CN102851090A - Biogas dry-type filtering desulphurization system and preparation method thereof - Google Patents
Biogas dry-type filtering desulphurization system and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a desulphurization system and especially to a biogas dry-type filtering desulphurization system and a preparation method thereof. According to the method, the procedure of purification of biogas for production of clean biogas and sulfide is realized by successively utilizing an air inlet cabinet, a desulphurizing absorption tower, a gas-liquid separator, a gas washing tower, a dry-type desulfurizer, a deduster and a compressor; the procedure of production of elementary sulfur from a solution produced after desulphurization of the biogas and the procedure of cyclic action are respectively realized by successively utilizing the desulphurizing absorption tower, a solution reaction tank, a rich solution pump, an injector, a regeneration tower, a sulfur foam separating tank, a sulfur melting kettle and a mold and successively utilizing the regeneration tower, a liquid level regulator, a lean solution pump and the desulphurizing absorption tower. According to the biogas dry-type filtering desulphurization system and the preparation method thereof provided by the invention, the structure of the system is compact, biogas quality is improved, and energies are cyclically utilized.
Description
Technical field
The present invention is a kind of desulphurization system, particularly a kind of biogas dry filtration desulphurization system and preparation method thereof.
Background technology
The sulfur method of biogas of the prior art is immature, makes the foreign matter content in the biogas more, and it is insufficient to cause burning, and affects burning quality, reduces the biogas quality.
Summary of the invention
The present invention solves the deficiencies in the prior art, compact construction, and can remove the impurity of biogas, methane energy is fully burnt, biogas dry filtration desulphurization system of the natural gas of increasing operation rate and biogas and preparation method thereof.
Above-mentioned technical problem of the present invention is mainly solved by following technical proposals:
A kind of biogas dry filtration desulphurization system, comprise the biogas inlet pipe, described biogas inlet pipe is connected with the air inlet cabinet, described air inlet cabinet is connected with desulfuration absorbing tower, the top of described desulfuration absorbing tower is connected with gas-liquid separator, described gas-liquid separator is connected with gas wash tower, described gas wash tower is connected with the dry desulfurization device, the top of described dry desulfurization device is connected with fly-ash separator, the bottom of described dry desulfurization device is connected with the sulfuration property management, described fly-ash separator is connected with compressor, and described compressor goes out pipe with biogas and is connected;
The bottom of described desulfuration absorbing tower is connected with the solution reaction groove, described solution reaction groove is connected with the rich solution pump, described rich solution pump is connected with injector, described injector is connected with regenerator column, the top of described regenerator column is connected with the sulphur foam separator, described sulphur foam separator is connected with sulfur melting kettle, described sulfur melting kettle is connected with mold, described mold is connected with the elemental sulfur pipe, described regenerator column the exit be connected with regulator of level, described regulator of level is connected with lean pump, and described lean pump is back in the desulfuration absorbing tower again.
As preferably, be provided with supercharging blower between described air inlet cabinet and desulfuration absorbing tower, the below of described rich solution pump is provided with the rich solution pump I that is in parallel with it, and the below of described lean pump is provided with the lean pump I that is in parallel with it.
The preparation method of biogas dry filtration desulfurization, carry out according to the following steps:
(1), raw material biogas enters to that the air inlet cabinet cushions and voltage stabilizing is processed from the biogas inlet pipe, the pressure of biogas is 1000～3000Pa, the time of voltage stabilizing is 10～60 seconds;
(2), biogas is pressurized to 27～31KPa through supercharging blower, the temperature of biogas is 15～30 ℃, the time of supercharging is 1～10 second;
(3), the biogas after the supercharging enters from the bottom of desulfuration absorbing tower, with the doctor solution counter current contact that contains catalyzer that sprays on the desulfuration absorbing tower, H in the biogas
2S is desulfurized liquid and absorbs, and the reaction times of doctor solution and biogas is 2～3 minutes, and doctor solution is for containing the catalyst carbon acid sodium solution, and the chemical formula that contains the catalyst carbon acid sodium solution is: Na
2C0
3
The chemical equation Na of biogas and doctor solution
2C0
3+ H
2S=NaHS+NaHC0
3
Under V5+ catalysis, the HS-reaction generates elemental sulfur:
NaHS＋NaHC0
3＋2NaV0
3＝Na
2V
20
5＋Na
2C0
3＋S＋H
20
Tannin extract quinone attitude component through overcuring is oxidized to V5+ with V4+, and tannin extract quinone attitude becomes tannin extract phenol attitude, and tannin extract quinone attitude is TQ, and tannin extract phenol attitude is THQ:
Na
2V
20
5＋TQ＝NaV0
3＋THQ；
(4), the biogas after the desulfurization draws from the cat head of desulfuration absorbing tower, carries out separating treatment through gas-liquid separator, the disengaging time of gas-liquid separator is 3～5 minutes;
(5), biogas enters to gas wash tower, the doctor solution in the flush away gas, washing time is 3～5 minutes;
The chemical equation of biogas and doctor solution: Na
2C0
3+ CaCl
2=2NaCl+CaCO
3
(6), biogas bottom from gas wash tower after wet desulphurization enters the dry desulfurization device, sweetening agent in hydrogen sulfide in the biogas and the dry desulfurization device reacts, hydrogen sulfide is converted into sulfide and elemental sulfur is deposited in the vulcanizing agent bed, thereby with the hydrogen sulfide stripping in the thick desulfurization biogas, the reaction times of biogas in the dry desulfurization device is 5～10 minutes, and the temperature of reaction of biogas in the dry desulfurization device is 15～30 ℃;
Chemical equation: Fe2O3H2O+3H2S=Fe2S3H2O+3H2O+Q;
(7), with the Base top contact of biogas from the dry desulfurization device, enter in the fly-ash separator, the time of biogas in fly-ash separator is 1～5 second, it is 100～500Nm that fly-ash separator is processed air quantity
3/ h, the sulfide in the dry desulfurization device is discharged through the sulfuration property management;
(8), biogas enters to compressor after dedusting, be 1～10 second the working time of compressor, and the power of compressor is 10～45KW, is pressurized to 0.7Mpa by reciprocating type Marsh gas compression machine two stages of compression, after temperature is increased to 40 ℃, goes out pipe by biogas and enter to decarbonization process; Decarbonization process adopts with two sections pressure swing absorption process, decarbonization process comprises PSA-1 operation and PSA-2 operation, and the PSA-1 operation mainly is the invalid gas of carbon dioxide removal, guarantees simultaneously effective gases methane loss reduction, the PSA-2 operation mainly be that the work in-process air lift is pure, obtain products C H
4, the pressure of decarbonization process is 0.4～0.6MPa;
(9), generation contains H in the desulfuration absorbing tower
2The rich solution of S and sodium hydrogen carbonate solution are discharged at the bottom of the tower of desulfuration absorbing tower, and the chemistry of rich solution is called sodium hydrosulfide, and the chemical formula of sodium hydrosulfide is NaHS, and the chemical formula of sodium hydrogen carbonate solution is NaHC0
3
Main chemical equation: Na
2C0
3+ H
2S=NaHS+NaHC0
3
(10), rich solution enters in the solution reaction groove through fluid-tight, the reaction times of rich solution in the solution reaction groove is 2～5 minutes, rich solution and the H that is dissolved in the rich solution
2S continues reaction at reactive tank and produces Sodium sulfhydrate and sodium bicarbonate, continues to generate elemental sulfur under the effect of catalyzer;
Chemical equation: Na
2C0
3+ H
2S=NaHS+NaHC0
3
Under V5+ catalysis, the HS-reaction generates elemental sulfur:
NaHS＋NaHC0
3＋2NaV0
3＝Na
2V
20
5＋Na
2C0
3＋S＋H
20；
Tannin extract quinone attitude component through overcuring is oxidized to V5+ with V4+, and tannin extract quinone attitude becomes tannin extract phenol attitude, and tannin extract quinone attitude is TQ, and tannin extract phenol attitude is THQ:
Na
2V
20
5＋TQ＝NaV0
3＋THQ；
(11), in the solution reaction groove, continue to react after with the rich solution pumping toward injector, the rich solution pump adopts IS type horizontal single-stage impeller pump, flow Q:5.4～400m
3/ h, lift H:4～125m;
(12), risen by the regenerator column bottom from injector afterbody two-phase fluid out, airborne oxygen is oxidized to tannin extract quinone attitude with tannin extract phenol attitude, has simultaneously hydrogen peroxide to generate;
The chemical reaction following steps:
0
2＋THQ＝2TQ＋H
20
2?；
H
20
2Oxidation V4+ and HS-:
1/2?H
20
2＋V4+＝V5+＋OH-；
H
20
2＋HS-＝H
20＋S＋OH-；
(13), the sulphur foam that overflows of regenerator column top puts into to sulfur melting kettle through the sulphur foam separator and melts sulphuring treatment, the time of molten sulphur is 30～50 minutes, produces sulphur;
(14), sulphur puts into to mold and form the sulphur ingot after cooling, the cooling temperature of mold is 15～30 ℃, 10～30 minutes of the cooling time of mold;
(15), will not contain H
2The lean solution of S is drawn by the lean solution exit of regenerator column, and lean solution is pumped back to thionizer through poor stream again through regulator of level and carries out circulating reaction; Liquid phase and vapour phase signal pipe are arranged in the regulator of level, when liquid level descends, the vapour phase signal increases, reduce the effective flow area of pipeline, solution flow is reduced, reach the purpose of effective control flow, move in circles, can realize automatically regulating liquid level, poor stream pump adopts IS type horizontal single-stage impeller pump, flow Q:5.4～400m
3/ h, lift H:4～125m;
Lean solution is the sodium carbonate solution that contains catalyzer.
Fluid-tight: rich solution goes out to manage in the insertion reaction groove under the rich solution liquid level, forms a fluid-tight, prevents H
2S goes out to manage loss from rich solution; Two-phase fluid is mainly sodium hydrosulfide (NaHS) and sodium hydrogen carbonate solution (NaHC0
3) and air, a small amount of H
2S gas.
Therefore, biogas dry filtration desulphurization system provided by the invention and preparation method thereof, compact construction promotes the biogas quality, heat recovery.
Description of drawings
Fig. 1 is structural representation of the present invention.
Embodiment
Below by embodiment, and by reference to the accompanying drawings, technical scheme of the present invention is described in further detail.
Embodiment 1: as shown in Figure 1, a kind of biogas dry filtration desulphurization system, comprise biogas inlet pipe 1, described biogas inlet pipe 1 is connected with air inlet cabinet 2, described air inlet cabinet 2 is connected with desulfuration absorbing tower 3, the top of described desulfuration absorbing tower 3 is connected with gas-liquid separator 4, described gas-liquid separator 4 is connected with gas wash tower 5, described gas wash tower 5 is connected with dry desulfurization device 6, the top of described dry desulfurization device 6 is connected with fly-ash separator 7, the bottom of described dry desulfurization device 6 is connected with sulfuration property management 8, and described fly-ash separator 7 is connected with compressor 9, and described compressor 9 goes out pipe 10 with biogas and is connected;
The bottom of described desulfuration absorbing tower 3 is connected with solution reaction groove 11, described solution reaction groove 11 is connected with rich solution pump 12, described rich solution pump 12 is connected with injector 13, described injector 13 is connected with regenerator column 14, the top of described regenerator column 14 is connected with sulphur foam separator 15, described sulphur foam separator 15 is connected with sulfur melting kettle 16, described sulfur melting kettle 16 is connected with mold 17, described mold 17 is connected with elemental sulfur pipe 18, described regenerator column 14 the exit be connected with regulator of level 19, described regulator of level 19 is connected with lean pump 20, and described lean pump 20 is back in the desulfuration absorbing tower 3 again.
3 of described air inlet cabinet 2 and desulfuration absorbing towers are provided with supercharging blower 21, and the below of described rich solution pump 12 is provided with the rich solution pump I 22 that is in parallel with it, and the below of described lean pump 20 is provided with the lean pump I 23 that is in parallel with it.
The preparation method of biogas dry filtration desulfurization is characterized in that carrying out according to the following steps:
(1), raw material biogas enters to that the air inlet cabinet cushions and voltage stabilizing is processed from the biogas inlet pipe, the pressure of biogas is 1000Pa, the time of voltage stabilizing is 10 seconds;
(2), biogas is pressurized to 27KPa through supercharging blower, the temperature of biogas is 15 ℃, the time of supercharging is 1 second;
(3), the biogas after the supercharging enters from the bottom of desulfuration absorbing tower, with the doctor solution counter current contact that contains catalyzer that sprays on the desulfuration absorbing tower, H in the biogas
2S is desulfurized liquid and absorbs, and the reaction times of doctor solution and biogas is 2 minutes, and doctor solution is for containing the catalyst carbon acid sodium solution, and the chemical formula that contains the catalyst carbon acid sodium solution is: Na
2C0
3
The chemical equation Na of biogas and doctor solution
2C0
3+ H
2S=NaHS+NaHC0
3
Under V5+ catalysis, the HS-reaction generates elemental sulfur:
NaHS＋NaHC0
3＋2NaV0
3＝Na
2V
20
5＋Na
2C0
3＋S＋H
20
Tannin extract quinone attitude component through overcuring is oxidized to V5+ with V4+, and tannin extract quinone attitude becomes tannin extract phenol attitude, and tannin extract quinone attitude is TQ, and tannin extract phenol attitude is THQ:
Na
2V
20
5＋TQ＝NaV0
3＋THQ；
(4), the biogas after the desulfurization draws from the cat head of desulfuration absorbing tower, carries out separating treatment through gas-liquid separator, the disengaging time of gas-liquid separator is 3 minutes;
(5), biogas enters to gas wash tower, the doctor solution in the flush away gas, washing time is 3 minutes;
The chemical equation of biogas and doctor solution: Na
2C0
3+ CaCl
2=2NaCl+CaCO
3
(6), biogas bottom from gas wash tower after wet desulphurization enters the dry desulfurization device, sweetening agent in hydrogen sulfide in the biogas and the dry desulfurization device reacts, hydrogen sulfide is converted into sulfide and elemental sulfur is deposited in the vulcanizing agent bed, thereby with the hydrogen sulfide stripping in the thick desulfurization biogas, the reaction times of biogas in the dry desulfurization device is 5 minutes, and the temperature of reaction of biogas in the dry desulfurization device is 15 ℃;
Chemical equation: Fe2O3H2O+3H2S=Fe2S3H2O+3H2O+Q;
(7), with the Base top contact of biogas from the dry desulfurization device, enter in the fly-ash separator, the time of biogas in fly-ash separator is 1 second, it is 100Nm that fly-ash separator is processed air quantity
3/ h, the sulfide in the dry desulfurization device is discharged through the sulfuration property management;
(8), biogas enters to compressor after dedusting, be 1 second the working time of compressor, and the power of compressor is 10KW, is pressurized to 0.7Mpa by reciprocating type Marsh gas compression machine two stages of compression, after temperature is increased to 40 ℃, goes out pipe by biogas and enter to decarbonization process; Decarbonization process adopts with two sections pressure swing absorption process, decarbonization process comprises PSA-1 operation and PSA-2 operation, and the PSA-1 operation mainly is the invalid gas of carbon dioxide removal, guarantees simultaneously effective gases methane loss reduction, the PSA-2 operation mainly be that the work in-process air lift is pure, obtain products C H
4, the pressure of decarbonization process is 0.4MPa;
(9), generation contains H in the desulfuration absorbing tower
2The rich solution of S and sodium hydrogen carbonate solution are discharged at the bottom of the tower of desulfuration absorbing tower, and the chemistry of rich solution is called sodium hydrosulfide, and the chemical formula of sodium hydrosulfide is NaHS, and the chemical formula of sodium hydrogen carbonate solution is NaHC0
3
Main chemical equation: Na
2C0
3+ H
2S=NaHS+NaHC0
3
(10), rich solution enters in the solution reaction groove through fluid-tight, the reaction times of rich solution in the solution reaction groove is 2 minutes, rich solution and the H that is dissolved in the rich solution
2S continues reaction at reactive tank and produces Sodium sulfhydrate and sodium bicarbonate, continues to generate elemental sulfur under the effect of catalyzer;
Chemical equation: Na
2C0
3+ H
2S=NaHS+NaHC0
3
Under V5+ catalysis, the HS-reaction generates elemental sulfur:
NaHS＋NaHC0
3＋2NaV0
3＝Na
2V
20
5＋Na
2C0
3＋S＋H
20；
Tannin extract quinone attitude component through overcuring is oxidized to V5+ with V4+, and tannin extract quinone attitude becomes tannin extract phenol attitude, and tannin extract quinone attitude is TQ, and tannin extract phenol attitude is THQ:
Na
2V
20
5＋TQ＝NaV0
3＋THQ；
(11), in the solution reaction groove, continue to react after with the rich solution pumping toward injector, the rich solution pump adopts IS type horizontal single-stage impeller pump, flow Q:5.4m
3/ h, lift H:4m;
(12), risen by the regenerator column bottom from injector afterbody two-phase fluid out, airborne oxygen is oxidized to tannin extract quinone attitude with tannin extract phenol attitude, has simultaneously hydrogen peroxide to generate;
The chemical reaction following steps:
0
2＋THQ＝2TQ＋H
20
2?；
H
20
2Oxidation V4+ and HS-:
1/2?H
20
2＋V4+＝V5+＋OH-；
H
20
2＋HS-＝H
20＋S＋OH-；
(13), the sulphur foam that overflows of regenerator column top puts into to sulfur melting kettle through the sulphur foam separator and melts sulphuring treatment, the time of molten sulphur is 30 minutes, produces sulphur;
(14), sulphur puts into to mold and form the sulphur ingot after cooling, the cooling temperature of mold is 15 ℃, 10 minutes of the cooling time of mold;
(15), will not contain H
2The lean solution of S is drawn by the lean solution exit of regenerator column, and lean solution is pumped back to thionizer through poor stream again through regulator of level and carries out circulating reaction; Liquid phase and vapour phase signal pipe are arranged in the regulator of level, when liquid level descends, the vapour phase signal increases, reduce the effective flow area of pipeline, solution flow is reduced, reach the purpose of effective control flow, move in circles, can realize automatically regulating liquid level, poor stream pump adopts IS type horizontal single-stage impeller pump, flow Q:5.4m
3/ h, lift H:4m;
Lean solution is the sodium carbonate solution that contains catalyzer.
Embodiment 2: the preparation method of biogas dry filtration desulfurization is characterized in that carrying out according to the following steps:
(1), raw material biogas enters to that the air inlet cabinet cushions and voltage stabilizing is processed from the biogas inlet pipe, the pressure of biogas is 2000Pa, the time of voltage stabilizing is 30 seconds;
(2), biogas is pressurized to 29KPa through supercharging blower, the temperature of biogas is 22 ℃, the time of supercharging is 5 seconds;
(3), the biogas after the supercharging enters from the bottom of desulfuration absorbing tower, with the doctor solution counter current contact that contains catalyzer that sprays on the desulfuration absorbing tower, H in the biogas
2S is desulfurized liquid and absorbs, and the reaction times of doctor solution and biogas is 2.5 minutes, and doctor solution is for containing the catalyst carbon acid sodium solution, and the chemical formula that contains the catalyst carbon acid sodium solution is: Na
2C0
3
The chemical equation Na of biogas and doctor solution
2C0
3+ H
2S=NaHS+NaHC0
3
Under V5+ catalysis, the HS-reaction generates elemental sulfur:
NaHS＋NaHC0
3＋2NaV0
3＝Na
2V
20
5＋Na
2C0
3＋S＋H
20
Tannin extract quinone attitude component through overcuring is oxidized to V5+ with V4+, and tannin extract quinone attitude becomes tannin extract phenol attitude, and tannin extract quinone attitude is TQ, and tannin extract phenol attitude is THQ:
Na
2V
20
5＋TQ＝NaV0
3＋THQ；
(4), the biogas after the desulfurization draws from the cat head of desulfuration absorbing tower, carries out separating treatment through gas-liquid separator, the disengaging time of gas-liquid separator is 4 minutes;
(5), biogas enters to gas wash tower, the doctor solution in the flush away gas, washing time is 4 minutes;
The chemical equation of biogas and doctor solution: Na
2C0
3+ CaCl
2=2NaCl+CaCO
3
(6), biogas bottom from gas wash tower after wet desulphurization enters the dry desulfurization device, sweetening agent in hydrogen sulfide in the biogas and the dry desulfurization device reacts, hydrogen sulfide is converted into sulfide and elemental sulfur is deposited in the vulcanizing agent bed, thereby with the hydrogen sulfide stripping in the thick desulfurization biogas, the reaction times of biogas in the dry desulfurization device is 8 minutes, and the temperature of reaction of biogas in the dry desulfurization device is 22 ℃;
Chemical equation: Fe2O3H2O+3H2S=Fe2S3H2O+3H2O+Q;
(7), with the Base top contact of biogas from the dry desulfurization device, enter in the fly-ash separator, the time of biogas in fly-ash separator is 3 seconds, it is 250Nm that fly-ash separator is processed air quantity
3/ h, the sulfide in the dry desulfurization device is discharged through the sulfuration property management;
(8), biogas enters to compressor after dedusting, be 5 seconds the working time of compressor, and the power of compressor is 25KW, is pressurized to 0.7Mpa by reciprocating type Marsh gas compression machine two stages of compression, after temperature is increased to 40 ℃, goes out pipe by biogas and enter to decarbonization process; Decarbonization process adopts with two sections pressure swing absorption process, decarbonization process comprises PSA-1 operation and PSA-2 operation, and the PSA-1 operation mainly is the invalid gas of carbon dioxide removal, guarantees simultaneously effective gases methane loss reduction, the PSA-2 operation mainly be that the work in-process air lift is pure, obtain products C H
4, the pressure of decarbonization process is 0.5MPa;
(9), generation contains H in the desulfuration absorbing tower
2The rich solution of S and sodium hydrogen carbonate solution are discharged at the bottom of the tower of desulfuration absorbing tower, and the chemistry of rich solution is called sodium hydrosulfide, and the chemical formula of sodium hydrosulfide is NaHS, and the chemical formula of sodium hydrogen carbonate solution is NaHC0
3
Main chemical equation: Na
2C0
3+ H
2S=NaHS+NaHC0
3
(10), rich solution enters in the solution reaction groove through fluid-tight, the reaction times of rich solution in the solution reaction groove is 4 minutes, rich solution and the H that is dissolved in the rich solution
2S continues reaction at reactive tank and produces Sodium sulfhydrate and sodium bicarbonate, continues to generate elemental sulfur under the effect of catalyzer;
Chemical equation: Na
2C0
3+ H
2S=NaHS+NaHC0
3
Under V5+ catalysis, the HS-reaction generates elemental sulfur:
NaHS＋NaHC0
3＋2NaV0
3＝Na
2V
20
5＋Na
2C0
3＋S＋H
20；
Tannin extract quinone attitude component through overcuring is oxidized to V5+ with V4+, and tannin extract quinone attitude becomes tannin extract phenol attitude, and tannin extract quinone attitude is TQ, and tannin extract phenol attitude is THQ:
Na
2V
20
5＋TQ＝NaV0
3＋THQ；
(11), in the solution reaction groove, continue to react after with the rich solution pumping toward injector, the rich solution pump adopts IS type horizontal single-stage impeller pump, flow Q:200m
3/ h, lift H:70m;
(12), risen by the regenerator column bottom from injector afterbody two-phase fluid out, airborne oxygen is oxidized to tannin extract quinone attitude with tannin extract phenol attitude, has simultaneously hydrogen peroxide to generate;
The chemical reaction following steps:
0
2＋THQ＝2TQ＋H
20
2?；
H
20
2Oxidation V4+ and HS-:
1/2?H
20
2＋V4+＝V5+＋OH-；
H
20
2＋HS-＝H
20＋S＋OH-；
(13), the sulphur foam that overflows of regenerator column top puts into to sulfur melting kettle through the sulphur foam separator and melts sulphuring treatment, the time of molten sulphur is 40 minutes, produces sulphur;
(14), sulphur puts into to mold and form the sulphur ingot after cooling, the cooling temperature of mold is 22 ℃, 20 minutes of the cooling time of mold;
(15), will not contain H
2The lean solution of S is drawn by the lean solution exit of regenerator column, and lean solution is pumped back to thionizer through poor stream again through regulator of level and carries out circulating reaction; Liquid phase and vapour phase signal pipe are arranged in the regulator of level, when liquid level descends, the vapour phase signal increases, reduce the effective flow area of pipeline, solution flow is reduced, reach the purpose of effective control flow, move in circles, can realize automatically regulating liquid level, poor stream pump adopts IS type horizontal single-stage impeller pump, flow Q:200m
3/ h, lift H:70m;
Lean solution is the sodium carbonate solution that contains catalyzer.
Embodiment 3: the preparation method of biogas dry filtration desulfurization is characterized in that carrying out according to the following steps:
(1), raw material biogas enters to that the air inlet cabinet cushions and voltage stabilizing is processed from the biogas inlet pipe, the pressure of biogas is 3000Pa, the time of voltage stabilizing is 60 seconds;
(2), biogas is pressurized to 31KPa through supercharging blower, the temperature of biogas is 30 ℃, the time of supercharging is 10 seconds;
(3), the biogas after the supercharging enters from the bottom of desulfuration absorbing tower, with the doctor solution counter current contact that contains catalyzer that sprays on the desulfuration absorbing tower, H in the biogas
2S is desulfurized liquid and absorbs, and the reaction times of doctor solution and biogas is 3 minutes, and doctor solution is for containing the catalyst carbon acid sodium solution, and the chemical formula that contains the catalyst carbon acid sodium solution is: Na
2C0
3
The chemical equation Na of biogas and doctor solution
2C0
3+ H
2S=NaHS+NaHC0
3
Under V5+ catalysis, the HS-reaction generates elemental sulfur:
NaHS＋NaHC0
3＋2NaV0
3＝Na
2V
20
5＋Na
2C0
3＋S＋H
20
Tannin extract quinone attitude component through overcuring is oxidized to V5+ with V4+, and tannin extract quinone attitude becomes tannin extract phenol attitude, and tannin extract quinone attitude is TQ, and tannin extract phenol attitude is THQ:
Na
2V
20
5＋TQ＝NaV0
3＋THQ；
(4), the biogas after the desulfurization draws from the cat head of desulfuration absorbing tower, carries out separating treatment through gas-liquid separator, the disengaging time of gas-liquid separator is 5 minutes;
(5), biogas enters to gas wash tower, the doctor solution in the flush away gas, washing time is 5 minutes;
The chemical equation of biogas and doctor solution: Na
2C0
3+ CaCl
2=2NaCl+CaCO
3
(6), biogas bottom from gas wash tower after wet desulphurization enters the dry desulfurization device, sweetening agent in hydrogen sulfide in the biogas and the dry desulfurization device reacts, hydrogen sulfide is converted into sulfide and elemental sulfur is deposited in the vulcanizing agent bed, thereby with the hydrogen sulfide stripping in the thick desulfurization biogas, the reaction times of biogas in the dry desulfurization device is 10 minutes, and the temperature of reaction of biogas in the dry desulfurization device is 30 ℃;
Chemical equation: Fe2O3H2O+3H2S=Fe2S3H2O+3H2O+Q;
(7), with the Base top contact of biogas from the dry desulfurization device, enter in the fly-ash separator, the time of biogas in fly-ash separator is 5 seconds, it is 500Nm that fly-ash separator is processed air quantity
3/ h, the sulfide in the dry desulfurization device is discharged through the sulfuration property management;
(8), biogas enters to compressor after dedusting, be 10 seconds the working time of compressor, and the power of compressor is 45KW, is pressurized to 0.7Mpa by reciprocating type Marsh gas compression machine two stages of compression, after temperature is increased to 40 ℃, goes out pipe by biogas and enter to decarbonization process; Decarbonization process adopts with two sections pressure swing absorption process, decarbonization process comprises PSA-1 operation and PSA-2 operation, and the PSA-1 operation mainly is the invalid gas of carbon dioxide removal, guarantees simultaneously effective gases methane loss reduction, the PSA-2 operation mainly be that the work in-process air lift is pure, obtain products C H
4, the pressure of decarbonization process is 0.6MPa;
(9), generation contains H in the desulfuration absorbing tower
2The rich solution of S and sodium hydrogen carbonate solution are discharged at the bottom of the tower of desulfuration absorbing tower, and the chemistry of rich solution is called sodium hydrosulfide, and the chemical formula of sodium hydrosulfide is NaHS, and the chemical formula of sodium hydrogen carbonate solution is NaHC0
3
Main chemical equation: Na
2C0
3+ H
2S=NaHS+NaHC0
3
(10), rich solution enters in the solution reaction groove through fluid-tight, the reaction times of rich solution in the solution reaction groove is 5 minutes, rich solution and the H that is dissolved in the rich solution
2S continues reaction at reactive tank and produces Sodium sulfhydrate and sodium bicarbonate, continues to generate elemental sulfur under the effect of catalyzer;
Chemical equation: Na
2C0
3+ H
2S=NaHS+NaHC0
3
Under V5+ catalysis, the HS-reaction generates elemental sulfur:
NaHS＋NaHC0
3＋2NaV0
3＝Na
2V
20
5＋Na
2C0
3＋S＋H
20；
Tannin extract quinone attitude component through overcuring is oxidized to V5+ with V4+, and tannin extract quinone attitude becomes tannin extract phenol attitude, and tannin extract quinone attitude is TQ, and tannin extract phenol attitude is THQ:
Na
2V
20
5＋TQ＝NaV0
3＋THQ；
(11), in the solution reaction groove, continue to react after with the rich solution pumping toward injector, the rich solution pump adopts IS type horizontal single-stage impeller pump, flow Q:400m
3/ h, lift H:125m;
(12), risen by the regenerator column bottom from injector afterbody two-phase fluid out, airborne oxygen is oxidized to tannin extract quinone attitude with tannin extract phenol attitude, has simultaneously hydrogen peroxide to generate;
The chemical reaction following steps:
0
2＋THQ＝2TQ＋H
20
2?；
H
20
2Oxidation V4+ and HS-:
1/2?H
20
2＋V4+＝V5+＋OH-；
H
20
2＋HS-＝H
20＋S＋OH-；
(13), the sulphur foam that overflows of regenerator column top puts into to sulfur melting kettle through the sulphur foam separator and melts sulphuring treatment, the time of molten sulphur is 50 minutes, produces sulphur;
(14), sulphur puts into to mold and form the sulphur ingot after cooling, the cooling temperature of mold is 30 ℃, 30 minutes of the cooling time of mold;
(15), will not contain H
2The lean solution of S is drawn by the lean solution exit of regenerator column, and lean solution is pumped back to thionizer through poor stream again through regulator of level and carries out circulating reaction; Liquid phase and vapour phase signal pipe are arranged in the regulator of level, when liquid level descends, the vapour phase signal increases, reduce the effective flow area of pipeline, solution flow is reduced, reach the purpose of effective control flow, move in circles, can realize automatically regulating liquid level, poor stream pump adopts IS type horizontal single-stage impeller pump, flow Q:400m
3/ h, lift H:125m; Lean solution is the sodium carbonate solution that contains catalyzer.
Claims (3)
1. biogas dry filtration desulphurization system, it is characterized in that: comprise biogas inlet pipe (1), described biogas inlet pipe (1) is connected with air inlet cabinet (2), described air inlet cabinet (2) is connected with desulfuration absorbing tower (3), the top of described desulfuration absorbing tower (3) is connected with gas-liquid separator (4), described gas-liquid separator (4) is connected with gas wash tower (5), described gas wash tower (5) is connected with dry desulfurization device (6), the top of described dry desulfurization device (6) is connected with fly-ash separator (7), the bottom of described dry desulfurization device (6) is connected with sulfuration property management (8), described fly-ash separator (7) is connected with compressor (9), and described compressor (9) goes out pipe (10) with biogas and is connected; The bottom of described desulfuration absorbing tower (3) is connected with solution reaction groove (11), described solution reaction groove (11) is connected with rich solution pump (12), described rich solution pump (12) is connected with injector (13), described injector (13) is connected with regenerator column (14), the top of described regenerator column (14) is connected with sulphur foam separator (15), described sulphur foam separator (15) is connected with sulfur melting kettle (16), described sulfur melting kettle (16) is connected with mold (17), described mold (17) is connected with elemental sulfur pipe (18), described regenerator column (14) the exit be connected with regulator of level (19), described regulator of level (19) is connected with lean pump (20), and described lean pump (20) is back in the desulfuration absorbing tower (3) again.
2. biogas dry filtration desulphurization system according to claim 1, it is characterized in that: be provided with supercharging blower (21) between described air inlet cabinet (2) and desulfuration absorbing tower (3), the below of described rich solution pump (12) is provided with the rich solution pump I (22) that is in parallel with it, and the below of described lean pump (20) is provided with the lean pump I (23) that is in parallel with it.
3. the preparation method of biogas dry filtration according to claim 1 and 2 desulfurization is characterized in that carrying out according to the following steps:
(1), raw material biogas enters to that the air inlet cabinet cushions and voltage stabilizing is processed from the biogas inlet pipe, the pressure of biogas is 1000～3000Pa, the time of voltage stabilizing is 10～60 seconds;
(2), biogas is pressurized to 27～31KPa through supercharging blower, the temperature of biogas is 15～30 ℃, the time of supercharging is 1～10 second;
(3), the biogas after the supercharging enters from the bottom of desulfuration absorbing tower, with the doctor solution counter current contact that contains catalyzer that sprays on the desulfuration absorbing tower, H in the biogas
2S is desulfurized liquid and absorbs, and the reaction times of doctor solution and biogas is 2～3 minutes, and doctor solution is for containing the catalyst carbon acid sodium solution, and the chemical formula that contains the catalyst carbon acid sodium solution is: Na
2C0
3
The chemical equation Na of biogas and doctor solution
2C0
3+ H
2S=NaHS+NaHC0
3
Under V5+ catalysis, the HS-reaction generates elemental sulfur:
NaHS＋NaHC0
3＋2NaV0
3＝Na
2V
20
5＋Na
2C0
3＋S＋H
20
Tannin extract quinone attitude component through overcuring is oxidized to V5+ with V4+, and tannin extract quinone attitude becomes tannin extract phenol attitude, and tannin extract quinone attitude is TQ, and tannin extract phenol attitude is THQ:
Na
2V
20
5＋TQ＝NaV0
3＋THQ；
(4), the biogas after the desulfurization draws from the cat head of desulfuration absorbing tower, carries out separating treatment through gas-liquid separator, the disengaging time of gas-liquid separator is 3～5 minutes;
(5), biogas enters to gas wash tower, the doctor solution in the flush away gas, washing time is 3～5 minutes;
The chemical equation of biogas and doctor solution: Na
2C0
3+ CaCl
2=2NaCl+CaCO
3
(6), biogas bottom from gas wash tower after wet desulphurization enters the dry desulfurization device, sweetening agent in hydrogen sulfide in the biogas and the dry desulfurization device reacts, hydrogen sulfide is converted into sulfide and elemental sulfur is deposited in the vulcanizing agent bed, thereby with the hydrogen sulfide stripping in the thick desulfurization biogas, the reaction times of biogas in the dry desulfurization device is 5～10 minutes, and the temperature of reaction of biogas in the dry desulfurization device is 15～30 ℃;
Chemical equation: Fe2O3H2O+3H2S=Fe2S3H2O+3H2O+Q;
(7), with the Base top contact of biogas from the dry desulfurization device, enter in the fly-ash separator, the time of biogas in fly-ash separator is 1～5 second, it is 100～500Nm that fly-ash separator is processed air quantity
3/ h, the sulfide in the dry desulfurization device is discharged through the sulfuration property management;
(8), biogas enters to compressor after dedusting, be 1～10 second the working time of compressor, and the power of compressor is 10～45KW, is pressurized to 0.7Mpa by reciprocating type Marsh gas compression machine two stages of compression, after temperature is increased to 40 ℃, goes out pipe by biogas and enter to decarbonization process; Decarbonization process adopts with two sections pressure swing absorption process, decarbonization process comprises PSA-1 operation and PSA-2 operation, and the PSA-1 operation mainly is the invalid gas of carbon dioxide removal, guarantees simultaneously effective gases methane loss reduction, the PSA-2 operation mainly be that the work in-process air lift is pure, obtain products C H
4, the pressure of decarbonization process is 0.4～0.6MPa;
(9), generation contains H in the desulfuration absorbing tower
2The rich solution of S and sodium hydrogen carbonate solution are discharged at the bottom of the tower of desulfuration absorbing tower, and the chemistry of rich solution is called sodium hydrosulfide, and the chemical formula of sodium hydrosulfide is NaHS, and the chemical formula of sodium hydrogen carbonate solution is NaHC0
3
Main chemical equation: Na
2C0
3+ H
2S=NaHS+NaHC0
3
(10), rich solution enters in the solution reaction groove through fluid-tight, the reaction times of rich solution in the solution reaction groove is 2～5 minutes, rich solution and the H that is dissolved in the rich solution
2S continues reaction at reactive tank and produces Sodium sulfhydrate and sodium bicarbonate, continues to generate elemental sulfur under the effect of catalyzer;
Chemical equation: Na
2C0
3+ H
2S=NaHS+NaHC0
3
Under V5+ catalysis, the HS-reaction generates elemental sulfur:
NaHS＋NaHC0
3＋2NaV0
3＝Na
2V
20
5＋Na
2C0
3＋S＋H
20；
Tannin extract quinone attitude component through overcuring is oxidized to V5+ with V4+, and tannin extract quinone attitude becomes tannin extract phenol attitude, and tannin extract quinone attitude is TQ, and tannin extract phenol attitude is THQ:
Na
2V
20
5＋TQ＝NaV0
3＋THQ；
(11), in the solution reaction groove, continue to react after with the rich solution pumping toward injector, the rich solution pump adopts IS type horizontal single-stage impeller pump, flow Q:5.4～400m
3/ h, lift H:4～125m;
(12), risen by the regenerator column bottom from injector afterbody two-phase fluid out, airborne oxygen is oxidized to tannin extract quinone attitude with tannin extract phenol attitude, has simultaneously hydrogen peroxide to generate;
The chemical reaction following steps:
0
2＋THQ＝2TQ＋H
20
2?；
H
20
2Oxidation V4+ and HS-:
1/2?H
20
2＋V4+＝V5+＋OH-；
H
20
2＋HS-＝H
20＋S＋OH-；
(13), the sulphur foam that overflows of regenerator column top puts into to sulfur melting kettle through the sulphur foam separator and melts sulphuring treatment, the time of molten sulphur is 30～50 minutes, produces sulphur;
(14), sulphur puts into to mold and form the sulphur ingot after cooling, the cooling temperature of mold is 15～30 ℃, 10～30 minutes of the cooling time of mold;
(15), will not contain H
2The lean solution of S is drawn by the lean solution exit of regenerator column, and lean solution is pumped back to thionizer through poor stream again through regulator of level and carries out circulating reaction; Liquid phase and vapour phase signal pipe are arranged in the regulator of level, when liquid level descends, the vapour phase signal increases, reduce the effective flow area of pipeline, solution flow is reduced, reach the purpose of effective control flow, move in circles, can realize automatically regulating liquid level, poor stream pump adopts IS type horizontal single-stage impeller pump, flow Q:5.4～400m
3/ h, lift H:4～125m; Lean solution is the sodium carbonate solution that contains catalyzer.
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| CN106110827A (en) * | 2016-08-30 | 2016-11-16 | 温州乐享科技信息有限公司 | A kind of method that flue gas is carried out desulfurization |
| CN106215686A (en) * | 2016-08-30 | 2016-12-14 | 温州乐享科技信息有限公司 | The method that flue gas is carried out desulfurization |
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| CN106215686A (en) * | 2016-08-30 | 2016-12-14 | 温州乐享科技信息有限公司 | The method that flue gas is carried out desulfurization |
| CN106110827A (en) * | 2016-08-30 | 2016-11-16 | 温州乐享科技信息有限公司 | A kind of method that flue gas is carried out desulfurization |
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| CN106345267A (en) * | 2016-08-30 | 2017-01-25 | 温州乐享科技信息有限公司 | Method for flue gas desulfurization |
| CN106377996A (en) * | 2016-08-30 | 2017-02-08 | 温州乐享科技信息有限公司 | Flue gas desulphurization method |
| CN107446642A (en) * | 2017-09-05 | 2017-12-08 | 四川沃兹凯兰科技有限公司 | A kind of efficient natural desulfurization system and its sulfur removal technology |
| CN109777545A (en) * | 2019-03-21 | 2019-05-21 | 青岛中海环境工程有限公司 | A kind of biogas desulfurization system and sulfur method |
| CN117259383A (en) * | 2023-10-30 | 2023-12-22 | 河南理工大学 | Organic solid waste treatment process |
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