CN105154160A - Method for purifying biogas and co-producing nano calcium carbonate - Google Patents
Method for purifying biogas and co-producing nano calcium carbonate Download PDFInfo
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- CN105154160A CN105154160A CN201510628328.2A CN201510628328A CN105154160A CN 105154160 A CN105154160 A CN 105154160A CN 201510628328 A CN201510628328 A CN 201510628328A CN 105154160 A CN105154160 A CN 105154160A
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 62
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title abstract description 23
- 239000012528 membrane Substances 0.000 claims abstract description 78
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000000746 purification Methods 0.000 claims abstract description 26
- 238000003860 storage Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 23
- 239000012071 phase Substances 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 15
- 238000012806 monitoring device Methods 0.000 claims description 7
- 239000007792 gaseous phase Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000010865 sewage Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 239000000047 product Substances 0.000 abstract description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 13
- 238000003763 carbonization Methods 0.000 abstract description 12
- 239000000292 calcium oxide Substances 0.000 abstract description 7
- 235000012255 calcium oxide Nutrition 0.000 abstract description 7
- 239000000839 emulsion Substances 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 4
- 238000012544 monitoring process Methods 0.000 abstract description 4
- 239000012065 filter cake Substances 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract 1
- 235000011941 Tilia x europaea Nutrition 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000002737 fuel gas Substances 0.000 abstract 1
- 239000004571 lime Substances 0.000 abstract 1
- 239000008267 milk Substances 0.000 abstract 1
- 210000004080 milk Anatomy 0.000 abstract 1
- 235000013336 milk Nutrition 0.000 abstract 1
- 239000000920 calcium hydroxide Substances 0.000 description 21
- 235000011116 calcium hydroxide Nutrition 0.000 description 21
- 239000011575 calcium Substances 0.000 description 16
- 238000007670 refining Methods 0.000 description 13
- 239000000725 suspension Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 6
- 229930006000 Sucrose Natural products 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000005720 sucrose Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000005255 carburizing Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
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- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229940045511 barium chloride Drugs 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- -1 papermaking Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a method for purifying biogas to enable the methane content to reach the vehicle fuel gas standard and obtaining high value-added nano calcium carbonate in the purification process. Slaking quicklime, filtering to obtain lime milk fine slurry, adding into a storage tank of a carbonization device, and adding a dispersing agent. And introducing methane into the membrane reactor, carrying out carbonization reaction, monitoring on line, and stopping the reaction when the pH is lower than 7. The membrane reactor a and the membrane reactor b in the process respectively represent a purification stage and a carbonization stage, so that the complete purification of the biogas and the complete carbonization of the calcium carbonate product are ensured. And centrifuging the reacted calcium carbonate emulsion to obtain a calcium carbonate filter cake, and drying and crushing to obtain the product nano calcium carbonate. The method utilizes the novel membrane reactor to purify the methane to obtain high-purity biomethane and simultaneously can obtain the nano calcium carbonate with excellent performance.
Description
this case is original applying number is 201410153531.4, and the applying date is the divisional application of the application for a patent for invention on April 17th, 2014.
Technical field
The present invention relates to a kind of method of methane purification, belong to separation engineering technology.Utilize membrane reactor while purifying marsh gas obtains high purity biological methane, the nano-calcium carbonate of excellent.
Background technology
The calorific value of biogas is about 20-25MJ/m
3, lm
3the calorific value of biogas is equivalent to 0.8kg Sweet natural gas, than biological methane calorific value (39.8MJ/m
3) low, its use range is limited, and efficiency of energy utilization is low.Scholars more both domestic and external are also in more use value of research biogas.In biogas except methane, also has the CO of about 40%
2, a small amount of water and hydrogen sulfide.In order to improve calorific value and the use value of biogas, purification is necessary means.
Biogas can obtain highly purified biological methane through advanced purification technology, biological methane is a kind of energy of high-quality and important industrial chemicals, main resultant after burning is carbonic acid gas and water, and its greenhouse gases produced only have 1/2 of coal, are 2/3 of oil.Biological methane is used for life fuel and vehicle fuel by compression, Cemented filling, is the best biomass energy of the fossil oils such as replacing gasoline, liquefied gas and coal.Biogas obtains highly purified biological methane and by product CO through purification techniques
2, with CO
2the novel process that nano-calcium carbonate can reach a kind of Zero-discharge non-pollution is prepared as industrial raw material.Reclaim and utilize CO
2, can reduce environmental pollution, be the core that green energy resource is produced.
By product nano-calcium carbonate can be used as novel filler additive, is widely used in the industry of coating, papermaking, rubber, plastics, ink etc.The special calcium development such as medicine, food is also tended in present research, because its relative low price can substitute the filler of high price; Because its excellent mechanical property is widely used as the additive of matrix material, development space is very large.
Chinese patent ZL202898377U discloses the device of a kind of Methane decarbonization interlock system for nano-calcium carbonate.This device includes a calcium hydroxide storage tank, the liquid outlet of calcium hydroxide storage tank passes into micro passage reaction inner chamber, the biogas entrance of micro passage reaction is connected with biogas source with air pump through microporous membrane, the outlet of micro passage reaction connects gas-liquid separator, the liquid exit of gas-liquid separation junctor is connected through the fluid inlet of liquid feeding pump with calcium hydroxide storage tank, and the pneumatic outlet of gas-liquid separator connects purified gas pipeline; Bottom micro passage reaction, ultrasonic generator is installed.Said apparatus can remove CO in biogas
2while obtain nano-calcium carbonate product, adopt ultrasonic cavitation effect in its production process, the dissolving of calcium hydroxide can be promoted, promote calcium hydroxide and CO
2reaction, improve CO
2removal efficiency; The dispersiveness of nano-calcium carbonate can be promoted simultaneously, reduce and reunite, improve product quality.
But said apparatus pressure reaches 1.6MPa, utilize air pump to be connected with biogas, power is large, big energy-consuming; This reaction is step carburizing reagent, discontinuous reaction, and carbonation rate is low, too increases cost of investment; Do not have tail gas Monitoring systems and pH to detect in device, the termination of reacting can not be controlled timely and effectively, sampling be carried out and survey pH yet; And the present invention is continuous print reaction, ensure that gets back while biogas is purified completely is carbonized calcium carbonate product completely; Present invention utilizes CO
2sensor is to the CO in the biogas after purification
2content on-line monitoring; The present invention can observe the process of reaction timely and effectively.
Summary of the invention
The present invention be directed to the method removing a kind of purification of proposition of biogas component, to provide one can by common methane purification, be refined into the technology of the processing requirement that can meet natural gas used for automobile, and in scavenging process, obtain the new technology having high added value nano-calcium carbonate.The present invention is the carburizing reagent of continous way, and ensure that gets back while biogas is purified completely is carbonized calcium carbonate product completely, and CO
2sensor device is to the CO in the biogas after purification
2content on-line monitoring, does not need to carry out sampling and surveys pH, just can observe the process of reaction timely and effectively.
The method of methane purification coproduction nano-calcium carbonate of the present invention comprises the steps:
(1) Ca (OH) is prepared
2mass percent concentration is the milk of lime refining of 3%-10%:
(2) carbonization and purification: add dispersion agent according to the mass ratio of 0.1%-1% in milk of lime refining, pass into membrane reactor after mixing, pass into biogas in membrane reactor, control temperature is no more than 60 DEG C, pressure reacts lower than below 0.4MPa, when pH lower than 7 time stopped reaction, obtain CaCO
3emulsion;
(3) by CaCO
3emulsion is centrifugal, and gained calcium carbonate filter cake is dry, pulverizing, obtains nano-calcium carbonate;
Wherein, described membrane reactor comprises membrane reactor a and membrane reactor b, and milk of lime refining enters membrane reactor a and membrane reactor b successively from feed sump, and biogas passes into membrane reactor b, in membrane reactor b, carry out carburizing reagent, enter membrane reactor a after reaction terminates and carry out purification.
The present invention's principles of chemistry used in the process of marsh gas purifying and by-product nano-calcium carbonate are as follows:
CaO+H
2O=Ca(OH)
2
Ca(OH)
2+CO
2=CaCO
3+H
2O
The present invention's process engineering principle used in the process of marsh gas purifying and by-product nano-calcium carbonate is as follows:
Unslaked lime, after digestion, slaking, sieving, pumps in membrane reactor, as external phase with the form of calcium hydroxide suspension; Biogas under certain pressure drives from membrane reactor the opposite side of film through film, and become disperse phase with the form of micro bubble.The carburizing reagent that membrane module in membrane reactor carries out for biogas and calcium hydroxide suspension provides limited space, can strengthen mass-transfer efficiency between the two, and the carbonic acid gas in biogas is removed fully.
Method of the present invention, wherein said step (1) is: by unslaked lime slaking 24h, and then filter respectively through 150 orders, 325 object filter sieve, obtain milk of lime refining, namely thin up obtains Ca (OH)
2mass percent concentration is the milk of lime refining of 3%-10%.Ca (OH) in preferred milk of lime refining
2mass percent concentration is 6%.Milk of lime refining prepared by above-mentioned condition eliminates impurity with anti-clogging plug film pipe, also ensure that the whiteness of product and controls particle size distribution range.
In step of the present invention (2), the gas of biogas and the amount of substance ratio of liquid are 1:1-1:3, preferred 1:2, to control better to react more fully, guarantee to be obtained by membrane reactor b to be carbonized calcium carbonate product completely, purified completely by membrane reactor a methane energy.
Dispersion agent of the present invention is Zinc vitriol, bariumchloride, EDTA or sucrose.The sucrose of preferably described dispersion agent is add-on to be mass ratio be 0.1%-1%, more preferably 0.5%.After the present invention enters specific dispersion agent, glossiness can be promoted and reduce viscosity, also can prevent calcium carbonate emulsion sedimentation and the cohesion of formation, occur agglomeration.
The present invention selects sucrose to be under dispersion agent, and gained nano-calcium carbonate is cubic type.
Invention further provides the device realizing aforesaid method.
The above-mentioned device for methane purification coproduction nano-calcium carbonate, comprise the feed sump, membrane reactor a, gas-liquid separator a, membrane reactor b, gas-liquid reactor b and the product storage tank that connect successively, and being connected to separately tank for sewage gas and the biogas conveying assembly of membrane reactor b, the gaseous phase outlet of described gas-liquid separator b is connected with membrane reactor a; The gaseous phase outlet of membrane reactor a connects CO
2sensor; Also part flow arrangement is provided with between gas-liquid separator a and feed sump.
Wherein said membrane reactor a and membrane reactor b is identical known structure, and the mean pore size of dispersion membrane is 6 μm, and 19 microchannels side by side, are pressed into another phase by gas phase by pressure, two-phase Quick uniform mixing in the reactor.
Membrane reactor a, as the cleansing phase of whole reaction, ensures that biogas is cleaned completely in this process; And as the membrane reactor b of carbonation stage, being to ensure that suspension can be carbonized completely, obtaining the nano-calcium carbonate calcium product of high added value.Gas phase and the liquid phase entrance of membrane reactor a and b are oppositely arranged, and to realize mixing more fully, complete purification and carbonization.
Adopt above-mentioned membrane reactor, the present invention while guaranteeing purification rate, can obtain the byproduct that added value is high.
Wherein, described biogas conveying assembly comprises gas flow and takes into account tensimeter; Described part flow arrangement is diverting valve; Be provided with whipping appts bottom described feed sump, between feed sump and membrane reactor a, be provided with pump and under meter.
Described device also comprises Controlling System, and described control device comprises computer and pH monitoring device, and this pH monitoring device is connected the control realized part flow arrangement with part flow arrangement, described Controlling System also with CO
2sensor is connected.In technical scheme of the present invention, tank for sewage gas and biogas conveying assembly are connected with membrane reactor b, carburizing reagent is there is in biogas and milk of lime refining in membrane reactor b, namely calcium carbonate product is obtained after gas-liquid separator b, enter into product storage tank, gas (biogas after carbonization) after gas-liquid separator b is separated enters membrane reactor a, again react at membrane reactor a and milk of lime refining liquid, this process is clean-up stage, guarantees that biogas is cleaned completely in this process.CO is drained into by the pneumatic outlet of gas-liquid separator a
2sensor detects gas.
The invention has the beneficial effects as follows:
1. the methane content after purifying is increased to more than 97% by 50%-60%, is effectively stripped of CO
2, reach natural gas used for automobile and use standard.
2. in membrane module, biogas is cut into the bubble of nominal particle size by the external phase (liquid) flowed by small duct, with external phase calcium hydroxide suspension Homogeneous phase mixing, the formation of micro bubble adds gas-liquid two-phase contact area, accelerate the carrying out of reaction, by controlling suitable reaction conditions, nanometer level calcium carbonate particle can be obtained; The methane not participating in reacting is reclaimed by gas-liquid separator.The present invention design new membrane reactor in reaction process pressure-controlling at 0.1-0.4MPa.Pressure disclosed in China Patent Publication No. CN102382698 is 1.2-1.8MPa, and the carbonization of high pressure requires that equipment is complicated, consumes energy high.
3. add dispersion agent before the carbonization of milk of lime refining, avoid the phenomenon that nano-calcium carbonate is reunited, effectively control calcium carbonate granule size, products obtained therefrom particle diameter is within 100nm.
4. the present invention utilizes the mode of secondary membrane reactors in series to react, and ensure that gets back while biogas is purified completely is carbonized calcium carbonate product completely, and diverting valve is monitored by pH meter and controlled, and guarantees that slurries are carbonized completely.
5. the membrane reactor purifying marsh gas that adopts of the present invention, number of devices is few, and control simple, floor space is little, only needs geometry simply to amplify according to treatment scale size, has the advantage that less investment, working cost are low etc. compared with the purifying method such as pressure-variable adsorption.Due to CO in scavenging process
2generate the nano-calcium carbonate calcium product of high added value as reactant, therefore, the present invention defines one " zero carbon emission pattern ", meets the requirement of green chemistry process, has good environmental protection and social effect.
Accompanying drawing explanation
Fig. 1 is experimental installation sketch of the present invention; Wherein, 1 is whipping appts; 2 is feed sump; 3 is pump; 4 is under meter; 5 is membrane reactor a; 6 is gas-liquid separator a; 7 is membrane reactor b; 8 is gas-liquid separator b; 9 is tensimeter; 10 is gas meter; 11 is tank for sewage gas; 12 is product storage tank; 13 is pH monitoring device; 14 is computer; 15 is CO
2sensor; 16 is diverting valve.
Fig. 2 is the TEM figure of nano-calcium carbonate calcium product.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
embodiment 1
As shown in Figure 1 for the device of methane purification coproduction nano-calcium carbonate, comprise the feed sump 2, membrane reactor a5, gas-liquid separator a6, membrane reactor b7, gas-liquid reactor b8 and the product storage tank 12 that connect successively, and being connected to separately tank for sewage gas 11 and the biogas conveying assembly of membrane reactor b8, the gaseous phase outlet of gas-liquid separator b8 is connected with membrane reactor a5; The gaseous phase outlet of membrane reactor a5 connects CO
2sensor 15; Diverting valve 16 is also provided with between gas-liquid separator a and feed sump.
Wherein, described membrane reactor a and membrane reactor b is identical known structure, and the mean pore size of dispersion membrane is 6 μm, and 19 microchannels side by side, are pressed into another phase by gas phase by pressure, two-phase Quick uniform mixing in the reactor.
Membrane reactor a, as the cleansing phase of whole reaction, ensures that biogas is cleaned completely in this process; And as the membrane reactor b of carbonation stage, being to ensure that suspension can be carbonized completely, obtaining the nano-calcium carbonate calcium product of high added value.
Above-mentioned two membrane reactors, liquid phase and the entrance of gas phase are oppositely arranged to obtain to have contacted more fully and purify and carbonation stage.
Above-mentioned biogas conveying assembly comprises pneumatic tube and the gas meter 10 be located on pneumatic tube and tensimeter 9; Be provided with whipping appts 1 bottom feed sump 2, between feed sump 2 and membrane reactor a5, be provided with pump 3 and under meter 4.
Device described in the present embodiment also comprises Controlling System (see dotted portion), described control device comprises computer 14 and pH monitoring device 13, this pH monitoring device 13 is connected with part flow arrangement (i.e. diverting valve 16) control realized part flow arrangement, described Controlling System also with CO
2sensor 15 is connected to monitor biogas purity.
embodiment 2
Milk of lime refining is prepared in quicklime slaking, slaking, filtration, dilution.Be in Ca (OH) 2 suspension of 3% in concentration, add the sucrose that mass ratio is 0.1%, inject feed sump, control to enter membrane reactor a and membrane reactor b successively through pump and under meter, in membrane reactor b, pass into biogas, control liquid flow rate, the pH=6.72 of termination reaction, the nano-calcium carbonate calcium solution obtained carries out centrifugal, dry at 70 DEG C.From membrane reactor a, expellant gas enters membrane reactor a and carries out purification again, reaches 96% by the methane content in the biogas after vapor detection carbonization and purification.Observe under transmission electron microscope, calcium carbonate granule has agglomeration to exist, and size distribution is at 40-100nm, and dispersed effect is undesirable.When this illustrates that the mass ratio that adds of dispersion agent is 0.1%, dispersion effect does not reach the ideal value of expection, there is agglomeration, and size distribution is wider, and in system, liquid phase amount of substance is than during for 1:1, and suspension concentration is less when being 3%, and decarburization effect is slightly on the low side.
embodiment 3:
Milk of lime refining is prepared in quicklime slaking, slaking, filtration, dilution.Be in Ca (OH) 2 suspension of 6% in concentration, add the sucrose that mass ratio is 0.5%, inject feed sump, control to enter membrane reactor a and membrane reactor b successively through pump and under meter, in reactor b, pass into biogas, control liquid flow rate, the pH=6.82 of termination reaction, the nano-calcium carbonate calcium solution obtained carries out centrifugal, dry at 60 DEG C.From membrane reactor a, expellant gas enters membrane reactor a and carries out purification again, reaches 98% by the methane content in the biogas after vapor detection carbonization and purification.Observe under transmission electron microscope, calcium carbonate granule is cubic type (see figure 2), and better dispersed, average particle size distribution is about 50nm.When this illustrates that the mass ratio that dispersion agent adds is 0.5%, dispersion effect is better, and size distribution is narrow, and in system, liquid phase amount of substance is than during for 1:2, and when suspension concentration is 6%, carbon-drop rate is desirable.
embodiment 4:
Milk of lime refining is prepared in quicklime slaking, slaking, filtration, dilution.Be in Ca (OH) 2 suspension of 10% in concentration, add the sucrose that mass ratio is 1%, inject feed sump, control to enter membrane reactor a and membrane reactor b successively through pump and under meter, in reactor b, pass into biogas, control liquid flow rate, the pH=6.75 of termination reaction, the nano-calcium carbonate calcium solution obtained carries out centrifugal, dry at 80 DEG C.From membrane reactor a, expellant gas enters membrane reactor a and carries out purification again, reaches 97% by the methane content in the biogas after vapor detection carbonization and purification.Observe under transmission electron microscope, calcium carbonate granule is cubic type (see figure 2), and good dispersity, size distribution is at 60nm.When this illustrates that the mass ratio that dispersion agent adds is 1%, dispersion effect is good, and size distribution is narrow, and in system, liquid phase amount of substance is than during for 1:3, and when suspension concentration is 10%, carbon-drop rate is desirable.
Although above with general explanation, embodiment and test, the present invention is described in detail, and on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (4)
1. the device for methane purification coproduction nano-calcium carbonate, comprise the feed sump, membrane reactor a, gas-liquid separator a, membrane reactor b, gas-liquid reactor b and the product storage tank that connect successively, and being connected to separately tank for sewage gas and the biogas conveying assembly of membrane reactor b, the gaseous phase outlet of described gas-liquid separator b is connected with membrane reactor a; The gaseous phase outlet of membrane reactor a connects CO
2sensor; Also part flow arrangement is provided with between gas-liquid separator a and feed sump.
2. device according to claim 1, it is characterized in that: described membrane reactor a and membrane reactor b is identical known structure, the mean pore size of dispersion membrane is 6 μm, 19 microchannels side by side, gas phase is pressed into another phase by pressure, two-phase Quick uniform mixing in the reactor.
3. device according to claim 1 and 2, is characterized in that: described biogas conveying assembly comprises gas flow and takes into account tensimeter; Described part flow arrangement is diverting valve; Be provided with whipping appts bottom described feed sump, between feed sump and membrane reactor a, be provided with pump and under meter.
4. device according to claim 1 and 2, it is characterized in that: described device also comprises Controlling System, described control device comprises computer and pH monitoring device, and this pH monitoring device is connected the control realized part flow arrangement with part flow arrangement, described Controlling System also with CO
2sensor is connected.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410153531.4A CN103911197A (en) | 2014-04-17 | 2014-04-17 | Method for purifying biogas and co-producing nano calcium carbonate |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410153531.4A Division CN103911197A (en) | 2014-04-17 | 2014-04-17 | Method for purifying biogas and co-producing nano calcium carbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105154160A true CN105154160A (en) | 2015-12-16 |
Family
ID=51037208
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
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| CN201410153531.4A Pending CN103911197A (en) | 2014-04-17 | 2014-04-17 | Method for purifying biogas and co-producing nano calcium carbonate |
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| CN105623769A (en) * | 2016-03-28 | 2016-06-01 | 南京工业大学 | Process for co-producing nano calcium carbonate by biogas purification |
| CN108624370A (en) * | 2017-03-20 | 2018-10-09 | 中国石油化工股份有限公司 | The method that biogas UF membrane purifies biological methane processed |
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| EP3124436A1 (en) | 2015-07-31 | 2017-02-01 | Omya International AG | Precipitated calcium carbonate with improved resistance to structural breakdown |
| CN108102655A (en) * | 2017-12-20 | 2018-06-01 | 安徽省上行山茶叶有限公司 | A kind of soil remediation additive for cadmium pollution white tea plantation field |
| CN110577232B (en) * | 2019-10-24 | 2022-07-12 | 长江师范学院 | Preparation method of nano calcium carbonate |
| CN114229879A (en) * | 2022-01-27 | 2022-03-25 | 张文斌 | Industrialized negative carbon emission biomass energy utilization technology BECCU method |
| CN116477652A (en) * | 2023-03-13 | 2023-07-25 | 上海林海生态技术股份有限公司 | Method for preparing black conductive nano calcium carbonate by biogas slurry synchronous double decomposition coating method |
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