
(OH)2Mass percent is 0.5%-10%；Alkalescence pretreatment is aided with the operation such as grinding, microwave treatment, heat treatment, guarantees mixing
Sufficiently；It is separated by solid-liquid separation and the physical separation methods such as centrifugation, filtering can be used.
Step 2: 3 seed sludge of residue, i.e. bottle 6 will be pre-processed, carries out anaerobic fermentation Biogas；
Step 3: biogas is passed through pretreatment waste liquid 2 by reflux unit；To guarantee removal effect, CO in biogas2It is dense
Degree is 30%-60%, and temperature is 20 DEG C -40 DEG C；The rate that is passed through of biogas is 10-100mL/mL pretreatment fluid/min, when being passed through
Between be 1-30min；Reflux unit is mainly conduit, connection pretreatment waste liquid bottle 2 and bottle 6, connects the pretreatment waste liquid bottle 2
Conduit deeply pre-processes under waste liquid liquid level, and the conduit connects the gas outlet of the bottle 6.Wherein reflux type and device can replace
It changes, reaches reflux purpose, gas sampling bag such as can be used and collect biogas, be manually passed into pretreatment waste liquid.
Step 4: will be passed through the pretreatment waste liquid after biogas and be separated by solid-liquid separation, gained supernatant, that is, 4 seed sludge of bottle, i.e. bottle 5
After can continue anaerobic fermentation Biogas, gained biogas is reflowable to pretreatment waste liquid bottle 2；After pre-processing waste liquid bottle 2
Biogas is purified biogas 7；The purified biogas 7 pretreatment waste liquid bottle 2, further removes CO2；
Bottle 5 is provided with gas outlet, and gas outlet is communicated with conduit.
Embodiment 2: it is passed through different volumes CO2Afterwards to Ca after sugarcane skin crushing and alkalescence pretreatment2+The influence of removal rate
The sugarcane skin for weighing certain mass obtains bagasse after medicinal herb grinder crushes；Conical flask is added in bagasse
In, the Ca (OH) of mass fraction 4% is added according to mass ratio 1:102Solution is heated 10 minutes in micro-wave oven with 700W power,
The moisture of evaporation loss is supplemented after cooling.Pre-treated solid obtained above and liquid are passed through into centrifuge separation.
CO is passed through into pretreatment waste liquid2, making its pH is respectively 6,7,8,9,10,11, obtains supernatant by centrifugation, is surveyed
Fixed Ca therein2+Content.
By experimental data it is found that former pre-process Ca in waste liquid2+Content is 5424mg/L, at various ph values, Ca2+Contain
Amount is declined (table 1), and analytical table 1 is it is found that be passed through CO into pretreatment waste liquid2Higher calcium removal rate can be obtained, at most
Up to 33.26%.
Table 1: it is passed through the CO of different volumes2Ca in waste liquid is pre-processed afterwards2+Content and Ca2+Removal rate
Embodiment 3:
Rice straw is collected, crushed 20 meshes with crusher, it is spare.Setting solid-liquid ratio is 1:10, Ca (OH)2Dosage is set
It is set to 10g/L.Take 10 triangular flasks, each packing 100mL Ca (OH)2Solution and 8.93g rice straw pass through micro-wave oven
It is filtered to obtain pre-treated solid and pretreatment waste liquid with gauze after 700w, microwave 10min are cooling.The spy of the expression rice straw of table 2
Property and pretreatment parameter.
2 rice straw characteristic of table and pretreatment parameter
Embodiment 4: temperature and CO2Intake is to pretreatment waste liquid Ca2+Removal influence
In order to study temperature to Ca2+Removal influence, under the same conditions, three gradients of experimental setup do reference, every
Test tube is added 30mL pretreatment fluid and each leads into CO at 20,30,40 DEG C respectively2Content be 50% biogas (60mL, 100mL,
140mL, 240mL, 400mL), the flow control of biogas is in 30mL/min.Precipitating liquid is then allowed to stand to be centrifuged by 3500r/min
Supernatant is taken to measure the pH value of waste liquid, Ca respectively with liquid-transfering gun after 10min2+Content is measured in parallel two groups, is then averaged,
And in best Ca2+Total sugar amount under the conditions of removal, total phenol equal size.
Although CO2With Ca2+It can form precipitating, but excess CO2Also it can make CaCO3Become Ca (HCO3)2, and become again
At Ca2+And enter waste liquid, therefore pH value is to influence CaCO3An important factor for sedimentation effect.As shown in Fig. 2, pretreatment waste liquid is normal
The lower initial pH value of temperature is 8.84, with CO2Intake increases, the different degrees of decline of solution ph.At 20 °C, molten
Liquid pH value has obvious downward trend, with CO2Intake increase, pH value constantly reducing.It is molten under the conditions of 30 DEG C
Liquid pH value has obvious fluctuating change, with CO2Intake increase, pH value first reduces to rise again and reduce again, but always
Lower than initial value.Under the conditions of 40 DEG C, solution ph has obvious variation tendency, with CO2Intake increase, solution
PH value is nearby reduced rapidly by 8.2, is then slowly risen again.It can totally find out temperature to solution final ph by Fig. 2
Influence is smaller, and temperature is excessively high, CaCO3It can be precipitated.CO2Intake is only the principal element for influencing pH value, with CO2It is continuous plus
Enter, solution ph, which can reduce, is finally reached more stable state.
As shown in figure 3, solution can be with CO after pretreatment2Intake increase and reduce Ca2+Concentration, removal rate are final
Reach relative balance state.No matter under the conditions of 20 DEG C, 30 DEG C or 40 DEG C, with CO2Be continuously added, Ca in solution2+Contain
Amount is being reduced.Meanwhile Ca2+Removal rate is gradually increased, and is finally reached certain equilibrium state.As shown in Figure 3, Ca2+Removal rate
Under the conditions of 30 DEG C, maximum Ca2+Removal rate can reach 65% or so, and the variation sequence of final removal rate is 30 DEG C of >, 20 DEG C of > 40
℃.This is because CaCO3Precipitating can be reduced as temperature increases solubility, then Ca2+Removal rate reduces, and is finally reached relatively flat
The state of weighing apparatus.Auxiliary agent and CO are taken compared to Zhu Zhenxing etc.2Combination method is to Ca in waste water2+Removal, the experimental results such as Zhu Zhenxing
CO in the case where guaranteeing certain flow rate2, Ca after auxiliary agent is added2+Removal rate is up to 90% or more, the initial Ca that uses2+Concentration is about
500mg/L, and the initial Ca of pretreatment waste liquid that this test is used2+About 2800mg/L, higher initial Ca2+Concentration is to removal rate
It is affected.In addition, this experiment purpose is the Ca of the introducing too high levels in removal pretreatment waste liquid2+, it is subsequent pretreatment
Waste liquid anaerobic fermentation provides raw material, and being added without auxiliary agent, there will be no other impurity to be mixed into.If Ca2+With other impurities ion concentration
It is excessively high, serious depression effect will be generated to the subsequent anaerobic fermentation of waste liquid.In conclusion select 30 DEG C as CO2Remove Ca2+
Optimum temperature, CO2Intake is 120mL, i.e., the intake of biogas is 240mL.
Embodiment 5: the time is to pretreatment waste liquid Ca2+The influence of removal rate
It is search time to pretreatment waste liquid Ca2+The influence of removal rate, after pretreatment and be cooled to room temperature pretreatment it is useless
Liquid is at 30 DEG C, 0.5min, 1min, 2min, 5min near theoretical value, with the speed of 30mL/min under the conditions of 10min, 30min
Biogas is each led under degree, obtained liquid staticly settles, and then takes supernatant measurement useless after 3500r/min is centrifuged 10min
The pH value of liquid, Ca2+Content is measured in parallel two groups, is then averaged and records.
CO is passed through with the flow velocity of 30mL/min into pretreatment waste liquid at 30 DEG C2, it is useless to pretreatment to analyze different time
The influence of liquid pH value.As shown in Figure 4.With CO within 2min2The pH value for being passed through solution sharply decline and drop to 7.9 by 8.3
Left and right, this is because CO2It is just added and forms a large amount of carbonic acid and pH value is caused to decline.Subsequent 2-10min solution ph increases again,
This is because a large amount of CO3 2-With the Ca to dissociate in solution2+In conjunction with generation CaCO3Precipitating, causes pH value to rise.And after 10 minutes
Solution ph will be slow reduction, this is because with CaCO3Saturation, and CaCO3It is not very stable for precipitating, with a large amount of CO2It is logical
Enter, part CaCO3Dissolution, becomes Ca (HCO3)2, pH value is caused to decline.From the variation of pH value it is found that being passed through 2min can achieve
Appropriate pH value meets the optimal pH range of fermentation if the waste liquid is used for anaerobic fermentation.
As shown in Figure 5 and Figure 6, according to removal front and back Ca2+Concentration calculation obtain Ca2+Removal rate, the time is to Ca2+It goes
Influence and CO except rate2Intake to Ca2+Removal rate influences similar.Under the conditions of 30 DEG C, CO is constantly passed through into solution2,
Start in 2min just, Ca in solution2+Content can sharply decline, because of major part Ca2+Rapidly with the CO that is dissolved in water3 2-Ion
In conjunction with generation CaCO3Precipitating.But then within 5min, Ca2+Concentration slowly reduces.After 5min, as the time increases,
Ca2+Concentration variation is smaller, tends to metastable concentration.Ca2+Removal rate and Ca2+Concentration curve is exactly the opposite, as shown in fig. 6,
Ca2+Removal rate increased dramatically before this, and then increase tendency is slowed by, Ca2+Removal rate can achieve maximum in 10min or so
Removal rate.As the time is to increase, after 10min, final Ca2+Removal rate tends to more stable state.At any time to removal rate
Between variation data carry out nonlinear fitting, obtain maximum material removal rate be 64.45%.
Embodiment 6: temperature, CO2The influence of intake and time to total phenol content in pretreatment waste liquid
Oxygenation pretreatment can generally generate phenolic substances, and the presence of total phenol plays inhibiting effect to subsequent anaerobic fermentation, institute
It is critically important to detect total phenol content in waste liquid.By Fig. 7-8 it is found that with CO under the conditions of 20 DEG C and 30 DEG C2Be passed through in solution
The removal rate of total phenol all shows downward trend, and when temperature increases to 40 DEG C, the removal rate of total phenol becomes very unstable,
It may be that temperature influences Ca2+Content has then influenced the content of total phenol.And under the conditions of 30 DEG C, as the time is continuously increased,
Then total phenol removal rate reduced before this in solution increases again.So comprehensive analysis combination chart, the content of total phenol can be in solution
Precipitating generation and reduce, with temperature, CO2The influence of intake and time, there is no direct linear relationships.It is passed through CO2It is heavy
Shallow lake Ca2+So that the content of total phenol reduces 6%-10%, there is positive effect to subsequent waste liquid anaerobic fermentation.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that the ordinary skill of this field is without wound
The property made labour, which according to the present invention can conceive, makes many modifications and variations.Therefore, all technician in the art
Pass through the available technology of logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Scheme, all should be within the scope of protection determined by the claims.
Claims (10)
1. a kind of processing method of agriculture and forestry organic waste material alkaline pretreatment coupling marsh gas purifying, which comprises the following steps:
Step 1: Ca (OH) is added after agriculture and forestry organic waste material is crushed2Solution carries out alkalescence pretreatment, after being sufficiently mixed, is separated by solid-liquid separation
It obtains pretreatment residue and pre-processes waste liquid；
Step 2: the pretreatment residue is mixed with seed sludge, carries out anaerobic fermentation Biogas；
Step 3: biogas is passed through the pretreatment waste liquid by reflux unit；
Step 4: the pretreatment waste liquid after biogas will be passed through and be separated by solid-liquid separation, continued after gained supernatant seed sludge
Anaerobic fermentation Biogas, the biogas pretreatment waste liquid.
2. the processing method of agriculture and forestry organic waste material alkaline pretreatment coupling marsh gas purifying as described in claim 1, which is characterized in that
In the step 1, the Ca (OH)2Ca (OH) in solution2Mass percent is 0.5%-10%.
3. the processing method of agriculture and forestry organic waste material alkaline pretreatment coupling marsh gas purifying as described in claim 1, which is characterized in that
In the step 1, the alkalescence pretreatment is aided with including but not limited to grinding, microwave treatment, heat treatment.
4. the processing method of agriculture and forestry organic waste material alkaline pretreatment coupling marsh gas purifying as described in claim 1, which is characterized in that
In the step 1, the separation of solid and liquid including but not limited to centrifugation, filtering.
5. the processing method of agriculture and forestry organic waste material alkaline pretreatment coupling marsh gas purifying as described in claim 1, which is characterized in that
In the step 3, CO in the biogas reflux2Concentration be 30%-60%, temperature be 20 DEG C -40 DEG C.
6. the processing method of agriculture and forestry organic waste material alkaline pretreatment coupling marsh gas purifying as described in claim 1, which is characterized in that
In the step 3, the rate that is passed through of the biogas is 10-100mL/mL pretreatment fluid/min, and being passed through the time is 1-30min.
7. the processing method of agriculture and forestry organic waste material alkaline pretreatment coupling marsh gas purifying as described in claim 1, which is characterized in that
In the step 3, CO in the biogas2Intake is 120mL, and temperature is 30 DEG C.
8. the processing method of agriculture and forestry organic waste material alkaline pretreatment coupling marsh gas purifying as described in claim 1, which is characterized in that
In the step 3, the reflux unit includes conduit, connects the pretreatment waste liquid and the biogas generation apparatus, connects institute
The conduit for stating pretreatment waste liquid gos deep under the pretreatment waste liquid liquid level, and the conduit connects the outlet of the biogas generation apparatus
Mouthful.
9. the processing method of agriculture and forestry organic waste material alkaline pretreatment coupling marsh gas purifying as described in claim 1, which is characterized in that
In the step 4, the purified biogas pretreatment waste liquid further removes CO2。
10. the processing method of agriculture and forestry organic waste material alkaline pretreatment coupling marsh gas purifying as claimed in claim 8, feature exist
In in the step 4, the supernatant seed sludge is connect by gas outlet with the conduit.
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| US20050153410A1 (en) * | 2004-01-08 | 2005-07-14 | Dakota Ag Energy, Inc. | Integrated process for producing "clean beef" (or milk), ethanol, cattle feed and bio-gas/bio-fertilizer |
| CN102382698A (en) * | 2011-04-29 | 2012-03-21 | 王嘉兴 | Method for producing calcium carbonate during marsh gas purification |
| CN104031944A (en) * | 2014-06-26 | 2014-09-10 | 浙江大学 | Method for increasing output of bagasse anaerobic digestion biogas through pretreatment |
| CN106277646A (en) * | 2016-09-23 | 2017-01-04 | 嘉兴学院 | A kind of utilize helotisn body synchronous purification biogas slurry and the system of former biogas |
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| US20050153410A1 (en) * | 2004-01-08 | 2005-07-14 | Dakota Ag Energy, Inc. | Integrated process for producing "clean beef" (or milk), ethanol, cattle feed and bio-gas/bio-fertilizer |
| CN102382698A (en) * | 2011-04-29 | 2012-03-21 | 王嘉兴 | Method for producing calcium carbonate during marsh gas purification |
| CN104031944A (en) * | 2014-06-26 | 2014-09-10 | 浙江大学 | Method for increasing output of bagasse anaerobic digestion biogas through pretreatment |
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| CN112322366A (en) * | 2020-11-13 | 2021-02-05 | 北京建筑大学 | Method for preparing natural gas by mixing and gasifying solar biomass |
| CN112322366B (en) * | 2020-11-13 | 2022-02-01 | 北京建筑大学 | Method for preparing natural gas by mixing and gasifying solar biomass |
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