WO2018145459A1 - 用于提取土壤憎水富里酸的设备 - Google Patents

用于提取土壤憎水富里酸的设备 Download PDF

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Publication number
WO2018145459A1
WO2018145459A1 PCT/CN2017/101710 CN2017101710W WO2018145459A1 WO 2018145459 A1 WO2018145459 A1 WO 2018145459A1 CN 2017101710 W CN2017101710 W CN 2017101710W WO 2018145459 A1 WO2018145459 A1 WO 2018145459A1
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Prior art keywords
adsorption
outlet
inlet
tank
fulvic acid
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PCT/CN2017/101710
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English (en)
French (fr)
Inventor
白英臣
吴丰昌
廖海清
蒲生彦
郭飞
常明
魏源
王国静
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中国环境科学研究院
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Priority claimed from CN201710069443.XA external-priority patent/CN106706404B/zh
Priority claimed from CN201710069140.8A external-priority patent/CN106872231B/zh
Application filed by 中国环境科学研究院 filed Critical 中国环境科学研究院
Publication of WO2018145459A1 publication Critical patent/WO2018145459A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor

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  • This invention relates to the field of fulvic acid extraction, and more particularly to an apparatus for extracting soil hydrazine fulvic acid.
  • Fulvic acid is a kind of polydisperse acidic natural organic substance, generally brown or brownish yellow. It is widely distributed in environmental media such as soil, water and sediment, and is one of the main components of humus. Fulvic acid contains a large amount of phenolic hydroxyl groups, carbonyl groups, etc., which are soluble in acid and alkali, and can interact with metal ions and organic pollutants, thereby affecting chemical degradation, photocatalytic degradation, bioabsorption, migration and volatilization of pollutants. Fulvic acid also improves soil compaction and affects soil fertility. Hydrophobic acid is more likely to interact with organic pesticides and persistent pollutants. It is currently the focus and hotspot of agronomy, geosciences and environmental science. Due to the low content of fulvic acid in the muddy water and the difficulty in extraction, the enrichment and separation of fulvic acid in the swill is the bottleneck of fulvic acid research.
  • Chinese invention patent (201510586221.6: a method for extracting sub-components of soil fulvic acid) discloses a method for fractionating and extracting sub-components of soil fulvic acid, which comprises the following steps:
  • a method for extracting sub-components of soil fulvic acid characterized in that the extraction method comprises the following steps:
  • Step a pretreatment of the soil sample: weigh the natural soil, remove the roots and stones, air dry, grind and sieve, and obtain the pretreated soil sample;
  • Step b Gradient extraction of soil organic matter:
  • step a Add deionized water to the pretreated soil sample in step a to make the solid-liquid ratio between 1:10 and 3:10, continuously stir for 2 to 5 hours, let stand for 20 to 28 hours, and then centrifuge to obtain Clear liquid 1 and soil sample 1;
  • Deionized water was added to the soil sample 1, and the solid-liquid ratio was between 1:10 and 3:10, and the mixture was continuously stirred for 2 to 5 hours. After standing for 20 to 28 hours, the mixture was centrifuged to obtain the supernatant 2 and the soil. Sample 2;
  • Step c Preparation of fractionated fulvic acid subcomponent crude product: the supernatant 1 to the supernatant 10 in step b, a total of 10 supernatants are respectively adjusted to a pH value of between 1.0 and 2.0, and then stirred separately 2 ⁇ 5h, respectively, standing for 20 ⁇ 28h, centrifugation, 10 parts of the supernatant were labeled as crude fulvic acid sub-component solution 1 ⁇ crude fulvic acid sub-component solution 10;
  • Step d grading and concentrating the fulvic acid subcomponent crude product: the crude fulvic acid subcomponent solution 1 to the crude fulvic acid subcomponent solution 10 in step c, a total of 10 parts of the crude fulvic acid subcomponent solution respectively 10 to 20 times column volume / h flow rate through the XAD-8 resin column;
  • the XAD-8 resin column is washed with 0.4 to 0.8 column volumes of deionized water at a flow rate of 10 to 20 column volumes/h, respectively, and then 0.5 to 0.5 times at a flow rate of 3 to 5 column volumes/h. 3 column volumes of 0.1 to 1.0 mol/L oxyhydrogen
  • the XAD-8 resin column is washed with sodium solution and 1-3 times column volume of deionized water, and the effluent is immediately acidified to a pH between 1.0 and 3.0, and finally corresponding to 10 parts of crude fulvic acid subcomponent. 10 parts of acidified solution;
  • Step e Purification of the fulvic acid subcomponent sample: the above-mentioned 10 parts of the acidified solution are separately added to the hydrofluoric acid, and the solution is allowed to stand when the hydrofluoric acid concentration in each of the acidifying solutions is 0.1 to 0.3 mol/L. ⁇ 48h, then labeled as no silicon solution 1 ⁇ no silicon solution 10, a total of 10 parts of silicon-free solution;
  • the XAD-8 resin column is washed with 0.4 to 0.8 column volumes of deionized water at a flow rate of 10 to 20 column volumes/h, and the effluent is discarded, and then the flow rate is 3 to 5 column volumes/h.
  • the XAD-8 resin column is washed successively with 0.5 to 3 column volumes of 0.1 to 0.3 mol/L sodium hydroxide solution and 1 to 3 column volumes of deionized water, and the effluent is discharged through a hydrogen ion-saturated hydrogen-type cation exchange resin.
  • the liquid is labeled as fulvic acid subcomponent 1 - fulvic acid subcomponent 10;
  • the fulvic acid subcomponent 1 to fulvic acid subcomponent 10 was freeze-dried separately to finally obtain 10 parts of a solid fulvic acid subcomponent fractionated sample.
  • the method for extracting soil fulvic acid disclosed in the above invention mainly relies on a laboratory method for gradually extracting fulvic acid subcomponents in soil, and preparing different grades of fulvic acid subcomponent fraction samples; this method relies on laboratory and a large number of The manual operation, the operation process is complicated, and the degree of automation is low; in addition, the fulvic acid extraction method disclosed in the patent of the present invention is greatly affected by human influence and operation, and the extraction and comparison of a large amount of fulvic acid cannot be realized, and the implementation is poor.
  • the invention provides an apparatus for extracting soil hydrazine fulvic acid, which can realize efficient extraction of soil hydrazine fulvic acid, convenient operation and high degree of automation.
  • the present invention provides an apparatus for extracting soil hydrophobic fulvic acid, comprising a reaction kettle, a pH adjusting unit, a first filtering and purifying unit, an acidizing tank, a pH adjusting unit, a second filtering and purifying unit, a liquid reservoir, a fulvic acid extraction unit and a total control system;
  • An inlet of the reaction vessel is connected to an outlet of the pH adjusting unit, and an outlet of the reaction vessel is connected to an inlet of the first filtration purification unit;
  • An outlet of the first filtration purification unit is connected to an inlet of the acidification tank, an inlet of the acidification tank is further connected to an outlet of the pH adjustment unit, an outlet of the acidification tank and a second filtration purification unit An inlet connection, an outlet of the second filtration purification unit being connected to an inlet of the liquid reservoir;
  • the pH adjusting unit and the pH adjusting unit are connected to the total control system;
  • the fulvic acid extraction unit includes a rinsing device, an organic solvent medicinal tank, a first sorption and enrichment device, and a second sorption and enrichment device; an inlet of the first sorption and enrichment device is connected to an outlet of the liquid reservoir, An outlet thereof is connected to an inlet of the second adsorption-concentrating device;
  • the outlet of the rinsing device and the outlet of the organic solvent solution tank are both connected to the inlet of the first adsorption and enrichment device and the inlet of the second adsorption and enrichment device;
  • the bottom of the first adsorption and concentration device and the bottom of the second adsorption and concentration device are each provided with a waste liquid discharge valve.
  • the first adsorptive enrichment device comprises an adsorption column and a filler, and the filler is disposed in the adsorption column, and the filler is one of XAD-8 resin, DAX-8 resin and XAD-7 resin or A variety.
  • the second adsorption-concentrating device comprises an adsorption column and a filler, the filler is disposed in the adsorption column, and the filler is XAD-4 resin.
  • the fulvic acid extraction unit comprises a rinsing device, an organic solvent solution tank and a first-stage adsorption and enrichment device; the inlet of the first-stage adsorption and enrichment device is respectively connected to the outlet of the liquid reservoir and the leaching device Export, export connection of organic solvent tank;
  • the bottom of the first-stage adsorption and concentration device is provided with a waste liquid discharge valve.
  • the first-stage adsorption and enrichment device comprises an adsorption column and a filler, and the filler is disposed in the adsorption column, and the filler is one of XAD-8 resin, DAX-8 resin and XAD-7 resin or A variety.
  • the reaction vessel is provided with a soil storage chamber supported by the support and located in the reaction kettle; the outer wall of the soil storage chamber is provided with a plurality of holes having a pore diameter of less than 1 mm.
  • the fulvic acid extraction unit comprises a rinse device, a second dosing device, an adsorption enrichment device and an ion exchange device, the inlet of the adsorption enrichment device being connected to the outlet of the liquid reservoir, the adsorption An inlet of the enrichment device is further connected to an outlet of the eluent device and an outlet of the second dosing device, and an outlet of the adsorption enrichment device is connected to an inlet of the ion exchange device, and a bottom of the adsorption enrichment device There is a waste liquid discharge valve;
  • the inlet of the ion exchange device is also connected to the outlet of the rinsing device.
  • the adsorption and enrichment device comprises an adsorption column and a filler, wherein the filler is disposed in the adsorption column, and the filler is one or more of XAD-8 resin, DAX-8 resin and XAD-7 resin. ;
  • the ion exchange device includes an adsorption column and a filler, the filler is disposed in the adsorption column, and the filler is a hydrogen type cation exchange resin.
  • the fulvic acid extraction unit comprises a rinse device, a second dosing device, a first adsorption and concentration device, a first ion exchange device, a second adsorption and concentration device, and a second ion exchange device;
  • An inlet of the adsorption and enrichment device is connected to an outlet of the liquid storage device, and an outlet of the first-stage adsorption and enrichment device is respectively connected to an outlet of the first ion exchange device and an inlet of the second adsorption and concentration device;
  • An outlet of the adsorption enrichment device is connected to an inlet of the second ion exchange device;
  • an outlet of the elution device is respectively connected to an inlet of the first-stage adsorption enrichment device, an inlet of the first ion exchange device, and a second-stage adsorption rich
  • an outlet of the second dosing device is respectively connected to an in
  • the bottom of the first-stage adsorption and concentration device, the bottom of the second-stage adsorption and concentration device, the bottom of the first ion exchange device, and the bottom of the second ion exchange device are all provided with a waste liquid discharge valve.
  • the first-stage adsorption and enrichment device comprises an adsorption column and a filler, and the filler is disposed in the adsorption column, and the filler is one of XAD-8 resin, DAX-8 resin and XAD-7 resin or Multiple
  • the secondary adsorption enrichment device comprises an adsorption column and a filler, the filler is disposed in the adsorption column, and the filler is XAD-4 resin.
  • the first ion exchange device and the second ion exchange device each comprise an adsorption column and a filler, the filler is disposed in the adsorption column, and the filler is a hydrogen type cation exchange resin.
  • the pH adjusting unit comprises a first metering dosing pump and a first dosing device, and a first metering dosing pump is disposed between the first dosing device and the reaction kettle, the first metering An inlet of the dosing pump is coupled to an outlet of the first dosing device, and an outlet of the first metered dosing pump is coupled to an inlet of the reaction vessel.
  • the first filtration purification unit comprises a first filter and a vacuum pump; an inlet of the first filter is connected to an outlet of the reaction vessel through a pipe, an outlet of the first filter and the acidification tank An inlet connection; the vacuum pump is connected to the acidification tank;
  • the pipeline between the reaction vessel and the first filter extends into the reaction vessel, and the height of the pipeline extending into the reactor is 1/20-1/10 of the height of the reactor, and the protection is externally provided.
  • a pipe between the first filter and the acidification tank extends into the acidification tank, the pipeline extending into the acidification tank is located above the liquid level in the acidification tank; the suction port of the vacuum pump is located at the Above the liquid level in the acidification tank.
  • the acidification tank adopts an acid-resistant and alkali-resistant material, and has a sealing cover on the upper side and a funnel shape on the lower end, and at least five through holes are provided on the end surface of the sealing cover.
  • the first filtration purification unit comprises a first filter and a vacuum pump
  • the first filter comprises a sample chamber, a filter membrane and a sand core
  • the filter membrane is disposed in the sample chamber
  • the sand is Core support
  • the filter membrane has a pore size ranging from 0.1 to 0.7 ⁇ m.
  • the pH adjustment unit comprises a pH sensor, a stirrer, a first acid solution tank, a second acid solution tank and a second metering dosing pump; the pH sensor and the agitator are disposed in the acidification tank
  • the first acid liquid medicine tank and the second acid liquid medicine tank are arranged side by side; the inlet of the second metering medicine pump is respectively connected with the outlet of the first acid liquid medicine tank and the outlet of the second acid liquid medicine tank,
  • the outlet of the second metering dosing pump is connected to the inlet of the acidification tank.
  • the second filter purification unit comprises a second filter and an evacuation pump, an inlet of the second filter is connected to an outlet of the acidification tank, an outlet of the second filter is connected to the liquid reservoir An inlet connection; an outlet of the liquid reservoir is coupled to an inlet of the first adsorption enrichment device; an intake port of the vacuum pump is located above a liquid level in the liquid reservoir.
  • the pipe between the acidification tank and the second filter protrudes into the acidification tank, and the height of the pipeline extending into the acidification tank is 1/20-1/10 of the height of the acidification tank, and A filter cover is disposed outside, and the filter cover is provided with a plurality of holes having a hole diameter of 100 ⁇ m.
  • the second filter comprises a sample chamber, a filter membrane and a sand core, the filter membrane is disposed in the sample chamber and supported by the sand core; the membrane has a pore diameter ranging from 0.1 to - 0.7 ⁇ m.
  • the conduit between the liquid reservoir and the adsorption-concentrating device extends into the liquid reservoir, and the height of the pipeline extending into the liquid reservoir is 1/30-1 of the height of the liquid reservoir.
  • a filter cover is disposed outside, and the filter cover is provided with a plurality of holes having a hole diameter of 100 ⁇ m.
  • the reaction kettle is made of an alkali-resistant material, and has a sealing cover on the upper side and a funnel shape on the lower end, and a stirrer, a liquid level sensor and a pH sensor are further disposed in the reaction kettle; the end surface of the sealing cover is provided with at least 5 Through holes.
  • the total control system comprises a control unit and a touch screen, and the control unit is respectively connected with a pH sensor, a stirrer, a liquid level sensor, a first metering dosing pump, and a second metering dosing in the reaction kettle.
  • the method for extracting soil hydrazine fulvic acid component by using the apparatus for extracting soil hydrazine fulvic acid comprises the following steps:
  • the first metering dosing pump receives the pH sensor signal in the reaction kettle to start the lye addition procedure, and the first dosing device injects the alkali solution into the reaction vessel through the alkali resistant pipeline, and simultaneously starts the reaction kettle.
  • the stirring motor in the so that the alkali liquid is evenly dispersed until the preset pH value is reached, and the first metering dosing pump stops working;
  • the second metering dosing pump receives the pH sensor signal located in the acidification tank to initiate the acid addition procedure, and the second metering dosing pump draws the acid solution from the first acid solution tank through the first passage.
  • the first acid-resistant pipeline injects a non-oxidizing acid into the acidizing tank, and starts the stirring motor in the acidizing tank, so that the acid liquid is evenly dispersed until the preset pH value is reached, and the first metering dosing pump first channel plus acid program Stop working, the sensor lifts raise the pH sensor probe;
  • the second metering dosing pump draws hydrofluoric acid from the second acid solution tank through the second passage into the acidification tank through the second acid-proof pipeline until the preset hydrofluoric acid concentration is reached, and the second metering dosing pump stops working;
  • the outlet valve of the acidification tank is opened, and the vacuum pump is started at the same time, and the pressure is applied by the vacuum pump, and the solution in the acidification tank flows into the liquid reservoir through the second filter, and the acid-insoluble impurities are used in the second filter.
  • the filter membrane is removed and removed, and the crude fulvic acid solution after removing impurities flows into the liquid reservoir through the filter membrane;
  • the communication valve between the leaching device and the first adsorption and enrichment device is opened, and the waste liquid discharge valve at the bottom of the first adsorption and enrichment device is opened, and the first adsorption and enrichment device and the second adsorption are closed.
  • the communication valve between the enrichment devices; the pure water in the ejecting device is injected into the first adsorption enrichment device through the pipeline for flushing, and the flushing liquid is discharged through the waste liquid discharge valve to complete the flushing of the first adsorption enrichment device;
  • the fulvic acid solution 1 and the fulvic acid solution 2 are combined, rotary evaporated and nitrogen-blown or naturally air-dried to obtain a solid soil hydrazine fulvic acid.
  • the lye in the first dosing device is a saturated or near-saturated strong alkali solution, and the alkali-resistant pipeline is required to withstand a saturated strong alkali; the pH of the liquid in the reactor is preset to be 10- 14.
  • the first acid-resistant pipeline is required to withstand 10 mol/L of non-oxidizing strong acid; the second acid-resistant pipeline is required to withstand 6 mol/L of hydrofluoric acid; the preset concentration of hydrofluoric acid in the acidizing tank It is 0.01-1 mol/L; the pH of the liquid in the acidification tank is preset to be 0.5-1.5.
  • the alkali solution in the second dosing device is a strong base of 0.001-0.5 mol/L, and the alkali-resistant pipe is required to withstand a strong base of 0.001-0.5 mol/L.
  • the organic solvent tank and the weakly polar volatile organic solvent in the organic pipeline are methanol, ethanol or a mixture thereof.
  • the total control system adopts low-voltage power distribution
  • the voltage level of the power supply and distribution equipment is 220VAC
  • the low-voltage power distribution cabinet is provided to supply power to the process system power equipment; the power switch and the electric control cabinet door interlock protection in the control system, It can achieve dustproof, fast heat dissipation and easy installation.
  • the device for extracting soil hydrazine fulvic acid provided by the invention has the advantages of simple structure, convenient operation and high degree of automation, and can effectively extract soil hydrazine fulvic acid and obtain a high concentration solution;
  • a filter cover is placed outside the pipe extending into the acidification tank, and the height of the pipe extending into the acidification tank is 1/20-1/10 of the height of the acidification tank, and the pipe peripherals extending into the liquid storage tank With a filter cover, the height of the pipe extending into the acid tank is 1/30-1/20 of the height of the liquid reservoir, which guarantees the maximum Limiting the collection of fulvic acid improves the efficiency of the device, and effectively prevents the impurities particles from being mixed into the sample, thereby ensuring the purity of the extract;
  • the pH adjustment and pH adjustment unit are fully automatic, saving labor, and the accuracy of the adjusted pH value is relatively high; the first acid solution tank and the second acid solution tank share a metering dosing pump, After further optimization of the pH adjustment unit and the pH adjustment unit, a multi-channel metering dosing pump can be shared to further reduce the production cost; the acidification tank and the liquid reservoir share a vacuum pump, which reduces the production cost;
  • the filler used in the adsorption and enrichment device in the fulvic acid extraction unit is one or more of XAD-8 resin, DAX-8 resin and XAD-7 resin, and the filler in the ion exchange device adopts hydrogen type cation exchange resin. , which can more effectively adsorb and purify impurities in concentrated water to obtain a dissolved organic liquid with a higher concentration;
  • the reaction vessel is provided with an inert gas inlet and an outlet.
  • an inert gas such as nitrogen or helium is introduced to effectively suppress the oxidation of the soil hydrazine fulvic acid under strong alkaline conditions.
  • Figure 1 is a schematic view showing the structure of a first embodiment provided by the present invention
  • FIG. 2 is a schematic structural view of a second embodiment provided by the present invention.
  • Figure 3 is a schematic structural view of a third embodiment provided by the present invention.
  • Figure 4 is a schematic view showing the structure of a fourth embodiment provided by the present invention.
  • the invention provides an apparatus for extracting soil hydrophobic fulvic acid, comprising a reaction kettle 1, a pH adjusting unit, a first filtering and purifying unit, an acidizing tank 11, a pH adjusting unit, a second filtering and purifying unit, and a liquid reservoir 14. a fulvic acid extraction unit and a total control system 6; wherein the reaction vessel 1 is provided with a soil storage chamber 2, a support 3, a stirrer, a liquid level sensor and a pH sensor, and the soil storage chamber 2 is supported by the support 3 and is located in the reaction kettle.
  • the outer wall of the soil storage chamber 2 is provided with a plurality of holes having a pore diameter of less than 1 mm;
  • the pH adjusting unit comprises a first metering dosing pump 4 and a first dosing device 5;
  • the first filtering and purifying unit comprises a filter 7 and a vacuum pump 12
  • the first filter 7 includes a sample chamber 71, a filter membrane 72, and a sand core 73.
  • the filter membrane 72 is disposed in the sample chamber 71 and supported by the sand core 73.
  • the pH adjustment unit includes a second metering dosing pump 8, An acid solution tank 9 and a second acid solution tank 10;
  • the second filter purification unit includes a second filter 13 and a vacuum pump 12, the second filter 13 including a sample chamber 131, a filter 132, and a sand core 133, a filter 132 is disposed in the sample chamber 131 and is composed of a sand core 13 3 Support;
  • the total control system 6 mainly adopts automatic control, wherein the centralized control operation is uniformly performed in the control cabinet, which enables the entire system to realize automatic control operation and manual operation.
  • the first dosing device 5 is connected to the reaction kettle 1 by a first metering dosing pump 4, the inlet of the first metering dosing pump 4 is connected to the first dosing device 5, and the outlet thereof is connected to the reaction vessel 1;
  • the outlet of 1 is connected to the inlet of the first filter 7, and the connecting pipe between the reaction vessel 1 and the first filter 7 is inserted into the reaction vessel 1, and the height of the pipe extending into the reactor is taken as 1 of the height of the reactor 1. /20-1/10, and a protective cover is disposed outside, and the protective cover is provided with a plurality of holes having a hole diameter of 1 mm; the outlet of the first filter 7 is connected to the inlet of the acidification tank 11, and the suction of the vacuum pump 12 is performed.
  • the mouth is placed in the cavity of the acidification tank 11; the first acid solution tank 9 and the second acid solution tank 10 are arranged side by side, and the second metering dosing pump 8 is disposed in the first acid solution tank 9 and the second acid solution
  • the inlet of the second metering dosing pump 8 is connected to the outlet of the first acid solution tank 9, the outlet of the second acid solution tank 10, and the outlet of the second metering dosing pump 8 is connected to the acidification tank 11.
  • the outlet of the acidification tank 11 is connected to the inlet of the second filter 13, and the acidification tank 11 is provided with a stirrer and a pH sensor;
  • the outlet of the second filter 13 is connected to the liquid reservoir 14, the vacuum pump 12 is connected to the liquid reservoir 14, and the outlet of the liquid reservoir 14 is connected to the fulvic acid extraction unit;
  • the overall control system 6 comprises a control unit and a touch screen, the control unit is connected to the touch screen, and the control unit is connected to the agitator, the liquid level sensor, the pH sensor, the first metering dosing pump 4, the second metering pump 8 and the vacuum pump 12. .
  • the total control system uses low-voltage power distribution, the voltage level of the power supply and distribution equipment is 220VAC, and the low-voltage power distribution cabinet is provided to supply power to the process system power equipment.
  • the control system is equipped with an independent operation of the control cabinet, as well as electrical switches and electrical components are concentrated in the control cabinet, the power switch and the electronic control cabinet door interlock protection, can achieve dust, heat dissipation and easy to install.
  • the fulvic acid extraction unit includes a rinsing device 15a, an organic solvent solution tank 16a, and a first adsorption and concentration device 17a.
  • a second adsorption enrichment device 18a wherein the inlet of the first adsorption-concentration device 17a is connected to the outlet of the liquid reservoir 14, the outlet of which is connected to the inlet of the second adsorption-concentration device 18a; the outlet 15a of the rinse device,
  • the outlet of the organic solvent reagent tank 16a is connected to the inlet of the first adsorption-concentration device 17a and the inlet of the second adsorption-concentration device 18a; the bottom of the first adsorption-concentration device 17a and the bottom of the second adsorption-concentration device 18a are both
  • a waste liquid discharge valve is provided.
  • the main power supply and the start button are turned on to make the whole system in working state, a certain amount of the ground soil sample is added to the soil storage chamber 2, and the soil storage chamber 2 is closed; the water injection process is started, and pure water is added to the reaction kettle 1,
  • the liquid level sensor in the reaction vessel 1 detects the water level in the reaction vessel 1. When the water level reaches 4/5 of the total volume of the reaction vessel, the liquid level sensor sends a liquid level signal to the overall control system 6 to stop the water injection process.
  • the first metering dosing pump 4 receives the pH sensor signal in the reaction vessel 1 to start the lye addition process.
  • the first dosing device 5 The alkali solution is injected into the reaction vessel 1 through the alkali-resistant pipeline, and the agitation motor in the reaction vessel 1 is started to uniformly disperse the alkali liquid until the preset pH value is reached, and the first metering dosing pump 4 stops working.
  • the soil sample leachate in the soil storage chamber 2 flows into the reaction vessel 1 through a hole in the outer wall of the soil storage chamber.
  • the outer wall of the soil storage chamber 2 is provided with a plurality of holes having a pore diameter of less than 1 mm, which can effectively prevent impurities in the soil from entering the liquid of the reaction vessel 1.
  • the reaction kettle 1 is made of an alkali-resistant material, and a sealing cover is arranged on the lower end.
  • the shape of the funnel is provided with an agitator, a liquid level sensor and a pH sensor, and the end surface of the sealing cover is provided with at least 5 through holes.
  • the outlet valve of the reaction vessel 1 is opened, and the vacuum pump 12 is started, and the pressure is applied by the vacuum pump 12.
  • the liquid in the reaction vessel 1 flows into the acidification tank 11 through the first filter 7, and the alkali-insoluble impurities are removed by the filtration membrane 72 to remove impurities.
  • the subsequent liquid flows into the acidification tank 11 through the filter membrane 72.
  • the acidification tank 11 is made of an acid-resistant and alkali-resistant material, and has a sealing cover on the upper surface and a funnel shape on the lower end, and at least five through holes are provided on the end surface of the sealing cover.
  • the pH adjustment unit is activated, the desired pH is set in the overall control system 6, the pH is set to 0.5-1.5, and the pH sensor signal is transmitted to the pH sensor located in the acidification tank 11, the pH sensor will pH
  • the value signal is transmitted to the second metering dosing pump 8, the second metering dosing pump 8 receives the pH sensor signal located in the acidification tank 11 to initiate the acid addition procedure, and the second metering dosing pump 8 is from the first acid solution tank 9
  • the acid solution is injected into the acidification tank 11 through the first acid-proof pipeline, and the non-oxidizing acid liquid is injected into the acidification tank 11, and the stirring motor is started in the acidification tank 11, so that the acid liquid is uniformly dispersed until the preset pH value is reached, and the second metering dosing pump 8 is obtained.
  • the first channel plus acid program stops working, and the sensor lifting platform raises the pH sensor probe;
  • the second metering dosing pump 8 extracts hydrofluoric acid from the second acid solution tank 10 through the second passage, and injects hydrofluoric acid into the acidification tank 11 through the second acid-resistant pipe until the preset hydrofluoric acid concentration is reached.
  • the second metering dosing pump 8 stops working.
  • the pH adjustment unit and the pH adjustment unit can share a multi-channel metering dosing pump.
  • the stirring motor in the acidification tank is operated for a certain time, the stirring motor is turned off, the impurities are sufficiently precipitated, the outlet valve of the acidification tank 11 is opened, the vacuum pump 12 is activated, and the solution in the acidification tank 11 is pressurized by the vacuum pump 12.
  • the second filter 13 flows into the liquid reservoir 14, and after the second filter 13, the acid-insoluble impurities are trapped on the filter 132, and the crude fulvic acid solution flows into the liquid reservoir 14.
  • the outlet valve of the liquid reservoir is opened, and the crude fulvic acid solution in the liquid reservoir flows into the first adsorption enrichment device 17a and the second adsorption enrichment device 18a through the pipeline, and the fulvic acid is adsorbed on the resin;
  • the communication valve between the eluent device 15a and the first adsorption enrichment device 17a is opened, and the waste liquid discharge valve at the bottom of the first adsorption enrichment device 17a is opened, and the first adsorption enrichment device 17a and the second are closed.
  • the communication valve between the elution device 15a and the first adsorption-concentration device 17a is closed, and the waste liquid discharge valve at the bottom of the first adsorption-concentration device 17a is closed, and the organic solvent solution tank 16a and the first adsorption-concentration device 17a are opened.
  • the communication valve between the organic solvent tanks injects the weakly polar volatile organic solvent into the first adsorption and enrichment device 17a through the organic-resistant pipeline, and the fulvic acid solution adsorbed by the resin occurs under the action of the weakly polar volatile organic solvent. Desorption, collecting the effluent labeled as fulvic acid solution 1;
  • the communication valve between the organic solvent solution tank 16a and the first adsorption-concentration device 17a is closed, the communication valve between the rinse device and the second adsorption-concentration device 18a is opened, and the waste at the bottom of the second adsorption-concentration device 18a is opened.
  • the liquid discharge valve, the pure water in the ejecting device is injected into the second adsorption and enrichment device 18a through the pipeline for flushing, and the flushing liquid is discharged through the waste liquid discharge valve to complete the flushing of the second adsorption and enrichment device 18a;
  • the communication valve between the elution device 15a and the second adsorption-concentration device 18a is closed, and the waste liquid discharge valve at the bottom of the second adsorption-concentration device 18a is closed, and the organic solvent solution tank 16a and the second adsorption-concentration device 18a are opened.
  • the communication valve between the organic solvent tank 16a injects the weakly polar volatile organic solvent into the second adsorption and enrichment device 18a through the organic-resistant pipeline, and the fulvic acid solution adsorbed by the resin is under the action of the weakly polar volatile organic solvent. Desorption occurs, and the collected effluent is labeled as fulvic acid solution 2;
  • the fulvic acid solution 1 and the fulvic acid solution 2 are combined, rotary evaporated and nitrogen-blown or naturally air-dried to obtain a solid soil hydrazine fulvic acid.
  • the fulvic acid extraction unit includes a rinsing device 15b, an organic solvent reagent tank 16b, and a first-stage adsorption and enrichment device 17b.
  • the first-stage adsorption and enrichment device The inlet of 17b is connected to the outlet of the liquid reservoir 14, and the outlets of the eluent device and the organic solvent reagent tank are respectively connected to the inlet of the first-stage adsorption and enrichment device 17b; the bottom of the first-stage adsorption and enrichment device 17b is provided with a waste liquid discharge valve. .
  • the filtration of soil organic matter, the adjustment of pH and the process of crude fulvic acid extraction are the same as in the first embodiment, except that the fulvic acid extraction unit is different.
  • the extraction process of fulvic acid is as follows: complete filtration Thereafter, the outlet valve of the liquid reservoir is opened, and the crude fulvic acid solution in the liquid reservoir flows into the first-stage adsorption and enrichment device 17b through the pipeline, and the fulvic acid is adsorbed on the resin;
  • the communication valve between the rinsing device 15b and the first-stage adsorption and enrichment device 17b is opened, and at the same time, the waste liquid discharge valve at the bottom of the first-stage adsorption and concentration device 17b is opened; the pure water in the rinsing device 15b is injected through the pipe
  • the first-stage adsorption and enrichment device 17b performs rinsing, and the rinsing liquid is discharged through the waste liquid discharge valve to complete the rinsing of the first-stage adsorption and enrichment device 17b;
  • the communication valve between the ejecting device 15b and the first-stage adsorption and enrichment device 17b is closed, and the waste liquid discharge valve at the bottom of the first-stage adsorption and enrichment device 17b is closed, and the organic solvent chemical tank 16b and the first-stage adsorption and enrichment device 17b are opened.
  • the communication valve between the organic solvent tank 16b injects the weakly polar volatile organic solvent into the first-stage adsorption and enrichment device 17b through the organic-resistant pipeline, and the fulvic acid solution adsorbed by the resin is under the action of the weakly polar volatile organic solvent. Desorption occurs, and the collected effluent is labeled as fulvic acid solution, rotary evaporated and nitrogen blown or naturally air-dried to obtain solid soil hydrazine fulvic acid.
  • FIG. 3 is a schematic structural view of a third embodiment provided by the present invention.
  • the fulvic acid extraction unit includes a rinse device 15c, a second dosing device 16c, an adsorption enrichment device 17c, and an ion exchange device 18c; wherein the inlet of the adsorption enrichment device 17c is connected to the outlet of the liquid reservoir 14.
  • the outlet of the adsorption-enrichment device 17c is connected to the inlet of the ion exchange device 18c, and the outlet of the elution device 15c is connected to the inlet of the adsorption-enrichment device 17c and the inlet of the ion exchange device 18c, respectively, and the outlet of the second dosing device 16c is
  • the inlet of the adsorption and concentration device 17c is connected; the bottom of the adsorption and concentration device 17c and the bottom of the ion exchange device 18c are provided with a waste liquid discharge valve.
  • the filtration of soil organic matter, the adjustment of pH and the process of crude fulvic acid extraction are the same as in the first embodiment, except that the fulvic acid extraction unit is different.
  • the extraction process of fulvic acid is as follows: complete filtration Thereafter, the outlet valve of the liquid reservoir 14 is opened, and the crude fulvic acid solution in the liquid reservoir 14 flows into the adsorption enrichment device 17c through the pipe, and the fulvic acid is adsorbed on the resin;
  • the communication valve between the elution device 15c and the adsorption and enrichment device 17c is opened, and the waste liquid discharge valve at the bottom of the adsorption and concentration device 17c is opened, and the pure water in the rinse device 15c is injected into the adsorption and enrichment device through the pipeline. 17c, the adsorption and concentration device 17c is flushed, and the rinse liquid is directly discharged from the waste liquid discharge valve to complete the flushing of the adsorption and concentration device 17c;
  • the dosing device 16c injects the alkali solution into the adsorption and enrichment device 17c through the alkali-resistant pipe, and the hydrophobic fulvic acid adsorbed by the resin is desorbed by the action of the alkali solution, and the desorbed liquid flows into the ion exchange device 18c through the ion exchange.
  • the hydrogen-type cation exchange resin in the device 18c is exchanged and discharged, and the discharged liquid is a soil-bored fulvic acid solution to be extracted, and freeze-dried to obtain a solid soil hydrophobic fulvic acid.
  • FIG. 4 is a schematic structural view of a fourth embodiment provided by the present invention.
  • the fulvic acid extraction unit includes a rinsing device 15d, a second medicating device 16d, a first-stage adsorption and enrichment device 17d, a first ion exchange device 18d, a secondary adsorption-enrichment device 19d, and a second ion exchange device. 20d; wherein, the inlet of the first-stage adsorption and concentration device 17d is connected to the outlet of the liquid reservoir 14, and the outlet of the adsorption-enrichment device 17d is respectively connected to the inlet of the first ion exchange device 18d and the second-stage adsorption and concentration device 19d.
  • An inlet connection; an outlet of the secondary adsorption enrichment device 19d is connected to an inlet of the second ion exchange device 20d; an outlet of the elution device 15d is respectively connected to an inlet of the first-stage adsorption and concentration device 17d, An inlet of an ion exchange device 18d, an inlet of the secondary adsorption enrichment device 19d, and an inlet connection of the second ion exchange device 20d; an outlet of the second dosing device 16d and the first-stage adsorption enrichment device 17d, respectively An inlet connection of the inlet and secondary adsorption enrichment device 19d;
  • a waste liquid discharge valve is provided at the bottom of the first-stage adsorption and concentration device 17d, the bottom of the first ion exchange unit 18d, the bottom of the second-stage adsorption and accumulation unit 19d, and the bottom of the second ion exchange unit 20d.
  • the filtration of soil organic matter, the adjustment of pH and the crude process of fulvic acid are the same as in the first embodiment, except that the fulvic acid extraction unit is different.
  • the extraction process of fulvic acid is as follows: After filtration, the outlet valve of the liquid reservoir 14 is opened, and the crude fulvic acid solution in the liquid reservoir 14 is sequentially flowed through the pipe to the first-stage adsorption and enrichment device 17d and the second-stage adsorption and enrichment device 19d, and the fulvic acid is adsorbed on the resin. ;
  • First-stage adsorption and enrichment device lye elution: close the communication valve between the first-stage adsorption and enrichment device 17d and the second-stage adsorption and enrichment device 19d, and close the first-stage adsorption and enrichment device 17d and the first ion exchange device 18d Connected valve, open and rinse
  • the communication valve between the device 15d and the first-stage adsorption and enrichment device 17d opens the waste liquid discharge valve at the bottom of the first-stage adsorption and enrichment device 17d, and the pure water in the rinse device 15d is flushed through the pipeline to the first-stage adsorption and enrichment device 17d.
  • the flushing waste liquid is discharged through the waste liquid discharge valve, completes the flushing of the first-stage adsorption and enrichment device 17d, closes the waste liquid discharge valve at the bottom of the first-stage adsorption and enrichment device 17d, and closes the elution device 15d and the first-stage adsorption and enrichment device 17d.
  • Interconnecting valve
  • the flushing waste liquid is discharged through the waste liquid discharge valve, completes the flushing of the first ion exchange device 18d, closes the waste liquid discharge valve at the bottom of the first ion exchange device 18d, and closes the communication between the rinse device 15d and the first ion exchange device 18d. valve;
  • Opening a communication valve between the second dosing device 16d and the first adsorption enrichment device 17d, opening a communication valve between the primary adsorption enrichment device 17d and the first ion exchange device 18d, in the second dosing device 16d The lye is injected into the first-stage adsorption and enrichment device 17d through the alkali-resistant pipeline, and the fulvic acid adsorbed by the resin is desorbed by the action of the alkali solution, and the desorbed effluent passes through the hydrogen type in the first ion exchange device 18d. After the cation exchange resin is discharged, the discharged liquid is extracted, and directly freeze-dried and labeled as fulvic acid subcomponent 1;
  • the second-stage adsorption and enrichment device lye elution: the communication valve between the second-stage adsorption and enrichment device 19d and the second ion exchange device 20d is closed, and the communication valve between the leaching device 15d and the second-stage adsorption and enrichment device 19d is opened.
  • the waste liquid discharge valve at the bottom of the second adsorption and concentration device 19d is opened, the pure water in the rinse device 15d is flushed through the pipeline to the secondary adsorption and enrichment device 19d, and the rinse waste liquid is discharged through the waste liquid discharge valve to complete the secondary adsorption rich Flushing of the collecting device 19d, closing the waste liquid discharge valve at the bottom of the secondary adsorption and enrichment device 19d, and closing the communication valve between the eluting device 15d and the secondary adsorption and enrichment device 19d;
  • the flushing waste liquid is discharged through the waste liquid discharge valve, completes the flushing of the second ion exchange device 20d, closes the waste liquid discharge valve at the bottom of the second ion exchange device 20d, and closes the communication between the rinse device 15d and the second ion exchange device 20d.
  • the alkali pipe injects the alkali solution into the secondary adsorption and enrichment device 19d, and the fulvic acid solution adsorbed by the resin is desorbed by the action of the alkali solution, and the desorbed effluent is exchanged for hydrogen type cations in the second ion exchange device 20d.
  • the discharged liquid is extracted, and directly freeze-dried and labeled as fulvic acid subcomponent 2;
  • the combined fulvic acid subcomponents 1, 2 are fulvic acid solid samples.
  • the pH adjustment process in the pH adjustment unit and the pH adjustment unit is a fully automated process, which saves labor, reduces production costs, and has a high precision of the pH value to be prepared, and the process efficiency of the preparation process is also high.
  • the agitator motor is turned on to agitate the liquid in the reaction vessel 1 and the acidification tank 11 to avoid local high or low pH.
  • the filter membrane used in the first filter is a disposable filter membrane, the filter membrane needs to be able to withstand 1 mol/L strong alkali, and the filter membrane is stored and used as required, but a silicon-containing filter membrane such as a glass fiber filter membrane cannot be used;
  • the filter used in the second filter is a disposable filter membrane, and the filter membrane needs to be able to withstand 0.5 mol/L of strong acid, and the filter membrane is stored and used as required, but a silicon-containing filter membrane such as a glass fiber filter membrane cannot be used.

Abstract

一种用于提取土壤憎水富里酸的设备，包括反应釜（1）、pH调节单元、第一过滤净化单元、酸化箱（11）、酸碱度调节单元、第二过滤净化单元、液体储存器（14）、富里酸提取单元和总控制系统（6）；其中，反应釜（1）的入口与pH调节单元的出口连接，其出口与第一过滤净化单元的入口连接；酸化箱（11）的入口与第一过滤净化单元出口、酸碱度调节单元连接，其出口与第二净化单元的入口连接；第二过滤净化单元的出口与液体储存器（14）的入口连接，液体储存器（14）的出口与富里酸提取单元的入口连接；pH调节单元、酸碱度调节单元与总控制系统（6）连接。提供的提取土壤憎水富里酸的设备结构简便，自动化程度高，可以有效地提取所需浓度的溶液。

Description

用于提取土壤憎水富里酸的设备 技术领域
本发明涉及富里酸提取领域，尤其涉及用于提取土壤憎水富里酸的设备。
背景技术
富里酸是一类多分散的酸性天然有机物质，一般呈棕色或棕黄色，它广泛分布于土壤、水体和底泥等环境介质，是腐殖质的主要成分之一。富里酸含有大量酚羟基、羰基等，既溶于酸又溶于碱，可与金属离子和有机污染物发生相互作用，从而影响污染物化学降解、光催化降解、生物吸收、迁移及挥发行为。富里酸还能改善土壤板结，影响土壤肥力。憎水富里酸更容易与有机农药和持久性污染物发生相互作用，目前是农学、地学和环境科学共同关注的重点和热点。由于憎水富里酸含量低，提取难度大，憎水富里酸的富集和分离是富里酸研究的瓶颈。
中国发明专利(201510586221.6：一种土壤富里酸亚组分分级提取方法)公开了一种土壤富里酸亚组分分级提取方法，其包括如下步骤：
1.一种土壤富里酸亚组分分级提取方法，其特征在于，所述提取方法包括如下步骤：
步骤a：土壤样品预处理：称取天然土壤，剔除树根和石子，风干，碾磨过筛，得到预处理土壤样品；
步骤b：土壤有机质的分级萃取：
向步骤a中的预处理土壤样品中加入去离子水，使其固液比介于1:10～3:10之间，连续搅拌2～5h，静置20～28h后，离心分离，得到上清液1及土壤样品1；
向土壤样品1中加入去离子水，使其固液比介于1:10～3:10之间，连续搅拌2～5h，静置20～28h后，离心分离，得到上清液2及土壤样品2；
向土壤样品2中加入去离子水，使其固液比介于1:5～3:10之间，用盐酸和氢氧化钠调节溶液pH介于1.0～3.0之间，继续加入0.1～1.0mol/L的盐酸溶液，使其固液比介于1:10～3:10之间，然后将溶液连续搅拌2～5h，静置20～28h后，离心分离，得到上清液3及土壤样品3；
向土壤样品3中加入0.1～1.0mol/L的盐酸溶液，使其固液比介于1:10～3:10之间，然后将溶液连续搅拌2～5h，静置20～28h后，离心分离，得到上清液4及土壤样品4；
向土壤样品4中加入去离子水，使其固液比介于1:5～1:3之间，用盐酸和氢氧化钠调节其pH值介于6.0～8.0之间，在氮气保护下，向溶液中加入焦磷酸钠溶液，使其固液比介于1:10～3:10之间且焦磷酸钠浓度介于0.1～0.2mol/L之间，然后将溶液连续搅拌2～5h，静置20～28h后，离心分离，得到上清液5及土壤样品5；
在氮气保护下，向土壤样品5中加入焦磷酸钠溶液，使其固液比介于1:10～3:10之间且焦磷酸钠浓度介于0.1～0.2mol/L之间，然后将溶液连续搅拌2～5h，静置20～28h后，离心分离，得到上清液6及土壤样品6；
在氮气保护下，向土壤样品6中加入焦磷酸钠溶液，使其固液比介于1:10～3:10之间且焦磷酸钠浓度介于0.1～0.2mol/L之间，然后将溶液连续搅拌2～5h，静置静置20～28h后，离心分离，得到上清液7及土壤样品7；
向土壤样品7中加入去离子水，使其固液比介于1:5～3:10之间，用盐酸和氢氧化钠调节其pH介于6.0～8.0之间，在氮气保护下，向溶液中加入氢氧化钠溶液，使其固液比介于1:10～3:10之间且氢氧化钠浓度介于0.1～0.3mol/L之间，然后将溶液连续搅拌2～5h，静置20～28h后，离心分离，得到上清液8及土壤样品8；
在氮气保护下，向土壤样品8中加入氢氧化钠溶液，使其固液比介于1:10～3:10之间且氢氧化钠浓度介于0.1～0.3mol/L之间，然后将溶液连续搅拌2～5h，静置20～28h后，离心分离，得到上清液9及土壤样品9；
在氮气保护下，向土壤样品9中加入氢氧化钠溶液，使其固液比介于1:10～3:10之间且氢氧化钠浓度介于0.1～0.3mol/L之间，然后将溶液连续搅拌2～5h，静置20～28h后，离心分离，得到上清液10及土壤样品10；
步骤c：分级富里酸亚组分粗品制备：将步骤b中的上清液1～上清液10，共计10份上清液分别调节至pH值介于1.0～2.0之间，再分别搅拌2～5h，分别静置20～28h，离心分离，将10份上清液分别标记为粗提富里酸亚组分溶液1～粗提富里酸亚组分溶液10；
步骤d：分级富里酸亚组分粗品浓缩：将步骤c中的粗提富里酸亚组分溶液1～粗提富里酸亚组分溶液10，共计10份粗提富里酸亚组分溶液分别以10～20倍柱体积/h的流速通过XAD-8树脂柱；
吸附完成后，分别以10～20倍柱体积/h的流速用0.4～0.8倍柱体积的去离子水洗涤XAD-8树脂柱，然后以3～5倍柱体积/h的流速依次用0.5～3倍柱体积的0.1～1.0mol/L氢氧 化钠溶液和1～3倍柱体积去离子水洗涤XAD-8树脂柱，流出液立即酸化至pH值介于1.0～3.0之间，最终得到与10份粗提富里酸亚组分相对应的10份酸化液；
步骤e：富里酸亚组分样品的纯化：将上述所述10份酸化液分别加入氢氟酸，使每份酸化液中的氢氟酸浓度为0.1～0.3mol/L时将溶液静置12～48h，然后分别标记为无硅溶液1～无硅溶液10，共计10份无硅溶液；
将上述10份无硅溶液分别以3～5倍柱体积/h流速通过XAD-8树脂柱；
吸附完成后，分别以10～20倍柱体积/h的流速用0.4～0.8倍柱体积去离子水洗涤XAD-8树脂柱，弃去流出液，然后以3～5倍柱体积/h的流速依次用用0.5～3倍柱体积0.1～0.3mol/L氢氧化钠溶液和1～3倍柱体积去离子水洗涤XAD-8树脂柱，流出液通过氢离子饱和的氢型阳离子交换树脂，流出液分别标记为富里酸亚组分1～富里酸亚组分10；
将富里酸亚组分1～富里酸亚组分10分别冷冻干燥，最终得到10份固体富里酸亚组分分级样品。
上述发明公开的土壤富里酸提取方法，主要是依赖于实验室方法将土壤中的富里酸亚组分逐步提取，并制备不同级别的富里酸亚组分分级样品；此方法依赖于实验室和大量的人工操作，操作过程复杂、自动化程度低；另外，本发明专利公开的富里酸提取方法受人为影响和操作影响较大，不能实现大量富里酸的提取及对比，可实施性不佳。
发明内容
为了有效提取并获取高浓度的土壤憎水富里酸，本发明提供了用于提取土壤憎水富里酸的设备，可以实现高效的提取土壤憎水富里酸，操作方便，自动化程度高。
为解决上述技术问题，本发明提供了一种用于提取土壤憎水富里酸的设备，包括反应釜、pH调节单元、第一过滤净化单元、酸化箱、酸碱度调节单元、第二过滤净化单元、液体储存器、富里酸提取单元和总控制系统；其中，
所述反应釜的入口与所述pH调节单元的出口连接，反应釜的出口与所述第一过滤净化单元的入口连接；
所述第一过滤净化单元的出口与所述酸化箱的入口连接，所述酸化箱的入口还与所述酸碱度调节单元的出口连接，所述酸化箱的出口与所述第二过滤净化单元的入口连接，所述第二过滤净化单元的出口与所述液体储存器的入口连接；
所述pH调节单元、酸碱度调节单元与所述总控制系统控制连接；
所述富里酸提取单元包括淋洗装置、有机溶剂药剂箱、第一吸附富集装置和第二吸附富集装置；所述第一吸附富集装置的入口与所述液体储存器的出口连接，其出口与所述第二吸附富集装置的入口连接；
所述淋洗装置的出口、有机溶剂药剂箱的出口均与所述第一吸附富集装置的入口、第二吸附富集装置的入口连接；
所述第一吸附富集装置的底部、第二吸附富集装置的底部均设有废液排出阀。
优选地，所述第一吸附富集装置包括吸附柱和填料，所述填料设于所述吸附柱内，所述填料为XAD-8树脂、DAX-8树脂和XAD-7树脂的一种或多种。
优选地，所述第二吸附富集装置包括吸附柱和填料，所述填料设于所述吸附柱内，所述填料为XAD-4树脂。
优选地，所述富里酸提取单元包括淋洗装置、有机溶剂药剂箱和一级吸附富集装置；所述一级吸附富集装置的入口分别与所述液体储存器的出口、淋洗装置的出口、有机溶剂药剂箱的出口连接；
所述一级吸附富集装置的底部设有废液排出阀。
优选地，所述一级吸附富集装置包括吸附柱和填料，所述填料设于所述吸附柱内，所述填料为XAD-8树脂、DAX-8树脂和XAD-7树脂的一种或多种。
优选地，所述反应釜内设有土壤储存室，所述土壤储存室由支架支撑并位于反应釜内；所述土壤储存室的外壁上设有多个孔径小于1mm的孔。
优选地，所述富里酸提取单元包括淋洗装置、第二加药装置、吸附富集装置和离子交换装置，所述吸附富集装置的入口与所述液体储存器的出口连接，所述吸附富集装置的入口还与所述淋洗装置的出口、第二加药装置的出口连接，所述吸附富集装置的出口与所述离子交换装置的入口连接，所述吸附富集装置的底部设有废液排出阀；
所述离子交换装置的入口还与所述淋洗装置的出口连接。
优选地，所述吸附富集装置包括吸附柱和填料，所述填料设于所述吸附柱内，所述填料为XAD-8树脂、DAX-8树脂和XAD-7树脂的一种或多种；
所述离子交换装置包括吸附柱和填料，所述填料设于所述吸附柱内，所述填料为氢型阳离子交换树脂。
优选地，所述富里酸提取单元包括淋洗装置、第二加药装置、一级吸附富集装置、第一离子交换装置、二级吸附富集装置、第二离子交换装置；所述一级吸附富集装置的入口与所述液体储存器的出口连接，一级吸附富集装置的出口分别与所述第一离子交换装置的出口、二级吸附富集装置的入口连接；所述二级吸附富集装置的出口与所述第二离子交换装置的入口连接；所述淋洗装置的出口分别与所述一级吸附富集装置的入口、第一离子交换装置的入口、二级吸附富集装置的入口、第二离子交换装置的入口连接；所述第二加药装置的出口分别与所述一级吸附富集装置的入口、二级吸附富集装置的入口连接；
所述一级吸附富集装置的底部、二级吸附富集装置的底部、第一离子交换装置的底部、第二离子交换装置的底部均设有废液排出阀。
优选地，所述一级吸附富集装置包括吸附柱和填料，所述填料设于所述吸附柱内，所述填料为XAD-8树脂、DAX-8树脂和XAD-7树脂的一种或多种；
所述二级吸附富集装置包括吸附柱和填料，所述填料设于所述吸附柱内，所述填料为XAD-4树脂。
优选地，所述第一离子交换装置和第二离子交换装置均包括吸附柱和填料，所述填料设于所述吸附柱内，所述填料为氢型阳离子交换树脂。
优选地，所述pH调节单元包括第一计量加药泵和第一加药装置，第一计量加药泵设于所述第一加药装置与所述反应釜之间，所述第一计量加药泵的入口与所述第一加药装置的出口连接，所述第一计量加药泵的出口与所述反应釜的入口连接。
优选地，所述第一过滤净化单元包括第一过滤器和真空泵；所述第一过滤器的入口通过管道与所述反应釜的出口连接，所述第一过滤器的出口与所述酸化箱的入口连接；所述真空泵与所述酸化箱连接；
所述反应釜与所述第一过滤器之间的管道伸入反应釜，所述伸入反应釜的管道高度取值为反应釜高度的1/20-1/10，且其外设有保护罩，所述保护罩上设有多个孔径为1mm的孔，可以避免土壤中的杂质流入到反应釜内；
所述第一过滤器与所述酸化箱之间的管道伸入酸化箱内，所述伸入酸化箱的管道位于所述酸化箱中液面之上；所述真空泵的吸气口位于所述酸化箱中液面之上。
优选地，所述酸化箱采用耐酸耐碱材料，其上面设有密封盖，下端为漏斗形状，所述密封盖的端面设有至少5个通孔。
优选地，所述第一过滤净化单元包括第一过滤器和真空泵，所述第一过滤器包括样品室、滤膜和砂芯，所述滤膜设于所述样品室内，且由所述砂芯支撑；所述滤膜的孔径取值范围为0.1-0.7μm。
优选地，所述酸碱度调节单元包括pH传感器、搅拌器、第一酸液药剂箱、第二酸液药剂箱和第二计量加药泵；所述pH传感器和搅拌器设于所述酸化箱内；所述第一酸液药剂箱和第二酸液药剂箱并列布置；所述第二计量加药泵的入口分别与第一酸液药剂箱的出口、第二酸液药剂箱的出口连接，第二计量加药泵的出口与所述酸化箱的入口连接。
优选地，所述第二过滤净化单元包括第二过滤器和真空泵，所述第二过滤器的入口与所述酸化箱的出口连接，所述第二过滤器的出口与所述液体储存器的入口连接；所述液体储存器的出口与所述第一吸附富集装置的入口连接；所述真空泵的吸气口位于所述液体储存器中液面之上。
优选地，所述酸化箱与所述第二过滤器之间的管道伸入酸化箱中，所述伸入酸化箱管道的高度取值为酸化箱的高度的1/20-1/10,且其外设有过滤罩，所述过滤罩上设有多个孔径为100μm的孔。
优选地，所述第二过滤器包括样品室、滤膜和砂芯，所述滤膜设于所述样品室内，且由所述砂芯支撑；所述滤膜的孔径取值范围为0.1-0.7μm。
优选地，所述液体储存器与所述吸附富集装置之间的管道伸入液体储存器中，所述伸入液体储存器管道的高度取值为液体储存器的高度的1/30-1/20,且其外设有过滤罩，所述过滤罩上设有多个孔径为100μm的孔。
优选地，所述反应釜采用耐碱材料，其上面设有密封盖，下端为漏斗形状，反应釜内还设有搅拌器、液位传感器和pH传感器；所述密封盖的端面设有至少5个通孔。
优选地，所述总控制系统包括控制单元和触屏器，所述控制单元均与所述反应釜内的pH传感器、搅拌器、液位传感器、第一计量加药泵、第二计量加药泵、真空泵、酸化箱内的pH传感器、搅拌器控制连接；所述pH传感器设有升降台，必要时可将pH传感器升起。
利用所述的用于提取土壤憎水富里酸的设备进行土壤憎水富里酸组分提取的方法，其包括如下步骤：
(1)土壤加入到土壤储存室中，并向反应釜中注入纯水；
(2)启动pH调节单元，第一计量加药泵接收位于反应釜中pH传感器信号启动碱液加入程序，第一加药装置通过耐强碱管道向反应釜中注入碱液，同时启动反应釜中的搅拌马达，使碱液均匀分散，直到达到预设的pH值，第一计量加药泵停止工作；
(3)打开反应釜的出口阀门，同时启动真空泵，反应釜中的液体经真空泵施压通过第一过滤器流入酸化箱内，碱不溶杂质被滤膜截留而去除，去除杂质后的液体通过滤膜流入酸化箱内；
(4)启动酸碱度调节单元，第二计量加药泵接收位于酸化箱中的pH传感器信号启动酸液加入程序，第二计量加药泵通过第一通道从第一酸液药剂箱抽取酸液通过第一耐酸管道向酸化箱中注入非氧化性酸液，同时启动酸化箱中搅拌马达，使得酸液均匀分散，直至达到预设的pH值，第二计量加药泵第一通道加酸液程序停止工作，传感器升降台升起pH传感器探头；
第二计量加药泵通过第二通道从第二酸液药剂箱抽取氢氟酸通过第二耐酸管道注入酸化箱中，直到达到预设的氢氟酸浓度，第二计量加药泵停止工作；
(5)完成pH值调节后，打开酸化箱的出口阀门，同时启动真空泵，通过真空泵施压，酸化箱中的溶液通过第二过滤器流入液体储存器中，酸不溶杂质被第二过滤器中的滤膜截留而去除，去除杂质后的粗体富里酸溶液通过滤膜流入液体储存器中；
(6)完成过滤后，打开液体储存器的出口阀门，液体储存器中的粗提富里酸溶液通过管道依次流入第一吸附富集装置和第二吸附富集装置，富里酸被吸附在树脂上；
(7)吸附完成后，打开淋洗装置与第一吸附富集装置之间的连通阀，同时打开第一吸附富集装置底部的废液排出阀，关闭第一吸附富集装置与第二吸附富集装置之间的连通阀；淋洗装置中的纯水通过管道注入第一吸附富集装置进行冲洗，冲洗液通过废液排出阀排出，完成对第一吸附富集装置的冲洗；
关闭淋洗装置与第一吸附富集装置之间的连通阀，同时关闭第一吸附富集装置底部的废液排出阀，打开有机溶剂药剂箱与第一吸附富集装置之间的连通阀，有机溶剂药剂箱通过耐有机管道向第一吸附富集装置中注入弱极性挥发性有机溶剂，被树脂吸附的富里酸溶液在弱极性挥发性有机溶剂的作用下发生解吸，收集流出液标记为富里酸溶液1；
(8)关闭有机溶剂药剂箱与第一吸附富集装置之间的连通阀，打开淋洗装置与第二吸附富集装置之间的连通阀，同时打开第二吸附富集装置底部的废液排出阀，淋洗装置中的纯水 通过管道注入第二吸附富集装置进行冲洗，冲洗液通过废液排出阀排出，完成对第二吸附富集装置的冲洗；
关闭淋洗装置与第二吸附富集装置之间的连通阀，同时关闭第二吸附富集装置底部的废液排出阀，打开有机溶剂药剂箱与第二吸附富集装置之间的连通阀，有机溶剂药剂箱通过耐有机管道向第二吸附富集装置中注入弱极性挥发性有机溶剂，被树脂吸附的富里酸溶液在弱极性挥发性有机溶剂的作用下发生解吸，收集流出液标记为富里酸溶液2；
合并富里酸溶液1和富里酸溶液2，旋转蒸发并氮吹或自然风干后得到固态土壤憎水富里酸。
优选地，所述第一加药装置中的碱液为饱和或近饱和强碱溶液，所述耐强碱管道要求能承受饱和强碱；所述反应釜中液体的pH预设值为10-14。
优选地，所述第一耐酸管道要求能承受10mol/L的非氧化性强酸；所述第二耐酸管道要求能承受6mol/L的氢氟酸；所述酸化箱中氢氟酸的预设浓度为0.01-1mol/L；所述酸化箱中液体的pH预设值为0.5-1.5。
优选地，所述第二加药装置中的碱液为0.001-0.5mol/L的强碱，所述耐碱管道要求能承受0.001-0.5mol/L的强碱。
优选地，所述有机溶剂药剂箱和耐有机管道中的弱极性挥发性有机溶剂为甲醇、乙醇或其混合物。
优选地，总控制系统采用低压配电，供配电设备的电压等级为220VAC，且设低压配电柜，向工艺系统动力设备供电；控制系统中的电源开关与电控柜门联锁保护，可以达到防尘、散热快且易于安装的效果。
与现有技术相比，本发明产生的有益效果是：
(1)本发明提供的用于提取土壤憎水富里酸的设备，结构简单，操作方便，自动化程度高，可以有效地提取土壤憎水富里酸，获取高浓度溶液；
(2)反应釜、酸化箱、液体储存器的底部均为漏斗形状，伸入反应釜、酸化箱的管道外设有过滤罩，伸入反应釜管道的高度取值为反应釜的高度的1/20-1/10，伸入酸化箱的管道外设有过滤罩，伸入酸化箱管道的高度取值为酸化箱高度的1/20-1/10，伸入液体储存器的管道外设有过滤罩，伸入酸化箱管道的高度取值为液体储存器高度的1/30-1/20，既可以保证最大 限度的收集富里酸，提高了装置效率，又可以有效的阻止杂质颗粒混入样品中，保证了提取液的纯度；
(3)pH值调节和酸碱度调节单元均是全自动的，节省了劳动力，调节的pH值的准确率比较高；第一酸液药剂箱和第二酸液药剂箱共用一个计量加药泵，经过进一步优化pH值调节单元和酸碱度调节单元可共用一个多通道的计量加药泵，进一步降低生产成本；酸化箱、液体储存器共用一个真空泵，降低了生产成本；
(4)富里酸提取单元中吸附富集装置采用的填料均为XAD-8树脂、DAX-8树脂和XAD-7树脂的一种或多种，离子交换装置中的填料采用氢型阳离子交换树脂，可以更有效地对浓水中的杂质吸附和净化，获取浓度较高的溶解有机质液体；
(5)反应釜预留了惰性气体入口和出口，在生产中通过通入氮气、氦气等惰性气体，可以有效抑制强碱性条件下土壤憎水富里酸的氧化。
附图说明
图1是本发明提供的第一个实施例的结构示意图；
图2是本发明提供的第二个实施例的结构示意图；
图3是本发明提供的第三个实施例的结构示意图；
图4是本发明提供的第四个实施例的结构示意图。
具体实施方式
下面结合附图，对本发明的具体实施方式作详细的说明。
本发明提供了一种用于提取土壤憎水富里酸的设备，包括反应釜1、pH调节单元、第一过滤净化单元、酸化箱11、酸碱度调节单元、第二过滤净化单元、液体储存器14、富里酸提取单元和总控制系统6；其中反应釜1内设有土壤储存室2、支架3、搅拌器、液位传感器和pH传感器，所述土壤储存室2由支架3支撑并位于反应釜1内，土壤储存室2的外壁设有多个孔径小于1mm的孔；pH调节单元包括第一计量加药泵4和第一加药装置5；第一过滤净化单元包括过滤器7和真空泵12，其中第一过滤器7包括样品室71、滤膜72和砂芯73，滤膜72设于样品室71内，并由砂芯73支撑；酸碱度调节单元包括第二计量加药泵8、第一酸液药剂箱9和第二酸液药剂箱10；第二过滤净化单元包括第二过滤器13和真空泵12，第二过滤器13包括样品室131、滤膜132和砂芯133，滤膜132设于样品室131内，并由砂芯133 支撑；总控制系统6主要采用自动控制，其中集控操作在控制柜中统一进行，可使整个系统实现自动控制操作和手动操作。
其中，第一加药装置5通过第一计量加药泵4与反应釜1连接，第一计量加药泵4的入口与第一加药装置5连接，其出口与反应釜1连接；反应釜1的出口与第一过滤器7的入口连接，反应釜1与第一过滤器7之间的连接管道伸入反应釜1中，伸入反应釜管道的高度取值为反应釜1高度的1/20-1/10,且其外设有保护罩，所述保护罩上设有多个孔径为1mm的孔；第一过滤器7的出口与酸化箱11的入口连接，真空泵12的吸气口置于酸化箱11的腔体内；第一酸液药剂箱9和第二酸液药剂箱10并列布置，第二计量加药泵8设于第一酸液药剂箱9和第二酸液药剂箱10之间，第二计量加药泵8的入口与第一酸液药剂箱9的出口、第二酸液药剂箱10的出口连接，第二计量加药泵8的出口与酸化箱11连接，酸化箱11的出口与第二过滤器13的入口连接，酸化箱11内设有搅拌器和pH传感器；
第二过滤器13的出口与液体储存器14连接，真空泵12与液体储存器14连接；液体储存器14的出口与富里酸提取单元连接；
总控制系统6包括控制单元和触屏器，控制单元与触屏器连接，控制单元与搅拌器、液位传感器、pH传感器、第一计量加药泵4、第二计量泵8和真空泵12连接。
总控制系统采用低压配电，供配电设备的电压等级为220VAC，且设低压配电柜，向工艺系统动力设备供电。另外，控制系统中配备独立操作的控制柜，以及电器开关和电气元件都集中在控制柜内，电源开关与电控柜门联锁保护，可以达到防尘、散热快且易于安装的效果。
实施例一
参图1所示，图1是本发明提供的第一个实施例的结构示意图；在图1中，富里酸提取单元包括淋洗装置15a、有机溶剂药剂箱16a、第一吸附富集装置17a和第二吸附富集装置18a；其中，第一吸附富集装置17a的入口与液体储存器14的出口连接，其出口与第二吸附富集装置18a的入口连接；淋洗装置的出口15a、有机溶剂药剂箱16a的出口均与第一吸附富集装置17a的入口、第二吸附富集装置18a的入口连接；第一吸附富集装置17a的底部、第二吸附富集装置18a的底部均设有废液排出阀。
采用图1所示的结构图进行土壤憎水富里酸提取的过程如下：
首先开启总电源和启动按钮，使整个系统处于工作状态，向土壤储存室2中加入一定量研磨后的土壤样品，并关闭土壤储存室2；启动注水程序，向反应釜1中加入纯水，反应釜1中的液位传感器对反应釜1中的水位进行检测，当水位达到反应釜总体积的4/5时，液位传感器向总控制系统6发送液位信号，停止注水过程。
向反应釜中通入惰性气体，在惰性气体的保护下，启动pH调节单元，第一计量加药泵4接收位于反应釜1中的pH传感器信号启动碱液加入程序，第一加药装置5通过耐强碱管道向反应釜1中注入碱液，同时启动反应釜1中的搅拌马达，使得碱液均匀分散，直到达到预设的pH值，第一计量加药泵4停止工作。
持续搅拌，土壤储存室2中的土壤样品浸取液通过土壤储存室外壁上的孔流入反应釜1中。土壤储存室2外壁上设有多个孔径小于1mm的孔，可以有效地阻止土壤中的杂质进入到反应釜1的液体中；其中反应釜1采用耐碱材料，其上面设有密封盖，下端为漏斗形状，其内设有搅拌器、液位传感器和pH传感器，所述密封盖的端面设有至少5个通孔。
打开反应釜1的出口阀门，同时启动真空泵12，通过真空泵12施压，反应釜1中的液体通过第一过滤器7流入酸化箱11中，碱不溶杂质被滤膜72截留而去除，去除杂质后的液体通过滤膜72流入酸化箱11中。
酸化箱11采用耐酸耐碱材料，其上面设有密封盖，下端为漏斗形状，所述密封盖的端面设有至少5个通孔。
启动酸碱度调节单元，在总控制系统6中设置所需的pH值，其设定的pH值为0.5-1.5，并将此pH传感器信号传递到位于酸化箱11中的pH传感器，pH传感器将pH值信号传递给第二计量加药泵8，第二计量加药泵8接收位于酸化箱11中的pH传感器信号启动酸液加入程序，第二计量加药泵8从第一酸液药剂箱9抽取酸液通过第一耐酸管道向酸化箱11中注入非氧化性酸液，同时启动酸化箱11中搅拌马达，使得酸液均匀分散，直到达到预设的pH值，第二计量加药泵8第一通道加酸液程序停止工作，传感器升降台升起pH传感器探头；
第二计量加药泵8通过第二通道从第二酸液药剂箱10中抽提氢氟酸，通过第二耐酸管道向酸化箱11中注入氢氟酸，直到达到预设的氢氟酸浓度，第二计量加药泵8停止工作。
pH值调节单元和酸碱度调节单元可共用一个多通道计量加药泵。
完成酸碱度调节后，酸化箱中搅拌马达工作一定时间后关闭搅拌马达，使杂质充分沉淀，打开酸化箱11的出口阀门，同时启动真空泵12，通过真空泵12施压，酸化箱11中的溶液 通过第二过滤器13流入液体储存器14中，经第二过滤器13后酸不溶杂质被截留在滤膜132上，粗体富里酸溶液流入液体储存器14中。
完成过滤后，打开液体储存器的出口阀门，液体储存器中的粗提富里酸溶液通过管道依次流入第一吸附富集装置17a和第二吸附富集装置18a，富里酸被吸附在树脂上；
吸附完成后，打开淋洗装置15a与第一吸附富集装置17a之间的连通阀，同时打开第一吸附富集装置17a底部的废液排出阀，关闭第一吸附富集装置17a与第二吸附富集装置18a之间的连通阀；淋洗装置中的纯水通过管道注入第一吸附富集装置17a进行冲洗，冲洗液通过废液排出阀排出，完成对第一吸附富集装置17a的冲洗；
关闭淋洗装置15a与第一吸附富集装置17a之间的连通阀，同时关闭第一吸附富集装置17a底部的废液排出阀，打开有机溶剂药剂箱16a与第一吸附富集装置17a之间的连通阀，有机溶剂药剂箱通过耐有机管道向第一吸附富集装置17a中注入弱极性挥发性有机溶剂，被树脂吸附的富里酸溶液在弱极性挥发性有机溶剂的作用下发生解吸，收集流出液标记为富里酸溶液1；
关闭有机溶剂药剂箱16a与第一吸附富集装置17a之间的连通阀，打开淋洗装置与第二吸附富集装置18a之间的连通阀，同时打开第二吸附富集装置18a底部的废液排出阀，淋洗装置中的纯水通过管道注入第二吸附富集装置18a进行冲洗，冲洗液通过废液排出阀排出，完成对第二吸附富集装置18a的冲洗；
关闭淋洗装置15a与第二吸附富集装置18a之间的连通阀，同时关闭第二吸附富集装置18a底部的废液排出阀，打开有机溶剂药剂箱16a与第二吸附富集装置18a之间的连通阀，有机溶剂药剂箱16a通过耐有机管道向第二吸附富集装置18a中注入弱极性挥发性有机溶剂，被树脂吸附的富里酸溶液在弱极性挥发性有机溶剂的作用下发生解吸，收集流出液标记为富里酸溶液2；
合并富里酸溶液1和富里酸溶液2，旋转蒸发并氮吹或自然风干后得到固态土壤憎水富里酸。
实施例二
参图2所示，图2为本发明中第二个实施例的结构示意图；在图2中，富里酸提取单元包括淋洗装置15b、有机溶剂药剂箱16b和一级吸附富集装置17b，其中，一级吸附富集装置 17b的入口与液体储存器14的出口连接，淋洗装置、有机溶剂药剂箱的出口分别与一级吸附富集装置17b的入口连接；一级吸附富集装置17b的底部设有废液排出阀。
本实施例中土壤有机质的过滤、酸碱度的调节及富里酸粗提的过程均与实施例一中相同，区别在于富里酸提取单元的不同，本实施例中，富里酸的提取过程如下：完成过滤后，打开液体储存器的出口阀门，液体储存器中的粗提富里酸溶液通过管道流入一级吸附富集装置17b，富里酸被吸附在树脂上；
吸附完成后，打开淋洗装置15b与一级吸附富集装置17b之间的连通阀，同时打开一级吸附富集装置17b底部的废液排出阀；淋洗装置15b中的纯水通过管道注入一级吸附富集装置17b进行冲洗，冲洗液通过废液排出阀排出，完成对一级吸附富集装置17b的冲洗；
关闭淋洗装置15b与一级吸附富集装置17b之间的连通阀，同时关闭一级吸附富集装置17b底部的废液排出阀，打开有机溶剂药剂箱16b与一级吸附富集装置17b之间的连通阀，有机溶剂药剂箱16b通过耐有机管道向一级吸附富集装置17b中注入弱极性挥发性有机溶剂，被树脂吸附的富里酸溶液在弱极性挥发性有机溶剂的作用下发生解吸，收集流出液标记为富里酸溶液，旋转蒸发并氮吹或自然风干后得到固态土壤憎水富里酸。
实施例三
参图3所示，图3为本发明提供的第三个实施例的结构示意图。在图3中，富里酸提取单元包括淋洗装置15c、第二加药装置16c、吸附富集装置17c和离子交换装置18c；其中，吸附富集装置17c的入口与液体储存器14的出口连接，吸附富集装置17c的出口与离子交换装置18c的入口连接，淋洗装置15c的出口分别与吸附富集装置17c的入口、离子交换装置18c的入口连接，第二加药装置16c的出口与吸附富集装置17c的入口连接；吸附富集装置17c的底部、离子交换装置18c的底部均设有废液排出阀。
本实施例中土壤有机质的过滤、酸碱度的调节及富里酸粗提的过程均与实施例一中相同，区别在于富里酸提取单元的不同，本实施例中，富里酸的提取过程如下：完成过滤后，打开液体储存器14的出口阀门，液体储存器14中的粗提富里酸溶液通过管道流入吸附富集装置17c，富里酸被吸附在树脂上；
吸附完成后，打开淋洗装置15c与吸附富集装置17c之间的连通阀，同时打开吸附富集装置17c底部的废液排出阀，淋洗装置15c中的纯水通过管道注入吸附富集装置17c，对吸附富集装置17c进行冲洗，冲洗液直接从废液排出阀排出，完成对吸附富集装置17c的冲洗；
关闭淋洗装置15c与吸附富集装置17c之间的连通阀，同时关闭吸附富集装置17c底部的废液排出阀；打开淋洗装置15c与离子交换装置18c之间的连通阀，同时打开离子交换装置18c底部的废液排出阀，淋洗装置15c中的纯水通过管道注入离子交换装置18c，对离子交换装置18c进行冲洗，冲洗液直接从废液排出阀排出，完成对离子交换装置18c的冲洗；
关闭淋洗装置15c与离子交换装置18c之间的连通阀，同时关闭离子交换装置18c底部的废液排出阀，打开第二加药装置16c与吸附富集装置17c之间的连通阀，第二加药装置16c通过耐碱管道向吸附富集装置17c中注入碱液，被树脂吸附后的憎水富里酸在碱液的作用下发生解吸，解吸后的液体流入离子交换装置18c，经离子交换装置18c中的氢型阳离子交换树脂交换后排出，所排出的液体为所需提取的土壤憎水富里酸溶液，冷冻干燥后得到固态土壤憎水富里酸。
实施例四
参图4所示，图4为本发明提供的第四个实施例的结构示意图。在图4中，富里酸提取单元包括淋洗装置15d、第二加药装置16d、一级吸附富集装置17d、第一离子交换装置18d、二级吸附富集装置19d、第二离子交换装置20d；其中，一级吸附富集装置17d的入口与液体储存器14的出口连接，吸附富集装置17d的出口分别与所述第一离子交换装置18d的入口、二级吸附富集装置19d的入口连接；所述二级吸附富集装置19d的出口与所述第二离子交换装置20d的入口连接；所述淋洗装置15d的出口分别与所述一级吸附富集装置17d的入口、第一离子交换装置18d的入口、二级吸附富集装置19d的入口、第二离子交换装置20d的入口连接；所述第二加药装置16d的出口分别与所述一级吸附富集装置17d的入口、二级吸附富集装置19d的入口连接；
一级吸附富集装置17d的底部、第一离子交换装置18d的底部、二级吸附富集装置19d的底部、第二离子交换装置20d的底部均设有废液排出阀。
本实施例中土壤有机质的过滤、酸碱度的调节及富里酸的粗体过程与实施例一是相同的，区别在于富里酸提取单元的不同，在本实施例中，富里酸的提取过程如下：完成过滤后，打开液体储存器14的出口阀门，液体储存器14中的粗提富里酸溶液通过管道依次流入一级吸附富集装置17d和二级吸附富集装置19d，富里酸被吸附在树脂上；
一级吸附富集装置碱液洗脱：关闭一级吸附富集装置17d与二级吸附富集装置19d之间的连通阀，关闭一级吸附富集装置17d与第一离子交换装置18d之间的连通阀门，打开淋洗 装置15d与一级吸附富集装置17d之间的连通阀，打开一级吸附富集装置17d底部的废液排出阀，淋洗装置15d中的纯水通过管道冲洗一级吸附富集装置17d，冲洗废液通过废液排出阀排出，完成一级吸附富集装置17d的冲洗，关闭一级吸附富集装置17d底部的废液排出阀，关闭淋洗装置15d与一级吸附富集装置17d之间的连通阀；
打开淋洗装置15d与第一离子交换装置18d之间的连通阀，打开第一离子交换装置18d底部的废液排出阀，淋洗装置15d中的纯水通过管道冲洗第一离子交换装置18d，冲洗废液通过废液排出阀排出，完成第一离子交换装置18d的冲洗，关闭第一离子交换装置18d底部的废液排出阀，关闭淋洗装置15d与第一离子交换装置18d之间的连通阀；
打开第二加药装置16d与第一吸附富集装置17d之间的连通阀，打开一级吸附富集装置17d与第一离子交换装置18d之间的连通阀，第二加药装置16d中的碱液通过耐碱管道向一级吸附富集装置17d中注入碱液，被树脂吸附的富里酸在碱液的作用下发生解吸，解吸后的流出液经第一离子交换装置18d中的氢型阳离子交换树脂后排出，提取所排出的液体，直接冷冻干燥标记为富里酸亚组分1；
二级吸附富集装置碱液洗脱：关闭二级吸附富集装置19d与第二离子交换装置20d之间的连通阀门，打开淋洗装置15d与二级吸附富集装置19d之间的连通阀，打开二级吸附富集装置19d底部的废液排出阀，淋洗装置15d中的纯水通过管道冲洗二级吸附富集装置19d，冲洗废液通过废液排出阀排出，完成二级吸附富集装置19d的冲洗，关闭二级吸附富集装置19d底部的废液排出阀，关闭淋洗装置15d与二级吸附富集装置19d之间的连通阀；
打开淋洗装置15d与第二离子交换装置20d之间的连通阀，打开第二离子交换装置20d底部的废液排出阀，淋洗装置15d中的纯水通过管道冲洗第二离子交换装置20d，冲洗废液通过废液排出阀排出，完成第二离子交换装置20d的冲洗，关闭第二离子交换装置20d底部的废液排出阀，关闭淋洗装置15d与第二离子交换装置20d之间的连通阀；
打开第二加药装置16d与二级吸附富集装置19d之间的连通阀，打开二级吸附富集装置19d与第二离子交换装置20d之间的连通阀，第二加药装置16d通过耐碱管道向二级吸附富集装置19d中注入碱液，被树脂吸附后的富里酸溶液在碱液的作用下发生解吸，解吸后的流出液经第二离子交换装置20d中的氢型阳离子交换树脂交换后排出，提取所排出的液体，直接冷冻干燥标记为富里酸亚组分2；
合并富里酸亚组分1、2为富里酸固态样品。
pH值调节单元和酸碱度调节单元中的pH值调节的过程均为全自动的过程，节省了劳动力，降低了生产成本，并且调制的pH值的精确度比较高，配制的过程效率也较高。在pH调节过程中，开启搅拌器马达使搅拌器搅拌反应釜1、酸化箱11中的液体，可避免局部的pH值偏高或偏低。
所述第一过滤器中使用的滤膜为一次性滤膜，滤膜需要能耐受1mol/L强碱，滤膜按要求存储及使用，但不可使用玻璃纤维滤膜等含硅滤膜；所述第二过滤器中使用的滤膜为一次性滤膜，滤膜需要能耐受0.5mol/L强酸，滤膜按要求存储及使用，但不可使用玻璃纤维滤膜等含硅滤膜。
上文所述的一系列的详细说明仅仅是针对本发明的可行性实施方式的具体说明，它们并不是用以限制本发明的保护范围，在所述技术领域普通技术人员所具备的知识范围内，在不脱离本发明宗旨的前提下作出的各种变化均属于本发明的保护范围。

Claims (12)

  1. 一种用于提取土壤憎水富里酸的设备，包括反应釜、pH调节单元、第一过滤净化单元、酸化箱、酸碱度调节单元、第二过滤净化单元、液体储存器、富里酸提取单元和总控制系统；其特征在于，
    所述反应釜的入口与所述pH调节单元的出口连接，反应釜的出口与所述第一过滤净化单元的入口连接；
    所述第一过滤净化单元的出口与所述酸化箱的入口连接，所述酸化箱的入口还与所述酸碱度调节单元的出口连接，所述酸化箱的出口与所述第二过滤净化单元的入口连接，所述第二过滤净化单元的出口与所述液体储存器的入口连接；
    所述pH调节单元、酸碱度调节单元与所述总控制系统连接；
    所述富里酸提取单元包括淋洗装置、有机溶剂药剂箱、第一吸附富集装置和第二吸附富集装置；所述第一吸附富集装置的入口与所述液体储存器的出口连接，其出口与所述第二吸附富集装置的入口连接；
    所述淋洗装置的出口、有机溶剂药剂箱的出口均与所述第一吸附富集装置的入口、第二吸附富集装置的入口连接；
    所述第一吸附富集装置的底部、第二吸附富集装置的底部均设有废液排出阀。
  2. 如权利要求1所述的用于提取土壤憎水富里酸的设备，其特征在于，所述富里酸提取单元包括淋洗装置、有机溶剂药剂箱和一级吸附富集装置；所述一级吸附富集装置的入口分别与所述液体储存器的出口、淋洗装置的出口、有机溶剂药剂箱的出口连接；
    所述一级吸附富集装置的底部设有废液排出阀。
  3. 如权利要求1所述的用于提取土壤憎水富里酸的设备，其特征在于，所述富里酸提取单元包括淋洗装置、第二加药装置、吸附富集装置和离子交换装置，所述吸附富集装置的入口与所述液体储存器的出口连接，所述吸附富集装置的入口还与所述淋洗装置的出口、第二加药装置的出口连接，所述吸附富集装置的出口与所述离子交换装置的入口连接，所述吸附富集装置的底部设有废液排出阀；
    所述离子交换装置的入口还与所述淋洗装置的出口连接。
  4. 如权利要求1所述的用于提取土壤憎水富里酸的设备，其特征在于，所述富里酸提取单元包括淋洗装置、第二加药装置、一级吸附富集装置、第一离子交换装置、二级吸附富集 装置、第二离子交换装置；所述一级吸附富集装置的入口与所述液体储存器的出口连接，一级吸附富集装置的出口分别与所述第一离子交换装置的出口、二级吸附富集装置的入口连接；所述二级吸附富集装置的出口与所述第二离子交换装置的入口连接；所述淋洗装置的出口分别与所述一级吸附富集装置的入口、第一离子交换装置的入口、二级吸附富集装置的入口、第二离子交换装置的入口连接；所述第二加药装置的出口分别与所述一级吸附富集装置的入口、二级吸附富集装置的入口连接；
    所述一级吸附富集装置的底部、二级吸附富集装置的底部、第一离子交换装置的底部、第二离子交换装置的底部均设有废液排出阀。
  5. 如权利要求1所述的用于提取土壤憎水富里酸的设备，其特征在于，所述反应釜内设有土壤储存室，所述土壤储存室由支架支撑并位于反应釜内；所述土壤储存室的外壁上设有多个孔径小于1mm的孔；
    所述反应釜采用耐碱材料，其上面设有密封盖，下端为漏斗形状，反应釜内还设有搅拌器、液位传感器和pH传感器；所述密封盖的端面设有至少5个通孔。
  6. 如权利要求1所述的用于提取土壤憎水富里酸的设备，其特征在于，所述pH调节单元包括第一计量加药泵和第一加药装置，第一计量加药泵设于所述第一加药装置与所述反应釜之间，所述第一计量加药泵的入口与所述第一加药装置的出口连接，所述第一计量加药泵的出口与所述反应釜的入口连接。
  7. 如权利要求1所述的用于提取土壤憎水富里酸的设备，其特征在于，所述第一过滤净化单元包括第一过滤器和真空泵；所述第一过滤器的入口通过管道与所述反应釜的出口连接，所述第一过滤器的出口与所述酸化箱的入口连接；所述真空泵与所述酸化箱连接；
    所述反应釜与所述第一过滤器之间的管道伸入反应釜，所述伸入反应釜的管道高度取值为反应釜高度的1/20-1/10，且其外设有保护罩，所述保护罩上设有多个孔径为1mm的孔；
    所述第一过滤器与所述酸化箱之间的管道伸入酸化箱内，所述伸入酸化箱的管道位于所述酸化箱中液面之上；所述真空泵的吸气口位于所述酸化箱中液面之上。
  8. 如权利要求1所述的用于提取土壤憎水富里酸的设备，其特征在于，所述酸碱度调节单元包括pH传感器、搅拌器、第一酸液药剂箱、第二酸液药剂箱和第二计量加药泵；所述pH传感器和搅拌器设于所述酸化箱内；所述第一酸液药剂箱和第二酸液药剂箱并列布置；所 述第二计量加药泵的入口分别与第一酸液药剂箱的出口、第二酸液药剂箱的出口连接，第二计量加药泵的出口与所述酸化箱的入口连接。
  9. 如权利要求1所述的用于提取土壤憎水富里酸的设备，其特征在于，所述第二过滤净化单元包括第二过滤器和真空泵，所述第二过滤器的入口与所述酸化箱的出口连接，所述第二过滤器的出口与所述液体储存器的入口连接；所述液体储存器的出口与所述第一吸附富集装置的入口连接；所述真空泵的吸气口位于所述液体储存器中液面之上。
  10. 如权利要求1所述的用于提取土壤憎水富里酸的设备，其特征在于，所述总控制系统包括控制单元和触屏器，所述控制单元均与所述反应釜内的pH传感器、搅拌器、液位传感器、第一计量加药泵、第二计量加药泵、真空泵、酸化箱内的pH传感器、搅拌器控制连接；所述pH传感器设有升降台。
  11. 利用权利要求1-10任一所述的用于提取土壤憎水富里酸的设备进行土壤憎水富里酸组分提取的方法，其特征在于，其包括如下步骤：
    (1)土壤加入到土壤储存室中，并向反应釜中注入纯水；
    (2)启动pH调节单元，第一计量加药泵接收位于反应釜中pH传感器信号启动碱液加入程序，第一加药装置通过耐强碱管道向反应釜中注入碱液，同时启动反应釜中的搅拌马达，使碱液均匀分散，直到达到预设的pH值，第一计量加药泵停止工作；
    (3)打开反应釜的出口阀门，同时启动真空泵，反应釜中的液体经真空泵施压通过第一过滤器流入酸化箱内，碱不溶杂质被滤膜截留而去除，去除杂质后的液体通过滤膜流入酸化箱内；
    (4)启动酸碱度调节单元，第二计量加药泵接收位于酸化箱中的pH传感器信号启动酸液加入程序，第二计量加药泵通过第一通道从第一酸液药剂箱抽取酸液通过第一耐酸管道向酸化箱中注入非氧化性酸液，同时启动酸化箱中搅拌马达，使得酸液均匀分散，直至达到预设的pH值，第二计量加药泵第一通道加酸液程序停止工作，传感器升降台升起pH传感器探头；
    第二计量加药泵通过第二通道从第二酸液药剂箱抽取氢氟酸通过第二耐酸管道注入酸化箱中，直到达到预设的氢氟酸浓度，第二计量加药泵停止工作；
    (5)完成pH值调节后，打开酸化箱的出口阀门，同时启动真空泵，通过真空泵施压，酸化箱中的溶液通过第二过滤器流入液体储存器中，酸不溶杂质被第二过滤器中的滤膜截留而去除，去除杂质后的粗体富里酸溶液通过滤膜流入液体储存器中；
    (6)完成过滤后，打开液体储存器的出口阀门，液体储存器中的粗提富里酸溶液通过管道依次流入第一吸附富集装置和第二吸附富集装置，富里酸被吸附在树脂上；
    (7)吸附完成后，打开淋洗装置与第一吸附富集装置之间的连通阀，同时打开第一吸附富集装置底部的废液排出阀，关闭第一吸附富集装置与第二吸附富集装置之间的连通阀；淋洗装置中的纯水通过管道注入第一吸附富集装置进行冲洗，冲洗液通过废液排出阀排出，完成对第一吸附富集装置的冲洗；
    关闭淋洗装置与第一吸附富集装置之间的连通阀，同时关闭第一吸附富集装置底部的废液排出阀，打开有机溶剂药剂箱与第一吸附富集装置之间的连通阀，有机溶剂药剂箱通过耐有机管道向第一吸附富集装置中注入弱极性挥发性有机溶剂，被树脂吸附的富里酸溶液在弱极性挥发性有机溶剂的作用下发生解吸，收集流出液标记为富里酸溶液1；
    (8)关闭有机溶剂药剂箱与第一吸附富集装置之间的连通阀，打开淋洗装置与第二吸附富集装置之间的连通阀，同时打开第二吸附富集装置底部的废液排出阀，淋洗装置中的纯水通过管道注入第二吸附富集装置进行冲洗，冲洗液通过废液排出阀排出，完成对第二吸附富集装置的冲洗；
    关闭淋洗装置与第二吸附富集装置之间的连通阀，同时关闭第二吸附富集装置底部的废液排出阀，打开有机溶剂药剂箱与第二吸附富集装置之间的连通阀，有机溶剂药剂箱通过耐有机管道向第二吸附富集装置中注入弱极性挥发性有机溶剂，被树脂吸附的富里酸溶液在弱极性挥发性有机溶剂的作用下发生解吸，收集流出液标记为富里酸溶液2；
    合并富里酸溶液1和富里酸溶液2，旋转蒸发并氮吹或自然风干后得到固态土壤憎水富里酸。
  12. 如权利要求11所述的土壤憎水富里酸组分提取方法，其特征在于，所述第一加药装置中的碱液为饱和或近饱和强碱溶液；所述耐强碱管道要求能承受饱和强碱，所述耐碱管道要求能承受0.001-0.5mol/L的强碱；所述反应釜中液体的pH预设值为10-14。
    所述第一耐酸管道要求能承受10mol/L的非氧化性强酸；所述第二耐酸管道要求能承受6mol/L的氢氟酸；所述酸化箱中氢氟酸的预设浓度为0.01-1mol/L；所述酸化箱中液体的pH预设值为0.5-1.5；
    所述有机溶剂药剂箱和耐有机管道中的弱极性挥发性有机溶剂为甲醇、乙醇或其混合物。
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