CN109485367A - A kind of preparation method and application of filling phosphorous gypsum body - Google Patents
A kind of preparation method and application of filling phosphorous gypsum body Download PDFInfo
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- CN109485367A CN109485367A CN201910012823.9A CN201910012823A CN109485367A CN 109485367 A CN109485367 A CN 109485367A CN 201910012823 A CN201910012823 A CN 201910012823A CN 109485367 A CN109485367 A CN 109485367A
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- phosphorous gypsum
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- 238000011049 filling Methods 0.000 title claims abstract description 54
- 239000010440 gypsum Substances 0.000 title claims abstract description 52
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 52
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 38
- 241000894006 Bacteria Species 0.000 claims abstract description 35
- 241000193395 Sporosarcina pasteurii Species 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 60
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- 239000004202 carbamide Substances 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000001110 calcium chloride Substances 0.000 claims description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 235000015097 nutrients Nutrition 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 5
- AIUDWMLXCFRVDR-UHFFFAOYSA-N dimethyl 2-(3-ethyl-3-methylpentyl)propanedioate Chemical compound CCC(C)(CC)CCC(C(=O)OC)C(=O)OC AIUDWMLXCFRVDR-UHFFFAOYSA-N 0.000 claims description 5
- 230000000813 microbial effect Effects 0.000 claims description 5
- 108010009004 proteose-peptone Proteins 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 238000012423 maintenance Methods 0.000 claims description 4
- 230000002045 lasting effect Effects 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 8
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 4
- 239000002068 microbial inoculum Substances 0.000 abstract description 4
- 101000965313 Legionella pneumophila subsp. pneumophila (strain Philadelphia 1 / ATCC 33152 / DSM 7513) Aconitate hydratase A Proteins 0.000 abstract description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002054 inoculum Substances 0.000 description 3
- 238000009630 liquid culture Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000001038 titanium pigment Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010430 carbonatite Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical group O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 206010035653 pneumoconiosis Diseases 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/142—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/143—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being phosphogypsum
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
- E21F15/00—Methods or devices for placing filling-up materials in underground workings
- E21F15/005—Methods or devices for placing filling-up materials in underground workings characterised by the kind or composition of the backfilling material
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Mining & Mineral Resources (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods of filling phosphorous gypsum body, comprising the following steps: the configuration of bacterium solution；The configuration of cementing solution；The preparation of ardealite slurry；The preparation of filling phosphorous gypsum slurry；The preparation of filling phosphorous gypsum body.The present invention utilizes the MICP technology of Bacillus pasteurii, utilize the interaction between bacterium solution, cementing solution, ardealite powder, so that it is generated part calcium carbonate realizes the secondary use of ardealite so that ardealite is changed into such a concretion state of obturation by loose state.The present invention is mainly that the microbial inoculum that utilizes prepares filling phosphorous gypsum body, and compared to traditional cementitious material is added, cost is greatly lowered, and from uniaxial compressive strength for, can reach 800KPa, met the requirement of obturation.Its soluble fluoride of the filling phosphorous gypsum body obtained by means of the present invention and soluble phosphorus pentoxide decreased significantly relative to the technique for being not added with microbial inoculum, reduce point danger of secondary pollution.
Description
Technical field
The invention belongs to phosphorous chemical industry waste material functionalization to utilize technical field, and in particular to a kind of preparation of filling phosphorous gypsum body
Method and application.
Background technique
Ardealite be in phosphoric acid production with sulfuric acid treating phosphorite when the by-product that generates, main component is sulfate dihydrate
Calcium causes serious environmental pollution, and the particle of ardealite wherein containing the objectionable impurities such as a large amount of residual acid and phosphorus, fluorine
Fugitive dust can more carefully be generated and cause dust pollution, and the little particle in fugitive dust easily enters human lung, will lead to pneumoconiosis for a long time very
It is huge to human health damage to causing slow poisoning, while periphery animal and plant growth is influenced, the ecological balance is destroyed, pole is caused
Bad social influence causes great economic loss to country and enterprise.For solve ardealite stockpiling bring environmental problem,
The waste utilization for realizing ardealite has Some Enterprises that just ardealite and some cementitious materials such as cement, alkali-activated carbonatite are gelled at present
The blendings such as agent are prepared into the obturation of ardealite, can be used for the back production filling in mine.But cement, the alkali-activated carbonatite gelling agent used
Etc. higher costs, the hydration reaction that preparation process usually occurs under alkaline condition come formed gel to ardealite material carry out
It is cementing, thus obturation is all in strong basicity within a very long time, causes greatly waste and environmental pollution；And it uses
The content of above-mentioned preparation method, the soluble fluoride of obtained filling phosphorous gypsum body and soluble phosphorus pentoxide is higher, Yi Zao
At secondary pollution.
Summary of the invention
The object of the present invention is to provide a kind of at low cost, the preparation method and application of few filling phosphorous gypsum body are polluted.
The preparation method of this filling phosphorous gypsum body of the present invention, comprising the following steps:
1) it the configuration of bacterium solution: after Bacillus pasteurii is activated, is cultivated in liquid medium, obtains bacterium solution；
2) configuration of cementing solution: aqueous solution of the configuration containing urea and calcium chloride, as cementing solution；
3) preparation of ardealite slurry: by the bacterium solution in step 1), the cementing solution in step 2) and ardealite according to setting
Certainty ratio is mixed, and after mixing pulp, obtains ardealite slurry；
4) preparation of filling phosphorous gypsum slurry: every setting time, the supernatant liquor of separation of phosphorus gypsum slurry, then to it
The middle mixed solution that fresh bacterium solution and cementing solution is added, after stirring and evenly mixing, lasting aeration keeps microbial activity, is continuously added into
After mixed solution 4~6 times, filling phosphorous gypsum slurry is obtained；
5) it the preparation of filling phosphorous gypsum body: by the filling phosphorous gypsum filled therewith in step 4) to goaf, is conserved
Afterwards, ardealite obturator is obtained.
In the step 1), fluid nutrient medium be containing soy peptone 5g/L, casein peptone 15g/L, sodium chloride 5g/L,
Urea 20g/L, pH 7.3；The OD of bacterium solution600Value should be between 1~2.
In the step 2), in the aqueous solution containing urea and calcium chloride, the concentration of urea is 0.5~1.5mol/L；Chlorination
The concentration of calcium is 0.5~1.5mol/L, and the molar ratio of urea and calcium chloride is 1:1.
In the step 3), the mass ratio of bacterium solution, cementing solution and ardealite is 1:(1~1.5): (1~3).
In the step 4), the mixed proportion of bacterium solution and cementing solution is 1:(1~1.5), mixed solution and ardealite are starched
The mass ratio of material is (5~12): 1；Setting time is 2~3 days, is added after mixed solution stirs and evenly mixs, need to stand 24~
48h。
In the step 5), the temperature of maintenance is 19~21 DEG C, and maintenance humidity is 90~95%.
Beneficial effects of the present invention: 1) present invention utilizes the MICP technology of Bacillus pasteurii, utilizes bacterium solution, cementing molten
Interaction between liquid, ardealite powder makes it generate part calcium carbonate, fills so that ardealite is changed by loose state
Such a concretion state of body is filled out, the secondary use of ardealite is realized.2) the microbial inoculum system that the present invention mainly utilizes
Standby filling phosphorous gypsum body, compared to traditional cementitious material is added, cost is greatly lowered, and from uniaxial compressive strength
For, reach 800KPa or more, meets the requirement of obturation.3) the filling phosphorous gypsum body obtained by means of the present invention
Its soluble fluoride and soluble phosphorus pentoxide relative to the technique for being not added with microbial inoculum, have dropped 98.3% He respectively
78.9%, the release of harmful substance in obturation is effectively reduced, point danger of secondary pollution is reduced.4) micro- life through the invention
The method of object cementing filling ardealite can make full use of nature microorganism resource, and production efficiently, while improving phosphorus
The mechanical property of gypsum base filler reduces harmful substance release, improves ardealite resource utilization rate, reduce enterprise
The filling phosphorous gypsum cost environments of industry pollute.
Specific embodiment
Ardealite used in embodiment is the solid waste of phosphatic fertilizer company, opens phosphorus (group) Limited Liability from Guizhou
Company, ardealite pH are 6.29, and partial size nonuniform coefficent Cu is 4.08.
Embodiment 1
1) configuration of bacterium solution: soy peptone 5g, casein peptone 15g, sodium chloride 5g and 950mL deionized water are weighed and is prepared
Fluid nutrient medium is adjusted to pH=7.3 ± 0.2 with 2M NaOH.It weighs 20g urea to be dissolved in the deionized water of 50ml, Liquid Culture
Base adds the urea liquid filtered through 0.30um filter after 120 DEG C of autoclave sterilization 20min.With 1% inoculum concentration
Bacillus pasteurii is inoculated in configured fluid nutrient medium, obtains required bacterium for 24 hours in shaking table shaken cultivation at 30 DEG C
Liquid measures bacterium solution OD600It is 1.53.
2) cementing solution: the mixed aqueous solution for containing urea and calcium chloride is prepared as cementing solution；Wherein urea and chlorine
The concentration for changing calcium is 1mol/L.
3) preparation of ardealite slurry: according to ardealite: bacterium solution: the weight ratio of consolidating fluid is that 2:1:1 mixes ardealite,
After carrying out pulp, ardealite slurry is obtained.
4) preparation of filling phosphorous gypsum slurry: every 2 days, the clear liquid on separation of phosphorus gypsum slurry upper layer then added thereto
Entering the mixed solution of bacterium solution and cementing solution, (wherein bacterium solution and the mixed proportion of cementing solution are 1:1, mixed solution and ardealite
The mass ratio of slurry is 1:8), after stirring and evenly mixing, stands for 24 hours and continue aeration holding microbial activity.When according to above-mentioned interval
Between and operate, circulation 5 times after, obtain filling phosphorous gypsum slurry.
5) preparation of filling phosphorous gypsum body: relatively wet by filling phosphorous gypsum filled therewith to goaf, and at 20 ± 2 DEG C
Degree is is conserved in 95% filling environment after, ardealite obturator is obtained.
Comparative example
1) preparation of ardealite slurry: according to ardealite: the weight ratio of deionized water is that ardealite is mixed, carried out by 1:1
Pulp obtains ardealite slurry.
2) preparation of filling phosphorous gypsum slurry: the supernatant liquor in 2 days, separation of phosphorus gypsum slurry, then thereto
Deionized water (wherein the mass ratio of water and ardealite slurry is 1:8) is added, after stirring and evenly mixing, stands for 24 hours and continues to be aerated.It presses
Filling phosphorous gypsum slurry is obtained after recycling 5 times according to above-mentioned interval time and operation.
3) preparation of filling phosphorous gypsum body: relatively wet by filling phosphorous gypsum filled therewith to goaf, and at 20 ± 2 DEG C
Degree is is conserved in 95% filling environment after, ardealite obturator is obtained.
The supernatant liquor and obturation that step 4) obtained by embodiment and comparative example is isolated in 2 performance test of embodiment
Test analysis is carried out, specific test analysis mode is as follows:
1. the measurement of soluble impurity in supernatant liquor: taking out after filling diffusate and filtered using 0.45 μm of filter paper, obtained
It is spare to filtered diffusate.
(1) titanium pigment measures: taking 50ml supernatant liquor to move into 50ml color-comparison tube with pipette point, then fills in tool
10% ascorbic acid solution of 1ml is added in colorimetric cylinder, mixes.Add 2ml molybdate solution after 30s and mix well, places
15min is finally measured at 700nm wavelength using cuvette and spectrophotometer.
(2) soluble fluoride measures: then quasi- with the pH of hydrochloric acid or sodium hydroxide solution control supernatant liquor between 2~12
5mL solution is really measured in 50mL volumetric flask, then pipettes 25mL respectively, TISAB solution is then added in above-mentioned volumetric flask, uses
Deionized water dilution constant volume simultaneously shakes up, then moves it into 100ml polyethylene cup and be inserted into fluoride ion selective electrode, when measurement balances
Potential value, finally calculate fluorine content.
2. maximum uniaxial compressive strength measurement: using routine 10kN rock servo testing machine test filling sample without lateral confinement
Compression strength.By test specimen be placed in pressure testing machine bearing plate center, using 0.5mm/min loading speed to each group sample into
Row load is until destroy.
Specific test result such as table 1.
Table 1
| Test item | Comparative example | Embodiment 1 |
| Titanium pigment (mgl/L) | 13.5 | 2.8 |
| Soluble fluoride (mg/L) | 35.21 | 2.36 |
| Maximum uniaxial compressive strength (KPa) | 110 | 800 |
From the data in table 1, it can be seen that further can unexpectedly reduce filling slurry in the case where adding calcium source outside and secrete water outlet
The dissolution and promotion filling phosphorous gypsum body intensity of middle nuisance.And the oxidation of solubility five two in diffusate is filled in embodiment
The content of phosphorus and soluble fluoride is substantially reduced, and illustrates the processing mode of MICP, can reduce the precipitation of harmful solable matter.
Embodiment 3
1) configuration of bacterium solution: soy peptone 5g, casein peptone 15g, sodium chloride 5g and 950mL deionized water are weighed and is prepared
Fluid nutrient medium is adjusted to pH=7.3 ± 0.2 with 2M NaOH.It weighs 20g urea to be dissolved in the deionized water of 50ml, Liquid Culture
Base adds the urea liquid filtered through 0.30um filter after 120 DEG C of autoclave sterilization 20min.With 1% inoculum concentration
Bacillus pasteurii is inoculated in configured fluid nutrient medium, obtains required bacterium for 24 hours in shaking table shaken cultivation at 30 DEG C
Liquid measures bacterium solution OD600It is 1.53.
2) cementing solution: the mixed aqueous solution for containing urea and calcium chloride is prepared as cementing solution；Wherein urea and chlorine
The concentration for changing calcium is 0.5mol/L.
3) preparation of ardealite slurry: according to ardealite: bacterium solution: the weight ratio of consolidating fluid is 1:1:1.5, and ardealite is mixed
It closes, after carrying out pulp, obtains ardealite slurry.
4) preparation of filling phosphorous gypsum slurry: every 3 days, the clear liquid on separation of phosphorus gypsum slurry upper layer then added thereto
Entering the mixed solution of bacterium solution and cementing solution, (wherein bacterium solution and the mixed proportion of cementing solution are 1:1.2, mixed solution and phosphorus stone
The mass ratio of cream slurry is 1:5), after stirring and evenly mixing, stands 36h and continue aeration holding microbial activity.According to above-mentioned interval
Time and operation obtain filling phosphorous gypsum slurry after recycling 4 times.
5) preparation of filling phosphorous gypsum body: relatively wet by filling phosphorous gypsum filled therewith to goaf, and at 20 ± 2 DEG C
Degree is is conserved in 95% filling environment after, ardealite obturator is obtained.
Embodiment 4
1) configuration of bacterium solution: soy peptone 5g, casein peptone 15g, sodium chloride 5g and 950mL deionized water are weighed and is prepared
Fluid nutrient medium is adjusted to pH=7.3 ± 0.2 with 2M NaOH.It weighs 20g urea to be dissolved in the deionized water of 50ml, Liquid Culture
Base adds the urea liquid filtered through 0.30um filter after 120 DEG C of autoclave sterilization 20min.With 1% inoculum concentration
Bacillus pasteurii is inoculated in configured fluid nutrient medium, obtains required bacterium for 24 hours in shaking table shaken cultivation at 30 DEG C
Liquid measures bacterium solution OD600It is 1.53.
2) cementing solution: the mixed aqueous solution for containing urea and calcium chloride is prepared as cementing solution；Wherein urea and chlorine
The concentration for changing calcium is 1.5mol/L.
3) preparation of ardealite slurry: according to ardealite: bacterium solution: the weight ratio of consolidating fluid is that 3:1:1 mixes ardealite,
After carrying out pulp, ardealite slurry is obtained.
4) preparation of filling phosphorous gypsum slurry: every 2 days, the clear liquid on separation of phosphorus gypsum slurry upper layer then added thereto
Entering the mixed solution of bacterium solution and cementing solution, (wherein bacterium solution and the mixed proportion of cementing solution are 1:1.5, mixed solution and phosphorus stone
The mass ratio of cream slurry is 1:12), after stirring and evenly mixing, stands 48h and continue aeration holding microbial activity.According to above-mentioned interval
Time and operation obtain filling phosphorous gypsum slurry after recycling 6 times.
5) preparation of filling phosphorous gypsum body: relatively wet by filling phosphorous gypsum filled therewith to goaf, and at 20 ± 2 DEG C
Degree is is conserved in 95% filling environment after, ardealite obturator is obtained.
The supernatant liquor isolated in embodiment 3 and embodiment 4 is carried out to the measurement of soluble impurity, and is filled to obtained
It fills out body and carries out maximum uniaxial compressive strength measurement, result such as table 2
Table 2
| Test item | Embodiment 3 | Embodiment 4 |
| Titanium pigment (mgl/L) | 2.2 | 1.15 |
| Soluble fluoride (mg/L) | 1.87 | 1.59 |
| Maximum uniaxial compressive strength (KPa) | 742 | 744 |
Claims (6)
1. a kind of preparation method of filling phosphorous gypsum body, comprising the following steps:
1) it the configuration of bacterium solution: after Bacillus pasteurii is activated, is cultivated in liquid medium, obtains bacterium solution；
2) configuration of cementing solution: aqueous solution of the configuration containing urea and calcium chloride, as cementing solution；
3) preparation of ardealite slurry: by the bacterium solution in step 1), the cementing solution in step 2) and ardealite according to setting ratio
Example is mixed, and after mixing pulp, obtains ardealite slurry；
4) preparation of filling phosphorous gypsum slurry: every setting time, the supernatant liquor of separation of phosphorus gypsum slurry, then thereto in
The mixed solution of fresh bacterium solution Yu cementing solution is added, after stirring and evenly mixing, lasting aeration keeps microbial activity, is continuously added into mixed
After closing solution 4~6 times, filling phosphorous gypsum slurry is obtained；
5) preparation of filling phosphorous gypsum body: the filling phosphorous gypsum filled therewith in step 4) to goaf after being conserved, obtains
To ardealite obturator.
2. the preparation method of filling phosphorous gypsum body according to claim 1, which is characterized in that described in the step 1)
In step 1), fluid nutrient medium is to contain soy peptone 5g/L, casein peptone 15g/L, sodium chloride 5g/L, urea 20g/L, pH
It is 7.3；The OD of bacterium solution600Value should be between 1~2.
3. the preparation method of filling phosphorous gypsum body according to claim 1, which is characterized in that described in the step 2)
In step 2), in the aqueous solution containing urea and calcium chloride, the concentration of urea is 0.5~1.5mol/L；The concentration of calcium chloride is 0.5
The molar ratio of~1.5mol/L, urea and calcium chloride is 1:1.
4. the preparation method of filling phosphorous gypsum body according to claim 1, which is characterized in that described in the step 3)
In step 3), the mass ratio of bacterium solution, cementing solution and ardealite is 1:(1~1.5): (1~3).
5. the preparation method of filling phosphorous gypsum body according to claim 1, which is characterized in that described in the step 4)
In step 4), the mixed proportion of bacterium solution and cementing solution is 1:(1~1.5), the mass ratio of mixed solution and ardealite slurry is
(5~12): 1；Setting time is 2~3 days, after addition mixed solution stirs and evenly mixs, needs to stand 24~48h.
6. the preparation method of filling phosphorous gypsum body according to claim 1, which is characterized in that described in the step 5)
In step 5), the temperature of maintenance is 19~21 DEG C, and maintenance humidity is 90~95%.
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