The firming agent special reaction device of a kind of repairing heavy metal in soil pollution and producer thereof
Method
Technical field
The invention belongs to firming agent process and application, the firming agent being specifically related to the pollution of a kind of repairing heavy metal in soil is special
Use reaction unit.
Background technology
Heavy metal pollution of soil is the most important pollution source of groundwater, and lead, zinc are cause heavy metal pollution of soil main
Factor, it is considered that Pb in Soil Zn content i.e. may cause heavy metal pollution of soil more than 0.02mg/L.The source of Pb in Soil zinc
Including external source and endogenous, after external source is polluted and is effectively controlled, soil is vulnerable to the weak binding state phosphorus of environmental effect, lead
Bound phosphorus, organic phosphorus isoreactivity state phosphorus can be with environmental condition (such as temperature, pH, dissolved oxygen, oxidation-reduction potentials etc.)
Change and be gradually released to soil aquifer, form endogenous pollution, cause heavy metal pollution of soil and sudden soil water quality to deteriorate
Event.There are some researches show have the underground water pollution of 18.88% to derive from the release of soil, wherein in Scotland and England
Weak binding state phosphorus, zinc bound phosphorus, lead bound phosphorus isoreactivity state phosphorus ratio are relatively big, the most effectively control soil inside source release and are
The key that heavy metal pollution of soil is administered.
Remediation contaminated soil mainly has the methods such as physics, biology, chemistry, such as environmental dredging, biological restoration, in-situ passivation
Deng, pollutant in soil can directly be removed by environmental dredging, but its cost is high, and difficulty is big and is only applicable to less than 10 meters deeply
Environment;Bioremediation technology low cost, but speed is slow, is primarily suitable for shallow environment;At the deep environment of more than 10m, in situ
Passivating technique is most economical effective remediation contaminated soil technology, and the type soil horizon bathyliminion hydrodynamic force is more weak, to passivation
The disturbance of layer is little, can keep good passivation effect.
In-situ passivation technology is to utilize physico-chemical process to cut off flyway, by pollutant " fixing " in situ in soil,
It is suppressed to discharge to soil cover water-bearing layer.Use the activity that passivator can adsorb in a long time, precipitate in surface deposit
Lead, concurrently forms masking layer and stops soil to discharge lead to soil cover water-bearing layer, reach to reduce for a long time soil aquifer lead content,
Control the purpose of heavy metal pollution of soil, and processing cost is low, simple to operate.Finding efficient soil passivator is current original position
The key of passivating technique application.
Presently used passivator kind mainly includes aluminium salt (such as Alumen, poly-aluminum), iron salt (such as iron chloride) and calcium salt
(such as calcium carbonate), also includes that some contain the clay mineral of aluminum, ferrum, calcium.Aluminium salt is used to be that passivator has efficient, stable
Etc. advantage, but the pH scope being suitable for is between 6-8, and peracid or excessively alkali all can cause the release of phosphorus;Iron salt has as passivator
There is nontoxic feature, but be easily subject to Redox Condition and the impact of pH value change;The application of calcium salt can increase soil water-containing
Layer hardness, simultaneously as CO in soil water-containing solution2When content increases or pH value reduces, calcium carbonate and the dissolving of hydroxyapatite
To increase, the lead of absorption will be discharged into soil aquifer.Sodium bentonite is a kind of natural clay mineral, Main chemical component
It is SiO2、Al2O3And the oxide of ferrum, widely exist in stratum, source is wide, rich reserves, and has specific surface area
Greatly, the features such as absorption property is good, there is such as the cationes such as Cu, Mg, Na, K in layer structure simultaneously, easy and other sun from
Son exchange, has preferable ion exchangeable, can adsorb the heavy metal ion in soil aquifer.Sodium bentonite modification system
Standby passivator, has higher surface adsorption property, simultaneously because the addition of the modifiers such as Alumen, aluminum hydrolyzes in water,
Form gluey, amorphous and that there is high coagulability Al (OH)3Flock, strong adsorption PO4 3-, and gradually form stable state
AlPO4Or hydroxyl phosphate [Al (OH)y(PO4)z] precipitate and remove the phosphorus in soil aquifer, it is effectively reduced soil
Phosphorus is discharged, it is to avoid because of the restriction to soil aquifer pH value of the simple aluminium salt, at pH value widely to soil cover water-bearing layer
The lower release effectively controlling phosphorus.Aluminum hydrolysis equation is as follows:
①
②
③
Summary of the invention
In order to solve above-mentioned technical problem, the firming agent Special reverse that the present invention provides a kind of repairing heavy metal in soil to pollute should fill
Put,
Including: sealing lid 1, dense block 2, retort 3, cleaning door 4, finished product memorizer 5, finished product discharges electromagnetic valve 6, reaction
Tail gas discharges electromagnetic valve 7, reaction end gas collecting tank 8, controller 9, finished fluid bit detector 10;The described lid 1 that seals is half
Ball shape structure, half radius of a ball, between 1.5m~2.5m, seals lid 1 and is positioned at above retort 3, and retort 3 is by sealing
Lock 2 seals with sealing lid 1;Being provided with cleaning door 4 below described retort 3 sidewall, handle and the base of cleaning door 4 are not
Rust steel matter;Described finished product memorizer 5 is positioned at below retort 3, and finished product memorizer 5 is through with retort 3 to be connected;Described
Finished product memorizer 5 inner surface is provided with finished fluid bit detector 10;Described finished product is discharged electromagnetic valve 6 and is arranged at finished product memorizer 5
Lower section, finished product is discharged electromagnetic valve 6 and is connected by pipeline is through with finished product memorizer 5;Described reaction end gas collecting tank 8 is positioned at instead
Tank 3 side, reaction end gas collecting tank 8 is answered to be connected by pipeline is through with retort 3, be wherein provided with reaction end gas in the middle part of pipeline
Discharge electromagnetic valve 7;Described controller 9 is positioned at retort 3 side;
Described finished product discharges electromagnetic valve 6, reaction end gas discharges electromagnetic valve 7 and finished fluid bit detector 10 is respectively by wire and control
Device 9 controls to connect.
Further, described dense block 2 includes: upper bed-plate 2-1, spanner 2-2, otic placode 2-3, horizontal hair 2-4, U-shaped card
2-5, lower bottom base 2-6, snap close 2-7;Wherein said upper bed-plate 2-1 is fixedly connected on sealing lid 1 surface, outside upper bed-plate 2-1
Shape is rectangular configuration;Described otic placode 2-3 and upper bed-plate 2-1 upper surface seamless welding;Described spanner 2-2 one end is spheroid-like,
This end material is quality of rubber materials;The spanner 2-2 other end is stainless steel, and this end is forked, and this end and otic placode 2-3 hinge
Connect;Described horizontal hair 2-4 is positioned in the middle part of spanner 2-2, and horizontal hair 2-4 is vertical with spanner 2-2 to be connected;Described U-shaped card 2-5 opens
Putting end to be connected by nut is fixing with horizontal hair 2-4, U-shaped card 2-5 Guan Bi end is held in inside snap close 2-7;Described lower bottom base 2-6
Being positioned at retort 3 top, lower bottom base 2-6 is fixing with retort 3 outer wall to be connected;Described snap close 2-7 is fixedly connected on lower bottom base
2-6 surface, snap close 2-7 is pyrite nickel plating material, and snap close 2-7 profile is quadrant structure.
Further, described retort 3 includes: esterification promoters 3-1, reaction end gas concentration detector 3-2, Gu
Agent synthetic ratio detector 3-3, residue arrester 3-4;Wherein said esterification promoters 3-1 is vertically placed on retort
In 3, esterification promoters 3-1 quantity is no less than 3;Described residue arrester 3-4 is positioned at bottom retort 3;Institute
Stating reaction end gas concentration detector 3-2 and be positioned at above retort 3 inwall, described firming agent synthetic ratio detector 3-3 is positioned at reaction
Below tank 3 inwall, reaction end gas concentration detector 3-2 and firming agent synthetic ratio detector 3-3 respectively with controller 9 wire control
System connects.
Further, described esterification promoters 3-1 includes: esterification plate 3-1-1, catalyst release 3-1-2;
Wherein said esterification plate 3-1-1 profile is curved surface wave-like, and esterification plate 3-1-1 thickness is at 15mm~25mm;
Described catalyst release 3-1-2 is evenly distributed on surface inside and outside esterification plate 3-1-1, catalyst release 3-1-2 number
Amount is no less than 3500, and catalyst release 3-1-2 is chondritic, and its radius size is 20mm~30mm.
Further, described residue arrester 3-4 includes: residue stops plate 3-4-1, stops plate and fixes otic placode 3-4-2,
Turning arm 3-4-3, retort inwall fixes otic placode 3-4-4, residue gravity sensor 3-4-5;Wherein said residue stops plate 3-
4-1 is heat zinc coating plate material, and it is circular configuration that residue stops plate 3-4-1 profile, and circular radius is between 1.2m~2.2m, residual
Slag stops plate 3-4-1 surface has a large amount of water falling holes, and water falling hole aperture is between 4mm~6mm;Ear fixed by described obstruction plate
Plate 3-4-2 one end and residue obstruction plate 3-4-1 lower surface are fixed and are welded to connect, and stop plate and fix the otic placode 3-4-2 other end and rotation
Arm 3-4-3 chain connection;Described turning arm 3-4-3 is stainless steel tube, and the turning arm 3-4-3 other end passes through fastener shaft and retort
Inwall fixes otic placode 3-4-4 chain connection;Described retort inwall is fixed otic placode 3-4-4 and is fixedly connected on retort 3 inwall table
Face;Described residue gravity sensor 3-4-5 is positioned at residue and stops below plate 3-4-1, and residue gravity sensor 3-4-5 passes through wire
Control to be connected with controller 9.
Further, described esterification plate 3-1-1 is by macromolecular material pressing mold molding, the composition of esterification plate 3-1-1
Composition and manufacture process are as follows:
One, esterification plate 3-1-1 constituent:
Count by weight, 4-isopropyl-2-acrylic toluene 70~156 parts, d-frans-2,2-dimethyl-3-(2-methyl-1-propylene
Base) cyclopropane-carboxylic acid 84~144 parts, 2-methyl-2-acrylic acid 2-(4-morpholinyl) ethyl ester 26~78 parts, 2,3,5,6-tetrafluoro benzyls
Base (1R, 3S)-3-(2,2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid's ester 28~79 parts, (alpha-cyano-1-methyl) cyclobutenyl-
2,2-dimethyl-3-(2,2-dichloroethylene) cyclopropanecarboxylcompound 112~269 parts, the trans-3-of 1R-(2,2-dichloroethylene)-
2,2-dimethyl cyclopropane carboxylic acids-(2,3,5,6 ,-tetrafluoro phenyl) methyl ester 65~104 parts, concentration is the 3-of 32ppm~84ppm
Phenoxy benzyl-2,2-dimethyl-3-(2,2-dichloroethylene)-1-cyclopropanecarboxylcompound 15~53 parts, IR, S-are suitable, trans-2,2-bis-
Methyl-3-(2-metering system-1-base) cyclopropane-carboxylic acid 48~96 parts, trans-2,3-diaryl replaces-1-1-aminocyclopropane-1-carboxylic acid
58~115 parts, cross-linking agent 63~152 parts, 3-(ethylphenyl amino) propionitrile 116~208 parts, N-[2-[(2-chloro-4,6-dinitro
Base phenyl) azo]-5-(ethylamino)-4-(2-methoxy ethoxy) phenyl] acetamide 38~165 parts, N-[5-[two (2-acetoxyl groups)
Ethyl] amino]-2-[(2-chloro-4 nitrophenyl) azo] Phenylpropionamide 59~108 parts, [[(2-bromo-4,6-dinitrophenyl) is even for 2-for N-
Nitrogen]-5-[(2-cyanoethyl) ethylamino]-4-anisyl] acetamide 68~198 parts;
Described cross-linking agent is N, N-double (2-ethoxy)-4-methyl benzenesulfonamide, 2-(6-methyl-2-[4-morpholinodithio azo)-5-diethylamino
Any one in phenol, acetoacetyl p-ethoxyaniline;
Two, the manufacture process of esterification plate 3-1-1, comprises the steps of
1st step: add ultra-pure water 786~1561 parts that electrical conductivity is 3.22 μ S/cm~5.62 μ S/cm in a kettle., start
Agitator in reactor, rotating speed is 46rpm~108rpm, start heat pump, make reactor temperature rise to 56 DEG C~
89℃;It is sequentially added into 4-isopropyl-2-acrylic toluene, d-frans-2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropane
Carboxylic acid, 2-methyl-2-acrylic acid 2-(4-morpholinyl) ethyl ester, stirring is to being completely dissolved, and regulation pH value is 5.3~7.2, will stir
Mixing device rotating speed and be adjusted to 186rpm~268rpm, temperature is 87 DEG C~148 DEG C, esterification 9~28 hours;
2nd step: take 2,3,5,6-ptfe benzyl (1R, 3S)-3-(2,2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid's ester, (alpha-cyano
-1-methyl) cyclobutenyl-2,2-dimethyl-3-(2,2-dichloroethylene) cyclopropanecarboxylcompound pulverizes, powder diameter be 800~
2100 mesh;Add the trans-3-of 1R-(2,2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid-(2,3,5,6 ,-tetrafluoro phenyl) methyl ester
Mix homogeneously, is laid in pallet, and tiling thickness is 8mm~18mm, and using dosage is 2.5kGy~6.8kGy, energy
For the alpha ray irradiation 80 of 3.0MeV~16MeV~192 minutes, and the β x ray irradiation x 66 of Isodose~156 points
Clock;
3rd step: the mixed-powder processed through the 2nd step is dissolved in 3-phenoxy benzyl-2,2-dimethyl-3-(2,2-dichloroethylene)-1-ring third
In alkane carboxylate, adding reactor, agitator speed is 95rpm~168rpm, and temperature is 76 DEG C~159 DEG C, starts true
Empty pump makes the vacuum of reactor reach-1.25MPa~0.68MPa, keeps this state response 16~32 hours;Pressure release is also led to
Entering radon gas, making reacting kettle inner pressure is 0.35MPa~1.02MPa, and insulation stands 14~22 hours;Agitator speed promotes
To 120rpm~235rpm, simultaneous reactions still pressure release to 0MPa;It is sequentially added into IR, S-suitable, trans-2,2-dimethyl-3-(2-
Metering system-1-base) cyclopropane-carboxylic acid, trans-2,3-diaryl replaces after-1-1-aminocyclopropane-1-carboxylic acid is completely dissolved, and adds crosslinking
Agent stirring mixing so that the hydrophile-lipophile balance value of reactor solution is 6.2~7.3, and insulation stands 5~11 hours;
4th step: when agitator speed is 147rpm~236rpm, is sequentially added into 3-(ethylphenyl amino) propionitrile, N-[2-[(2-
Chloro-4,6-dinitrophenyl) azo]-5-(ethylamino)-4-(2-methoxy ethoxy) phenyl] acetamide, N-[5-[two (2-acetoxyl groups)
Ethyl] amino]-2-[(2-chloro-4 nitrophenyl) azo] Phenylpropionamide and N-[2-[(2-bromo-4,6-dinitrophenyl) azo]-5-[(2-
Cyanoethyl) ethylamino]-4-anisyl] acetamide, promote reactor pressure so that it is reach 1.12MPa~1.57MPa, temperature
Degree is 134 DEG C~208 DEG C, polyreaction 17~33 hours;After having reacted, reacting kettle inner pressure is down to 0MPa, cooling
To 24 DEG C~36 DEG C, discharging, enter molding press and can be prepared by esterification plate 3-1-1.
Further, the invention also discloses the work of the firming agent special reaction device that a kind of repairing heavy metal in soil pollutes
Method, the method includes following step:
1st step: the firming agent raw materials for production after staff will pulverize are immersed in pond, when firming agent raw materials for production moisture content reaches
When 65%~70%, staff opens sealing lid 1, and the firming agent raw materials for production after soaking are put in retort 3;Putting
When putting firming agent raw materials for production, making firming agent raw materials for production be evenly distributed on esterification plate 3-1-1 surface, firming agent produces former
Material tiling thickness is between 50mm~70mm;After firming agent raw materials for production have tiled, close and seal lid 1, fit sealing
Lock 2, makes retort 3 reach fully sealed position;
2nd step: the catalyst release 3-1-2 being attached on esterification plate 3-1-1 discharges catalyst, produces former with firming agent
Material produces anabolic effect, produces reaction end gas gas;When reaction end gas concentration detector 3-2 detects reaction tail in retort 3
When gas concentration is higher than 80ppm, feedback signal is sent to controller 9 by reaction end gas concentration detector 3-2, and controller 9 is opened
Reaction end gas discharges electromagnetic valve 7, and reaction end gas is delivered in reaction end gas collecting tank 8 by pipeline;When reaction end gas concentration is examined
Survey device 3-2 and detect that when reaction end gas concentration is less than 8ppm in retort 3, reaction end gas concentration detector 3-2 is by feedback letter
Number being sent to controller 9, controller 9 cuts out reaction end gas and discharges electromagnetic valve 7;
3rd step: the finished product produced during firming agent anabolic effect, the water falling hole inflow finished product stopped on plate 3-4-1 by residue is deposited
Reservoir 5, when during finished product liquid level detector 10 detects finished product memorizer 5, liquid level is higher than 30cm, finished product Level Detection
The signal of telecommunication is sent to controller 9 by device 10, and controller 9 is opened finished product and discharged electromagnetic valve 6, the finished product warp in finished product memorizer 5
Pipeline is discharged;When during finished product liquid level detector 10 detects finished product memorizer 5, liquid level is less than 5cm, finished product liquid level is examined
Surveying device 10 and the signal of telecommunication is sent to controller 9, controller 9 cuts out finished product and discharges electromagnetic valve 6;
4th step: the firming agent synthetic ratio in retort 3 is monitored by firming agent synthetic ratio detector 3-3 in real time, when firming agent synthetic ratio
When detector 3-3 detects firming agent synthetic ratio less than 8%, the signal of telecommunication is sent to controlling by firming agent synthetic ratio detector 3-3
Device 9, controller 9 sends alarm signal to staff;Staff, after receiving alarm signal, is manually pressed by controller
Control knob on 9, controls finished product discharge electromagnetic valve 6 and reaction end gas is discharged electromagnetic valve 7 and opened, and after 10min, work people
Member closes finished product and discharges electromagnetic valve 6 and reaction end gas discharge electromagnetic valve 7;
5th step: staff opens cleaning door 4, cleaning residue stops residue after the reaction on plate 3-4-1;When residue gravity sensing
Device 3-4-5 detects that when residue stops plate 3-4-1 gravity more than 10kg, the signal of telecommunication is sent to by residue gravity sensor 3-4-5
Controller 9, controller 9 controls turning arm 3-4-3 and rotates 25 °~45 °, makes residue stop plate 3-4-1 and produces inclination angle;
When residue gravity sensor 3-4-5 detects that residue stops plate 3-4-1 gravity less than 1.5kg, residue gravity sensor 3-4-5
The signal of telecommunication is sent to controller 9, and controller 9 controls turning arm 3-4-3 and returns back to initial position, makes residue stop plate 3-4-1
It is the level of state;After cleaning out, staff closes cleaning door 4, checks device miscellaneous part, is maintained at closed mode.
The firming agent special reaction device that a kind of repairing heavy metal in soil disclosed by the invention pollutes, has an advantage in that:
(1) this device recycling firming agent produces reaction end gas gas, energy-conserving and environment-protective;
(2) this apparatus structure is simple, easy to use;
(3) this device uses catalyst reaction, is effectively improved firming agent synthesis rate.
The firming agent special reaction device that a kind of repairing heavy metal in soil of the present invention pollutes, these device energy-conserving and environment-protective,
Simple in construction, automaticity is high, and firming agent synthesis rate is high.
Accompanying drawing explanation
Fig. 1 is the firming agent special reaction device structure chart that heretofore described a kind of repairing heavy metal in soil pollutes.
Fig. 2 is heretofore described dense block structural representation.
Fig. 3 is heretofore described retort internal structure schematic diagram.
Fig. 4 is heretofore described esterification promoters structural representation.
Fig. 5 is that heretofore described residue arrester structural diagrams is intended to.
Fig. 6 is that esterification panel material synthesising stability enhancing rate of the present invention changes over graph of a relation.
In figure 1 above~Fig. 5, sealing lid 1, dense block 2, upper bed-plate 2-1, spanner 2-2, otic placode 2-3, horizontal hair 2-4,
U-shaped card 2-5, lower bottom base 2-6, snap close 2-7, retort 3, esterification promoters 3-1, esterification plate 3-1-1, urge
Agent release 3-1-2, reaction end gas concentration detector 3-2, firming agent synthetic ratio detector 3-3, residue arrester 3-4,
Residue stops plate 3-4-1, stops plate and fixes otic placode 3-4-2, turning arm 3-4-3, and retort inwall fixes otic placode 3-4-4, residue
Gravity sensor 3-4-5, cleaning door 4, finished product memorizer 5, finished product discharge electromagnetic valve 6, reaction end gas discharge electromagnetic valve 7,
Reaction end gas collecting tank 8, controller 9, finished fluid bit detector 10.
Detailed description of the invention
The firming agent Special reverse that a kind of repairing heavy metal in soil provided the present invention with embodiment below in conjunction with the accompanying drawings pollutes should
Device is further described.
As it is shown in figure 1, be that the firming agent special reaction device that heretofore described a kind of repairing heavy metal in soil pollutes is tied
Composition, it is seen in fig. 1, that include: seal lid 1, dense block 2, retort 3, cleaning door 4, finished product memorizer 5, become
Product discharge electromagnetic valve 6, and reaction end gas discharges electromagnetic valve 7, reaction end gas collecting tank 8, controller 9, finished fluid bit detector
10;The described lid 1 that seals is dome-type structure, and half radius of a ball, between 1.5m~2.5m, seals lid 1 and is positioned in retort 3
Side, retort 3 covers 1 sealing by dense block 2 with sealing;It is provided with cleaning door 4, cleaning door below described retort 3 sidewall
Handle and the base of 4 are stainless steel;Described finished product memorizer 5 is positioned at below retort 3, and finished product memorizer 5 is with anti-
Answer the through connection of tank 3;Described finished product memorizer 5 inner surface is provided with finished fluid bit detector 10;Described finished product discharges electromagnetism
Valve 6 is arranged at below finished product memorizer 5, and finished product is discharged electromagnetic valve 6 and is connected by pipeline is through with finished product memorizer 5;Described
Reaction end gas collecting tank 8 is positioned at retort 3 side, and reaction end gas collecting tank 8 is connected by pipeline is through with retort 3, its
It is provided with reaction end gas in the middle part of middle pipeline and discharges electromagnetic valve 7;Described controller 9 is positioned at retort 3 side;
Described finished product discharges electromagnetic valve 6, reaction end gas discharges electromagnetic valve 7 and finished fluid bit detector 10 is respectively by wire and control
Device 9 controls to connect.
As in figure 2 it is shown, be heretofore described dense block structural representation, find out from Fig. 2 or Fig. 1, dense block 2
Including: upper bed-plate 2-1, spanner 2-2, otic placode 2-3, horizontal hair 2-4, U-shaped card 2-5, lower bottom base 2-6, snap close 2-7;Wherein
Described upper bed-plate 2-1 is fixedly connected on sealing lid 1 surface, and upper bed-plate 2-1 profile is rectangular configuration;Described otic placode 2-3 is with upper
Base 2-1 upper surface seamless welding;Described spanner 2-2 one end is spheroid-like, and this end material is quality of rubber materials;Spanner 2-2
The other end is stainless steel, and this end is forked, and this end and otic placode 2-3 chain connection;Described horizontal hair 2-4 is positioned at spanner 2-
In the middle part of in the of 2, horizontal hair 2-4 is vertical with spanner 2-2 to be connected;Described U-shaped card 2-5 open end and horizontal hair 2-4 are fixing even by nut
Connecing, U-shaped card 2-5 Guan Bi end is held in inside snap close 2-7;Described lower bottom base 2-6 is positioned at retort 3 top, lower bottom base 2-6
Fix with retort 3 outer wall and be connected;Described snap close 2-7 is fixedly connected on lower bottom base 2-6 surface, and snap close 2-7 is pyrite nickel plating
Material, snap close 2-7 profile is quadrant structure.
As it is shown on figure 3, be heretofore described retort internal structure schematic diagram, find out from Fig. 3 or Fig. 1, instead
Tank 3 is answered to include: esterification promoters 3-1, reaction end gas concentration detector 3-2, firming agent synthetic ratio detector 3-3, residual
Slag arrester 3-4;Wherein said esterification promoters 3-1 is vertically placed in retort 3, esterification promoters 3-1
Quantity is no less than 3;Described residue arrester 3-4 is positioned at bottom retort 3;Described reaction end gas concentration detector 3-2
Being positioned at above retort 3 inwall, described firming agent synthetic ratio detector 3-3 is positioned at below retort 3 inwall, and reaction end gas is dense
Degree detector 3-2 and firming agent synthetic ratio detector 3-3 is connected with controller 9 polygon control survey respectively.
As shown in Figure 4, it is heretofore described esterification promoters structural representation, as seen from Figure 4, esterification
Reaction promoters 3-1 includes: esterification plate 3-1-1, catalyst release 3-1-2;Wherein said esterification plate 3-1-1
Profile is curved surface wave-like, and esterification plate 3-1-1 thickness is at 15mm~25mm;Described catalyst release 3-1-2 is equal
Even being distributed in surface inside and outside esterification plate 3-1-1, catalyst release 3-1-2 quantity is no less than 3500, catalyst
Release 3-1-2 is chondritic, and its radius size is 20mm~30mm.
As it is shown in figure 5, be that heretofore described residue arrester structural diagrams is intended to, find out from Fig. 5 or Fig. 1,
Residue arrester 3-4 includes: residue stops plate 3-4-1, stops plate and fixes otic placode 3-4-2, and turning arm 3-4-3, in retort
Wall fixes otic placode 3-4-4, residue gravity sensor 3-4-5;It is heat zinc coating plate material that wherein said residue stops plate 3-4-1, residual
It is circular configuration that slag stops plate 3-4-1 profile, and circular radius is between 1.2m~2.2m, and residue stops plate 3-4-1 surface to be had
A large amount of water falling holes, water falling hole aperture is between 4mm~6mm;Described obstruction plate is fixed otic placode 3-4-2 one end and is stopped with residue
Plate 3-4-1 lower surface is fixing to be welded to connect, and stops plate and fixes the otic placode 3-4-2 other end and turning arm 3-4-3 chain connection;Described
Turning arm 3-4-3 is stainless steel tube, and the turning arm 3-4-3 other end fixes otic placode 3-4-4 hinge by fastener shaft and retort inwall
Connect;Described retort inwall is fixed otic placode 3-4-4 and is fixedly connected on retort 3 inner wall surface;Described residue gravity sensor
3-4-5 is positioned at residue and stops below plate 3-4-1, and residue gravity sensor 3-4-5 controls to be connected with controller 9 by wire.
The work process of the firming agent special reaction device that a kind of repairing heavy metal in soil of the present invention pollutes is:
1st step: the firming agent raw materials for production after staff will pulverize are immersed in pond, when firming agent raw materials for production moisture content reaches
When 65%~70%, staff opens sealing lid 1, and the firming agent raw materials for production after soaking are put in retort 3;Putting
When putting firming agent raw materials for production, making firming agent raw materials for production be evenly distributed on esterification plate 3-1-1 surface, firming agent produces former
Material tiling thickness is between 50mm~70mm;After firming agent raw materials for production have tiled, close and seal lid 1, fit sealing
Lock 2, makes retort 3 reach fully sealed position;
2nd step: the catalyst release 3-1-2 being attached on esterification plate 3-1-1 discharges catalyst, produces former with firming agent
Material produces anabolic effect, produces reaction end gas gas;When reaction end gas concentration detector 3-2 detects reaction tail in retort 3
When gas concentration is higher than 80ppm, feedback signal is sent to controller 9 by reaction end gas concentration detector 3-2, and controller 9 is opened
Reaction end gas discharges electromagnetic valve 7, and reaction end gas is delivered in reaction end gas collecting tank 8 by pipeline;When reaction end gas concentration is examined
Survey device 3-2 and detect that when reaction end gas concentration is less than 8ppm in retort 3, reaction end gas concentration detector 3-2 is by feedback letter
Number being sent to controller 9, controller 9 cuts out reaction end gas and discharges electromagnetic valve 7;
3rd step: the finished product produced during firming agent anabolic effect, the water falling hole inflow finished product stopped on plate 3-4-1 by residue is deposited
Reservoir 5, when during finished product liquid level detector 10 detects finished product memorizer 5, liquid level is higher than 30cm, finished product Level Detection
The signal of telecommunication is sent to controller 9 by device 10, and controller 9 is opened finished product and discharged electromagnetic valve 6, the finished product warp in finished product memorizer 5
Pipeline is discharged;When during finished product liquid level detector 10 detects finished product memorizer 5, liquid level is less than 5cm, finished product liquid level is examined
Surveying device 10 and the signal of telecommunication is sent to controller 9, controller 9 cuts out finished product and discharges electromagnetic valve 6;
4th step: the firming agent synthetic ratio in retort 3 is monitored by firming agent synthetic ratio detector 3-3 in real time, when firming agent synthetic ratio
When detector 3-3 detects firming agent synthetic ratio less than 8%, the signal of telecommunication is sent to controlling by firming agent synthetic ratio detector 3-3
Device 9, controller 9 sends alarm signal to staff;Staff, after receiving alarm signal, is manually pressed by controller
Control knob on 9, controls finished product discharge electromagnetic valve 6 and reaction end gas is discharged electromagnetic valve 7 and opened, and after 10min, work people
Member closes finished product and discharges electromagnetic valve 6 and reaction end gas discharge electromagnetic valve 7;
5th step: staff opens cleaning door 4, cleaning residue stops residue after the reaction on plate 3-4-1;When residue gravity sensing
Device 3-4-5 detects that when residue stops plate 3-4-1 gravity more than 10kg, the signal of telecommunication is sent to by residue gravity sensor 3-4-5
Controller 9, controller 9 controls turning arm 3-4-3 and rotates 25 °~45 °, makes residue stop plate 3-4-1 and produces inclination angle;
When residue gravity sensor 3-4-5 detects that residue stops plate 3-4-1 gravity less than 1.5kg, residue gravity sensor 3-4-5
The signal of telecommunication is sent to controller 9, and controller 9 controls turning arm 3-4-3 and returns back to initial position, makes residue stop plate 3-4-1
It is the level of state;After cleaning out, staff closes cleaning door 4, checks device miscellaneous part, is maintained at closed mode.
The firming agent special reaction device that a kind of repairing heavy metal in soil of the present invention pollutes, these device energy-conserving and environment-protective,
Simple in construction, automaticity is high, and firming agent synthesis rate is high.
The following is the embodiment of the manufacture process of esterification plate 3-1-1 of the present invention, embodiment is to further illustrate
Present disclosure, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, to this
Amendment that inventive method, step or condition are made and replacement, belong to the scope of the present invention.
If not specializing, the conventional means that technological means used in embodiment is well known to those skilled in the art.
Embodiment 1
Manufacture esterification plate 3-1-1 of the present invention according to following steps, and count by weight:
1st step: add the ultra-pure water 786 parts that electrical conductivity is 3.22 μ S/cm in a kettle., start agitator in reactor, turn
Speed is 46rpm, starts heat pump, makes reactor temperature rise to 56 DEG C;It is sequentially added into 4-isopropyl-2-acrylic toluene
70 parts, d-frans-2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropane-carboxylic acid 84 parts, 2-methyl-2-acrylic acid 2-(4-
Quinoline base) ethyl ester 26 parts, stirring is to being completely dissolved, and regulation pH value is 5.3, and agitator speed is adjusted to 186rpm, temperature
It is 87 DEG C, esterification 9 hours;
2nd step: take 2,3,5,6-ptfe benzyls (1R, 3S)-3-(2,2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid's ester 28 parts, (α
-cyano group-1-methyl) cyclobutenyl-2,2-dimethyl-3-(2,2-dichloroethylene) cyclopropanecarboxylcompound 112 parts pulverizes, powder
Particle diameter is 800 mesh;Add the trans-3-of 1R-(2,2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid-(2,3,5,6 ,-tetrafluoro phenyl)
65 parts of mix homogeneously of methyl ester, are laid in pallet, and tiling thickness is 8mm, and employing dosage is 2.5kGy, energy is 3.0
The alpha ray irradiation of MeV 80 minutes, and the β x ray irradiation x of Isodose 66 minutes;
3rd step: the mixed-powder processed through the 2nd step is dissolved in the 3-phenoxy benzyl-2,2-dimethyl-3-(2,2-bis-that concentration is 32ppm
Chlorovinyl) in-1-cyclopropanecarboxylcompound 15 parts, add reactor, agitator speed is 95rpm, and temperature is 76 DEG C, opens
Dynamic vacuum pump makes the vacuum of reactor reach-1.25MPa, keeps this state response 16 hours;Pressure release is also passed through radon gas, makes
Reacting kettle inner pressure is 0.35MPa, and insulation stands 14 hours;Agitator speed is promoted to 120rpm, and simultaneous reactions still is let out
It is depressed into 0MPa;It is sequentially added into IR, S-suitable, trans-2,2-dimethyl-3-(2-metering system-1-base) cyclopropane-carboxylic acid 48 parts, instead
Formula-2, after 3-diaryl replacement-1-1-aminocyclopropane-1-carboxylic acid 58 parts is completely dissolved, add cross-linking agent 63 parts stirring mixing so that anti-
The hydrophile-lipophile balance value answering still solution is 6.2, and insulation stands 5 hours;
4th step: when agitator speed is 147rpm, is sequentially added into 3-(ethylphenyl amino) propionitrile 116 parts, and [[(2-is chloro-for 2-for N-
4,6-dinitrophenyls) azo]-5-(ethylamino)-4-(2-methoxy ethoxy) phenyl] acetamide 38 parts, N-[5-[two (2-acetyl oxygen
Base) ethyl] amino]-2-[(2-chloro-4 nitrophenyl) azo] Phenylpropionamide 59 parts, [[(2-bromo-4,6-dinitrophenyl) is even for 2-for N-
Nitrogen]-5-[(2-cyanoethyl) ethylamino]-4-anisyl] acetamide 68 parts, promote reactor pressure so that it is reach 1.12MPa,
Temperature is 134 DEG C, polyreaction 17 hours;After having reacted, reacting kettle inner pressure is down to 0MPa, is cooled to 24 DEG C,
Discharging, enters molding press and can be prepared by esterification plate 3-1-1;
Described cross-linking agent is double (2-the ethoxy)-4-methyl benzenesulfonamide of N, N-.
Embodiment 2
Manufacture esterification plate 3-1-1 of the present invention according to following steps, and count by weight:
1st step: add the ultra-pure water 1145 parts that electrical conductivity is 4.23 μ S/cm in a kettle., start agitator in reactor,
Rotating speed is 84rpm, starts heat pump, makes reactor temperature rise to 76 DEG C;It is sequentially added into 4-isopropyl-2-acrylic first
Benzene 113 parts, d-frans-2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropane-carboxylic acid 114 parts, 2-methyl-2-acrylic acid 2-
(4-morpholinyl) ethyl ester 53 parts, stirring is to being completely dissolved, and regulation pH value is 6.4, and agitator speed is adjusted to 225rpm,
Temperature is 127 DEG C, esterification 18 hours;
2nd step: take 2,3,5,6-ptfe benzyls (1R, 3S)-3-(2,2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid's ester 52 parts, (α
-cyano group-1-methyl) cyclobutenyl-2,2-dimethyl-3-(2,2-dichloroethylene) cyclopropanecarboxylcompound 195 parts pulverizes, powder
Particle diameter is 1600 mesh;Add the trans-3-of 1R-(2,2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid-(2,3,5,6 ,-tetrafluoro phenyl)
92 parts of mix homogeneously of methyl ester, are laid in pallet, and tiling thickness is 13mm, and employing dosage is 4.6kGy, energy is
The alpha ray irradiation of 9.6MeV 139 minutes, and the β x ray irradiation x of Isodose 115 minutes;
3rd step: the mixed-powder processed through the 2nd step is dissolved in the 3-phenoxy benzyl-2,2-dimethyl-3-(2,2-bis-that concentration is 58ppm
Chlorovinyl) in-1-cyclopropanecarboxylcompound 35 parts, add reactor, agitator speed is 136rpm, and temperature is 118 DEG C,
Starting vacuum pump makes the vacuum of reactor reach-0.84MPa, keeps this state response 24 hours;Pressure release is also passed through radon gas,
Making reacting kettle inner pressure is 0.74MPa, and insulation stands 18 hours;Agitator speed is promoted to 176rpm, simultaneous reactions still
Pressure release is to 0MPa;It is sequentially added into IR, S-suitable, trans-2,2-dimethyl-3-(2-metering system-1-base) cyclopropane-carboxylic acid 70 parts,
Trans-2, after 3-diaryl replacement-1-1-aminocyclopropane-1-carboxylic acid 88 parts is completely dissolved, adds cross-linking agent 104 parts stirring mixing, make
The hydrophile-lipophile balance value obtaining reactor solution is 6.8, and insulation stands 8 hours;
4th step: when agitator speed is 192rpm, is sequentially added into 3-(ethylphenyl amino) propionitrile 164 parts, and [[(2-is chloro-for 2-for N-
4,6-dinitrophenyls) azo]-5-(ethylamino)-4-(2-methoxy ethoxy) phenyl] acetamide 102 parts, N-[5-[two (2-acetyl oxygen
Base) ethyl] amino]-2-[(2-chloro-4 nitrophenyl) azo] Phenylpropionamide 84 parts, [[(2-bromo-4,6-dinitrophenyl) is even for 2-for N-
Nitrogen]-5-[(2-cyanoethyl) ethylamino]-4-anisyl] acetamide 165 parts, promote reactor pressure so that it is reach 1.33MPa,
Temperature is 171 DEG C, polyreaction 25 hours;After having reacted, reacting kettle inner pressure is down to 0MPa, is cooled to 30 DEG C,
Discharging, enters molding press and can be prepared by esterification plate 3-1-1;
Described cross-linking agent is acetoacetyl p-ethoxyaniline.
Embodiment 3
Manufacture esterification plate 3-1-1 of the present invention according to following steps, and count by weight:
1st step: add the ultra-pure water 1561 parts that electrical conductivity is 5.62 μ S/cm in a kettle., start agitator in reactor,
Rotating speed is 108rpm, starts heat pump, makes reactor temperature rise to 89 DEG C;It is sequentially added into 4-isopropyl-2-acrylic
Toluene 156 parts, d-frans-2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropane-carboxylic acid 144 parts, 2-methyl-2-acrylic acid
2-(4-morpholinyl) ethyl ester 78 parts, stirring is to being completely dissolved, and regulation pH value is 7.2, and agitator speed is adjusted to 268rpm,
Temperature is 148 DEG C, esterification 28 hours;
2nd step: take 2,3,5,6-ptfe benzyls (1R, 3S)-3-(2,2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid's ester 79 parts, (α
-cyano group-1-methyl) cyclobutenyl-2,2-dimethyl-3-(2,2-dichloroethylene) cyclopropanecarboxylcompound 269 parts pulverizes, powder
Particle diameter is 2100 mesh;Add the trans-3-of 1R-(2,2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid-(2,3,5,6 ,-tetrafluoro phenyl)
104 parts of mix homogeneously of methyl ester, are laid in pallet, and tiling thickness is 18mm, and employing dosage is 6.8kGy, energy is
The alpha ray irradiation of 16MeV 192 minutes, and the β x ray irradiation x of Isodose 156 minutes;
3rd step: the mixed-powder processed through the 2nd step is dissolved in the 3-phenoxy benzyl-2,2-dimethyl-3-(2,2-bis-that concentration is 84ppm
Chlorovinyl) in-1-cyclopropanecarboxylcompound 53 parts, add reactor, agitator speed is 168rpm, and temperature is 159 DEG C,
Starting vacuum pump makes the vacuum of reactor reach 0.68MPa, keeps this state response 32 hours;Pressure release is also passed through radon gas,
Making reacting kettle inner pressure is 1.02MPa, and insulation stands 22 hours;Agitator speed is promoted to 235rpm, simultaneous reactions still
Pressure release is to 0MPa;It is sequentially added into IR, S-suitable, trans-2,2-dimethyl-3-(2-metering system-1-base) cyclopropane-carboxylic acid 96 parts,
Trans-2, after 3-diaryl replacement-1-1-aminocyclopropane-1-carboxylic acid 115 parts is completely dissolved, adds cross-linking agent 152 parts stirring mixing, make
The hydrophile-lipophile balance value obtaining reactor solution is 7.3, and insulation stands 11 hours;
4th step: when agitator speed is 236rpm, is sequentially added into 3-(ethylphenyl amino) propionitrile 208 parts, and [[(2-is chloro-for 2-for N-
4,6-dinitrophenyls) azo]-5-(ethylamino)-4-(2-methoxy ethoxy) phenyl] acetamide 165 parts, N-[5-[two (2-acetyl oxygen
Base) ethyl] amino]-2-[(2-chloro-4 nitrophenyl) azo] Phenylpropionamide 108 parts, [[(2-bromo-4,6-dinitrophenyl) is even for 2-for N-
Nitrogen]-5-[(2-cyanoethyl) ethylamino]-4-anisyl] acetamide 198 parts, promote reactor pressure so that it is reach 1.57MPa,
Temperature is 208 DEG C, polyreaction 33 hours;After having reacted, reacting kettle inner pressure is down to 0MPa, is cooled to 36 DEG C,
Discharging, enters molding press and can be prepared by esterification plate 3-1-1;
Described cross-linking agent is 2-(6-methyl-2-[4-morpholinodithio azo)-5-diethylamino phenol.
Reference examples
Reference examples is the esterification plate of certain brand commercially available service condition in firming agent building-up process.
Embodiment 4
Esterification plate described in esterification plate 3-1-1 embodiment 1~3 prepared and reference examples carries out using effect contrast.
The two synthesis yield enhancing rate, synthesis strength enhancing rate, implant replacement cycle, firming agent yield enhancing rate are added up,
Result is as shown in table 1.
As seen from Table 1, esterification plate 3-1-1 of the present invention, its synthesis yield enhancing rate, synthesis strength enhancing rate,
The indexs such as implant replacement cycle, firming agent yield enhancing rate are superior to the product that prior art produces.
Additionally, as shown in Figure 6, be esterification plate 3-1-1 materials synthesis stability enhancing rate of the present invention in time
Variation relation figure.Finding out in figure, esterification plate 3-1-1 used by embodiment 1~3, its material surface is long-pending relatively big with volume ratio,
Materials synthesis stability enhancing rate changes over degree and is significantly better than existing product.