CN204710843U - A kind of alkali ash-cinder reutilization system - Google Patents
A kind of alkali ash-cinder reutilization system Download PDFInfo
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- CN204710843U CN204710843U CN201520383705.6U CN201520383705U CN204710843U CN 204710843 U CN204710843 U CN 204710843U CN 201520383705 U CN201520383705 U CN 201520383705U CN 204710843 U CN204710843 U CN 204710843U
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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
Abstract
The utility model provides a kind of alkali ash-cinder reutilization system, belongs to catalytic coal gasifaction technical field, achieves the recycling of alkali ash-cinder, effectively avoids being discharged in environment the injury caused environment.Described alkali ash-cinder reutilization system comprises catalytic gasification unit and the biodiesel that is connected with described catalytic gasification unit prepares unit, wherein, the alkali ash-cinder that described catalytic gasification unit produces is provided to described biodiesel and prepares catalyst as production biodiesel in unit.The utility model can be used for the lime-ash effectively processing the generation of catalytic coal gasifaction process.
Description
Technical field
The utility model relates to catalytic coal gasifaction technical field, particularly relates to a kind of alkali ash-cinder reutilization system.
Background technology
Catalytic coal gasifaction technology is clean and a kind of important way of efficiency utilization coal.In catalytic coal gasifaction technology, coal at relatively low temperature with water vapour (H
2o), hydrogen (H
2), the gasifying agent that forms of carbon monoxide (CO) carries out gasification reaction under the catalytic action of catalyst, generates the methane (CH of high concentration
4).
The inorganic compound of catalyst mainly alkali metal, alkaline-earth metal and transition metal etc. that catalytic coal gasifaction technology uses, wherein the catalytic activity of base metal catalysts is relatively better, effectively can improve gasification reaction speed, improve gasification furnace outlet methane content, but, containing a large amount of base metal catalysts in lime-ash after gasification, need to recycle, but catalyst recovery process energy consumption is high, cost is high, greatly have impact on the economy of catalytic gasification technology; Meanwhile, the alkali metal compound recovery in gasification lime-ash is usual and incomplete, can environmental pollution in environment if be directly discharged into.Therefore the alkali ash-cinder that how efficiency utilization catalysis gasification technique produces is subject to extensive concern in the art, but there is no good solution at present.
Utility model content
The utility model provides a kind of alkali ash-cinder reutilization system, achieves the recycling of alkali ash-cinder, efficiently avoid the problem of environmental pollution being discharged into and causing in environment.
For achieving the above object, the utility model adopts following technical scheme:
The utility model provides a kind of alkali ash-cinder reutilization system, described alkali ash-cinder reutilization system comprises catalytic gasification unit and the biodiesel that is connected with described catalytic gasification unit prepares unit, wherein, the alkali ash-cinder that described catalytic gasification unit produces is provided to described biodiesel and prepares catalyst as production biodiesel in unit.
Further, described alkali ash-cinder reutilization system also comprises the both culturing microalgae unit be connected with described catalytic gasification unit, and wherein, the waste gas that described catalytic gasification unit produces, waste water are provided to described both culturing microalgae unit.
Preferably, described both culturing microalgae unit is also prepared unit with described biodiesel and is connected.
Particularly, described catalytic gasification unit is prepared unit by methanation or Poly-generation unit with described biodiesel and is connected, and described methanation or Poly-generation unit are configured to the gas from described catalytic gasification unit to carry out methanation or Poly-generation and the methyl alcohol obtained is supplied to described biodiesel prepare unit.
Particularly, described catalytic gasification unit is connected with described methanation or Poly-generation unit by gas purification unit, and described gas purification unit is also connected with described both culturing microalgae unit, described gas purification unit is configured to carry out purification separation to the gas from described catalytic gasification unit and the waste water containing organic matter and/or ammonia obtained and CO 2 waste gas is supplied to described both culturing microalgae unit, and purified gas is supplied to described methanation or Poly-generation unit.
Further, described both culturing microalgae unit is prepared unit by micro-algae processing unit with described biodiesel and is connected, and described micro-algae processing unit is configured to from the micro-algae from described both culturing microalgae unit, extract algae oil and described algae oil is supplied to described biodiesel prepare unit; Or be configured to carry out drying with shape algae powder to the micro-algae from described both culturing microalgae unit described algae powder is supplied to described biodiesel prepares unit.
Preferably, described catalytic gasification unit is prepared unit by alkali ash-cinder pretreatment unit with described biodiesel and is connected, described alkali ash-cinder pretreatment unit is configured to carry out pretreatment to described alkali ash-cinder, makes the alkali metal compound in described alkali ash-cinder and/or alkaline earth metal compound be converted into corresponding carbonate.
Alternatively, described catalytic gasification unit is connected with described alkali ash-cinder pretreatment unit by catalyst recovery unit, and described catalyst recovery unit is configured to wash with recovery section soluble alkali metal containing alkali cpd and/or alkaline earth metal compound described alkali ash-cinder.
Alternatively, described catalytic gasification unit is connected with described alkali ash-cinder pretreatment unit by Quench unit, and described Quench unit is configured to carry out Quench to the high temperature alkali ash-cinder from described catalytic gasification unit.
Alternatively, described alkali ash-cinder reutilization system also comprises the catalyst dispensing unit be connected with described catalytic gasification unit, described catalyst dispensing unit is also connected with described catalyst recovery unit, and described catalyst recovery unit is also configured to the soluble alkali metal compound of recovery or alkaline earth metal compound to be supplied to described catalyst dispensing unit.
The utility model provides a kind of alkali ash-cinder reutilization system, catalytic gasification unit and biodiesel are prepared unit and are connected by this system, and the alkali ash-cinder that catalytic gasification unit produces is fed to biodiesel and prepares in unit, due in the alkali ash-cinder that catalytic gasification unit produces, described " alkali " is generally alkali metal compound or is alkaline earth metal compound; And biodiesel is prepared in unit, these alkali metal compounds or alkaline earth metal compound can be carried out catalysis grease with the ester exchange reaction between methyl alcohol as catalyst, thus production biodiesel, like this, the utility model achieves the recycling of alkali ash-cinder, avoids being discharged in environment causing environmental pollution;
In addition, prepare in unit in biodiesel, lime-ash in alkali ash-cinder can be regarded as the carrier of catalyst, namely catalyst (alkali metal compound or alkaline earth metal compound) is equivalent to load on lime-ash, like this, catalyst would not be doped in generated liquid biological diesel oil, thus catalyst can be made to be easy to be separated with biodiesel, thus solve biodiesel and the difficult problem be separated of catalyst of the initiation of prior art employing homogeneous catalyst, and these catalyst can also be cycled to used in biodiesel and prepare unit after separation and recovery, thus improve the economy of preparation of biodiesel.
Accompanying drawing explanation
The structural representation of a kind of alkali ash-cinder reutilization system that Fig. 1 provides for the utility model embodiment;
The structural representation of the another kind of alkali ash-cinder reutilization system that Fig. 2 provides for the utility model embodiment;
The structural representation of the another kind of alkali ash-cinder reutilization system that Fig. 3 provides for the utility model embodiment;
The structural representation of the another kind of alkali ash-cinder reutilization system that Fig. 4 provides for the utility model embodiment.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the utility model embodiment, be clearly and completely described the technical scheme in the utility model embodiment, obviously, described embodiment is only the utility model part embodiment, instead of whole embodiments.Based on the embodiment in the utility model, those of ordinary skill in the art are not making the every other embodiment obtained under creative work prerequisite, all belong to the scope of the utility model protection.
As shown in Figure 1, the utility model embodiment provides a kind of alkali ash-cinder reutilization system, the biodiesel comprising catalytic gasification unit 10 and be connected with catalytic gasification unit 10 prepares unit 20, wherein, the alkali ash-cinder that described catalytic gasification unit 10 produces is provided to biodiesel and prepares catalyst as production biodiesel in unit 20.
The utility model provides a kind of alkali ash-cinder reutilization system, catalytic gasification unit 10 and biodiesel are prepared unit 20 and are connected by this system, and the alkali ash-cinder that catalytic gasification unit 10 produces is fed to biodiesel and prepares in unit 20, due in the alkali ash-cinder that catalytic gasification unit 10 produces, described " alkali " is generally alkali metal compound or is alkaline earth metal compound; And biodiesel is prepared in unit 20, these alkali metal compounds or alkaline earth metal compound can be carried out catalysis grease with the ester exchange reaction between methyl alcohol as catalyst, thus production biodiesel, like this, the utility model achieves the recycling of alkali ash-cinder, avoids being discharged in environment causing environmental pollution;
In addition, prepare in unit 20 in biodiesel, lime-ash in alkali ash-cinder can be regarded as the carrier of catalyst, namely catalyst (alkali metal compound or alkaline earth metal compound) is equivalent to load on lime-ash, like this, catalyst would not be doped in generated liquid biological diesel oil, thus catalyst can be made to be easy to be separated with biodiesel, thus solve biodiesel and the difficult problem be separated of catalyst of the initiation of prior art employing homogeneous catalyst, and these catalyst can also be cycled to used in preparation of biodiesel after separation and recovery, thus improve the economy of preparation of biodiesel.
It should be noted that, in the utility model, catalytic gasification unit 10 and biodiesel prepare unit 20 " being connected ", should refer to " being connected " that catalytic gasification unit 10 and biodiesel were prepared unit 20 and be related, the alkali ash-cinder that catalytic gasification unit 10 can be made to produce is provided to biodiesel to be prepared in unit 20 and as the catalyst of production biodiesel; And might not refer to that the machinery on entity apparatus is connected.Such as, " being connected " should can refer to that two unit were directly connected by pipeline, also can refer to that two unit are connected indirectly by transferring device, the alkali ash-cinder such as produced by catalytic gasification unit 10 by dolly is manually pushed to biodiesel and prepares in unit 20, or catalytic gasification unit 10 is provided to biodiesel after processing alkali ash-cinder via other devices again to be prepared in unit 20.Similarly, in the following, can with reference to explanation explanation herein to the understanding be connected.
In the utility model, catalytic gasification unit 10 can be gasification installation conventional in catalytic gasification technology, is such as gasification furnace etc.Biodiesel is prepared unit 20 and ester exchange reaction can be occurred thus generate the device of biodiesel, as ester exchange reaction device for utilizing methyl alcohol and grease (vegeto-animal grease etc.).
In the utility model embodiment, as shown in Figure 1, catalytic gasification unit 10 can be prepared unit 20 by alkali ash-cinder pretreatment unit 30 and biodiesel and be connected, alkali ash-cinder pretreatment unit 30 is configured to carry out pretreatment to alkali ash-cinder, makes the alkali metal compound in alkali ash-cinder and/or alkaline earth metal compound be converted into corresponding carbonate.
Particularly, this pretreatment can be: at CO
2under gas effect, the catalytically inactive of the alkali metal compound (such as potassium sulfide, potassium silicate) in alkali ash-cinder and/or alkaline earth metal compound (such as calcium sulfide) or the more weak alkali metal of catalytic activity or alkaline-earth metal existence form are converted into carbonate existence form, like this, the reaction that the carbonate form utilizing catalytic efficiency higher in unit 20 comes between catalysis methanol and grease can be prepared, efficiently to generate biodiesel rapidly in biodiesel.
Further, CO is being carried out to alkali ash-cinder
2after activating pretreatment, the pretreatment such as drying, pulverizing can also be carried out to these lime-ash, to reduce lime-ash particle diameter, be conducive to improving the catalytic efficiency of alkali ash-cinder at preparation of biodiesel.
As shown in Figure 1, catalytic gasification unit 10 can be connected with alkali ash-cinder pretreatment unit 30 by catalyst recovery unit 40, and this catalyst recovery unit 40 can be configured to wash alkali ash-cinder with recovery section soluble alkali metal compound and/or alkaline earth metal compound.
Like this, can recovery section soluble catalyst by catalyst recovery unit 40, thus the content of alkali in alkali ash-cinder can be adjusted; And the part soluble catalyst reclaimed can also again mix with coal dust and be provided in catalytic gasification unit 10, thus improve the economy of catalytic gasification system.
Such as, if what use in catalytic gasification unit 10 is potassium-containing compound containing base catalyst, the alkali ash-cinder that potassium content is very high is produced after catalytic gasification, alkali ash-cinder first in catalyst recovery unit 40 through washing recovery section solubility potassium-containing compound, the potassium-containing compounds such as part potash, potassium aluminosilicate, potassium sulfide, potassium silicate are still retained, via CO in alkali ash-cinder pretreatment unit 30 in remaining alkali ash-cinder
2activating pretreatment, be converted into potash by lime-ash with the catalytically inactives such as potassium aluminosilicate, potassium sulfide, potassium silicate or the more weak potassium existence form of catalytic activity, afterwards again through pulverizing, be supplied to biodiesel after dry process and prepare in unit 20 and be used as solid containing base catalyst.The addition that biodiesel prepares alkali ash-cinder in unit 20 is determined according to the amount of potassium in lime-ash, and general control potash quality is the 5-30% of oil quality.
In the utility model embodiment, as shown in Figure 1, catalytic gasification unit 10 can also be connected with alkali ash-cinder pretreatment unit 30 by Quench unit 50, and wherein, Quench unit 50 is configured to carry out Quench to the alkali ash-cinder from catalytic gasification unit 10.In Quench unit 50, carry out Quench process by spray water to high temperature alkali ash-cinder, the alkali ash-cinder of high temperature is met after water Quench can particle diameter be thinner all to pieces, duct is abundanter, specific area is larger, thus is conducive to the catalytic efficiency improving ester exchange reaction.
After this, can via CO in alkali ash-cinder pretreatment unit 30
2gas activation, pulverizing, dry process, alkali metal in lime-ash and/or alkaline earth metal compound are more uniformly distributed in mainly with carbonate form to be had on the lime-ash skeleton of loose structure, like this, the alkali ash-cinder after process has catalytic efficiency more efficiently to catalyzed transesterification.
As shown in Figure 2, described alkali ash-cinder reutilization system can also comprise the both culturing microalgae unit 60 be connected with catalytic gasification unit 10, and wherein, the waste gas that catalytic gasification unit 10 produces, waste water are provided to both culturing microalgae unit 60.
Like this, waste water, waste gas etc. that catalytic gasification unit 10 produces are supplied to both culturing microalgae unit 60 as the nutritional labeling needed for both culturing microalgae together with other nutritional labeling, thus effectively recycled these waste water, waste gas, furthermore achieved that recycling and further reduce air pollution.
Preferably, as shown in Figure 2, both culturing microalgae unit 60 is also prepared unit 20 and is connected with biodiesel, and micro-algae that both culturing microalgae unit 60 is produced is provided to biodiesel and prepares unit 20.In this embodiment, catalytic gasification unit 10, both culturing microalgae unit 60 and biodiesel are prepared unit 20 and are connected each other, form the system that makes full use of of a resource: the waste water that catalytic gasification unit 10 produces, waste gas as the raw material of both culturing microalgae unit 60 for the production of micro-algae, micro-algae of producing is provided to biodiesel and prepares in unit 20, and generates biodiesel by ester exchange reaction under the catalytic action of the alkali ash-cinder of catalytic gasification unit 10 generation.
In the utility model embodiment, catalytic gasification unit 10 can be connected with both culturing microalgae unit 60 by gas purification unit 16, further, gas purification unit 16 unit is configured to carry out purification separation to the gas from catalytic gasification unit 10 and the waste water containing organic matter and/or ammonia obtained and CO 2 waste gas is supplied to both culturing microalgae unit 60.
Particularly, the gaseous product that catalytic gasification process produces comprises CH
4, CO, H
2, and CO
2, H
2s and NH
3, after gas purification unit 16 purified treatment, CO in raw gas
2and H
2the sour gas cognition such as S are removed, wherein, and the H be removed
2s can be used for produce sulphur, and be removed be rich in CO
2waste gas can be supplied in both culturing microalgae unit 60 for the carbon source needed for micro algae growth; In addition, in raw gas, undecomposed water vapour is mingled with some organic matters, NH
3get off with liquid form condensation Deng meeting, thus obtain the waste water containing organic matter and/or ammonia, and be supplied to both culturing microalgae unit 60, for other nutritional labelings that micro algae growth needs.
Further, catalytic gasification unit 10 can be connected with gas purification unit 16 by gas solid separation unit 14.Dust can be entrained with in the gaseous product that catalytic gasification unit 10 is discharged, the gas crude product that gas solid separation unit 14 can be configured to the gasification unit of self-catalysis in the future 10 carries out gas solid separation, isolated dust is back to catalytic gasification unit 10 and again carries out gasification reaction, and the raw gas after being separated is delivered in gas purification unit 16.Gas solid separation unit 14 can be such as single-stage or multi-cyclone.
Like this, in alkali ash-cinder reutilization system as shown in Figure 2, achieve the zero-emission of catalytic gasification system, efficiently solve the emission problem of catalytic coal gasifaction process percent of greenhouse gases and waste water.
Particularly, in the alkali ash-cinder reutilization system shown in Fig. 2, the product in each stage or be supplied in downstream units, prepares the solid catalyst of unit 20, hydrogen sulfide for making sulphur, containing the waste water of organic matter and/or ammonia and CO as alkali ash-cinder is used as biodiesel
2waste gas is provided to both culturing microalgae unit 60 as the nutritional labeling needed for micro-algae; Be back in upstream units and reuse, dust as isolated in gas solid separation unit 14 again enters catalytic gasification unit 10, again enters catalytic gasification unit 10 via the catalyst that catalyst recovery processing unit 40 is partially recycled, in whole service process, the intermediate product in each stage is obtained for effective recycling, and does not have poisonous and hazardous material to be discharged in environment.
Preferably, as shown in Figure 2, catalytic gasification unit 10 can also be prepared unit 20 by methanation or Poly-generation unit 18 with biodiesel and be connected, and the gas that methanation or Poly-generation unit 18 are configured in the future self-catalysis gasification unit 10 carries out methanation or Poly-generation and the methyl alcohol obtained is supplied to biodiesel preparing unit 20.
Wherein, in methanation or Poly-generation unit 18, CO and H that catalytic gasification unit 10 produces
2the gases such as natural gas, methyl alcohol, dimethyl ether are generated by methanation reaction or Poly-generation reaction Deng gas.In the present embodiment, directly these methyl alcohol can be used as the raw material of ester exchange reaction.
Particularly, catalytic gasification unit 10 can be connected with methanation or Poly-generation unit 18 via gas purification unit 16, gas separation unit 17 successively, gas separation unit 17 is configured to the coal gas being rich in methane after to purification and is separated, and will be separated CO and H obtained
2be fed to methanation or Poly-generation unit 18.Like this, further separation and purification is carried out to raw gas, and by CO and H
2etc. being fed to methanation or Poly-generation unit 18 is used as raw methanogenic raw material, and therefrom obtain methyl alcohol, the methyl alcohol obtained can be supplied to again biodiesel to be prepared in unit 20 and is used as raw material.
Be understandable that, in catalytic gasification unit 10, gas solid separation unit 14, gas purification unit 16, gas separation unit 17 and methanation or Poly-generation unit 18, other devices can also be connected with between interconnective two unit, fully realize the efficient resource of each intermediate product that middle each stage produces further.Such as, gas solid separation unit 14 can be connected with gas purification unit 16 by heat-exchanger rig 15, heat exchange is carried out from the water vapour of steam generation device 19 and the exit gas of other gasifying agents and catalytic gasification unit 10 for making, and the overheated gasifying agent after heat exchange is delivered to catalytic gasification unit 10, particularly, the temperature of this overheated gasifying agent can between 300 ~ 600 DEG C.Particularly, steam generation device 19 can be boiler, in order to the water producing water vapor of water processing system conveying.
As shown in Figure 2, feed unit 11 can also be connected with before catalytic gasification unit 10, feed unit 11 can comprise: normal pressure feed bin 11a, high pressure feed bin 11b and feeding device (not shown), for making coal dust enter feeding device after normal pressure feed bin 11a and high pressure feed bin 11b, under the effect of feeding device, being delivered to catalytic gasification unit 10 thus being carried out gasification reaction.Particularly, the pressure of feeding device can between 0 ~ 5 MPa, and the pressure differential between the pressure of feeding device and catalytic gasification unit 10 can between 0.02 ~ 0.1 MPa.
Particularly, alkali ash-cinder reutilization system can also comprise the catalyst dispensing unit 12 be connected with catalytic gasification unit 10, particularly, catalyst dispensing unit 12 can be connected with catalytic gasification unit 10 by feed unit 11, like this, the aqueous solution of coal dust and catalyst carries out hybrid infusion according to a certain ratio in catalyst dispensing unit 12, and by agitator, mixed slurries are stirred, to be then transported in catalytic gasification unit 10 by feed unit 11 after drying process thus to carry out gasification reaction.
Preferably, catalyst dispensing unit 12 can also be connected with catalyst recovery unit 40, and catalyst recovery unit 40 is also configured to the soluble alkali metal compound of recovery and/or alkaline earth metal compound to be supplied to catalyst dispensing unit 12.
Advantageously, micro-algae of cultivation directly can be supplied to biodiesel and prepare unit 20 by both culturing microalgae unit 60, also first micro-algae of cultivation can be supplied to biodiesel again via process and prepare unit 20.
Particularly, both culturing microalgae unit 60 is prepared unit 20 by micro-algae processing unit and biodiesel and is connected, micro-algae processing unit is configured to prepare unit 20 from from extracting algae oil micro-algae of both culturing microalgae unit 60 and algae oil being supplied to biodiesel, or is configured to carry out drying with shape algae powder to the micro-algae from both culturing microalgae unit 60 and described algae powder is supplied to biodiesel prepares unit 20.Particularly, as shown in Figure 3, micro-algae processing unit can be algae oil extraction unit 70, or as shown in Figure 4, micro-algae processing unit can also be micro-algae drying unit 80.
Figure 3 shows that another alkali ash-cinder reutilization system that the utility model embodiment provides, catalytic gasification unit 10 is successively by catalyst recovery unit 40, alkali ash-cinder pretreatment unit 30 unit and biodiesel are prepared unit 20 and are connected, like this, first alkali ash-cinder from catalytic gasification unit 10 carries out washing via catalyst recovery unit 40 and reclaims, and the partially catalyzed agent of recovery is delivered in catalyst dispensing unit be again mixed and fed into coal catalytic gasification unit 10 catalysis coal gasification again reaction, alkali ash-cinder after washing then enters into alkali ash-cinder pretreatment unit 30, activate via carbon dioxide in alkali ash-cinder pretreatment unit 30, being supplied to biodiesel containing base catalyst and preparing in unit 20 of carbonate form will be changed into after dry process.
Gaseous product from catalytic gasification unit 10 can also via a series of process, and some product in processing procedure can also be fully used.Particularly, as shown in Figure 3, after catalytic gasification unit 10, gas solid separation unit 14, gas purification unit 16 is also connected with in turn.Like this, first gas crude product from catalytic gasification unit 10 carries out gas solid separation, and the dust of separation is turned back in catalytic gasification unit 10 again participate in gasification reaction, raw gas after separation then enters gas purification unit 16, after gas purification process, by process gained containing organic matter and/or NH
3waste water and CO
2waste gas is fed in both culturing microalgae unit 60.
Methanation or Poly-generation unit 18 is also connected with after gas purification unit 16, like this, the coal gas being rich in methane after gas purification unit 16 purified treatment enters in methanation or Poly-generation unit 18 and methanation reaction occurs, generate the gases such as methane, methyl alcohol, dimethyl ether, consequent methyl alcohol directly can be fed to biodiesel to be prepared in unit 20.
Both culturing microalgae unit 60 is prepared unit 20 by algae oil extraction unit 70 with biodiesel and is connected, like this, micro-algae from both culturing microalgae unit 60 obtains algae oil through process such as super-dry, algae oil extract in algae oil extraction unit 70, and the algae oil obtained can be fed to biodiesel and prepare in unit 20 raw material being used as to prepare biodiesel.
Prepare in unit 20 in biodiesel, there is ester exchange reaction thus generate biodiesel in the methyl alcohol from methanation or Poly-generation unit 18 and the oil of the algae from both culturing microalgae unit 60 under the catalytic action of alkali ash-cinder.
As shown in Figure 3, this alkali ash-cinder reutilization system have effectively achieved the zero-emission of catalytic gasification system: alkali ash-cinder is supplied to biodiesel and prepares the solid catalyst being used as catalyzed transesterification in unit 20; The gaseous product that catalytic gasification unit 10 produces obtains the higher natural gas of purity through gas solid separation, gas purification process, wherein, in processing procedure, the dust that gaseous product is carried secretly again turns back in catalytic gasification unit 10 and continues gasification reaction, the hydrogen sulfide be mingled with is for the production of sulphur, the organic matter be mingled with, ammonia, water and carbon dioxide are passed in both culturing microalgae unit 60 and are used as nutritional labeling, CO, H
2then be supplied to and be fed to biodiesel Deng gas in methanation or Poly-generation unit 18 and by the methyl alcohol obtained and prepare unit 20 and be used as raw material, so far, the intermediate product in each stage is obtained for recycling effectively, whole system does not endanger environment by poisonous and hazardous mass emissions to environment in running, the serialization simultaneously facilitating system runs, and improves the economy of system.
The another kind of alkali ash-cinder reutilization system that Fig. 4 provides for the utility model embodiment, compared with Fig. 3, achieve the zero-emission of catalytic gasification system equally, unlike, micro-algae processing unit is configured to the withering micro-algae drying unit 80 of micro-algae, and catalytic gasification unit 10 is connected with alkali ash-cinder pretreatment unit 30 by Quench unit 30.Because the idiographic flow of Fig. 4 is roughly similar to the alkali ash-cinder reutilization system shown in Fig. 3, therefore it is no longer repeated at this for the utility model.
In order to further describe the reutilization system of alkali ash-cinder described in the utility model, be described with specific embodiment below.
Embodiment 1
Particularly, embodiment 1 includes two groups of alkali ash-cinder reutilization system arranged side by side respectively, is respectively:
A) as shown in Figure 1, alkali ash-cinder reutilization system comprises catalytic gasification unit 10.Wherein, coal dust enters catalytic gasification unit 10 through feed unit, reacts under the effect of catalyst potash with gasifying agent generating gasification, generates CH
4, CO, H
2deng available gas composition and CO
2, a small amount of H
2s and NH
3deng other environmentally harmful gas componants, wherein, catalytic gasification unit 10 is gasification furnace, and the reaction temperature in gasification furnace 10 is 600 ~ 800 DEG C, and pressure is 0 ~ 4MPa.
Catalyst recovery unit 40 is connected with after gasification furnace 10.Catalyst is rich in alkali ash-cinder after gasification furnace 10 gasifies, first can through washing recovery section soluble catalyst in catalyst recovery unit 40 after slag bucket is discharged, the catalyst reclaimed again loads to pulverized coal particle passes in gasification furnace 10 and again carries out catalytic gasification reaction, and remaining alkali ash-cinder then enters alkali ash-cinder pretreatment unit 30.
After alkali ash-cinder pretreatment unit 30 is connected to catalyst recovery unit 40, for receiving remaining alkali ash-cinder.In alkali ash-cinder pretreatment unit 30, first under carbon dioxide effect, being converted into potash by lime-ash with the catalytically inactive such as potassium sulfide, potassium silicate or the more weak K existence form of catalytic activity, preparing in unit 20 as passing into biodiesel containing alkali solid catalyst after pulverizing dry process more afterwards.
Biodiesel is prepared after unit 20 is connected to alkali ash-cinder pretreatment unit 30, is configured to ester exchange reaction device.Prepare in unit 20 in biodiesel, there is ester exchange reaction with animal and plant fat in methyl alcohol, product obtains biodiesel after separator 21 is separated under the above-mentioned effect containing alkali solid catalyst; Wherein, in ester-exchange reaction, potash quality is the 5-30% of algae oil quality, and to control methyl alcohol with algae molar equivalent be 5-15, reaction temperature 50-80 DEG C, reaction time 0.5-5h.
B) as shown in Figure 1, alkali ash-cinder reutilization system comprises catalytic gasification unit 10.Wherein, coal dust enters gasification furnace 10 through feed unit, reacts under the effect of catalyst with gasifying agent generating gasification, generates CH
4, CO, H
2deng available gas composition and CO
2, a small amount of H
2s and NH
3etc. other gas environmentally harmful, wherein, the reaction temperature of gasification furnace 10 is 600 ~ 800 DEG C, and pressure is 0 ~ 4MPa.
Quench unit 50 is connected with after gasification furnace 10.First the lime-ash that gasification furnace 10 is discharged carries out Quench process by spray water in Quench unit 50, obtains the alkali ash-cinder particle that particle diameter is thinner, duct is abundanter, specific area is larger.
Subsequently in alkali ash-cinder pretreatment unit 30, pass into carbon dioxide, K in lime-ash is uniformly distributed in potassium as potassium carbonate more to be had on the lime-ash skeleton of loose structure, then can as passing into ester exchange reaction device China catalyzed transesterification production biodiesel containing alkali solid catalyst after pulverizing dry process.
Particularly, run alkali ash-cinder reutilization system described in the utility model under the above-described reaction conditions, compared for respectively using pure potash as catalyst and using the alkali ash-cinder (quality of potash is 5%, 15%, 30% of algae oil quality) after catalytic gasification as during catalyst on the impact of biodiesel production rate and the separation degree on catalyst and biodiesel oil product, result is as shown in table 1.
Table 1: adopt pure potash as catalyst and adopt alkali ash-cinder as the catalytic performance of solid base catalyst to catalyzed transesterification
Embodiment 2
As shown in Figure 2, alkali ash-cinder reutilization system specifically can comprise:
The aqueous solution of coal dust and catalyst carries out hybrid infusion in catalyst dispensing unit 12, uses agitator to be stirred by mixed slurries.The proportioning of catalyst and coal dust can be 2 ~ 20%.After this mixed serum is carried out dehydrating process, the coal dust obtained is sent into feed unit 11.Generally ground by raw coal as coal dust, screening process is to suitable particle diameter (0 ~ 10mm), and the raw coal adopted can be bituminous coal, ub-bituminous coal, anthracite or brown coal.
Coal dust enters feeding device after normal pressure feed bin 11a and high pressure feed bin 11b, and under the effect of feeding device, coal dust is admitted to catalytic gasification unit 10 and carries out gasification reaction.The pressure of feeding device can between 0 ~ 5 MPa, and the pressure of feeding device and the pressure differential of catalytic gasification unit 10 can between 0.02 ~ 0.1 MPas.
Catalytic gasification unit 10 is gasification furnace, for coal dust and gasifying agent, generating gasification under the effect of catalyst is reacted here, catalyst can adopt the carbonate of alkali metal, alkaline-earth metal, hydroxide and congruent melting salt mixture, the mixture of the carbonate of alkali metal, alkaline-earth metal, hydroxide and transition metal, papermaking wastewater, industrial alkali waste, plant ash etc.; Gasifying agent is superheated steam, or O
2, CO, H
2, CO
2in at least one and the mist of superheated steam, pass in gasification furnace 10 through gasification furnace lower part fabric swatch.Gasification product comprises: methane, hydrogen, carbon monoxide, carbon dioxide, hydrogen sulfide, ammonia, dust etc. are discharged from gasification furnace 10 top.The operating temperature of gasification furnace is 600 ~ 800 DEG C, and the reaction such as catalytic gasification, methanation occurs under the effect of catalyst, generates CH
4, CO, H
2deng available gas composition.The pressure of gasification furnace 10 can between 0 ~ 5 MPa (MPa).
After gasification furnace 10, be connected with gas solid separation unit 14, for gasification furnace 10 top exit gas product is carried out gas solid separation, and isolated dust is returned gasification furnace 10 again carry out gasification reaction.Gas solid separation unit 14 can be multi-cyclone.
Gas solid separation unit 14 is also connected with heat transmission equipment 15, for carrying out heat exchange by from the water vapour of steam generation device 9 and the exit gas of other gasifying agents and described gasification furnace 10, and the overheated gasifying agent after heat exchange is sent into gasification furnace 10, temperature can between 300 ~ 600 DEG C, and gasification furnace 10 utilizes this gasifying agent to carry out gasification reaction.The water producing water vapor of boiler 19 specifically for utilizing water treatment system to send here.
After heat-exchanger rig 15, be connected with the raw gas after for heat exchanging carry out purification separation, in outlet coal gas, undecomposed water vapour is mingled with some organic matter, ammonia etc. and gets off with liquid form condensation, obtains the waste water containing organic matter/ammonia.Through gas purification process process, by the acid gas removal such as carbon dioxide and hydrogen sulfide in gasification furnace 10 exit gas, the coal gas being rich in methane can be obtained.
The hydrogen sulfide removed in gas purification unit 16 can be used for producing sulphur; And other nutritional labelings of the waste water containing organic matter and/or ammonia obtained at gas purification unit 16 and rich carbonated waste gas mixing micro algae growth needs are made into nutrient solution and pass into both culturing microalgae unit 60, wherein, carbon dioxide can be used as the photosynthetic carbon source of micro-algae, and ammonia, organic matter etc. can as the nutriments needed for micro algae growth in waste water, the growth of micro-algae can be promoted, improve the absorption and use efficiency of carbon dioxide simultaneously.The algae selecting cultivation can be Euglena, green alga, stonewort, chrysophyceae, dinoflagellate, red algae, diatom, chlamydomonas, xanthophyta, brown alga or blue-green algae, and the algae that preferred oil content is higher, as chlorella, Wild Vitis species etc.
After gas purification unit 16, be connected with gas separation unit 17, for being again separated the coal gas being rich in methane, and the methane that after being separated, the purity that obtains is higher can be used as gas product is collected, and isolated CO, H
2be supplied in methanation and synthesis gas Poly-generation unit 18 Deng gas, thus obtain natural gas and the chemical products such as methyl alcohol, dimethyl ether of pipeline grade, and the methyl alcohol obtained directly can be supplied to biodiesel prepares in unit 20.
The algae powder obtained or algae oil can be passed into biodiesel and prepare unit 20 by micro-algae that both culturing microalgae unit 60 obtains after dehydration, drying or the oily extraction of algae.
On the other hand, the alkali ash-cinder being rich in catalyst that gasification furnace 10 produces is discharged through slag bucket.First be fed in alkali ash-cinder pretreatment unit 30, under carbon dioxide effect, potash is converted into the catalytically inactive such as potassium sulfide, potassium silicate or the more weak K existence form of catalytic activity by lime-ash, after pulverizing, dry process, prepare unit 20 catalysis methanol with the ester exchange reaction between algae oil or algae powder as passing into biodiesel containing alkali solid catalyst more afterwards, product obtains biodiesel after separator 21 separation.
Embodiment 3
As shown in Figure 3, alkali ash-cinder reutilization system specifically can comprise:
Catalytic gasification unit 10, for coal dust and gasifying agent, generating gasification under the effect of catalyst is reacted, here, catalytic gasification unit 10 is fluidized-bed gasification furnace, operating temperature is 600 ~ 800 DEG C, and the reaction such as catalytic gasification, methanation occurs under the effect of catalyst, generates CH
4, CO, H
2deng available gas composition.The pressure of fluidized-bed gasification furnace 10 can at 0 ~ 4MPa.Gasifying agent is superheated steam and oxygen, and temperature is 300 ~ 600 DEG C, bottom gasification furnace, enter fluidized-bed gasification furnace 10 through distribution grid, and water carbon mol ratio controls 1 ~ 3, oxygen concentration 0 ~ 20mol%.
After fluidized-bed gasification furnace 10, be connected with gas solid separation unit 14, for fluidized-bed gasification furnace 10 top outlet gas-phase product is carried out gas solid separation, the dust carried secretly returned fluidized-bed gasification furnace 10 carry out gasification reaction in isolated, gaseous product.Gas solid separation unit 14 can be multi-cyclone.
Be connected with gas purification unit 16 after gas solid separation unit 14, carry out purification separation for the raw gas after heat exchanging, in outlet coal gas, undecomposed water vapour is mingled with some organic matter, ammonia etc. and gets off with liquid form condensation, obtains the waste water containing organic matter/ammonia.Through gas purification process process, by acid gas removals such as the carbon dioxide in fluidized-bed gasification furnace 10 exit gas and hydrogen sulfide, the coal gas being rich in methane can be obtained.
The hydrogen sulfide be removed can be used for producing sulphur; Other nutritional labelings that the waste water containing organic matter/ammonia obtained and rich carbonated waste gas mixing micro algae growth need are made into nutrient solution and are passed into both culturing microalgae unit 60, use this nutrient solution cultivating microalgae, micro-algae constantly carries out photosynthesis absorbing carbon dioxide, and ammonia, organic matter etc. can as the nutriments needed for micro algae growth in waste water, the growth of micro-algae can be promoted, improve the absorption and use efficiency of carbon dioxide simultaneously.
Methanation and synthesis gas Poly-generation unit 18 is connected with after gas purification unit 16, can obtain natural gas and the chemical products such as methyl alcohol, dimethyl ether of pipeline grade in methanation and synthesis gas Poly-generation unit 18, the methyl alcohol obtained here can be supplied effectively directly into biodiesel to be prepared in unit 20.
Both culturing microalgae unit 60 is prepared unit by algae oil extraction unit 70 with biodiesel and is connected, from micro-algae of both culturing microalgae unit 60 in algae oil extraction unit 70 via after dry, the oily extraction of algae, the algae obtained oil is directly sent into biodiesel and prepares in unit 20.
The alkali ash-cinder being rich in catalyst that fluidized-bed gasification furnace 10 produces is discharged through slag bucket.Containing the potassium that content is very high in lime-ash, first catalyst recovery unit 40 is entered, mixture preparation is carried out with coal through washing recovery section catalyst return catalizer dispensing unit, part potash is still retained in residual gas ashing slag, potassium aluminosilicate, potassium sulfide, potassium silicates etc. are containing K compound, then be fed in alkali ash-cinder pretreatment unit 30, under carbon dioxide effect, by in lime-ash with potassium aluminosilicate, potassium sulfide, the catalytically inactives such as potassium silicate or the more weak K existence form of catalytic activity are converted into potash, afterwards again through pulverizing, unit 20 catalysis methanol is prepared with the ester exchange reaction between algae oil as passing into biodiesel containing alkali solid catalyst after dry process, product obtains biodiesel after separator 21 is separated.
The addition of alkali ash-cinder is determined according to the amount of K in lime-ash, and control the 5-30% that potash quality is algae oil quality, controlling methyl alcohol is 5-15, reaction temperature 50-80 DEG C with algae molar equivalent, reaction time 0.5-5h.
Embodiment 4
As shown in Figure 4, alkali ash-cinder reutilization system specifically can comprise:
As different from Example 3, the catalyst lime-ash that is rich in that fluidized-bed gasification furnace 10 produces is discharged through slag bucket.Containing the potassium that content is very high in lime-ash, first Quench unit 50 is entered, through water Quench, obtain the coal ash particle that particle diameter is thinner, duct is abundanter, specific area is larger, then in alkali ash-cinder pretreatment unit 30, carbon dioxide is passed into, K in lime-ash is more uniformly distributed in mainly with potassium as potassium carbonate to be had on the lime-ash skeleton of loose structure, after after pulverizing dry process, prepare unit 20 as passing into biodiesel containing alkali solid catalyst.
From after micro-algae process algae powder of both culturing microalgae unit 60 under the effect of solid base catalyst through supercritical methanol one-step synthesis method biodiesel.
Discussion of results:
From embodiment 1, alkali ash-cinder reutilization system described in the utility model achieves the recycling of the alkali ash-cinder that catalysis gasification technique produces, and as can be seen from Table 1, adopt the alkali ash-cinder after catalytic gasification as catalyst and the pure potash of employing as compared with catalyst, because the alkali ash-cinder after high-temperature gasification has loose structure, thus improve the dispersiveness of potash, therefore the catalytic efficiency of ester exchange reaction is substantially increased, and solid-phase catalyst and biodiesel constitute solid-liquid double-phase system and are thus easy to be separated, and catalyst can repeatedly recycle, reaction condition is gentle.
From embodiment 2-4, each product or be collected as product, as methane; Again be back in upstream units, as the dust obtained after partially recycled catalyst, gas solid separation; Be supplied in downstream units, the alkali ash-cinder produced as catalytic gasification unit, after the process of gas purification purification unit containing organic matter/ammonia waste water, CO 2 waste gas etc., so far, described alkali ash-cinder reutilization system achieves the zero-emission of catalysis gasification technique, avoid the discharge of greenhouse gases and waste water, solve the problem of environmental pollution brought because of the discharge of waste gas waste water.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still in the protection domain that the utility model creates.
Claims (10)
1. an alkali ash-cinder reutilization system, it is characterized in that, described alkali ash-cinder reutilization system comprises catalytic gasification unit and the biodiesel that is connected with described catalytic gasification unit prepares unit, wherein, the alkali ash-cinder that described catalytic gasification unit produces is provided to described biodiesel and prepares catalyst as production biodiesel in unit.
2. alkali ash-cinder reutilization system according to claim 1, it is characterized in that, described alkali ash-cinder reutilization system also comprises the both culturing microalgae unit be connected with described catalytic gasification unit, and wherein, the waste gas that described catalytic gasification unit produces, waste water are provided to described both culturing microalgae unit.
3. alkali ash-cinder reutilization system according to claim 2, is characterized in that, described both culturing microalgae unit is also prepared unit with described biodiesel and is connected.
4. alkali ash-cinder reutilization system according to claim 2, it is characterized in that, described catalytic gasification unit is prepared unit by methanation or Poly-generation unit with described biodiesel and is connected, and described methanation or Poly-generation unit are configured to the gas from described catalytic gasification unit to carry out methanation or Poly-generation and the methyl alcohol obtained is supplied to described biodiesel prepare unit.
5. alkali ash-cinder reutilization system according to claim 4, it is characterized in that, described catalytic gasification unit is connected with described methanation or Poly-generation unit by gas purification unit, and described gas purification unit is also connected with described both culturing microalgae unit, described gas purification unit is configured to carry out purification separation to the gas from described catalytic gasification unit and the waste water containing organic matter and/or ammonia obtained and CO 2 waste gas is supplied to described both culturing microalgae unit, and purified gas is supplied to described methanation or Poly-generation unit.
6. alkali ash-cinder reutilization system according to claim 3, it is characterized in that, described both culturing microalgae unit is prepared unit by micro-algae processing unit with described biodiesel and is connected, and described micro-algae processing unit is configured to from the micro-algae from described both culturing microalgae unit, extract algae oil and described algae oil is supplied to described biodiesel prepare unit; Or be configured to carry out drying with shape algae powder to the micro-algae from described both culturing microalgae unit described algae powder is supplied to described biodiesel prepares unit.
7. the alkali ash-cinder reutilization system according to any one of claim 1 ~ 6, it is characterized in that, described catalytic gasification unit is prepared unit by alkali ash-cinder pretreatment unit with described biodiesel and is connected, described alkali ash-cinder pretreatment unit is configured to carry out pretreatment to described alkali ash-cinder, makes the alkali metal compound in described alkali ash-cinder and/or alkaline earth metal compound be converted into corresponding carbonate.
8. alkali ash-cinder reutilization system according to claim 7, it is characterized in that, described catalytic gasification unit is connected with described alkali ash-cinder pretreatment unit by catalyst recovery unit, and described catalyst recovery unit is configured to wash described alkali ash-cinder with recovery section soluble alkali metal compound and/or alkaline earth metal compound.
9. alkali ash-cinder reutilization system according to claim 7, it is characterized in that, described catalytic gasification unit is connected with described alkali ash-cinder pretreatment unit by Quench unit, and described Quench unit is configured to carry out Quench to the alkali ash-cinder from described catalytic gasification unit.
10. alkali ash-cinder reutilization system according to claim 8, it is characterized in that, described alkali ash-cinder reutilization system also comprises the catalyst dispensing unit be connected with described catalytic gasification unit, described catalyst dispensing unit is also connected with described catalyst recovery unit, and described catalyst recovery unit is also configured to the soluble alkali metal compound of recovery or alkaline earth metal compound to be supplied to described catalyst dispensing unit.
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| CN107312572A (en) * | 2017-08-18 | 2017-11-03 | 新奥科技发展有限公司 | A kind of catalytic coal gasifaction method |
| CN108753360A (en) * | 2018-06-01 | 2018-11-06 | 新奥科技发展有限公司 | A kind of dreg removing system, catalytic coal gasifaction system and catalytic coal gasifaction method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107312572A (en) * | 2017-08-18 | 2017-11-03 | 新奥科技发展有限公司 | A kind of catalytic coal gasifaction method |
| CN107312572B (en) * | 2017-08-18 | 2020-04-21 | 新奥科技发展有限公司 | Catalytic coal gasification method |
| CN108753360A (en) * | 2018-06-01 | 2018-11-06 | 新奥科技发展有限公司 | A kind of dreg removing system, catalytic coal gasifaction system and catalytic coal gasifaction method |
| CN110075823A (en) * | 2019-05-30 | 2019-08-02 | 新奥科技发展有限公司 | Preparation method, preparation facilities and the application method of DEC catalyst for synthesizing |
| CN110075823B (en) * | 2019-05-30 | 2022-04-12 | 新奥科技发展有限公司 | Preparation method, preparation device and application method of catalyst for DEC synthesis |
| CN112403464A (en) * | 2020-11-20 | 2021-02-26 | 王立鹏 | Modified gasified slag biodiesel catalyst and preparation method and application thereof |
| CN112403464B (en) * | 2020-11-20 | 2023-08-11 | 江苏海洋大学 | Modified gasification slag biodiesel catalyst and preparation method and application thereof |
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