CN208027162U - Sodium peroxydisulfate and potassium peroxydisulfate process units DCS control systems - Google Patents
Sodium peroxydisulfate and potassium peroxydisulfate process units DCS control systems Download PDFInfo
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- CN208027162U CN208027162U CN201820476893.0U CN201820476893U CN208027162U CN 208027162 U CN208027162 U CN 208027162U CN 201820476893 U CN201820476893 U CN 201820476893U CN 208027162 U CN208027162 U CN 208027162U
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- CN
- China
- Prior art keywords
- process units
- peroxydisulfate
- potassium peroxydisulfate
- sodium
- control systems
- Prior art date
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 title claims abstract description 223
- 238000000034 method Methods 0.000 title claims abstract description 116
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 title claims abstract description 115
- 235000019394 potassium persulphate Nutrition 0.000 title claims abstract description 113
- 238000004519 manufacturing process Methods 0.000 claims abstract description 49
- 238000001704 evaporation Methods 0.000 claims abstract description 46
- 230000008020 evaporation Effects 0.000 claims abstract description 43
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 140
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 116
- 229910021529 ammonia Inorganic materials 0.000 claims description 70
- 239000007788 liquid Substances 0.000 claims description 59
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 58
- 238000002425 crystallisation Methods 0.000 claims description 42
- 230000008025 crystallization Effects 0.000 claims description 42
- 238000003786 synthesis reaction Methods 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000010521 absorption reaction Methods 0.000 claims description 27
- 239000006096 absorbing agent Substances 0.000 claims description 26
- 230000008014 freezing Effects 0.000 claims description 23
- 238000007710 freezing Methods 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 20
- 239000000498 cooling water Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 14
- 239000012452 mother liquor Substances 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 12
- 238000012544 monitoring process Methods 0.000 claims description 11
- 238000012546 transfer Methods 0.000 claims description 11
- 238000004891 communication Methods 0.000 claims description 10
- 239000012141 concentrate Substances 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 239000000047 product Substances 0.000 description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 12
- 230000009615 deamination Effects 0.000 description 9
- 238000006481 deamination reaction Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 5
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 5
- 229910052939 potassium sulfate Inorganic materials 0.000 description 5
- 235000011151 potassium sulphates Nutrition 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 238000004176 ammonification Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 101000671620 Homo sapiens Usher syndrome type-1C protein-binding protein 1 Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 102100040093 Usher syndrome type-1C protein-binding protein 1 Human genes 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000010977 unit operation Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- -1 drying machine Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P90/00—Enabling technologies with a potential contribution to greenhouse gas [GHG] emissions mitigation
- Y02P90/02—Total factory control, e.g. smart factories, flexible manufacturing systems [FMS] or integrated manufacturing systems [IMS]
Abstract
The utility model discloses a kind of sodium peroxydisulfates and potassium peroxydisulfate process units DCS control systems.It includes DCS control systems, sodium peroxydisulfate process units and potassium peroxydisulfate process units；DCS control systems include master controller, exchanger, active station；Real-time control of the master controller for sodium peroxydisulfate, potassium peroxydisulfate process units；Sodium peroxydisulfate, potassium peroxydisulfate process units are provided with the live stations I/O, PLC controller and the stations scene I/O of individual field devices connect；Each stations scene I/O are connect by DP buses with the master controller of DCS control systems respectively.Application of the utility model due to DCS robot control system(RCS)s, so that the purpose of the evaporation of each large size, the use of crystallizer and steady production can be achieved completely in sodium peroxydisulfate and potassium peroxydisulfate production process, to make the process units of sodium peroxydisulfate and potassium peroxydisulfate reach increasingly automated, enlarged and modernization.
Description
Technical field
The utility model belongs to chemical production technical field, is related to a kind of sodium peroxydisulfate and potassium peroxydisulfate process units DCS
Control system.
Background technology
Sodium peroxydisulfate, potassium peroxydisulfate are important auxiliary chemicals.It can be widely applied to high-grade electronics industry wiring board production
Special assistant, the special initiator of polymerization of vinyl monomer, high-grade textile printing and dyeing inorganic agent, soil-repairing agent, environmentally friendly water process
Agent, analytical reagent etc..
The production technology of sodium peroxydisulfate has：Using the electrolysis technique of electrolytic sulfite, ammonium sulfate and sulfuric acid mixture liquid, or
The chemical synthesis for obtaining sodium peroxydisulfate is reacted with sodium hydroxide using ammonium persulfate.The work of sodium peroxydisulfate is obtained using electrolysis
Skill is complicated, technology requires height, and waste water is more, but product quality is high.The technology letter of sodium peroxydisulfate is obtained using chemical synthesis
It is single, coordinate with good deamination and ammonia recovery system, the sodium peroxydisulfate product of high quality also can be obtained.Therefore, general useization
It learns synthetic method and produces sodium peroxydisulfate.
The production technology of potassium peroxydisulfate has：The side recrystallized after metathesis reaction is carried out using ammonium persulfate and potassium sulfate
Method, or the chemical synthesis for obtaining potassium peroxydisulfate is reacted with potassium hydroxide using ammonium persulfate.The method and process complexity of recrystallization,
Technology requires high.The technology that potassium peroxydisulfate is obtained using chemical synthesis is simple, coordinates with good deamination and recovery ammonia
The potassium peroxydisulfate product of high quality can be obtained in system.Therefore, general that potassium peroxydisulfate is produced using chemical synthesis.
It is as follows that chemical synthesis produces sodium peroxydisulfate, the production technology of potassium peroxydisulfate product：
(1) sodium peroxydisulfate product processes (chemical synthesis)
A certain proportion of ammonium persulfate and liquid sodium hydroxide can react at normal temperatures generates the sodium peroxydisulfate solution containing ammonia,
By deamination unit operation deamination, recovery ammonia adjusts pH value for the ammonification of ammonium persulfate workshop.In decompression close under vacuum state,
The heated evaporative crystallization of sodium peroxydisulfate solution is centrifugally separating to obtain and is crystallized containing wet sodium peroxydisulfate, by it is dry be sodium peroxydisulfate at
Product.Sodium peroxydisulfate product processes are as shown in Figure 2.
(2) potassium peroxydisulfate product processes (chemical synthesis)
A certain proportion of ammonium persulfate and liquid potassium hydroxide can react at normal temperatures generates the potassium persulfate solution containing ammonia,
By deamination unit operation deamination.In decompression close to the heated evaporative crystallization of potassium persulfate solution under vacuum state, centrifuge
It obtains crystallizing containing wet potassium peroxydisulfate, by dry for potassium peroxydisulfate finished product.Potassium peroxydisulfate product processes are as shown in Figure 3.
Currently, sodium peroxydisulfate and potassium peroxydisulfate production industry not yet use (the i.e. distributed control of large-scale DCS control systems
System processed, Distributed Control System) to carry out automation control to process units.Due to the particularity of the sector, or even connect instrument
Table automation control it is also few, many factories are all also in workshop-based production model, and labor productivity is low, product matter
Measure it is low, it is unstable.
Utility model content
The purpose of the utility model is to overcome the deficiencies in the prior art, provide it is a kind of using DCS control systems to over cure
The sodium peroxydisulfate and potassium peroxydisulfate process units DCS control systems that sour sodium and potassium peroxydisulfate production system carry out automatically controlling.
The technical solution of the utility model is as follows：
A kind of sodium peroxydisulfate of the utility model and potassium peroxydisulfate process units DCS control systems, it includes DCS controls system
System, sodium peroxydisulfate process units and potassium peroxydisulfate process units；DCS control systems include master controller, exchanger, active station；
Master controller is connect by exchanger with active station；Master controller is used for the real-time control of sodium peroxydisulfate, potassium peroxydisulfate process units
System；For exchanger for the operation information between master controller and active station, status information communication, operating personnel will by active station
Operational order is sent to master controller, and real-time status is then sent to active station by master controller, completes real-time communication, operation, control
System；There is live I/O to stand in the site setup of sodium peroxydisulfate process units and potassium peroxydisulfate process units, each of scene band PLC is controlled
The PLC controller of the equipment of device processed is connected with the stations scene I/O；Each stations scene I/O pass through DP buses and DCS control systems respectively
Master controller connection.
Further, two I/O switch boards, each I/O switch boards is dragged to produce fill with sodium peroxydisulfate respectively under master controller
It sets, the connection of all AI, AO, DI, DO points at potassium peroxydisulfate process units scene, is responsible for sodium peroxydisulfate, potassium peroxydisulfate process units
The real time monitoring of all AI, AO, DI, DO points in scene, and connect with the PLC controller of all equipment with PLC controller in scene,
Carry out real-time communication.
Further, 1 scene I/O is respectively set at the scene of sodium peroxydisulfate process units and potassium peroxydisulfate process units
It stands and (is respectively provided with 1 I/O switch board in sodium peroxydisulfate process units and potassium peroxydisulfate process units), live I/O stands defeated
Enter/output equipment is connected and communicate with by profibus_DP buses and the second master controller；The live stations I/O are wrapped by production scene
Include ammonium persulfate solution configuration system, sodium peroxydisulfate or potassium peroxydisulfate synthesis reaction system, ammonia absorption system, evaporative crystallization
Each system including system, centrifugal separation system, drying system, mother liquid disposal system, cooling water recirculation system, exhaust treatment system
The operation information for each live running equipment of uniting, detection information and environmental protection treatment containing ammonia and dust-laden (particulate matter) gas are set in tail gas
The operation information and all equipment with PLC controller applied include the operation information of centrifuge, material transfer equipment, are passed through
DP buses are transmitted to the active station of the central control room of DCS control systems, while all operations that the operator of active station sends out
The PLC for each live running equipment for entering each I/O equipment by DP buses and being connected with each I/O equipment is controlled in instruction
Device processed；The pH value and tail gas that absorbing liquid in the ammonia absorber of emission is monitored by DCS control systems contain ammonia density, monitoring
The temperature and liquid level of evaporation and crystallization system and mother liquid disposal system, monitor the operating condition of centrifuge, monitor the liquid level of each groove tank
With the operating condition of each dynamic equipment and the operating condition of other each production subsystems.
Further, sodium peroxydisulfate process units includes the ammonium persulfate solution configuration system being linked in sequence, sodium peroxydisulfate
Synthesis reaction system, ammonia absorption system, evaporation and crystallization system, centrifugal separation system, drying system further include and evaporative crystallization
The cooling water recirculation system of system connection, further includes the mother liquid disposal system being connect with centrifugal separation system, further includes and ammonia
The exhaust treatment system of absorption system connection；Ammonium persulfate solution configuration system includes water measuring tank, ammonium persulfate solution configuration
Slot and material transfer equipment；Sodium peroxydisulfate synthesis reaction system includes in sodium peroxydisulfate synthesis reaction vessel, sodium peroxydisulfate reaction solution
Between slot；Ammonia absorption system includes ammonia absorber；Evaporation and crystallization system includes sodium peroxydisulfate freezing kettle and evaporative crystallization kettle；Centrifugation
Piece-rate system includes centrifuge；Drying system includes drying machine, screw conveyor, product storage tank；Cooling water recirculation system includes
Water cooler, water tank and its circulating pump；Mother liquid disposal system includes concentrate freezing kettle, mother liquor water storage tank, mother liquid evaporation kettle, mother liquor
Evaporative condenser；Exhaust treatment system includes tail gas absorber；Wherein, water measuring tank, ammonium persulfate solution configured slot, persulfuric acid
These equipment belt PLC controllers of sodium synthesis reaction vessel, sodium peroxydisulfate freezing kettle, evaporative crystallization kettle, ammonia absorber, drying machine；?
The site setup of sodium peroxydisulfate process units has 1 station scene I/O, the PLC controller of the live each equipment with PLC controller
It is that I/O switch boards are connect with the stations live I/O, the live stations I/O are connect by DP buses with the 11# master controllers of DCS control systems.
Further, potassium peroxydisulfate process units includes the ammonium persulfate solution configuration system being linked in sequence, potassium peroxydisulfate
Synthesis reaction system, ammonia absorption system, evaporation and crystallization system, centrifugal separation system, drying system further include and evaporative crystallization
The cooling water recirculation system of system connection, further includes the mother liquid disposal system being connect with centrifugal separation system, further includes and ammonia
The exhaust treatment system of absorption system connection；Ammonium persulfate solution configuration system includes water measuring tank, ammonium persulfate solution configuration
Slot and material transfer equipment；Potassium peroxydisulfate synthesis reaction system includes in potassium peroxydisulfate synthesis reaction vessel, potassium peroxydisulfate reaction solution
Between slot；Ammonia absorption system includes ammonia absorber；Evaporation and crystallization system includes potassium peroxydisulfate freezing kettle and evaporative crystallization kettle；Centrifugation
Piece-rate system includes centrifuge；Drying system includes drying machine, screw conveyor, product storage tank；Cooling water recirculation system includes
Water cooler, water tank and its circulating pump；Mother liquid disposal system includes concentrate freezing kettle, mother liquor water storage tank, mother liquid evaporation kettle, mother liquor
Evaporative condenser；Exhaust treatment system includes tail gas absorber；Wherein, water measuring tank, ammonium persulfate solution configured slot, persulfuric acid
These equipment belt PLC controllers of potassium freezing kettle, evaporative crystallization kettle, ammonia absorber, drying machine；In showing for potassium peroxydisulfate process units
Field is provided with the station 1 scene I/O, and each equipment with PLC controller in scene includes that the centrifuge with PLC controller, material are defeated
The PLC controller and the stations scene I/O for sending equipment connect.
The beneficial effects of the utility model：
The sodium peroxydisulfate and potassium peroxydisulfate process units DCS control systems of the utility model, can be significantly increased labor
Dynamic productivity, the utilization rate improvement environmental protection for improving product quality, improving raw material.Due to the application of DCS robot control system(RCS)s so that mistake
Completely may be used to the evaporation, the use of crystallizer and the purpose of steady production of each large size in sodium sulphate and potassium peroxydisulfate production process
It realizes, to make the process units of sodium peroxydisulfate and potassium peroxydisulfate reach increasingly automated, enlarged and modernization.Using
DCS control systems carry out automatically controlling sodium peroxydisulfate and potassium peroxydisulfate production system, have great economic benefit and society to imitate
Benefit.
The sodium peroxydisulfate of the utility model and the advance of potassium peroxydisulfate process units DCS control systems be mainly reflected in
Lower several respects：
A, centrifuge carries out Automatic Control using the program of closed-loop operation by DCS control systems, improves efficiency,
Operating environment is improved, good environment protecting has been reached.
B, potassium peroxydisulfate production is measured using high-precision mass flowmenter, and feeding flow is automatically controlled by DCS control systems
Amount, realize accurately control, continuous production, not only improved product yield, quality, but also reduce labor intensity and improve operation
Environment.
Description of the drawings
Fig. 1 is that the overall structure of a kind of sodium peroxydisulfate of the utility model and potassium peroxydisulfate process units DCS control systems is shown
It is intended to；
Fig. 2 is the sodium peroxydisulfate product processes flow chart in the utility model；
Fig. 3 is the potassium peroxydisulfate product processes flow chart in the utility model.
Specific implementation mode
The utility model is further described below in conjunction with drawings and examples.
Embodiment
As shown in Figure 1, Figure 2, Figure 3 shows, a kind of sodium peroxydisulfate of the utility model and potassium peroxydisulfate process units DCS controls system
System, it includes DCS control systems, sodium peroxydisulfate process units and potassium peroxydisulfate process units.
The block diagram of the DCS control systems of the utility model is shown in Fig. 1, entire DCS control systems, including is set to central control room
Two systems cabinet (each system cabinet set there are one master controller), further include be located at ammonium persulfate process units scene three
I/O switch boards, and be located at sodium peroxydisulfate, potassium peroxydisulfate process units scene two I/O switch boards.
Central control room in Fig. 1 is set there are two master controller (10# master controllers, 11# master controllers), two exchangers
(exchanger A, exchanger B), two printers, four active stations (51# active stations, 52# active stations, 53# active stations, 54# behaviour
Stand) and engineer's active station (50# engineer stations).Two master controllers are used for the real-time control of production process.Wherein,
11# master controllers are used for the real-time control of sodium peroxydisulfate in the utility model, potassium peroxydisulfate process units, under the master controller
Drag two I/O switch boards, each I/O switch boards respectively with sodium peroxydisulfate process units, the institute at potassium peroxydisulfate process units scene
There is the connection of AI, AO, DI, DO point, is responsible for the real-time of live 557 AI, AO, DI, DO points of sodium peroxydisulfate, potassium peroxydisulfate process units
Monitoring, and with the equipment of live 6 cuff PLC controllers (including ammonium persulfate solution configured slot, sodium peroxydisulfate synthesis reaction vessel,
Potassium peroxydisulfate synthesis reaction vessel, sodium peroxydisulfate freezing kettle, potassium peroxydisulfate freezing kettle, evaporative crystallization kettle, ammonia absorber, drying machine
Deng) PLC controller connection, carry out real-time communication.Another 10# master controller is then used for the real-time of ammonium persulfate process units
It controls, three I/O switch boards is dragged under the master controller, be responsible for live 470 AI, AO, DI, DO points of ammonium persulfate process units
Real time monitoring, and connect with the PLC controller of the equipment of the live 11 cuff PLC controllers of ammonium persulfate process units, progress
Real-time communication.
Two exchangers are respectively used to two operation information, the states between master controller and engineer station and operator station
Operational order is sent to master controller by information communication, operating personnel by active station, and master controller then sends real-time status
To active station, real-time communication, operation, control are completed.
Be located at sodium peroxydisulfate, potassium peroxydisulfate process units scene two I/O switch boards (extension cabinet), including：It was located at
Sodium sulphate, potassium peroxydisulfate process units electric control room (i.e. motor control center MCC2) MCC2 I/O extension cabinets,
And be located at sodium peroxydisulfate, potassium peroxydisulfate process units scene I/O-2 extension cabinets.
AI refers to analog input, such as the amount of temperature, pressure, rotating speed, electric current consecutive variations, signal be 4~20MA or
0~10V；AO refers to analog output, i.e. Analog control signal, and the control of such as continuously adjustable actuator aperture, frequency converter turn
Velocity modulation section, signal are 4~20MA or 0~10V, 0~5V.
DI refers to digital quantity (switching value) input, is exactly electric secondary circuit break-make in fact, certain feedback of status, and signal is
24VDC or 220VAC；DO refers to digital quantity (switching value) output, i.e., the control signal or status signal sent out from controller, letter
Number be 24VDC or 220VAC.
The production process of entire sodium peroxydisulfate and potassium peroxydisulfate is completed by two sets of process units, first set process units
Production sodium peroxydisulfate is reacted with ammonium persulfate by sodium hydroxide, second set of process units reacts life with potassium hydroxide by ammonium persulfate
Produce potassium peroxydisulfate.DCS controls are all used in process of production, and DCS control systems behaviour is all concentrated in the production of two covering devices
Make to form a DCS control system.
The utility model automates the production process of entire sodium peroxydisulfate and potassium peroxydisulfate using DCS control systems
Control, used control program is state-of-the-art profibus DP field-bus structures.In sodium peroxydisulfate process units and mistake
The site setup of potassium sulfate production device has 2 stations scene I/O (2 I/O switch boards).The live stations I/O are set to scene, and I is
Input is inputted, and O exports for output.The live stations I/O are equipped with I/O equipment (input-output apparatus).Each of scene band PLC is controlled
The PLC controller of the equipment of device processed is connect with the scene I/O I/O equipment (input-output apparatus) stood；Each scene I/O stands defeated
Enter/output equipment is connected and communicate with by profibus_DP buses and the master controller of DCS control systems respectively.
Above-mentioned sodium peroxydisulfate, the control method of potassium peroxydisulfate process units DCS control systems are as follows：
At the scene of sodium peroxydisulfate process units and potassium peroxydisulfate process units, each 1 scene I/O of setting stands, and production is existing
Field includes ammonium persulfate solution configuration system, synthesis reaction system, ammonia absorption system, evaporation and crystallization system, centrifuges system
Each scene operation of each system including system, drying system, mother liquid disposal system, cooling water recirculation system, exhaust treatment system is set
Standby operation information, the operation information of detection information and environment treating facility containing ammonia and dusty gas in tail gas, and it is all
Equipment with PLC controller includes sodium peroxydisulfate synthesis reaction vessel, potassium peroxydisulfate synthesis reaction vessel, sodium peroxydisulfate freezing kettle, mistake
(ammonium persulfate solution configures for potassium sulfate freezing kettle, evaporative crystallization kettle, centrifuge, ammonia absorber, drying machine, material transfer equipment
Slot, various delivery pumps etc.) operation information, the active station of the central control room of DCS control systems is transmitted to by DP buses, together
When active station all operational orders for sending out of operator will enter each I/O equipment by DP buses and be set with each I/O
The PLC controller of the standby live running equipment of each to be connected, achievees the purpose that production, technique, equipment control and emergency processing.
Here, contain ammonia density in the pH value of absorbing liquid and the tail gas of discharge in DCS control systems monitoring ammonia absorber, with
Maintain the operation of environment-friendly disposal system；The temperature and liquid level for monitoring evaporation and crystallization system and mother liquid disposal system, to control product
Quality maintains normal production；The operating condition for monitoring centrifuge, to ensure that production can remotely take emergency measures when improper；
The liquid level of each groove tank and the operating condition of each dynamic equipment and other each production subsystems are monitored, normal production is maintained.
The sodium peroxydisulfate, potassium peroxydisulfate process units of the utility model, specific sodium peroxydisulfate, potassium peroxydisulfate production technology
And DCS control methods are as follows：
The sodium peroxydisulfate, potassium peroxydisulfate process units of the utility model, react acquisition with potassium hydroxide using ammonium persulfate
The chemical synthesis of potassium peroxydisulfate produces potassium peroxydisulfate, reacts the chemistry for obtaining sodium peroxydisulfate with sodium hydroxide using ammonium persulfate
Synthetic method produces potassium peroxydisulfate；Chemical synthesis produces sodium peroxydisulfate, chemical synthesis produces the production technology of potassium peroxydisulfate such as
Under：
One, sodium peroxydisulfate production technology (as shown in Figure 2)
A certain proportion of ammonium persulfate and liquid sodium hydroxide carry out synthetic reaction and generate the mistake containing ammonia at a certain temperature
Metabisulfite solution, by deammoniation tower deamination, recovery ammonia adjusts pH value for the ammonification of ammonium persulfate workshop；Then, close in decompression
Under vacuum state, sodium peroxydisulfate solution is crystallized through evaporative crystallization kettle heating evaporation, then contains wet mistake through centrifuge is isolated
Sulfate crystal, it is sodium peroxydisulfate finished product most to be dried afterwards through drying machine.Mother liquor after centrifugation is handled through mother liquid disposal system
After recycle.Tail gas is handled through tail gas absorber, makes to contain ammonia and the rear discharge up to standard of dusty gas concentration in tail gas.
Sodium peroxydisulfate process units includes the ammonium persulfate solution configuration system being linked in sequence, sodium peroxydisulfate synthetic reaction system
System, ammonia absorption system, evaporation and crystallization system, centrifugal separation system, drying system, further include being connect with evaporation and crystallization system
Cooling water recirculation system further includes the mother liquid disposal system being connect with centrifugal separation system, further includes connecting with ammonia absorption system
The exhaust treatment system connect；It includes that water measuring tank, ammonium persulfate solution configured slot and material are defeated that ammonium persulfate solution, which configures system,
Send equipment；Sodium peroxydisulfate synthesis reaction system includes sodium peroxydisulfate synthesis reaction vessel and sodium peroxydisulfate reaction solution medial launder；Ammonia
Absorption system (deamination system) includes ammonia absorber (deammoniation tower)；Evaporation and crystallization system includes that sodium peroxydisulfate freezing kettle and evaporation are tied
Brilliant kettle；Centrifugal separation system includes centrifuge；Mother liquid disposal system includes concentrate freezing kettle, mother liquor water storage tank, mother liquid evaporation
Kettle, mother liquid evaporation condenser；Cooling water recirculation system includes water cooler, water tank and its circulating pump；Drying system include drying machine,
Screw conveyor, product storage tank；Exhaust treatment system includes tail gas absorber.Wherein, ammonium persulfate solution configured slot, persulfuric acid
6 complete equipments such as sodium synthesis reaction vessel, sodium peroxydisulfate freezing kettle, evaporative crystallization kettle, ammonia absorber, drying machine band PLC controller.
There are 1 station scene I/O, the live each equipment with PLC controller in the site setup of sodium peroxydisulfate process units
The PLC controller of (including the centrifuge with PLC controller, material transfer equipment) connects with the stations scene I/O (i.e. I/O switch boards)
It connects, the live stations I/O are connect by DP buses with the 11# master controllers of DCS control systems.Production scene is included by the live stations I/O
Ammonium persulfate solution configures system, reaction system, ammonia absorption system, evaporation and crystallization system, centrifugal separation system, dry system
The operation letter of each live running equipment of each system including system, mother liquid disposal system, cooling water recirculation system, exhaust treatment system
It ceases, the operation information of detection information and environment treating facility containing ammonia and dusty gas and all band PLC controllers in tail gas
Centrifuge, material transfer equipment operation information, the operation of the central control room of DCS control systems is transmitted to by DP buses
Stand, at the same all operational orders for sending out of the operator of active station will be entered by DP buses each I/O equipment and with each
The PLC controller for each live running equipment that I/O equipment is connected reaches the mesh of production, technique, equipment control and emergency processing
's.
Sodium peroxydisulfate product processes include：Ammonium persulfate solution configuration process, sodium peroxydisulfate synthetic reaction process, ammonia
Aspiration process, evaporation and crystal process, centrifugal drying process, mother liquid disposal process, vent gas treatment process.
In ammonium persulfate solution configuration process, water measuring tank liquid level is controlled 75~80% by DCS control systems, is added
Temperature is to 65~70 DEG C；Sodium peroxydisulfate production ammonium persulfate solution dispensing is controlled, is formulated and is：Ammonium persulfate siccative adds per 500kg
Sodium hydroxide 540kg, amount of water 225kg；With temperature is postponed, summer is no more than 35 DEG C, and winter is no more than 29 DEG C.
In sodium peroxydisulfate synthetic reaction process, is controlled in sodium peroxydisulfate synthesis reaction vessel and reacted by DCS control systems
For temperature at 50-55 DEG C, liquid level is maintained at 75~80%.
In ammonia absorption process, controlled by DCS control systems：The pH value of absorbing liquid is in 5-7, discharge in ammonia absorber
Tail gas in containing ammonia density less than 22mg/m3。
In evaporation and crystal process, controlled by DCS control systems：Evaporating temperature is at 27~45 DEG C；System vacuum exists
0.095MPa or more；PH value is 8~10 in evaporating kettle.
During mother liquid disposal, controlled by DCS control systems：8~12 DEG C of cryogenic temperature in concentrate freezing kettle；Liquid
Position is in 50-60%.
During centrifugal drying, controlled by DCS control systems：70~80 DEG C of sodium peroxydisulfate drying bed temperature of charge；
10~12cm of dry bed body bed depth.
During vent gas treatment, controlled by DCS control systems：Through the dust-laden in tail gas absorber treated tail gas
Particle concentration is less than 22.5mg/m in gas3。
Two, potassium peroxydisulfate production technology (as shown in Figure 3)
A certain proportion of ammonium persulfate and liquid potassium hydroxide carry out synthetic reaction and generate the mistake containing ammonia at a certain temperature
Potassium sulfate solution, by deammoniation tower deamination, recovery ammonia adjusts pH value for the ammonification of ammonium persulfate workshop；Then, close in decompression
Under vacuum state, sodium peroxydisulfate solution is crystallized through evaporative crystallization kettle heating evaporation, then contains wet mistake through centrifuge is isolated
Potassium sulfate crystallizes, and it is potassium peroxydisulfate finished product most to be dried afterwards through drying machine.Mother liquor after centrifugation is handled through mother liquid disposal system
After recycle.Tail gas is handled through tail gas absorber, makes to contain ammonia and the rear discharge up to standard of dusty gas concentration in tail gas.
Potassium peroxydisulfate process units includes the ammonium persulfate solution configuration system being linked in sequence, potassium peroxydisulfate synthetic reaction system
System, ammonia absorption system, evaporation and crystallization system, centrifugal separation system, drying system, further include being connect with evaporation and crystallization system
Cooling water recirculation system further includes the mother liquid disposal system being connect with centrifugal separation system, further includes connecting with ammonia absorption system
The exhaust treatment system connect；It includes that water measuring tank, ammonium persulfate solution configured slot and material are defeated that ammonium persulfate solution, which configures system,
Send equipment；Potassium peroxydisulfate synthesis reaction system includes potassium peroxydisulfate synthesis reaction vessel and potassium peroxydisulfate reaction solution medial launder；Ammonia
Absorption system includes ammonia absorber；Evaporation and crystallization system includes evaporative crystallization kettle；Centrifugal separation system includes centrifuge；At mother liquor
Reason system includes concentrate freezing kettle, mother liquor water storage tank, mother liquid evaporation kettle, mother liquid evaporation condenser；Cooling water recirculation system packet
Include water cooler, water tank and its circulating pump；Drying system includes drying machine, screw conveyor, product storage tank；Exhaust treatment system packet
Include tail gas absorber.Wherein, ammonium persulfate solution configured slot, potassium peroxydisulfate synthesis reaction vessel, potassium peroxydisulfate freezing kettle, evaporation knot
The 6 complete equipment band PLC controller such as brilliant kettle, ammonia absorber, drying machine.
There are 1 station scene I/O, the live each equipment with PLC controller in the site setup of potassium peroxydisulfate process units
PLC controller and the scene I/O station connection of (including the centrifuge with PLC controller, material transfer equipment)；The live stations I/O
Include ammonium persulfate solution configuration system, potassium peroxydisulfate synthesis reaction system, ammonia absorption system, evaporative crystallization by production scene
Each system including system, centrifugal separation system, drying system, mother liquid disposal system, cooling water recirculation system, exhaust treatment system
The operation information for each live running equipment of uniting, the operation of detection information and environment treating facility containing ammonia and dusty gas in tail gas
The operation information of information and all centrifuges with PLC controller, material transfer equipment is transmitted to DCS controls by DP buses
The active station of the central control room of system processed, at the same all operational orders for sending out of the operator of active station will by DP buses into
Enter each I/O equipment and the PLC controller of be connected with each I/O equipment each live running equipment, reaches production, work
Skill, the purpose of equipment control and emergency processing.
Potassium peroxydisulfate product processes include：Ammonium persulfate solution configuration process, potassium peroxydisulfate synthetic reaction process, ammonia
Aspiration process, evaporation and crystal process, centrifugal drying process, mother liquid disposal process, vent gas treatment process.
In ammonium persulfate solution configuration process, water measuring tank liquid level is controlled 75~80% by DCS control systems, is added
Temperature is to 65~70 DEG C；Potassium peroxydisulfate production ammonium persulfate solution dispensing is controlled, is formulated and is：Ammonium persulfate siccative adds per 500kg
Potassium hydroxide 750kg, amount of water 600kg, about 70 DEG C of coolant-temperature gage of control dispensing.
In potassium peroxydisulfate synthetic reaction process, potassium peroxydisulfate synthesis reaction vessel reaction temperature is controlled by DCS control systems
For degree at 65~70 DEG C, liquid level is maintained at 75~80%.
In ammonia absorption process, controlled by DCS control systems：The pH value of absorbing liquid is in 5-7, discharge in ammonia absorber
Tail gas in containing ammonia density less than 22mg/m3。
In evaporation and crystal process, controlled by DCS control systems：
Cathode material acidity：≥2.0mol/L；Liquid potassium hydroxide feed rate：0.5~0.7T/h；
Liquid ammonium persulfate solution flow：1.1~1.5T/h；Evaporating temperature (circulating-heating temperature)：50~55 DEG C；
Feed liquid cryogenic temperature：5~8 DEG C；System vacuum：0.085~0.093MPa.
During centrifugal drying, controlled by DCS control systems：70~85 DEG C of potassium peroxydisulfate drying bed temperature of charge；
10~12cm of dry bed body bed depth.
During mother liquid disposal, controlled by DCS control systems：8~12 DEG C of cryogenic temperature in concentrate freezing kettle；Liquid
Position is in 50-60%.
During vent gas treatment, controlled by DCS control systems：Through the dust-laden in tail gas absorber treated tail gas
Particle concentration is less than 22.5mg/m in gas3。
The sodium peroxydisulfate of the utility model and the advance of potassium peroxydisulfate process units DCS control systems be mainly reflected in
Lower several respects：
A, centrifuge carries out Automatic Control using the program of closed-loop operation by DCS control systems, improves efficiency,
Operating environment is improved, good environment protecting has been reached.
B, potassium peroxydisulfate production is measured using high-precision mass flowmenter, and feeding flow is automatically controlled by DCS control systems
Amount, realize accurately control, continuous production, not only improved product yield, quality, but also reduce labor intensity and improve operation
Environment.
For the utility model in DCS control system real-time controls, the control to electrolysis temperature, pressure, electric current can reduce energy
Consumption, the yield and product quality for improving product；Monitoring to circulating cooling water temperature can reduce the energy consumption and water consume of recirculated water；It is right
The monitoring of the pH value of production system, the uncontrollable discharge and systematicness that can reduce ammonia discharge, and recycle ammonia as much as possible
With the consumption for reducing ammonia.
The utility model uses newest DCS automatic control schemes to sodium peroxydisulfate and potassium peroxydisulfate system, then carries significantly
The high production capacity of device so that the conversion ratio of production process can reach 99% or more, greatly reduce in production to each
The consumption of raw material decreases the generation of many byproducts, greatly reduces production cost.
Application of the utility model due to DCS robot control system(RCS)s so as to each in sodium peroxydisulfate and potassium peroxydisulfate production process
The use of large-scale evaporation, crystallizer and the purpose of steady production can be achieved completely, to make sodium peroxydisulfate and potassium peroxydisulfate
Process units reached it is increasingly automated, enlarged and modernization.
The utility model carries out automatically controlling sodium peroxydisulfate and potassium peroxydisulfate production system using DCS control systems, can
Labor productivity is significantly increased, product quality is improved, improves the utilization rate of raw material, improves environmental protection, there is great warp
Benefit of helping and social benefit.
Claims (5)
1. a kind of sodium peroxydisulfate and potassium peroxydisulfate process units DCS control systems, which is characterized in that it include DCS control systems,
Sodium peroxydisulfate process units and potassium peroxydisulfate process units；DCS control systems include master controller, exchanger, active station；Master control
Device processed is connect by exchanger with active station；Real-time control of the master controller for sodium peroxydisulfate, potassium peroxydisulfate process units；It hands over
Parallel operation will be operated for the operation information between master controller and active station, status information communication, operating personnel by active station
Instruction is sent to master controller, and real-time status is then sent to active station by master controller, completes real-time communication, operation, control；?
The site setup of sodium peroxydisulfate process units and potassium peroxydisulfate process units has live I/O to stand, and each of scene is with PLC controller
The PLC controller of equipment is connected with the stations scene I/O；Each stations scene I/O pass through the main control of DP buses and DCS control systems respectively
Device connects.
2. sodium peroxydisulfate as described in claim 1 and potassium peroxydisulfate process units DCS control systems, which is characterized in that master control
Drag two I/O switch boards, each I/O switch boards existing with sodium peroxydisulfate process units, potassium peroxydisulfate process units respectively under device processed
Sodium peroxydisulfate, all AI, AO, DI, DO points in potassium peroxydisulfate process units scene are responsible in all AI, AO, DI, DO points connection of field
Real time monitoring, and connect with the PLC controller of all equipment with PLC controller in scene, progress real-time communication.
3. sodium peroxydisulfate as described in claim 1 and potassium peroxydisulfate process units DCS control systems, which is characterized in that in mistake
Each 1 scene I/O of setting in the scene of sodium sulphate process units and potassium peroxydisulfate process units stands, i.e., in sodium peroxydisulfate process units
It is respectively provided with 1 I/O switch board with potassium peroxydisulfate process units, the input-output apparatus at the live stations I/O passes through profibus_DP
Bus is connected and communicate with master controller；Production scene is included ammonium persulfate solution configuration system, sodium peroxydisulfate by the live stations I/O
Or potassium peroxydisulfate synthesis reaction system, ammonia absorption system, evaporation and crystallization system, centrifugal separation system, drying system, mother liquor
The operation information of each live running equipment of each system including processing system, cooling water recirculation system, exhaust treatment system, tail gas
In detection information and environment treating facility containing ammonia and dusty gas operation information and all equipment with PLC controller
Operation information including centrifuge, material transfer equipment, the behaviour of the central control room of DCS control systems is transmitted to by DP buses
Stand, at the same all operational orders for sending out of the operator of active station will be entered by DP buses each I/O equipment and with it is each
The PLC controller for each live running equipment that platform I/O equipment is connected；The ammonia that emission is monitored by DCS control systems is inhaled
The pH value and tail gas for receiving absorbing liquid in tower contain ammonia density, monitor the temperature and liquid level of evaporation and crystallization system and mother liquid disposal system,
The operating condition for monitoring centrifuge monitors the liquid level of each groove tank and the operating condition of each dynamic equipment and the fortune of each production subsystem
Market condition.
4. sodium peroxydisulfate as described in claim 1 and potassium peroxydisulfate process units DCS control systems, which is characterized in that over cure
Sour sodium process units includes the ammonium persulfate solution configuration system being linked in sequence, sodium peroxydisulfate synthesis reaction system, ammonia absorption
System, evaporation and crystallization system, centrifugal separation system, drying system further include the cooling water circulation being connect with evaporation and crystallization system
System further includes the mother liquid disposal system being connect with centrifugal separation system, further includes at the tail gas being connect with ammonia absorption system
Reason system；It includes water measuring tank, ammonium persulfate solution configured slot and material transfer equipment that ammonium persulfate solution, which configures system,；Over cure
Sour sodium synthesis reaction system includes sodium peroxydisulfate synthesis reaction vessel, sodium peroxydisulfate reaction solution medial launder；Ammonia absorption system includes
Ammonia absorber；Evaporation and crystallization system includes sodium peroxydisulfate freezing kettle, evaporative crystallization kettle；Mother liquid disposal system includes concentrate freezing
Kettle, mother liquor water storage tank, mother liquid evaporation kettle, mother liquid evaporation condenser；Centrifugal separation system includes centrifuge；Cooling water recirculation system
Including water cooler, water tank and its circulating pump；Drying system includes drying machine, screw conveyor, product storage tank；Exhaust treatment system
Including tail gas absorber；Wherein, water measuring tank, ammonium persulfate solution configured slot, sodium peroxydisulfate freezing kettle, evaporative crystallization kettle, ammonia
Absorption tower, centrifuge, drying machine these equipment belt PLC controllers；There is 1 scene in the site setup of sodium peroxydisulfate process units
I/O stands, and PLC controller and the stations scene I/O of the live each equipment with PLC controller are that I/O switch boards are connect, live I/O
It stands and is connect with the 11# master controllers of DCS control systems by DP buses.
5. sodium peroxydisulfate as described in claim 1 and potassium peroxydisulfate process units DCS control systems, which is characterized in that over cure
Sour potassium process units includes the ammonium persulfate solution configuration system being linked in sequence, potassium peroxydisulfate synthesis reaction system, ammonia absorption
System, evaporation and crystallization system, centrifugal separation system, drying system further include the cooling water circulation being connect with evaporation and crystallization system
System further includes the mother liquid disposal system being connect with centrifugal separation system, further includes at the tail gas being connect with ammonia absorption system
Reason system；It includes water measuring tank, ammonium persulfate solution configured slot and material transfer equipment that ammonium persulfate solution, which configures system,；Over cure
Sour potassium synthesis reaction system includes potassium peroxydisulfate synthesis reaction vessel, potassium peroxydisulfate reaction solution medial launder；Ammonia absorption system includes
Ammonia absorber；Evaporation and crystallization system includes potassium peroxydisulfate freezing kettle, evaporative crystallization kettle；Mother liquid disposal system includes concentrate freezing
Kettle, mother liquor water storage tank, mother liquid evaporation kettle, mother liquid evaporation condenser；Centrifugal separation system includes centrifuge；Cooling water recirculation system
Including water cooler, water tank and its circulating pump；Drying system includes drying machine, screw conveyor, product storage tank；Exhaust treatment system
Including tail gas absorber；Wherein, water measuring tank, ammonium persulfate solution configured slot, potassium peroxydisulfate freezing kettle, evaporative crystallization kettle, ammonia
Absorption tower, centrifuge, drying machine these equipment belt PLC controllers；There is 1 scene in the site setup of potassium peroxydisulfate process units
I/O stands, and PLC controller and the stations scene I/O of the live each equipment with PLC controller connect.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108227668A (en) * | 2018-04-04 | 2018-06-29 | 上海天坛助剂有限公司 | Sodium peroxydisulfate and potassium peroxydisulfate process units DCS control systems and control method |
| CN114917849A (en) * | 2022-05-31 | 2022-08-19 | 湖南福尔程环保科技有限公司 | Energy-concerving and environment-protective thiram production system |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108227668A (en) * | 2018-04-04 | 2018-06-29 | 上海天坛助剂有限公司 | Sodium peroxydisulfate and potassium peroxydisulfate process units DCS control systems and control method |
| CN114917849A (en) * | 2022-05-31 | 2022-08-19 | 湖南福尔程环保科技有限公司 | Energy-concerving and environment-protective thiram production system |
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