CN116730467B - Method for treating coking gas desulfurization and decyanation waste liquid by utilizing ozone generator - Google Patents
Method for treating coking gas desulfurization and decyanation waste liquid by utilizing ozone generator Download PDFInfo
- Publication number
- CN116730467B CN116730467B CN202310741443.5A CN202310741443A CN116730467B CN 116730467 B CN116730467 B CN 116730467B CN 202310741443 A CN202310741443 A CN 202310741443A CN 116730467 B CN116730467 B CN 116730467B
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- Prior art keywords
- sampling
- waste liquid
- sampling tube
- pool
- pressing plate
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- 239000007788 liquid Substances 0.000 title claims abstract description 137
- 239000002699 waste material Substances 0.000 title claims abstract description 85
- 238000007255 decyanation reaction Methods 0.000 title claims abstract description 42
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 42
- 230000023556 desulfurization Effects 0.000 title claims abstract description 42
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004939 coking Methods 0.000 title claims abstract description 12
- 238000005070 sampling Methods 0.000 claims abstract description 299
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000012452 mother liquor Substances 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims description 15
- 230000007704 transition Effects 0.000 claims description 12
- 230000005540 biological transmission Effects 0.000 claims description 5
- 230000000149 penetrating effect Effects 0.000 claims description 5
- 230000001276 controlling effect Effects 0.000 claims description 3
- 230000001960 triggered effect Effects 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 10
- 230000009471 action Effects 0.000 description 9
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000007363 regulatory process Effects 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/10—Devices for withdrawing samples in the liquid or fluent state
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
Abstract
The invention relates to the technical field of desulfurization and decyanation waste liquid treatment, in particular to a method for treating coking gas desulfurization and decyanation waste liquid by utilizing an ozone generator; the method comprises the following steps: s1: firstly, the desulfurization and decyanation waste liquid in the same batch is injected along a liquid inlet of a sampling pool, and then the liquid inlet is closed; s2: the sampling tube moves downwards to trigger the sampling channel, the waste liquid in the sampling tube flows out and is collected along the sampling channel, and after the pH value of the sample is regulated, the sulfuric acid capacity W X of the residual waste liquid in the sampling tank is obtained; s3: finally, enabling mother liquor in the sampling pool to flow into the reaction device, pouring sulfuric acid with the capacity of W X into the reaction device, stirring, and introducing ozone; according to the invention, the desulfurization and decyanation waste liquid of each batch is sampled in proportion by the sampling device, so that the capacity of adjusting the pH value of the desulfurization and decyanation waste liquid can be rapidly obtained by adjusting the pH value of the sample.
Description
Technical Field
The invention relates to the technical field of desulfurization and decyanation waste liquid treatment, in particular to a method for treating coking gas desulfurization and decyanation waste liquid by utilizing an ozone generator.
Background
Ozone oxidation is a common treatment method for ammonium thiosulfate in desulfurization and decyanation waste liquid. Ozone oxidation is to oxidize ammonium thiosulfate into harmless products by utilizing ozone molecules with strong oxidability, so that the purposes of waste liquid treatment and environmental protection are achieved. In the ozone oxidation process, ozone (O 3 ) Can react with sulfur element in ammonium thiosulfate as strong oxidant to oxidize the sulfur element into sulfate ion (SO 4 2- ). This oxidation reaction can be carried out by ozone and sulfur in the waste liquidAmmonium thiosulfate contact occurs or is achieved by injecting ozone gas directly into the desulfurization and decyanation waste stream.
Before the reaction of ozone on ammonium thiosulfate in the waste liquid, the pH value of the desulfurization and decyanation waste liquid needs to be regulated to about pH6.0-7.0, and 4O is directly oxidized by ozone under the acidic condition 3 +2S 2 O 3 +4H 2 O→4H 2 SO 4 +3O 2 To reduce the content of ammonium thiosulfate.
The method for regulating the pH value greatly influences the treatment efficiency of the desulfurization and decyanation waste liquid, especially in the case of larger capacity of the desulfurization and decyanation waste liquid of each batch, the process for regulating the pH value is slower, and for the desulfurization and decyanation waste liquid of a plurality of batches with different sources, the pH value regulation is needed before each time ozone oxidation is utilized in order to ensure the effect of ozone oxidation of ammonium thiosulfate in the waste liquid, which definitely consumes a great amount of time, so that the treatment progress of the desulfurization and decyanation waste liquid is slow.
In view of the above, the present invention provides a method for treating coking gas desulfurization and decyanation waste liquid by using an ozone generator, which solves the above technical problems.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides a method for treating coking gas desulfurization and decyanation waste liquid by utilizing an ozone generator.
The technical scheme adopted for solving the technical problems is as follows: the invention relates to a method for treating coking gas desulfurization and decyanation waste liquid by utilizing an ozone generator, which comprises the following steps:
s1: firstly, injecting the desulfurization and decyanation waste liquid in the same batch along a liquid inlet of a sampling tank in a sampling device, wherein a gap is reserved between a lower port of a sampling pipe and the bottom of the sampling tank, the waste liquid in the sampling tank enters the sampling pipe along the lower port of the sampling pipe, and the liquid inlet is closed after a certain amount of waste liquid is injected into the sampling tank along with the rise of the liquid level of the waste liquid in the sampling tank;
s2: then pressing a sampling tube in the sampling device to move downwards, wherein the sampling tube is contacted and sealed with the bottom of a sampling pool after moving downwards, and the sampling channel is triggered along with the continuous downward movement of the sampling tube, so that the sampling channel is opened, waste liquid in the sampling tube flows out along the sampling channel and is collected by a worker, and after the pH value of a sample is regulated, the sulfuric acid capacity W X of the residual waste liquid in the sampling pool to be added is obtained;
s3: finally, a worker opens a liquid outlet of a sampling pool in the sampling device, so that mother liquor in the sampling pool flows into the reaction device, a sample with the pH value adjusted is also poured into the reaction device, sulfuric acid with the capacity of W X is poured into the reaction device, and ozone is introduced after stirring;
wherein the sampling device used in S1-S3 comprises:
a sampling pool; the bottom of the sampling pool is placed on the ground through a bracket; the outer wall of the sampling pool is provided with a liquid inlet and a liquid outlet; valves are arranged in the liquid inlet and the liquid outlet, and the liquid inlet and the liquid outlet are arranged close to the bottom of the sampling pool;
a guide ring; the guide ring is fixedly connected to a tank opening of the sampling tank;
a sampling tube; the sampling tube is a straight tubular object with an upper opening and a lower opening; the sampling tube penetrates through the guide ring and is in sliding connection with the guide ring;
a sampling channel; the sampling channel is arranged at the inner bottom of the sampling pool, is opened after the sampling pipe is downwards moved, and is closed after the sampling pipe is upwards moved;
a controller; the controller is used for controlling the sampling device to automatically operate.
Preferably, the sampling channel comprises a groove, a sliding block, a first spring and an inverted L-shaped hole; the groove is arranged on the inner bottom wall of the sampling pool and is positioned right below the sampling pipe; the projection of the groove in the overlooking state covers the projection of the sampling tube in the overlooking state; the sliding block is connected in the groove in a sliding way; the first spring is connected between the sliding block and the bottom of the groove; the inverted L-shaped hole is arranged at the bottom of the sampling pool, one end of the inverted L-shaped hole is communicated with the side wall of the groove, and the other end of the inverted L-shaped hole is contacted with the lower end face of the sampling pool; the upper end surface of the sliding block is flush with the bottom of the sampling tank under the action of a spring I; the upper end face of the sliding block is communicated with the side wall through a positive L-shaped hole; the positive L-shaped hole is communicated with the inverted L-shaped hole after the sliding block moves downwards;
a reset ring is arranged above the guide ring; the reset ring is fixedly connected to the outer wall of the sampling tube; the reset ring is connected with the guide ring through a reset spring;
a pressing plate is arranged above the sampling tube; the pressing plate is connected with a hydraulic cylinder; the hydraulic cylinder is vertically and fixedly connected to the wall of the sampling tank; the pressure plate moves downwards under the drive of the hydraulic cylinder, so that the upper port of the sampling tube is extruded by the pressure plate.
Preferably, the upper end face of the sliding block is provided with an annular groove; the diameter of the inner side wall of the annular groove is equal to the inner diameter of the sampling pipe; the outer wall of the annular groove is equal to the outer diameter of the sampling tube; the annular groove is internally connected with an annular plate in a sliding and sealing manner; the annular groove is consistent with the external air pressure, so that the movement of the annular plate is not hindered; the annular plate is connected with the bottom of the annular groove through a second spring; the upper end face of the annular plate is flush with the upper end face of the sliding block under the action of a second spring; the lower part of the sampling tube is in sliding fit with the annular groove.
Preferably, the center of the lower end of the sampling pool is fixedly connected with a negative pressure cylinder; the lower end of the negative pressure cylinder is communicated with the other end of the inverted L-shaped hole, and the lower end of the negative pressure cylinder is connected with a liquid outlet pipe; the negative pressure cylinder is connected with a piston in a sliding and sealing manner; the piston is connected with the inner bottom end of the negative pressure cylinder through a third spring; the piston is provided with a negative pressure hole in a penetrating way up and down; check valves are arranged in the negative pressure hole and the inverted L-shaped hole; the center of the upper end of the piston is connected with a slide bar; the sliding rod penetrates through the sampling pool and extends to the upper part of the guide ring; the sliding rod is in sliding sealing connection with the sampling pool; one end of the sliding rod, which is far away from the piston, is connected with a pushing disc; the pushing disc is higher than the upper port of the sampling tube in the initial state; the piston divides the space in the negative pressure cylinder into an upper cavity and a lower cavity, and the movement space of the piston in the negative pressure cylinder is larger than the space inside the sampling tube; the pushing disc is positioned below the pressing plate.
Preferably, the output shaft of the hydraulic cylinder is fixedly connected with a cross rod; one end of the cross rod extends to the position right above the push disc; a through hole is formed in one end of the cross rod in a vertically penetrating manner; the pressing plate is strip-shaped; the center of the upper end of the pressing plate is fixedly connected with a ring sleeve; the ring sleeve is rotationally connected to the lower port of the through hole; the upper end of the pushing disc is fixedly connected with a transition rod; the upper end of the transition rod is fixedly connected with a screw rod; the screw rod passes through the center of the pressing plate, the inner side of the ring sleeve and the through hole; the screw is in threaded transmission connection with the center of the pressing plate; the number of the sampling tubes is at least two; the sampling tubes are evenly distributed around the center of the sampling cell.
Preferably, the upper end surface of the pushing disc is provided with a first tooth in the circumferential direction; and second teeth are arranged around the center of the lower end surface of the pressing plate and correspond to the pushing disc.
Preferably, a strip-shaped groove is formed at the contact position of the lower end surface of the pressing plate and the sampling tube; the strip-shaped groove extends to the edge of the pressing plate; the number of the strip-shaped grooves is multiple, and the distance between the adjacent strip-shaped grooves is smaller than the inner diameter of the sampling tube.
Preferably, the width of the end part of the pressing plate is larger than the distance between two adjacent sampling pipes.
The beneficial effects of the invention are as follows:
1. according to the invention, the desulfurization and decyanation waste liquid of each batch is sampled in proportion by the sampling device, so that the capacity of adjusting the pH value of the desulfurization and decyanation waste liquid can be quickly obtained by adjusting the pH value of the sample, and compared with the prior art that the pH value is adjusted by directly adding sulfuric acid into the desulfurization and decyanation waste liquid in sequence, the pH value adjusting efficiency of the desulfurization and decyanation waste liquid is higher, and the treatment efficiency of the desulfurization and decyanation waste liquid is higher.
2. According to the invention, the lower part of the sampling tube can move into the annular groove after downwards moving, the inner wall of the sampling tube is sealed with the annular groove by the inner groove wall, the outer wall of the sampling tube is sealed with the annular groove by the outer groove wall, and the lower end surface of the sampling tube is sealed with the upper end surface of the annular plate under the action of the second spring, so that compared with the prior end surface sealing, the sealing effect is better, the waste liquid in the sampling tank is separated from the sample of the sampling tube, and the accuracy of the subsequent waste liquid pH value adjustment is ensured.
3. After the pressure plate moves downwards continuously, the pressure plate can squeeze the sampling tube, so that the sampling tube moves downwards to contact with the sliding block and drive the sliding block to move downwards, the inner side of the sampling tube is communicated with the inverted L-shaped hole through the positive L-shaped hole, a sample at the inner side of the sampling tube enters the upper cavity along the positive L-shaped hole and the inverted L-shaped hole under the negative pressure effect, in addition, redundant external gas flows along the inner side of the sampling tube and is sucked into the upper cavity, the gas can drive the redundant sample to enter the upper cavity, the residual is avoided, the way of sucking the sample under the negative pressure is also avoided, and the smooth flow of the sample is realized.
Drawings
The invention will be further described with reference to the drawings and embodiments.
FIG. 1 is a flow chart of the method of the present invention;
FIG. 2 is a perspective view of a sampling device according to the present invention;
FIG. 3 is an enlarged view at A in FIG. 2;
fig. 4 is an enlarged view at B in fig. 2;
FIG. 5 is a diagram of the position of tooth number two in the sampling device of the present invention;
FIG. 6 is an enlarged view at C in FIG. 5;
FIG. 7 is a diagram showing the internal structure of the sampling device according to the present invention;
fig. 8 is an enlarged view of D in fig. 7;
FIG. 9 is a block diagram of an annular groove and annular plate of the present invention;
fig. 10 is a block diagram of the method of the present invention.
In the figure: the sampling tank 1, the bracket 11, the liquid inlet 12, the liquid outlet 13, the guide ring 2, the reset ring 21, the reset spring 22, the sampling tube 3, the sampling channel 4, the groove 41, the sliding block 42, the first spring 43, the inverted L-shaped hole 44, the positive L-shaped hole 45, the annular groove 46, the annular plate 47, the second spring 48, the pressing plate 5, the hydraulic cylinder 51, the cross rod 52, the through hole 521, the annular sleeve 53, the second tooth 54, the strip groove 55, the negative pressure cylinder 6, the liquid outlet pipe 61, the piston 62, the negative pressure hole 621, the third spring 63, the sliding rod 64, the push disc 7, the transition rod 71, the screw 72 and the first tooth 73.
Detailed Description
The invention is further described in connection with the following detailed description in order to make the technical means, the creation characteristics, the achievement of the purpose and the effect of the invention easy to understand.
As shown in fig. 1 to 10, the method for treating coking gas desulfurization and decyanation waste liquid by using an ozone generator according to the invention comprises the following steps:
s1: firstly, the desulfurization and decyanation waste liquid in the same batch is injected along a liquid inlet 12 of a sampling pool 1 in a sampling device, a gap is reserved between the lower port of a sampling pipe 3 and the bottom of the sampling pool 1, the waste liquid in the sampling pool 1 enters the inside of the sampling pipe 3 along the lower port of the sampling pipe 3, the liquid level in the sampling pipe 3 is increased along with the rise of the liquid level of the waste liquid in the sampling pool 1, and after a certain amount of waste liquid is injected into the sampling pool 1, the liquid inlet 12 is closed;
s2: then, pressing the sampling tube 3 in the sampling device to move downwards, and then, contacting and sealing the sampling tube 3 with the bottom of the sampling tank 1, and triggering the sampling channel 4 along with the continuous downward movement of the sampling tube 3, so that the sampling channel 4 is opened, and the waste liquid in the sampling tube 3 flows out along the sampling channel 4 and is collected by a worker, so that the sulfuric acid capacity W X required to be added in the residual waste liquid in the sampling tank 1 is obtained after the pH value of the sample is regulated;
s3: finally, a worker opens a liquid outlet 13 of the sampling pool 1 in the sampling device, so that mother liquor in the sampling pool 1 flows into the reaction device, a sample with the pH value adjusted is also poured into the reaction device, sulfuric acid with the volume W X is poured into the reaction device, and ozone is introduced after stirring;
wherein the sampling device used in S1-S3 comprises:
a sampling pool 1; the bottom of the sampling pool 1 is placed on the ground through a bracket 11; the outer wall of the sampling pool 1 is provided with a liquid inlet 12 and a liquid outlet 13; valves are arranged in the liquid inlet 12 and the liquid outlet 13, and the liquid inlet 12 and the liquid outlet 13 are arranged close to the bottom of the sampling tank 1;
a guide ring 2; the guide ring 2 is fixedly connected to the tank opening of the sampling tank 1;
a sampling tube 3; the sampling tube 3 is a straight tubular object with an upper opening and a lower opening; the sampling tube 3 passes through the guide ring 2 and is in sliding connection with the guide ring 2;
a sampling channel 4; the sampling channel 4 is arranged at the inner bottom of the sampling pool 1, and is opened after the sampling pipe 3 moves downwards and closed after the sampling pipe moves upwards;
a controller; the controller is used for controlling the sampling device to automatically operate;
when the method is used, 25% sulfuric acid is sequentially added into the waste liquid, after the sulfuric acid is added into the waste liquid each time, the pH value in the waste liquid can be detected by fully stirring the waste liquid until the detected pH value is within the numerical range of pH6.0-7.0, the pH value regulating method greatly influences the treatment efficiency of the desulfurization and decyanation waste liquid, particularly, in the case of larger capacity of the desulfurization and decyanation waste liquid of each batch, the pH value regulating process is slower, and for the desulfurization and decyanation waste liquid of a plurality of batches with different sources, in order to ensure the ozone oxidation effect of ammonium thiosulfate in the waste liquid, the pH value regulation is needed before each time of ozone oxidation, which definitely consumes a great amount of time, and leads to slow treatment progress of the desulfurization and decyanation waste liquid;
therefore, under the condition that the liquid outlet 13 of the sampling tank 1 is closed by the staff, the liquid inlet 12 is opened, and then the desulfurization and decyanation waste liquid of the same batch is injected along the liquid inlet 12 of the sampling tank 1, the lower port of the sampling tube 3 is far away from the sampling channel 4 in the initial state and is not contacted with the sampling channel 4, so that the sampling channel 4 is in the closed state, and a gap is reserved between the lower port of the sampling tube 3 and the tank bottom of the sampling tank 1Under the action of atmospheric pressure, waste liquid in the sampling tank 1 can enter into the inside of the sampling pipe 3 along the lower port of the sampling pipe 3, along with the rise of the liquid level of the waste liquid in the sampling tank 1, the liquid level in the sampling pipe 3 rises along with the rise, after a certain amount of waste liquid is injected into the sampling tank 1, the liquid inlet 12 is closed, then the sampling pipe 3 is pressed to move downwards, the sampling pipe 3 can be in contact with the bottom of the sampling tank 1, thereby the waste liquid in the sampling tank 1 and the waste liquid in the sampling pipe 3 are cut off, the sampling channel 4 can be triggered along with the continuous downward movement of the sampling pipe 3, the sampling channel 4 is opened, so that the waste liquid in the sampling pipe 3 flows out along the sampling channel 4 and is collected by a worker, the sample sampling work is completed, and the residual waste liquid in the sampling tank 1 is called a mother liquid. 4O (4O) 3 +2S 2 O 3 +4H 2 O→4H 2 SO 4 +3O 2 The content of ammonium thiosulfate is reduced, water generated by the reaction device is discharged, and tail gas generated by the reaction is absorbed by the tail gas absorbing device; after the waste liquid in the sampling pool 1 is discharged, a worker lifts the sampling tube 3 away from the sampling channel 4, the sampling channel 4 is closed by itself after the sampling tube 3 is separated, then the liquid outlet 13 is closed, the liquid inlet 12 is opened, and the sulfuric acid amount required by the mother liquid is obtained for the waste liquid of the next batch according to the same mode, and the steps are repeated;
according to the invention, the desulfurization and decyanation waste liquid of each batch is sampled in proportion by the sampling device, so that the capacity of adjusting the pH value of the desulfurization and decyanation waste liquid can be quickly obtained by adjusting the pH value of the sample, and compared with the prior art that the pH value is adjusted by directly adding sulfuric acid into the desulfurization and decyanation waste liquid in sequence, the pH value adjusting efficiency of the desulfurization and decyanation waste liquid is higher, and the treatment efficiency of the desulfurization and decyanation waste liquid is higher.
As an embodiment of the present invention, the sampling channel 4 includes a groove 41, a slider 42, a number one spring 43, and an inverted L-shaped hole 44; the groove 41 is arranged on the inner bottom wall of the sampling pool 1 and is positioned right below the sampling pipe 3; the projection of the groove 41 in the overlooking state covers the projection of the sampling tube 3 in the overlooking state; the sliding block 42 is slidably connected in the groove 41; the spring No. 43 is connected between the sliding block 42 and the bottom of the groove 41; the inverted L-shaped hole 44 is arranged at the bottom of the sampling pool 1, one end of the inverted L-shaped hole 44 is communicated with the side wall of the groove 41, and the other end of the inverted L-shaped hole is contacted with the lower end face of the sampling pool 1; the upper end surface of the sliding block 42 is flush with the bottom of the sampling pool 1 under the action of a first spring 43; the upper end surface of the sliding block 42 is communicated with the side wall through a positive L-shaped hole 45; the positive L-shaped hole 45 communicates with the inverted L-shaped hole 44 after the slider 42 moves down;
a reset ring 21 is arranged above the guide ring 2; the reset ring 21 is fixedly connected to the outer wall of the sampling tube 3; the reset ring 21 is connected with the guide ring 2 through a reset spring 22;
a pressing plate 5 is arranged above the sampling tube 3; the pressing plate 5 is connected with a hydraulic cylinder 51; the hydraulic cylinder 51 is vertically and fixedly connected to the wall of the sampling tank 1; the pressing plate 5 moves downwards under the drive of the hydraulic cylinder 51, so that the upper port of the sampling tube 3 is extruded by the pressing plate 5;
when in use, after waste liquid enters the sampling tank 1 along the liquid inlet 12, the liquid level in the sampling tube 3 and the sampling tank 1 is flush, then the controller controls the hydraulic cylinder 51 to drive the pressing plate 5 to move downwards, the pressing plate 5 can extrude the sampling tube 3, the sampling tube 3 drives the reset ring 21 to move downwards and extrude the reset spring 22, the sampling tube 3 can abut against the upper end face of the sliding block 42 to realize end face sealing after moving downwards, the sampling tube 3 can extrude the sliding block 42 to move close to the bottom of the groove 41 and extrude the spring 43, after the sliding block 42 moves downwards, the inner side of the sampling tube 3 is communicated with one end of the inverted L-shaped hole 44 by the positive L-shaped hole 45, so that a sample in the sampling tube 3 flows out along the positive L-shaped hole 45 and the inverted L-shaped hole 44, after W X data are obtained, the liquid outlet 13 of the sampling tank 1 is opened, the residual waste liquid in the sampling pool 1 is discharged, then the controller controls the hydraulic cylinder 51 to drive the pressing plate 5 to move upwards, the reset spring 22 can drive the reset plate to move upwards after the pressing plate 5 is separated from the sampling pipe 3, the reset plate moves upwards to drive the sampling pipe 3 to move upwards, the sampling pipe 3 moves upwards to separate from the sliding block 42 and keeps a gap with the bottom of the sampling pool 1, the sliding block 42 can drive the sliding block 42 to move upwards after the sampling pipe 3 is separated from contact, the positive L-shaped hole 45 and the inverted L-shaped hole 44 are staggered and communicated in the upward movement process of the sliding block 42, the closing of the sampling channel 4 is realized, after a new batch of waste liquid enters the sampling pool 1 along the liquid inlet 12, the sliding block 42 cannot move downwards under the action of the spring 43, the sampling channel 4 is kept in a closed state until the next time the pressing plate 5 moves downwards.
As one embodiment of the present invention, the upper end surface of the slider 42 is provided with an annular groove 46; the diameter of the inner side wall of the annular groove 46 is equal to the inner diameter of the sampling tube 3; the outer groove wall of the annular groove 46 is equal to the outer diameter of the sampling tube 3; the annular groove 46 is connected with an annular plate 47 in a sliding and sealing manner; the annular groove 46 is consistent with the external air pressure, so that the movement of the annular plate 47 is not blocked; the annular plate 47 is connected with the bottom of the annular groove 46 through a second spring 48; the upper end face of the annular plate 47 is flush with the upper end face of the sliding block 42 under the action of a second spring 48; the lower part of the sampling tube 3 is in sliding fit with the annular groove 46;
when the sampling tube 3 is used, the lower part of the sampling tube 3 which moves downwards is extruded by the pressing plate 5 and falls on the annular plate 47, the annular plate 47 is pressed and slides along the annular groove 46 and presses the second spring 48, the lower part of the sampling tube 3 moves into the annular groove 46 after moving downwards, the inner wall of the sampling tube 3 and the annular groove 46 are sealed by the inner groove wall, the outer wall of the sampling tube 3 and the annular groove 46 are sealed by the outer groove wall, the lower end face of the sampling tube 3 is sealed with the upper end face of the annular plate 47 under the action of the second spring 48, so that compared with the prior end face sealing, the sealing effect is better, the waste liquid in the sampling pool 1 and the sample of the sampling tube 3 are separated, the accuracy of the subsequent waste liquid pH value adjustment is ensured, and after the sampling tube 3 moves upwards and is separated from the annular plate 47, the second spring 48 drives the annular plate 47 to be away from the bottom of the annular groove 46, the upper end face of the annular groove 47 is flush with the upper end face of the sliding block 42, and the bottom of the annular groove 46 is communicated with the outside, and the movement of the annular plate 47 is not influenced.
As one embodiment of the invention, the center of the lower end of the sampling pool 1 is fixedly connected with a negative pressure cylinder 6; the lower end of the negative pressure cylinder 6 is communicated with the other end of the inverted L-shaped hole 44, and the lower end of the negative pressure cylinder 6 is connected with a liquid outlet pipe 61; the negative pressure cylinder 6 is connected with a piston 62 in a sliding and sealing way; the piston 62 is connected with the inner bottom end of the negative pressure cylinder 6 through a third spring 63; the piston 62 is provided with a negative pressure hole 621 penetrating up and down; check valves are arranged in the negative pressure hole 621 and the inverted L-shaped hole 44; the center of the upper end of the piston 62 is connected with a slide rod 64; the slide bar 64 extends through the sampling cell 1 to above the guide ring 2; the slide rod 64 is in sliding sealing connection with the sampling pool 1; the end of the slide rod 64 far away from the piston 62 is connected with the push disc 7; the pushing disc 7 is higher than the upper port of the sampling tube 3 in the initial state; the space in the negative pressure cylinder 6 is divided into an upper cavity and a lower cavity by the piston 62, and the movement space of the piston 62 in the negative pressure cylinder 6 is larger than the space inside the sampling tube 3; the pushing disc 7 is positioned below the pressing plate 5;
when the device is used, the pressure plate 5 moves downwards under the drive of the hydraulic cylinder 51, the pressure plate 5 can extrude the push plate 7, the push plate 7 is pressed and can drive the slide rod 64 to move downwards, the slide rod 64 moves downwards and can drive the piston 62 to move downwards in the negative pressure cylinder 6 and extrude the spring 63 with the third number, so that the space of the upper cavity becomes larger, negative pressure can be formed after the space of the upper cavity becomes larger, the pressure plate 5 can extrude the sampling tube 3 along with the continuous downwards movement of the pressure plate 5, the sampling tube 3 moves downwards to contact the sliding block 42 and drive the sliding block 42 to move downwards, the inner side of the sampling tube 3 is communicated with the inverted L-shaped hole 44 through the positive L-shaped hole 45, the sample on the inner side of the sampling tube 3 enters the upper cavity along with the positive L-shaped hole 45 and the inverted L-shaped hole 44 under the negative pressure effect, in addition, redundant external gas flows along the inner side of the sampling tube 3 and is sucked into the upper cavity, residues are avoided, the negative pressure suction mode of the sample can also avoid blocking, the smooth flow of the sample is realized, then the controller controls the hydraulic cylinder 51 to drive the pressure plate 5 to move upwards, the sampling tube 5 moves upwards, the sample 3 moves downwards and moves downwards along the negative pressure cylinder 3 along with the negative pressure cylinder 62, the negative pressure cylinder 3 moves upwards, the sample 3 moves upwards and is not completely along the negative pressure cylinder 3, and moves upwards, the sample 3 is completely and moves upwards, and moves upwards through the negative pressure cylinder, and is completely and completely through the negative pressure cylinder, and can be completely.
As one embodiment of the present invention, the output shaft of the hydraulic cylinder 51 is fixedly connected with a cross rod 52; one end of the cross rod 52 extends to the position right above the push disc 7; a through hole 521 is vertically provided at one end of the cross bar 52; the pressing plate 5 is strip-shaped; the center of the upper end of the pressing plate 5 is fixedly connected with a ring sleeve 53; the ring 53 is rotatably connected to the lower port of the through hole 521; the upper end of the pushing disc 7 is fixedly connected with a transition rod 71; the upper end of the transition rod 71 is fixedly connected with a screw rod 72; the screw 72 passes through the center of the pressing plate 5, the inner side of the ring sleeve 53 and the through hole 521; the screw 72 is in threaded transmission connection with the center of the pressing plate 5; the number of the sampling tubes 3 is at least two; the sampling pipes 3 are uniformly distributed around the center of the sampling pool 1;
when the sampling device is used, the cross rod 52 moves downwards along with the driving of the hydraulic cylinder 51, the cross rod 52 moves downwards to drive the annular sleeve 53 and the pressing plate 5 to move downwards, the sliding rod 64 and the sampling tank 1 only can slide up and down and can not rotate, so that the screw 72 is not rotated, the screw 72 is in threaded transmission connection with the center of the pressing plate 5, the pressing plate 5 moves downwards under the action of the threaded transmission, the pressing plate 5 still rotates along with the transition of the pressing plate 5 onto the transition rod 71, the pressing plate 5 moves downwards under the rotation, the pressing plate 5 is contacted with the push disc 7, the pressing plate 5 pushes the push disc 7 to move downwards, the pressing plate 5 which moves downwards randomly extrudes the sampling tube 3 to move downwards, so that sampling tubes 3 at different positions are randomly pressed, the sampling tubes 3 sample at a plurality of positions of the sampling tank 1, the errors of components of samples sampled by the sampling tube 3 and the components in the sampling tank 1 are reduced, the accuracy of the subsequent adjustment of the pH value of waste liquid is improved, and in the embodiment, a stirring assembly can be arranged in the sampling tank 1, and the components of the samples in the sampling tank 3 and the sampling tank 1 are more consistent with the components of the mother liquid through stirring; in this embodiment, the ratio of mother liquor to sample is determined according to the number of downshifts of the sampling tube 3, and when the number of downshifts of the sampling tube 3 is n, the capacity ratio is w= (c-nb)/na; the transition rod 71 has an outer diameter smaller than the diameter of the screw 72, so that the transition rod 71 can pass through the center of the platen 5.
As an embodiment of the present invention, the upper end surface of the push disc 7 is provided with a number one tooth 73 in the circumferential direction; a second tooth 54 is arranged around the center of the lower end surface of the pressing plate 5 and at a position corresponding to the pushing disc 7;
when the pressure plate 5 moves downwards along with the driving of the hydraulic cylinder 51, the pressure plate 5 moves downwards to drive the second tooth 54 of the lower end face to move downwards, the pressure plate 5 can rotate by itself after passing through the screw rod 72 and continue to rotate after passing through the transition rod 71, when the lower end face of the pressure plate 5 contacts with the upper end face of the push plate 7, the second tooth 54 contacts with the first tooth 73, and the pressure plate 5 cannot rotate continuously through the clamping between the second tooth 54 and the first tooth 73, so that the pressure plate 5 only moves downwards along with the driving of the hydraulic cylinder 51, and the pressure plate 5 can stabilize the upper end of the corresponding sampling tube 3.
As one embodiment of the present invention, a bar-shaped groove 55 is provided at a position where the lower end surface of the pressure plate 5 contacts the sampling tube 3; the strip-shaped groove 55 extends to the edge of the pressing plate 5; the number of the strip-shaped grooves 55 is plural, and the distance between the adjacent strip-shaped grooves 55 is smaller than the inner diameter of the sampling tube 3;
when the sampling tube 3 is used, the pressing plate 5 is arranged in the downward moving process of the corresponding sampling tube 3 through the arrangement of the strip-shaped groove 55, so that the outside air can be communicated with the inner side of the sampling tube 3 through the strip-shaped groove 55, the inner side of the sampling tube 3 and the sampling pool 1 are kept at the same air pressure, the liquid level of the sample and the liquid level of the mother liquor can be kept consistent before the sample and the mother liquor are separated, the error of the sample liquid level and the mother liquor level on the proportion is reduced, and meanwhile, the sampling tube 3 can flow out under the condition that the inner side of the sampling tube 3 is communicated with the outside air after the sampling channel 4 is opened through the arrangement of the strip-shaped groove 55.
As an embodiment of the present invention, the end width of the pressure plate 5 is greater than the distance between two adjacent sampling tubes 3; when the sampling tube 3 is used, the width of the end part of the pressure plate 5 is limited, so that the pressure plate 5 can fall above part of the sampling tube 3 no matter what angle the pressure plate 5 moves down, the condition that the pressure plate 5 falls down is avoided, and the stability of pushing the sampling tube 3 to move down is greatly improved.
The following is a description of the mechanism of ozone oxidation:
ozone oxidation ability is very strong, O 3 +2H + +2e→O 2 +H 2 Standard electrode potential e=2.07V for the O reaction system. Ozone decomposes in water to produce atomic oxygen and also produces a series of free radicals, which react as follows:
O 3 →O+O 2
O+O 3 →2O 2
O+H 2 O→2HO·
2HO·→H 2 O 2
2H 2 O 2 →2H 2 O+O 2
in particular in alkaline medium, O 3 The speed of decomposing and generating free radicals is very high, and the reaction formula is as follows:
O 3 +OH - →HO 2 ·+·O 2 -
O 3 +·O 2 - →·O 3 - +O 2
O 3 +HO 2 ·→HO·+2O 2
·O 2 - +HO·→O 2 +·H -
the newly generated hydroxyl radical is particularly active, has stronger oxidizing capability and is HO.cndot.H+H + +e→H 2 O, standard electrode potential E of reaction system 0 =2.80V. Under acidic conditions, ozone is slowly decomposed, O 3 Plays a major role in the direct oxidation reaction; under alkaline conditions, ozone decomposition is rapid, and the oxidation of hydroxyl radicals is increased. In addition, the temperature is increased, and the ozone decomposition speed is increased.
The following are experimental data displays of the present application: (time unit is h)
In the description of the present invention, it should be noted that the terms "center", "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in fig. 1, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or element in question must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the scope of the present invention, and furthermore, the terms "first", "second", "third", etc. are merely used for distinguishing the description, and should not be construed as indicating or implying relative importance.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. A method for treating coking gas desulfurization and decyanation waste liquid by utilizing an ozone generator is characterized in that: the method comprises the following steps:
s1: firstly, injecting desulfurization and decyanation waste liquid of the same batch into a sampling device along a liquid inlet (12) of a sampling tank (1), wherein a gap is reserved between the lower port of a sampling tube (3) and the bottom of the sampling tank (1), the waste liquid in the sampling tank (1) enters the sampling tube (3) along the lower port of the sampling tube (3), the liquid level in the sampling tube (3) rises along with the rising of the liquid level of the waste liquid in the sampling tank (1), and after a certain amount of waste liquid is injected into the sampling tank (1), the liquid inlet (12) is closed;
s2: then, pressing a sampling tube (3) in the sampling device to move downwards, wherein the sampling tube (3) is in contact and seal with the bottom of the sampling tank (1), and the sampling channel (4) is triggered along with the continuous downward movement of the sampling tube (3) so that the sampling channel (4) is opened, and the waste liquid in the sampling tube (3) flows out along the sampling channel (4) and is collected by a worker, so that the sulfuric acid capacity W X required to be added of the residual waste liquid in the sampling tank (1) is obtained after the pH value of the sample is regulated;
s3: finally, a worker opens a liquid outlet (13) of a sampling pool (1) in the sampling device, so that mother liquor in the sampling pool (1) flows into the reaction device, a sample with the pH value adjusted is also poured into the reaction device, sulfuric acid with the volume of W X is poured into the reaction device, and ozone is introduced after stirring;
wherein the sampling device used in S1-S3 comprises:
a sampling tank (1); the bottom of the sampling pool (1) is placed on the ground through a bracket (11); the outer wall of the sampling pool (1) is provided with a liquid inlet (12) and a liquid outlet (13);
a guide ring (2); the guide ring (2) is fixedly connected to a tank opening of the sampling tank (1);
a sampling tube (3); the sampling tube (3) is a straight tube-shaped object with an upper opening and a lower opening; the sampling tube (3) passes through the guide ring (2) and is in sliding connection with the guide ring (2);
a sampling channel (4); the sampling channel (4) is arranged at the inner bottom of the sampling pool (1) and is opened after the sampling tube (3) moves downwards and is closed after the sampling tube moves upwards;
a controller; the controller is used for controlling the sampling device to automatically operate;
the sampling channel (4) comprises a groove (41), a sliding block (42), a first spring (43) and an inverted L-shaped hole (44); the groove (41) is arranged on the inner bottom wall of the sampling pool (1) and is positioned right below the sampling pipe (3); the sliding block (42) is connected in the groove (41) in a sliding way; the first spring (43) is connected between the sliding block (42) and the bottom of the groove (41); the inverted L-shaped hole (44) is arranged at the bottom of the sampling pool (1), one end of the inverted L-shaped hole (44) is communicated with the side wall of the groove (41), and the other end of the inverted L-shaped hole is contacted with the lower end face of the sampling pool (1); the upper end surface of the sliding block (42) is communicated with the side wall through a positive L-shaped hole (45); the positive L-shaped hole (45) is communicated with the inverted L-shaped hole (44) after the sliding block (42) moves downwards;
a reset ring (21) is arranged above the guide ring (2); the reset ring (21) is fixedly connected to the outer wall of the sampling tube (3); the reset ring (21) is connected with the guide ring (2) through a reset spring (22);
a pressing plate (5) is arranged above the sampling tube (3); the pressing plate (5) is connected with a hydraulic cylinder (51); the hydraulic cylinder (51) is vertically and fixedly connected to the wall of the sampling tank (1);
an annular groove (46) is formed in the upper end face of the sliding block (42); the diameter of the inner wall of the annular groove (46) is equal to the inner diameter of the sampling tube (3); the outer groove wall of the annular groove (46) is equal to the outer diameter of the sampling tube (3); the annular groove (46) is connected with an annular plate (47) in a sliding and sealing way; the annular plate (47) is connected with the bottom of the annular groove (46) through a second spring (48); the lower part of the sampling tube (3) is in sliding fit with the annular groove (46);
the center of the lower end of the sampling pool (1) is fixedly connected with a negative pressure cylinder (6); the lower end of the negative pressure cylinder (6) is communicated with the other end of the inverted L-shaped hole (44), and the lower end of the negative pressure cylinder (6) is connected with a liquid outlet pipe (61); the negative pressure cylinder (6) is connected with a piston (62) in a sliding and sealing manner; the piston (62) is connected with the inner bottom end of the negative pressure cylinder (6) through a third spring (63); a negative pressure hole (621) is formed in the piston (62) in a penetrating manner up and down; the center of the upper end of the piston (62) is connected with a slide bar (64); the sliding rod (64) passes through the sampling pool (1) and extends to the upper part of the guide ring (2); the sliding rod (64) is in sliding sealing connection with the sampling pool (1); one end of the sliding rod (64) far away from the piston (62) is connected with a pushing disc (7);
the output shaft of the hydraulic cylinder (51) is fixedly connected with a cross rod (52); one end of the cross rod (52) extends to the position right above the push disc (7); a through hole (521) is formed in one end of the cross rod (52) in a vertically penetrating manner; the pressing plate (5) is in a strip plate shape; the center of the upper end of the pressing plate (5) is fixedly connected with a ring sleeve (53); the ring sleeve (53) is rotationally connected to the lower port of the through hole (521); the upper end of the pushing disc (7) is fixedly connected with a transition rod (71); the upper end of the transition rod (71) is fixedly connected with a screw rod (72); the screw (72) passes through the center of the pressing plate (5), the inner side of the ring sleeve (53) and the through hole (521); the screw (72) is in threaded transmission connection with the center of the pressing plate (5); the number of the sampling tubes (3) is plural; the sampling tubes (3) are uniformly distributed around the center of the sampling pool (1).
2. The method for treating coking gas desulfurization and decyanation waste liquid by utilizing an ozone generator as claimed in claim 1, wherein the method comprises the following steps: a first tooth (73) is arranged on the upper end surface of the pushing disc (7) in the circumferential direction; and a second tooth (54) is arranged at the periphery of the center of the lower end surface of the pressing plate (5) and corresponds to the pushing disc (7).
3. The method for treating coking gas desulfurization and decyanation waste liquid by utilizing an ozone generator as claimed in claim 1, wherein the method comprises the following steps: a strip groove (55) is formed in the position, where the lower end surface of the pressing plate (5) is in contact with the sampling tube (3); the strip-shaped groove (55) extends to the edge of the pressing plate (5); the number of the strip-shaped grooves (55) is multiple, and the distance between the adjacent strip-shaped grooves (55) is smaller than the inner diameter of the sampling tube (3).
4. The method for treating coking gas desulfurization and decyanation waste liquid by utilizing an ozone generator as claimed in claim 1, wherein the method comprises the following steps: the width of the end part of the pressing plate (5) is larger than the distance between two adjacent sampling pipes (3).
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| CN216472624U (en) * | 2021-12-27 | 2022-05-10 | 广州兰德环保资源科技有限公司 | Analytic reaction device for recycling L-carnitine from pharmaceutical wastewater |
| CN217542478U (en) * | 2021-08-18 | 2022-10-04 | 王彬蔚 | Waste water sampling and storing device for environmental monitoring |
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| CN115536124A (en) * | 2022-08-16 | 2022-12-30 | 昆明理工大学 | Method for improving quality and efficiency of ammonium sulfate product produced by ammonia-acid flue gas desulfurization wastewater |
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| KR100896646B1 (en) * | 2002-08-21 | 2009-05-08 | 주식회사 포스코 | An apparatus for automatically sampling acid in a pickling tank by using strip lifter |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN217542478U (en) * | 2021-08-18 | 2022-10-04 | 王彬蔚 | Waste water sampling and storing device for environmental monitoring |
| CN216472624U (en) * | 2021-12-27 | 2022-05-10 | 广州兰德环保资源科技有限公司 | Analytic reaction device for recycling L-carnitine from pharmaceutical wastewater |
| CN115536124A (en) * | 2022-08-16 | 2022-12-30 | 昆明理工大学 | Method for improving quality and efficiency of ammonium sulfate product produced by ammonia-acid flue gas desulfurization wastewater |
| CN115452483A (en) * | 2022-11-14 | 2022-12-09 | 胜利油田胜鑫防腐有限责任公司 | Sampling device and sampling method for petroleum detection |
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