CN106905382B - A kind of device of extraction soil hydrophobic humic acid - Google Patents
A kind of device of extraction soil hydrophobic humic acid Download PDFInfo
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- CN106905382B CN106905382B CN201710069441.0A CN201710069441A CN106905382B CN 106905382 B CN106905382 B CN 106905382B CN 201710069441 A CN201710069441 A CN 201710069441A CN 106905382 B CN106905382 B CN 106905382B
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Abstract
The present invention is supplied to a kind of device of extraction soil hydrophobic humic acid, including reaction kettle, pH adjust unit, filtration, purification unit, the first acidification case, the first acid-base value adjusting unit, adsorption and enrichment unit, the second acidification case, the second acid-base value and adjust unit, humic acid extraction unit and general control system；The device of extraction soil hydrophobic humic acid provided by the invention, simple in structure, easy to operate, high degree of automation can easily and effectively detach hydrophobic humic acid and other impurity, obtain high concentration hydrophobicity and dissolve humic acid solution.
Description
Technical field
The present invention relates to humic acid extraction field more particularly to a kind of devices of extraction soil hydrophobic humic acid.
Background technology
Humic acid is the organic mixture formed by complicated materialization and bioprocess by plant and animal residues, accounts for about soil
The 60-80% of total organic matter.
Humic acid plays an important roll in agricultural and environment.At present from the point of view of research, humic acid can stimulate the growth of crop,
Improve soil pH environment, mitigates soil hardening.Humic acid is the carbon source of microorganism.In addition, humic acid can with it is toxic in environment
Heavy metal ion and organic pollution etc. interact, and change pollutant environmental behaviour.Especially hydrophobicity humic acid with
The persistence organic pollutants such as PAHs combine it is more stable, control its transportion and transformation and biological effectiveness.Due in soil
Content of humic acid is totally relatively low, and the soil humic acid extracting method that world humic acid association is recommended at present can only be extracted in soil
The mixture of hydrophobic humic acid and hydrophilic humic acid.Therefore, carrying out soil hydrophobic humic acid extracting method and device research has
Important meaning.
Chinese invention patent (201510586520.X：A kind of method of XAD resin extraction soil small molecular humic acid)
A kind of method of XAD resin extraction soil small molecular humic acid is disclosed, extraction step is：
(a)：Soil treatment：
The sundries such as tree root and stone in natural soil are rejected, after air-drying, it is spare to obtain pedotheque for sieving of milling；
Step b：Sodium pyrophosphate extracts soil humic acid：
Deionized water is added in pedotheque into step a, and solid-to-liquid ratio is made to reach 1:5~1:15, it is adjusted with HCl and NaOH
Then HCl solution is added to solid-to-liquid ratio 1 in pH value of solution=1.0-3.0 thereto：10,20-40h is stood after continuously stirring 4-8h,
It is centrifugally separating to obtain soil solids sample 1；
Deionized water is added into soil solids sample 1, solid-to-liquid ratio is made to reach 1:3~1:5, it is adjusted with HCl and NaOH molten
Liquid pH=6-8 obtain solid-liquid mixed solution；Under the conditions of nitrogen protection, it is molten that sodium pyrophosphate solution is added into solid-liquid mixed solution
Liquid is used in combination deionized water to dilute, and makes a concentration of 0.1-0.2mol/L of sodium pyrophosphate, is stood again after continuing 4-8h of agitating solution
20-40h are centrifugally separating to obtain supernatant and soil solids sample 2；
Under the conditions of nitrogen protection, HCl is added into the supernatant, makes pH value of solution=1.0-3.0, stirs 15-30min
Afterwards, 20-40h are stood, humic acid sample 1 is centrifugally separating to obtain；
Step c:Sodium hydroxide extracts soil humic acid：
Deionized water is added into the soil solids sample 2 of step b, solid-to-liquid ratio is made to reach 1:3~1:5, with HCl and NaOH
Its pH=6-8 is adjusted, solidliquid mixture is obtained；Under the conditions of nitrogen protection, NaOH solution is added into solidliquid mixture, and
It is diluted with deionized water, it is 0.1-0.2mol/L to make NaOH concentration in solution, and 20-are stood again after continuing 1-4h of agitating solution
40h is centrifugally separating to obtain supernatant and soil residue；
Under the conditions of nitrogen protection, dense HCl is added into the supernatant, makes pH value of solution=1.0-3.0, stirring 15-
30min stands 20-40h afterwards, is centrifugally separating to obtain humic acid sample 2；
Merge humic acid sample 1 and humic acid sample 2, labeled as slightly carrying humic acid sample；
Step d:Remove fulvic acid impurity in humic acid：
HCl solution is added to thick carry in humic acid sample obtained by step c, makes its pH=1.0-3.0 and solid-to-liquid ratio 1:
5—1:10,4-8h are persistently stirred, and stand 20-40h, centrifugation obtains humic acid sample and supernatant；
It is dissolved by humic acid sample according to the method repetitive operation in step d, in the supernatant after centrifugation total
Organic carbon content<After 0.5mg/L, centrifugation obtained solid is collected, and labeled as humic acid sample after purification；
Step e:The separation of macromolecular humic acid and small molecule humic acid：
Under the conditions of nitrogen protection, the purifying humic acid sample obtained in step d is dissolved with NaOH, deionized water is added
Make solution humic acid concentration=10-100g/L, adjusts pH==6-8 with HCl and NaOH, obtain humic acid solution；
Humic acid solution is moved into 10000 dalton bag filters, and bag filter is placed in ultra-pure water, composition dialysis body
20-40h stir in system, and small molecule humic acid enters ultra-pure water by bag filter, forms small molecule humic acid solution；
Step f:Remove the siliceous mineral matter in small molecule humic acid：
Make its pH=1.0-3.0 with HCl acidifications small molecule humic acid solution, HF is added, stirs 15-30min, stands
20—40h；
Step g:The enrichment of small molecule humic acid is extracted：
Step f small molecular humic acid solutions are adjusted into pH=1-3 with HCl and NaOH, with 10-15 times of column volumes/h speed
Degree passes through 8 resin columns of XAD-；
Then 8 resin columns of XAD-are eluted with the speed of 10-15 times of column volume/h with 0.5-1 times of column volume ultra-pure water,
Discard efflux；
Again with 1-2 times of column volume NaOH solutions and 2-3 times of column volume ultra-pure waters successively with the speed of 3-10 times of column volume/h
Degree, elutes 8 resin columns of XAD-, and efflux exchanges tree with the speed of 3-10 times of column volume/h by the hydrogen ion that hydrogen ion is saturated
Fat removes sodium ion, and finally obtained efflux is freeze-dried to obtain soil small molecule humic acid constituents.
Soil humic acid extracting method disclosed in foregoing invention mainly utilizes the characterization of adsorption of XAD-8 resins, by small point
Sub- humic acid is adsorbed onto under the conditions of certain ph on XAD-8 resins, then by parsing, ion exchange, freeze-drying, is finally obtained
The humic acid of small molecule is obtained, the method depends on laboratory and a large amount of manual operation, and process is complicated, the degree of automation is low, rotten
The extracted amount for growing acid is few, and method is also not suitable for extensive sample collection, and exploitativeness is bad.
Invention content
It is including anti-in order to solve the above technical problem, the present invention provides a kind of device of extraction soil hydrophobic humic acid
It answers kettle, pH to adjust unit, filtration, purification unit, the first acidification case, the first acid-base value and adjusts unit, adsorption and enrichment unit, second
It is acidified case, the second acid-base value adjusts unit, humic acid extraction unit and general control system；It is characterized in that,
The outlet that the entrance of the reaction kettle adjusts unit with the pH is connect, the outlet of reaction kettle and the filtration, purification
The entrance of unit connects, and the outlet of the filtration, purification unit is connect with the entrance of the first acidification case, first acidification
The outlet that the entrance of case also adjusts unit with first acid-base value is connect；The outlet and the absorption of the first acidification case are rich
Collect the entrance connection of unit, the outlet of the adsorption and enrichment unit is connect with the entrance of the second acidification case, the second acidification case
Entrance also with second acid-base value adjust unit outlet connect, it is described second be acidified case outlet also with the humic acid
The entrance of extraction unit connects；
The pH adjusts unit, the first acid-base value adjusts unit, the second acid-base value adjust unit with the master control system
System connection.
Preferably, the humic acid extraction unit includes the second elution device, the second filter and liquid memory；It is described
The outlet of second elution device is connect with the entrance of second filter, and the entrance of second filter is also with described second
It is acidified the outlet connection of case, the outlet of second filter is connect with the entrance of the liquid memory.
Pipeline between the second acidification case and second filter stretches into the second acidification case, described to stretch into the second acid
The duct height value for changing case is the 1/20-1/10 of the second acidification case height, and it is externally provided with protective cover, is set on the protective cover
It is 100 μm of hole to have multiple apertures；
Preferably, second filter includes sample room, filter membrane and sand core, and the filter membrane is set in the sample room,
And supported by sand core, the aperture value range of the filter membrane is 0.1-0.7 μm；
The lower part of the liquid memory is equipped with liquid discharge valve.
Preferably, it includes the first metering dosing pump and the first chemicals dosing plant, the first metering dosing pump that the pH, which adjusts unit,
Between first chemicals dosing plant and the reaction kettle, the entrance of the first metering dosing pump is filled with first dosing
The outlet of the outlet connection set, the first metering dosing pump is connect with the entrance of the reaction kettle.
Preferably, soil storage room is equipped in the reaction kettle, the soil storage room is supported by holder and is set to reaction
In kettle；The outer wall of the soil storage room is equipped with the hole that multiple apertures are less than 1mm.
Pipeline between the first acidification case and the adsorption and enrichment device stretches into the first acidification case, described to stretch
The duct height value for entering the first acidification case is the described first 1/30-1/20 for being acidified case height, and it is externally provided with protective cover, institute
State the hole that protective cover is 100 μm equipped with multiple apertures；
Preferably, the filtration, purification unit includes first filter and vacuum pump, and the entrance of the first filter is logical
Piping is connect with the outbound of the reaction kettle, and the outlet of the first filter is connect with the entrance of the first acidification case；
The vacuum pump is connect with the first acidification case.
Preferably, the pipeline between the reaction kettle and the first filter stretches into reaction kettle, described to stretch into reaction kettle
Duct height value be reaction kettle height 1/20-1/10, and it is externally provided with protective cover, and the protective cover is equipped with multiple holes
Diameter is the hole of 1mm.
Preferably, the reaction kettle uses alkali resistant materials, is equipped with sealing cover above, lower end is funnel shaped, reaction kettle
Inside it is additionally provided with blender, liquid level sensor and pH sensors；The end face of the sealing cover is equipped at least five through-hole.
Preferably, the pipeline between the first filter and the first acidification case stretches into the first acidification case, described
The pipeline for stretching into the first acidification case is located in the first acidification case on liquid level；The air entry of the vacuum pump is located at described the
In one acidification case on liquid level.
Preferably, it includes pH sensors, blender, the first acid solution chemical tank, second that first acid-base value, which adjusts unit,
Acid solution chemical tank and the second metering dosing pump；The pH sensors and blender are set to described first and are acidified in case；Described first
Acid solution chemical tank and the second acid solution chemical tank are arranged in juxtaposition；It is described second metering dosing pump entrance respectively with the first acid solution medicament
The outlet of case, the outlet of the second acid solution chemical tank connection, the entrance of the outlet of the second metering dosing pump and the first acidification case
Connection.
Preferably, the adsorption and enrichment unit includes adsorption and enrichment device, the first elution device and the second chemicals dosing plant, institute
The entrance for stating adsorption and enrichment device is connect with the outlet of the first filter, the outlet of adsorption and enrichment device and second acid
Change the entrance connection of case；The outlet of first elution device, the outlet of the second chemicals dosing plant are filled with the adsorption and enrichment respectively
The entrance connection set；The bottom of the adsorption and enrichment device is equipped with waste liquid dump valve.
Preferably, the adsorption and enrichment device includes adsorption column and filler, and the filler is set in the adsorption column, described
Filler is the one or more of XAD-8 resins, DAX-8 resins, XAD-7 resins and XAD-4.
Preferably, it includes pH sensors, blender, third acid solution chemical tank, the 4th acid solution that the second acid-base value, which adjusts unit,
Chemical tank and third measure dosing pump；The pH sensors and blender are set to described second and are acidified in case；The third acid solution
Chemical tank and the 4th acid solution chemical tank are arranged in juxtaposition；The entrance of third metering dosing pump respectively with third acid solution chemical tank
Outlet, the outlet of the 4th acid solution chemical tank connection, the outlet of third metering dosing pump are connect with the entrance of the second acidification case.
Preferably, the general control system includes control unit and touch screen device, described control unit with the reaction kettle
Interior pH sensors, blender, liquid level sensor, the first metering dosing pump, the second metering dosing pump, third metering dosing pump,
Vacuum pump, the first acidification case and the pH sensors in the second acidification case, blender control connection；The pH sensors are equipped with lifting
Platform.
The method for carrying out the extraction of soil hydrophobic humic acid using the device of extraction soil hydrophobic humic acid comprising following step
Suddenly：
(1) soil is added in soil storage room, and pure water is injected into reaction kettle；
(2) start pH and adjust unit, the first metering dosing pump is received starts lye positioned at pH sensor signals in reaction kettle
Program is added, the first chemicals dosing plant injects lye into reaction kettle by the pipeline of resistance to highly basic, while starting the stirring in reaction kettle
Motor keeps lye evenly dispersed, and until reaching preset pH value, the first metering dosing pump is stopped；
(3) outlet valve of reaction kettle is opened, while starting vacuum pump, is pressed by vacuum pump, the solution in reaction kettle
The first acidification case is flowed into through first filter, the insoluble impurity of alkali is removed by membrane retention, is removed the liquid after impurity and is passed through filter
Film flows into the first acidification case；
(4) start the first acid-base value and adjust the first adjusting that unit carries out acid-base value, the second metering dosing pump reception is located at
The pH sensor signals being acidified in case start acid solution and program are added, and the second metering dosing pump is by first passage from the first acid solution medicine
Agent case extracts acid solution and injects non-oxidizable acid solution into acidification case by the first acid-resistant pipeline, while starting in acidification case and stirring horse
It reaching so that acid solution is evenly dispersed, until reach preset pH value, the second metering dosing pump first passage acid liquid program stopped work
Make, sensor lifting platform rises pH sensor probes；
Second metering dosing pump extracts hydrofluoric acid from the second acid solution chemical tank by second channel and passes through the second acid-resistant pipeline
In injection acidification case, until reaching preset hydrofluoric acid concentration, the second metering dosing pump is stopped；
(5) after completing first pH value adjusting, the outlet valve of the first acidification case is opened, liquid passes through in the first acidification case
Pipeline flows into adsorption and enrichment device, after the completion of absorption, the switch between the first elution device of opening and adsorption and enrichment device, and first
Pure water in elution device opens the waste liquid dump valve of adsorption and enrichment bottom of device by pipe flushing adsorption and enrichment device,
Flushing waste is discharged by pipeline, completes the flushing of adsorption and enrichment device, and closes waste liquid dump valve；
After completing the flushing of adsorption and enrichment device, the outlet valve of elution device is closed, opens the outlet of the second chemicals dosing plant
Valve, the second chemicals dosing plant inject lye by alkaline-resisting pipeline into adsorption and enrichment device, and natural by resin adsorption is dissolved with
Machine matter desorbs under the action of lye, and the liquid after desorption flows into the second acidification case through pipeline；
(6) start the second acid-base value and adjust the adjusting again that unit carries out acid-base value, third metering dosing pump reception is located at
PH sensor signals in second acidification case start acid solution and program are added, and it is sour from third by third channel that third measures dosing pump
Liquid chemical tank extracts acid solution and injects non-oxidizable acid solution into acidification case by third acid-resistant pipeline, while starting and being stirred in acidification case
Mix motor so that acid solution is evenly dispersed, until reaching preset pH value, third metering dosing pump third channel acid liquid program is stopped
It only works, sensor lifting platform rises pH sensor probes；
Third measures dosing pump and passes through the 4th acid-resistant pipeline from the 4th acid solution chemical tank extraction hydrofluoric acid by fourth lane
In injection acidification case, until reaching preset hydrofluoric acid concentration, third metering dosing pump is stopped；
(7) after completing secondary acid-base value adjusting, the outlet valve of the second acidification case is opened, while starting vacuum pump, is passed through
Vacuum pump presses, and by the membrane filtration in the second filter, hydrophobic humic acid is cut the organic matter solution in the second acidification case
It stays in above filter membrane, impurity flows into liquid memory；
(8) after organic matter completes filtering, the outlet valve of the second acidification case is closed, the outlet valve of the second elution device is opened
Door, under vacuum pump pressure, the pure water in the second elution device flows into the second filter by pipeline, is carried out to slightly carrying humic acid
It rinses, flushing liquor flows directly into liquid memory, and the liquid in liquid memory is fallen by dump valve direct emission, stays in filter
Organic matter on film is the soil hydrophobic humic acid of required extraction.
Preferably, the lye in first chemicals dosing plant is to be saturated or be closely saturated strong base solution, the pipeline of resistance to highly basic
It is required that saturation highly basic can be born；The pH preset values of liquid are 10-14 in the reaction kettle；Lye in second chemicals dosing plant
For the strong base solution of 0.1mol/L, the alkaline-resisting requirements for pipes can bear the highly basic of 0.5mol/L.
Preferably, first acid-resistant pipeline, third acid-resistant pipeline require that the non-oxidizable strong acid of 10mol/L can be born；
Second acid-resistant pipeline, the 4th acid-resistant pipeline require that the hydrofluoric acid of 6mol/L can be born；The first acidification case, the second acidification
The pH preset values of case are 0.5-1.5, and the preset concentration of hydrofluoric acid is 0.01-1mol/L.
Preferably, general control system uses low-voltage distribution, and the voltage class of power supplying and distributing equipment is 220VAC, and sets low pressure and match
Electric cabinet is powered to process system power-equipment；Power switch in control system is protected with power control cabinet gate interlock, can be reached anti-
Dirt, rapid heat dissipation and the effect being easily installed.
Compared with prior art, the beneficial effect comprise that：
(1) device of extraction soil hydrophobic humic acid provided by the invention, simple in structure, easy to operate, the degree of automation
Hydrophobic humic acid can be detached easily and effectively with impurity such as hydrophilic humic acid, fulvic acid, it is molten to extract a large amount of hydrophobicity by height
Humic acid is solved, extracted humic acid is preferably utilized；
(2) reaction kettle, the first acidification case, the second acidification bottom portion are funnel shaped, stretch into the height of reaction kettle pipeline
Value is the 1/20-1/10 of the height of reaction kettle, stretches into the first acidification case, the height value of the second pipeline for being acidified case is first
It is acidified the 1/30-1/20 of case height, reaction kettle, the first acidification case, the second pipeline for being acidified case is stretched into and is externally provided with filter mantle, both may be used
To ensure to collect humic acid to greatest extent, unit efficiency is improved, and effectively impurity particle can be prevented to be mixed into sample,
It ensure that the purity of extracting solution；
(3) it is full automatic that pH value, which is adjusted, the first acid-base value adjusts unit, the second acid-base value adjusts unit, is saved
The accuracy rate of labour, the pH value of adjusting are relatively high；First acid solution chemical tank and the second acid solution chemical tank share a metering and add
Teat pipette, third acid solution chemical tank and the 4th acid solution chemical tank share a metering dosing pump, are adjusted by advanced optimizing pH value
Unit, the first acid-base value adjust unit and the second acid-base value adjusts unit and can share the metering dosing pump of a multichannel, into one
Step reduces production cost；First acidification case, the second acidification case, liquid memory share a vacuum pump, reduce production cost；
It is such as not high to hydrophobic humic acid purity requirement, it can be not provided with the first elution device and the 4th acid solution medicament to further save cost
Case.
(4) reaction kettle has reserved inert gas entrance and outlet, in production by being passed through the indifferent gas such as nitrogen, helium
Body can effectively inhibit soil humic acid full constituent under strong alkaline condition to aoxidize.
Description of the drawings
Fig. 1 is a kind of process flow chart of the device of extraction soil hydrophobic humic acid provided by the invention.
Specific implementation mode
Below in conjunction with the accompanying drawings, the specific implementation mode of the present invention is described in detail.
Join shown in Fig. 1, Fig. 1 is a kind of process flow chart of the device of extraction soil hydrophobic humic acid provided by the invention.
The device of extraction soil hydrophobic humic acid provided by the invention, including reaction kettle 1, pH adjust unit, filtration, purification unit, first
It is acidified case 8, the first acid-base value adjusts unit, adsorption and enrichment unit, the second acidification case 22, the second acid-base value adjust unit, humic
Sour extraction unit and general control system 6；Wherein, soil storage room 2, holder 3, blender, liquid level sensor are equipped in reaction kettle 1
With pH sensors, soil storage room 2 is supported by holder 3 and in reaction kettle 1, and the outer wall of soil storage room 2 is equipped with multiple holes
Diameter is less than the hole of 1mm；It includes the first metering dosing pump 4 and the first chemicals dosing plant 5 that pH, which adjusts unit,；Filtration, purification unit includes the
Include sample room 71, filter membrane 72 and sand core 73 in one filter 7 and vacuum pump 12, wherein first filter 7, filter membrane 72 is set to sample
In product room 71, and supported by sand core 73；It includes the second metering dosing pump 9, the first acid solution chemical tank that first acid-base value, which adjusts unit,
10 and the second acid solution chemical tank 11；Adsorption and enrichment unit includes the first elution device 16, the second chemicals dosing plant 17 and adsorption and enrichment
Device 18；It includes third metering dosing pump 19, third acid solution chemical tank 20 and the 4th acid solution medicament that second acid-base value, which adjusts unit,
Case 21；Humic acid extraction unit includes the second elution device 13, vacuum pump 12, the second filter 14 and liquid memory 15,
In, the second filter 14 includes sample room 141, filter membrane 142 and sand core 143, and filter membrane 142 is set in sample room 141, and by sand core
143 supports；Mainly using automatically controlling, collection control operation therein is unified in switch board to be carried out general control system 6, can be made entire
System realization automatically controls operation and manual operation.
Wherein, the first chemicals dosing plant 5 is connect by the first metering dosing pump 4 with reaction kettle 1, the first metering dosing pump 4
Entrance is connect with the first chemicals dosing plant 5, and outlet is connect with reaction kettle 1；The entrance of the outlet and first filter 7 of reaction kettle 1
Connection, the connecting pipe between reaction kettle 1 and first filter 7 stretch into reaction kettle 1, stretch into the height value of reaction kettle pipeline
For the 1/20-1/10 of 1 height of reaction kettle, and it is externally provided with protective cover, and the protective cover is equipped with the hole that multiple apertures are 1mm；
The outlet of first filter 7 is connect with the first acidification case 8, and the air entry of vacuum pump 12 is placed in liquid in the cavity of the first acidification case 8
On face；First acid solution chemical tank 10 and the second acid solution chemical tank 11 are arranged in juxtaposition, and the second metering dosing pump 9 is set to the first acid solution
Between chemical tank 10 and the second acid solution chemical tank 11, the outlet of the entrance and the first acid solution chemical tank 10 of the second metering dosing pump 9,
The outlet of second acid solution chemical tank 11 connects, and the outlet of the second metering dosing pump 9 is connect with the first acidification case 8, the first acidification case 8
Outlet connect with the entrance of adsorption and enrichment device 18；Pipeline between first acidification case 8 and adsorption and enrichment device 18 stretches into the
In one acidification case 8, the duct height value for stretching into the first acidification case 8 is the 1/30-1/20 of the first acidification 8 height of case, and
It is externally provided with protective cover, and the protective cover is equipped with the hole that multiple apertures are 100 μm；The entrance of adsorption and enrichment device 18 is also with
The outlet of one elution device 16, the outlet of the second chemicals dosing plant 17 connection, the outlet of adsorption and enrichment device 18 and the second acidification case
22 entrance connection, the air entry of vacuum pump 12 are placed in the cavity of the second acidification case 22；
Third acid solution chemical tank 20 and the 4th acid solution chemical tank 21 are arranged in juxtaposition, and third measures dosing pump 19 and is set to third acid
Between liquid chemical tank 20 and the 4th acid solution chemical tank 21, third measures the entrance of dosing pump 19 and going out for third acid solution chemical tank 20
The outlet connection of mouth, the 4th acid solution chemical tank 21, the outlet of third metering dosing pump 19 are connect with the entrance of the second acidification case 22；
The outlet of second acidification case 22 is connect with the entrance of the second filter 14, the entrance of the second filter 14 also with the second elution device
13 outlet connection, the outlet of the second filter 14 are connect with the entrance of liquid memory 15, and the air entry of vacuum pump 12 is placed in
In the cavity of liquid memory 15 on liquid level, the lower part of liquid memory is equipped with waste liquid dump valve.
Pipeline between second acidification case 22 and the second filter 14 stretches into the second acidification case 22, described to stretch into the second acid
The duct height value for changing case 22 is the 1/20-1/10 of the second acidification 22 height of case, and it is externally provided with protective cover, the protective cover
It is equipped with the hole that multiple apertures are 100 μm；General control system 6 includes control unit and touch screen device, and control unit connects with touch screen device
It connects, control unit measures dosing pump 9, vacuum with blender, liquid level sensor, pH sensors, the first metering dosing pump 4, second
12 connection of pump.
General control system uses low-voltage distribution, and the voltage class of power supplying and distributing equipment is 220VAC, and sets low-voltage distribution cabinet, to
Process system power-equipment is powered.In addition, the switch board and electric switch of outfit independent operation and electrical member in control system
Part all concentrates in switch board, power switch and power control cabinet gate interlock are protected, and can reach dust-proof, rapid heat dissipation and be easily installed
Effect.
General supply and start button are first turned on, keeps whole system in running order, one is added into soil storage room 2
Pedotheque after quantitative grinding, and close soil storage room 2；Start water filling program, pure water is added into reaction kettle 1, reacts
Liquid level sensor in kettle 1 is detected the water level in reaction kettle 1, when water level reaches the 4/5 of reaction kettle total volume, liquid level
Sensor sends liquid level signal to general control system, stops the injecting process.
It is passed through inert gas into reaction kettle 1, under the protection of inert gas, starts pH and adjusts unit, the first metering adds
Teat pipette 4 receives the pH sensor signals being located in reaction kettle 1 and starts lye addition program, and the first chemicals dosing plant 5 passes through resistance to highly basic
Pipeline injects lye into reaction kettle 1, while starting the stirring motor in reaction kettle 1 so that lye is evenly dispersed, until reaching
Preset pH value, the first metering dosing pump 4 are stopped.
Lasting to stir, the pedotheque leaching liquid in soil storage room 2 stores the hole on chamber outer wall by soil and flows into instead
It answers in kettle 1.2 outer wall of soil storage room is equipped with the hole that multiple apertures are less than 1mm, can effectively prevent impurity in soil into
Enter into the liquid of reaction kettle 1；Wherein reaction kettle 1 uses alkali resistant materials, is equipped with sealing cover above, and lower end is funnel shaped,
Blender, liquid level sensor and pH sensors are equipped in it, the end face of the sealing cover is equipped at least five through-hole.
The outlet valve of reaction kettle 1 is opened, while starting vacuum pump 12, is pressed by vacuum pump 12, it is molten in reaction kettle 1
Liquid flows into the first acidification case 8 through first filter 7, and the insoluble impurity of alkali is removed by membrane retention, and it is logical to remove the liquid after impurity
Filter membrane flows into the first acidification case 8；
Start the first acid-base value and adjust the first adjusting that unit carries out acid-base value, the second metering pump of dosing 9, which receives, is located at the
Program is added in pH sensor signals startup acid solution in one acidification case 8, and the second metering dosing 9 pump is sour from first by first passage
Liquid chemical tank 10 extracts acid solution and injects non-oxidizable acid solution into acidification case by the first acid-resistant pipeline, while starting in acidification case
Stirring motor so that acid solution is evenly dispersed, until reach preset pH value, the second metering 9 first passage acid liquid journey of dosing pump
Sequence is stopped, and sensor lifting platform rises pH sensor probes；
Second metering dosing pump 9 extracts hydrofluoric acid from the second acid solution chemical tank 11 by second channel and passes through the second acid-proof pipe
In road injection acidification case, until reaching preset hydrofluoric acid concentration, the second metering dosing pump 9 is stopped；
After completing first pH value adjusting, the outlet valve of the first acidification case 8 is opened, liquid passes through in the first acidification case 8
Pipeline flows into adsorption and enrichment device 18, after the completion of absorption, opens opening between the first elution device 16 and adsorption and enrichment device 18
It closes, the pure water in the first elution device 16 opens 18 bottom of adsorption and enrichment device by pipe flushing adsorption and enrichment device 18
Waste liquid dump valve, flushing waste is discharged by pipeline, completes the flushing of adsorption and enrichment device 18, and closes waste liquid dump valve；
After completing 18 flushing of adsorption and enrichment device, the outlet valve of the first elution device 16 is closed, opens the second dosing dress
17 outlet valve is set, the second chemicals dosing plant 17 injects lye into adsorption and enrichment device 18 by alkaline-resisting pipeline, inhaled by resin
Attached natural dissolved organic matter desorbs under the action of lye, and under inert gas protection, the liquid after desorption is through pipeline
Flow into the second acidification case 22；
Start the second acid-base value and adjust the adjusting again that unit carries out acid-base value, third, which is measured dosing pump 19 and received, is located at the
PH sensor signals in diacid case start acid solution and program are added, and it is sour from third by third channel that third measures dosing pump 19
Liquid chemical tank 20 extracts acid solution and injects non-oxidizable acid solution into acidification case by third acid-resistant pipeline, while starting in acidification case
Stirring motor so that acid solution is evenly dispersed, until reaching preset pH value, third measures 19 third channel acid liquid journey of dosing pump
Sequence is stopped, and sensor lifting platform rises pH sensor probes；
It is acidproof by the 4th from the 4th acid solution chemical tank 21 extraction hydrofluoric acid by fourth lane that third measures dosing pump 19
In pipeline injection acidification case, until reaching preset hydrofluoric acid concentration, third metering dosing pump 19 is stopped；
After completing secondary acid-base value adjusting, the outlet valve of the second acidification case 22 is opened, while starting vacuum pump 12, is passed through
Vacuum pump 12 presses, and the organic matter solution in the second acidification case 22 passes through the membrane filtration in the second filter, hydrophobic humic acid
It is trapped within above filter membrane, impurity flows into liquid memory；
After organic matter completes filtering, the outlet valve of the second acidification case 22 is closed, the outlet of the second elution device 13 is opened
Valve, the pure water in the second elution device 13 flow into the second filter 14 by pipeline, are rinsed to slightly carrying humic acid, rinsed
Liquid flows directly into liquid memory 15, and the liquid in liquid memory 15 is fallen by dump valve direct emission, stays in filter membrane 142
On organic matter be required extraction soil hydrophobic humic acid.
PH value adjusts unit, the first acid-base value adjusts unit, the second acid-base value adjusts the process that the pH value in unit is adjusted
It is full automatic process, saves labour, reduces production cost, and the accuracy for the pH value modulated is relatively high, matches
The process efficiency of system is also higher.In pH adjustment processes, turn on agitator motor makes blender stirred autoclave 1, first be acidified
Case 8, second is acidified the liquid in case 22, and the pH value that can avoid part is higher or relatively low.Such as not to the purity requirement of hydrophobic humic acid
Height can be not provided with the first elution device 16 and the 4th acid solution chemical tank to further save cost.
The filter membrane used in the first filter is disposable filter membrane, and filter membrane needs to be resistant to 1mol/L highly basic, filter membrane
It stores and uses as required, but the siliceous filter membrane such as unusable glass fiber filter；The filter membrane used in second filter
For disposable filter membrane, filter membrane needs to be resistant to 0.5mol/L strong acid, and filter membrane is stored and used as required, but unusable glass fibers
Tie up the siliceous filter membranes such as filter membrane.
A series of detailed description described above is illustrated only for feasible embodiment of the invention,
They are not to limit the scope of the invention, in the knowledge that the technical field those of ordinary skill has
Interior, the various change made without departing from the purpose of the present invention all belongs to the scope of protection of the present invention.
Claims (9)
1. a kind of device of extraction soil hydrophobic humic acid, including reaction kettle, pH adjust unit, filtration, purification unit, the first acid
Change case, the first acid-base value adjusts unit, adsorption and enrichment unit, the second acidification case, the second acid-base value adjust unit, humic acid extraction
Unit and general control system；It is characterized in that,
The outlet that the entrance of the reaction kettle adjusts unit with the pH is connect, the outlet of reaction kettle and the filtration, purification unit
Entrance connection, the entrance that the outlet of the filtration, purification unit is acidified case with described first connect, and described first is acidified case
The outlet that entrance also adjusts unit with first acid-base value is connect；The outlet of the first acidification case and the adsorption and enrichment list
The entrance connection of member, the outlet of the adsorption and enrichment unit are connect with the entrance of the second acidification case, and the second acidification case enters
The outlet that mouth also adjusts unit with second acid-base value is connect, and the outlet of the second acidification case is also extracted with the humic acid
The entrance of unit connects；
The pH adjusts unit, the first acid-base value adjusts unit, the second acid-base value adjusts unit and connects with the general control system
It connects；
Soil storage room is equipped in the reaction kettle, the soil storage room is supported by holder and is set in reaction kettle；The soil
The outer wall of earth storage room is equipped with the hole that multiple apertures are less than 1mm；
The reaction kettle uses alkali resistant materials, is equipped with sealing cover above, lower end is funnel shaped, and stirring is additionally provided in reaction kettle
Device, liquid level sensor and pH sensors；The end face of the sealing cover is equipped at least five through-hole；
The filtration, purification unit includes first filter and vacuum pump, the entrance of the first filter by pipeline with it is described
The outbound of reaction kettle connects, and the outlet of the first filter is connect with the entrance of the first acidification case；The vacuum pump with
The first acidification case connection；
Pipeline between the reaction kettle and the first filter stretches into reaction kettle, and the duct height for stretching into reaction kettle takes
Value is the 1/20-1/10 of reaction kettle height, and it is externally provided with protective cover, and the protective cover is equipped with the hole that multiple apertures are 1mm；
Pipeline between the first filter and the first acidification case stretches into the first acidification case, described to stretch into the first acidification
The pipeline of case is located at described first and is acidified in case on liquid level；The air entry of the vacuum pump is located at described first and is acidified liquid in case
On face.
2. the device of extraction soil hydrophobic humic acid as described in claim 1, which is characterized in that the humic acid extraction unit
Including the second elution device, the second filter and liquid memory；It is filtered with described second the outlet of second elution device
The entrance of device connects, and the entrance of second filter is also connect with the outlet of the second acidification case, second filter
Outlet connect with the entrance of the liquid memory；
Pipeline between the second acidification case and second filter stretches into the second acidification case, described to stretch into second
The duct height value for being acidified case is the 1/30-1/20 of the second acidification case height, and it is externally provided with protective cover, on the protective cover
The hole for being 100 μm equipped with multiple apertures；
Second filter includes sample room, filter membrane and sand core, and the filter membrane is set in the sample room, and by sand core branch
The aperture value range of support, the filter membrane is 0.1-0.7 μm；
The lower part of the liquid memory is equipped with liquid discharge valve.
3. the device of extraction soil hydrophobic humic acid as described in claim 1, which is characterized in that the pH adjusts unit and includes
First metering dosing pump and the first chemicals dosing plant, the first metering dosing pump be set to first chemicals dosing plant and the reaction kettle it
Between, the entrance of the first metering dosing pump is connect with the outlet of first chemicals dosing plant, the first metering dosing pump
Outlet is connect with the entrance of the reaction kettle；
Pipeline between the first acidification case and the adsorption and enrichment device stretches into the first acidification case, described to stretch into the
The duct height value of one acidification case is the described first 1/30-1/20 for being acidified case height, and it is externally provided with protective cover, the guarantor
Shield is equipped with the hole that multiple apertures are 100 μm.
4. the device of extraction soil hydrophobic humic acid as described in claim 1, which is characterized in that first acid-base value is adjusted
Unit includes pH sensors, blender, the first acid solution chemical tank, the second acid solution chemical tank and the second metering dosing pump；The pH
Sensor and blender are set to described first and are acidified in case；The first acid solution chemical tank and the second acid solution chemical tank cloth arranged side by side
It sets；The entrance of the second metering dosing pump connects with the outlet of the first acid solution chemical tank, the outlet of the second acid solution chemical tank respectively
It connects, the outlet of the second metering dosing pump is connect with the entrance of the first acidification case.
5. the device of extraction soil hydrophobic humic acid as described in claim 1, which is characterized in that the adsorption and enrichment unit packet
Include adsorption and enrichment device, the first elution device and the second chemicals dosing plant, the entrance of the adsorption and enrichment device and first mistake
The outlet of filter connects, and the outlet of adsorption and enrichment device is connect with the entrance of the second acidification case；First elution device
Outlet, the second chemicals dosing plant outlet connect respectively with the entrance of the adsorption and enrichment device；The adsorption and enrichment device
Bottom is equipped with waste liquid dump valve.
6. the device of extraction soil hydrophobic humic acid as described in claim 1, which is characterized in that the second acid-base value adjusts unit
Dosing pump is measured including pH sensors, blender, third acid solution chemical tank, the 4th acid solution chemical tank and third；The pH sensings
Device and blender are set to described second and are acidified in case；The third acid solution chemical tank and the 4th acid solution chemical tank are arranged in juxtaposition；Institute
The entrance for stating third metering dosing pump is connect with the outlet of the outlet of third acid solution chemical tank, the 4th acid solution chemical tank respectively, the
The outlet of three metering dosing pumps is connect with the entrance of the second acidification case.
7. the device of extraction soil hydrophobic humic acid as described in claim 1, which is characterized in that the general control system includes
Control unit and touch screen device, described control unit in the reaction kettle pH sensors, blender, liquid level sensor,
In one metering dosing pump, the second metering dosing pump, third metering dosing pump, vacuum pump, the first acidification case and the second acidification case
PH sensors, blender control connection；The pH sensors are equipped with lifting platform.
8. carrying out soil hydrophobic humic acid using the device of any extraction soil hydrophobic humic acid of claim 1-7 to extract
Method, which is characterized in that it includes the following steps：
(1) soil is added in soil storage room, and pure water is injected into reaction kettle；
(2) start pH and adjust unit, the first metering dosing pump reception starts lye positioned at pH sensor signals in reaction kettle and is added
Program, the first chemicals dosing plant inject lye into reaction kettle by the pipeline of resistance to highly basic, while starting the stirring motor in reaction kettle,
Keep lye evenly dispersed, until reaching preset pH value, the first metering dosing pump is stopped；
(3) outlet valve for opening reaction kettle, while starting vacuum pump, is pressed by vacuum pump, and the solution in reaction kettle is through the
One filter flows into the first acidification case, and the insoluble impurity of alkali is removed by membrane retention, is removed the liquid after impurity and is passed through filter membrane stream
Enter the first acidification case；
(4) start the first acid-base value and adjust the first adjusting that unit carries out acid-base value, the second metering dosing pump, which receives, is located at acidification
PH sensor signals in case start acid solution and are added program, and the second metering dosing pump is by first passage from the first acid solution chemical tank
It extracts acid solution and non-oxidizable acid solution is injected into acidification case by the first acid-resistant pipeline, while starting stirring motor in acidification case,
So that acid solution is evenly dispersed, until reach preset pH value, the second metering dosing pump first passage acid liquid program stopped work,
Sensor lifting platform rises pH sensor probes；
Second metering dosing pump extracts hydrofluoric acid from the second acid solution chemical tank by second channel and is injected by the second acid-resistant pipeline
It is acidified in case, until reaching preset hydrofluoric acid concentration, the second metering dosing pump is stopped；
(5) after completing first pH value adjusting, the outlet valve of the first acidification case is opened, liquid passes through pipeline in the first acidification case
Adsorption and enrichment device is flowed into, after the completion of absorption, opens the switch between the first elution device and adsorption and enrichment device, the first elution
Pure water in device opens the waste liquid dump valve of adsorption and enrichment bottom of device by pipe flushing adsorption and enrichment device, rinses
Waste liquid is discharged by pipeline, completes the flushing of adsorption and enrichment device, and closes waste liquid dump valve；
After completing the flushing of adsorption and enrichment device, the outlet valve of elution device is closed, opens the outlet valve of the second chemicals dosing plant,
Second chemicals dosing plant injects lye by alkaline-resisting pipeline into adsorption and enrichment device, by the organic matter of resin adsorption lye work
It is desorbed with lower, the liquid after desorption flows into the second acidification case through pipeline；
(6) start the second acid-base value and adjust the adjusting again that unit carries out acid-base value, third, which is measured dosing pump and received, is located at second
The pH sensor signals being acidified in case start acid solution and program are added, and third measures dosing pump by third channel from third acid solution medicine
Agent case extracts acid solution and injects non-oxidizable acid solution into acidification case by third acid-resistant pipeline, while starting in acidification case and stirring horse
It reaches so that acid solution is evenly dispersed, until reaching preset pH value, third measures dosing pump third channel acid liquid program stopped work
Make, sensor lifting platform rises pH sensor probes；
Third is measured dosing pump and is injected from the 4th acid solution chemical tank extraction hydrofluoric acid by the 4th acid-resistant pipeline by fourth lane
It is acidified in case, until reaching preset hydrofluoric acid concentration, third metering dosing pump is stopped；
(7) after completing secondary acid-base value adjusting, the outlet valve of the second acidification case is opened, while starting vacuum pump, passes through vacuum
Pump presses, and by the membrane filtration in the second filter, hydrophobic humic acid is trapped within the organic matter solution in the second acidification case
Above filter membrane, impurity flows into liquid memory；
(8) after organic matter completes filtering, the outlet valve of the second acidification case is closed, the outlet valve of the second elution device is opened,
Pure water in second elution device flows into the second filter by pipeline, is rinsed to slightly carrying humic acid, flushing liquor directly flows
Enter in liquid memory, the liquid in liquid memory is fallen by dump valve direct emission, stays in the organic matter on filter membrane as institute
The soil hydrophobic humic acid that need to be extracted.
9. the method for soil hydrophobic humic acid extraction as claimed in claim 8, which is characterized in that in first chemicals dosing plant
Lye is saturation or is closely saturated strong base solution, the resistance to highly basic requirements for pipes can bear saturation highly basic；Liquid in the reaction kettle
The pH preset values of body are 10-14；The strong base solution that lye in second chemicals dosing plant is 0.1mol/L, the alkaline-resisting pipeline
It is required that the highly basic of 0.5mol/L can be born；
First acid-resistant pipeline, third acid-resistant pipeline require that the non-oxidizable strong acid of 10mol/L can be born；Described second is acidproof
Pipeline, the 4th acid-resistant pipeline require that the hydrofluoric acid of 6mol/L can be born；The pH preset values of the first acidification case, the second acidification case
Preset concentration for 0.5-1.5, hydrofluoric acid is 0.01-1mol/L.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710069441.0A CN106905382B (en) | 2017-02-08 | 2017-02-08 | A kind of device of extraction soil hydrophobic humic acid |
| PCT/CN2017/101707 WO2018145458A1 (en) | 2017-02-08 | 2017-09-14 | Equipment for use in extracting humic acid from soil and manufacturing method for equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710069441.0A CN106905382B (en) | 2017-02-08 | 2017-02-08 | A kind of device of extraction soil hydrophobic humic acid |
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| CN106905382A CN106905382A (en) | 2017-06-30 |
| CN106905382B true CN106905382B (en) | 2018-10-09 |
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| WO2018145458A1 (en) * | 2017-02-08 | 2018-08-16 | 中国环境科学研究院 | Equipment for use in extracting humic acid from soil and manufacturing method for equipment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153435A (en) * | 2015-09-16 | 2015-12-16 | 中国环境科学研究院 | Grading method of humic acid large-pore-size resin in frond |
| CN105203374A (en) * | 2015-09-16 | 2015-12-30 | 中国环境科学研究院 | Method for extracting small-molecule humic acid from soil through XAD resin |
| CN106365354A (en) * | 2016-10-21 | 2017-02-01 | 中国环境科学研究院 | Extracting device for hydrophobic dissolution humic acid in fresh water body |
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2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153435A (en) * | 2015-09-16 | 2015-12-16 | 中国环境科学研究院 | Grading method of humic acid large-pore-size resin in frond |
| CN105203374A (en) * | 2015-09-16 | 2015-12-30 | 中国环境科学研究院 | Method for extracting small-molecule humic acid from soil through XAD resin |
| CN106365354A (en) * | 2016-10-21 | 2017-02-01 | 中国环境科学研究院 | Extracting device for hydrophobic dissolution humic acid in fresh water body |
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| Title |
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| FRACTIONATION OF SOIL ORGANIC MATTER;EEF VELTHORST等;《International Journal of Environmental Analytical Chemistry》;20060922;第73卷(第3期);237-251页 * |
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