CN107694512A - A kind of preparation method of removal of heavy metal ions agent - Google Patents
A kind of preparation method of removal of heavy metal ions agent Download PDFInfo
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- CN107694512A CN107694512A CN201710868060.9A CN201710868060A CN107694512A CN 107694512 A CN107694512 A CN 107694512A CN 201710868060 A CN201710868060 A CN 201710868060A CN 107694512 A CN107694512 A CN 107694512A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The present invention provides a kind of preparation method of removal of heavy metal ions agent, uses discarded hardened cement concrete as raw material, and preparation method is warp just broken and pre-burning, crushing and separation, ball milling activation, selects powder to separate.The heavy metal ion in the waste water such as cupric, zinc, chromium, nickel can effectively be removed, process implementation process has that removing heavy metals ion velocity is fast, and the reaction time is short, removal effect is stable, the advantages that can operating at room temperature.By the technology applications expanding of petrifying water mudstone this building castoff in discarded concrete to heavy metal-polluted water harnessing field, in the absence of limit doped amount problem, the resource utilization efficiency of waste water mudstone is improved, improves the economic value added of waste water mudstone.
Description
Technical field
The present invention relates to utilization of waste as resource and technical field of heavy metal wastewater treatment, and in particular to one kind is based on useless
Abandon heavy metal wastewater thereby remover, the preparation method and application of petrifying water mudstone.
Background technology
Substantial amounts of building waste can be produced in the construction of building or structures, the construction industry activity such as finishing, removal, and
With the quickening quickly propelled with urbanization speed of China's infrastructure, building waste yield continues to increase.City according to statistics
It is building waste that 1/3 is there are about in city's rubbish；To its storage of the end of the year 2011 more than 2,000,000,000 tons, and newly-increased building waste exceedes every year
300000000 tons.Because the factory addressing of building waste landfill is improper in most cities or interim stacking, the big of land resource is not only caused
There is also great potential safety hazard for amount waste.For example, on December 20th, 2015, landslide, landslide occur for Shenzhen City, Guangdong Province
About 380,000 square metres of area coverage, victim 73 is had found by the end of on January 28th, 2016, and still there are 4 personnel's lost contacts.State
Institute " 1220 " landslide event disaster investigation group of being engaged in is assert through investigation, different from conventional landslide property, this time thing
Original massif does not slide in therefore, but by accumulating excess and the excessively steep landfill body of the gradient in the receiving factory of stacking building waste
Unstability collapses, slip causes.Meanwhile building waste during accumulation and landfill with the aqueous phase interaction in surrounding environment, its
Percolate can cause the pollution of surface water or underground water.
Discarded hardened cement concrete mainly includes discarded petrifying water mudstone, and it is the important component of building waste,
Account for the 34% of building waste total amount.And China's discarded concrete resource utilization rate is less than 5%.Recycling profit main at present
It is to prepare Aggregate of recycled concrete with approach, but a large amount of petrifying water mudstones is often adhered on regeneration aggregate surface, because it is higher
Porosity and water absorption rate and cause regeneration aggregate mechanical properties decrease compared with low-intensity, regeneration concrete workability is deteriorated, firmly
Volume stability deteriorates after change.So a large amount of petrifying water mudstones turn into the discarded concrete system of restriction in discarded hardened cement concrete
The principal element of standby regeneration aggregate.
To the relative shortage of research of utilization of petrifying water mudstone in discarded concrete, only research has focused largely on
Prepare building material field, such as prepare building block or again calcining prepare cement etc..But due to waste water mudstone porosity
Greatly, the building material product construction that thick water requirement is high, activity index is low, limit doped amount in use all be present, is prepared with it is marked
Performance and mechanical property are poor.Simultaneously because the gelled matrix separated from discarded concrete contains a certain amount of inertia titanium dioxide
Silicon, this is also next difficult to the burning zone of cement raw grinding and clinker, makes f-CaO contents increase in clinker, and clinker quality declines,
Production cost improves.
Be for one of more ripe processing mode of discarded concrete at present, by after discarded concrete crushing and screening to
Prepare Aggregate of recycled concrete.But a large amount of waste water mudstones are generated in the process, because its porosity is high, water absorption rate is big,
Low intensity, it is difficult to for preparing regeneration concrete, this turns into the main restricting factor of this technological means.In the prior art to useless
Abandoning the recycling of petrifying water mudstone in concrete also includes preparing building block or again calcined for production of Portland cement etc..
But because waste water mudstone porosity is big, mark that thick water requirement is high, activity index is low, limit doped amount in use all be present,
It is poor with the building material product workability and mechanical property of its preparation.Simultaneously because the gelled matrix separated from discarded concrete
Containing a certain amount of inertia silica, this is also next difficult to the burning zone of cement raw grinding and clinker, makes f-CaO in clinker
Content increase, clinker quality decline, and production cost improves.
On the other hand, the heavy metal pollution usually environmental pollution as caused by heavy metal ion and its compound, heavy metal
Pollution be difficult to degrade in the environment, can be progressively enriched with by food chain in animal and plant cylinder accumulation, into human body after to kidney
Dirty, liver, brain, nerve, eyesight etc. is caused compared with macrolesion, is to endanger one of maximum pollutant of human health.Heavy metal from
The source of son mainly based on the discharge of waste water in industrial production, such as non-ferrous metal pick up industry, plating, electrolysis, leather manufacture,
Printing and dyeing, coal preparation plant's discharge of wastewater etc..For handling process side's method of heavy metal wastewater thereby, it is conventional include chemical precipitation, electrolysis,
The multiple means such as electrodialysis and physical absorption, solvent extraction.Wherein chemical precipitation method due to handling process it is simple, adapt to
Property it is strong, easily operated the advantages that, turn into be most widely used at present processing heavy metal wastewater thereby technological means.And absorption method by
Had a clear superiority in terms of trace heavy metal ion is handled, so also having in the advanced treating of heavy metal wastewater thereby wide
Application.But above two method is required for adding a large amount of chemical agents in use, this turn into chemical precipitation method and
The main cost source of absorption method.How to reduce reagent cost, exploitation new material more cheap and easy to get and new process into
For the main direction of studying of heavy metal containing wastewater treatment.
The content of the invention
For deficiencies of the prior art, it is an object of the invention to provide a kind of removal of heavy metal ions agent
Preparation method, discarded hardened cement concrete is used as raw material, the secondary pollution for solving discarded hardened cement concrete, to realize
Recycling provides a new approach；Meanwhile solve heavy metal containing wastewater treatment and use the high problem of chemical agent cost.
Solves above-mentioned technical problem, the present invention adopts the following technical scheme that：A kind of preparation side of removal of heavy metal ions agent
Method, it is characterised in that discarded hardened cement concrete is used as raw material, activated through first broken and pre-burning, crushing and separation, ball milling,
Powder is selected to separate to obtain heavy metals removal agent.
Further, specifically comprise the following steps：
1）First broken and pre-burning：Take it is broken at the beginning of discarded hardened cement concrete, control just broken particle size facilitate pre-burning；In temperature control
30-45min is calcined under the conditions of 380 ~ 400 DEG C, then takes out and naturally cools to room temperature；
2）Crush and separate：By step 1）Discarded hardened cement concrete after pre-burning, cooling is crushed, then by thick bone
Material is separated with particle；
3）Ball milling activates：By step 2）Separating obtained particle carries out ball-milling treatment in ball mill and obtains adsorption particle, control
Granularity is less than 80 μm；
4）Select powder and separation：By step 3）Obtained adsorption particle carries out selecting powder and separation, and collection cut size is not more than 80 μm of suction
Attached particle is removal of heavy metal ions agent；Adsorption particle more than 80 μm is selected powder and separation again.
Further, the discarded hardened cement concrete includes discarded petrifying water mudstone, cement mortar or/and coagulating cement
Earth building blocks.The step 3）During ball-milling treatment, surfactant is added, Ball-milling Time is 20 ~ 50min.
The surfactant is the one or two of ethylene glycol or triisopropanolamine；Addition by ethylene glycol 0.02~
0.08%, triisopropanolamine 0.03~0.1%.
Compared with prior art, the present invention has the advantages that：
1st, the heavy metals removal agent prepared using the inventive method, main composition are the aquation that preparation is separated from discarded concrete
Gel of calcium silicate（C-S-H）, entringite (AFt), silica (SiO2) etc., above-mentioned material is made by thermal activation and mechanical activation
Material internal crystal structure defect increases, the increase of active site position, so as to the ability with stronger removal heavy metal ions in wastewater.
2nd, the method that the present invention prepares heavy metals removal agent based on discarded concrete fine powder, through first broken and pre-burning, crush and
Separation, ball milling, active particle is obtained after selecting powder separation activation, raw materials are that separating obtained Behavior of Hardened Cement Paste is broken in discarded mixed mud
Material, its wide material sources, cost are cheap, and this recycling discarded hardened cement for flood tide and be provides a new approach；
Also the improvement for heavy metal-containing waste waters such as China river, lake, industry and lives provides a kind of easy to operate, scope of application
Extensively, cost is cheap, the green, process that " can control poison with useless "；It meets the strategy of national development recycling economy will
Ask, enjoy national and local related industry policy support, there is wide development and application prospect.
Meanwhile by the technology applications expanding of petrifying water mudstone this building castoff in discarded concrete to heavy metal-polluted
Water harnessing field, in the absence of limit doped amount problem, improve the resource utilization efficiency of waste water mudstone.Improve waste cement
The economic value added of stone.A kind of operation letter is provided for the improvement of the heavy metal-containing waste waters such as China river, lake, industry and life
Just it is, applied widely, cost is cheap, the green, process that " can control poison with useless ".Also it is discarded petrifying water mudstone
High value added utilization provides a Technology Ways, overcomes it and is preparing regeneration concrete material, building block or forging again
High porosity, high water absorbing capacity, low-intensity, volume are limited etc. during baking cement clinker the problem of bringing.
3rd, on the one hand the present invention causes petrifying water mudstone dehydration shrinkage in burn-in process, and a large amount of microcracks occur reduces
Subsequent ball milling prepares difficulty；On the other hand petrifying water mudstone can be caused microcrack occur with interfacial transition zone, this to harden
Behavior of Hardened Cement Paste is separated from discarded concrete, is provided for the standby removal of heavy metal ions agent made of stones of hardened cement in discarded concrete
May.To improve the specific surface area of petrifying water mudstone, increase its surface-active, ball milling is added by the Behavior of Hardened Cement Paste for sieving separation
Ball-milling treatment in machine, the composite grinding aid of lignosulfonates, ethylene glycol or/and triisopropanolamine composition is added in mechanical milling process
Agent improves the decentralization of particle, and then further increase processing of the particle to heavy metal ions in wastewater to improve mill efficiency
Effect.
Brief description of the drawings
Fig. 1 is petrifying water mudstone and the transition region gathered materials in discarded concrete before and after calcining：a）Before pre-burning, b）After pre-burning
Fig. 2 is the temperature increasing schedule of discarded concrete burn-in process
Fig. 3 is the discarded concrete block for cutting and numbering
Fig. 4 is active particle scanning electron microscope (SEM) photograph after ball-milling treatment：a）2000 times；b）20000 times
Fig. 5 is that active particle removes Zn in waste water2+Capability result figure
Fig. 6 and active particle remove Cr in waste water3+Capability result figure
Fig. 7 is that active particle removes Ni in waste water2+Capability result figure
Fig. 8 is that active particle removes Cu in waste water2+Capability result figure.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
Embodiment 1：A kind of preparation method of removal of heavy metal ions agent, comprises the following steps：
1st, discarded concrete is chosen from building waste, and it is broken at the beginning of small-sized hammer mill is carried out, it is discarded mixed after just broken
Solidifying soil, which is fitted into resistance furnace, carries out precalcining, and 35min is calcined under the conditions of 400 DEG C, interface micro-crack insertion situation occurs, now
Ideal separation situation is reached.
2nd, discarded concrete is subjected to concussion processing in electromagnetic type shakes pulverizer, carries out point of coarse aggregate and particle
From.
3rd, separating obtained particle is added in ball mill and carried out；In order to further improve the specific surface area of petrifying water mudstone,
Increase its surface-active, ball-milling treatment 20min in ball mill is added by the Behavior of Hardened Cement Paste for sieving separation.Added in mechanical milling process
Lignosulfonates, ethylene glycol, the composite grinding aids of triisopropanolamine composition improve the scattered of particle to improve mill efficiency
Degree, and then further increase treatment effect of the particle to heavy metal ions in wastewater；Control granularity is less than 80 μm.
4th, the material by air flow grader after grinding carries out selecting powder and separation, and collection cut size≤80um active particle is
It is standby for heavy metal wastewater thereby remover；Rest materials again return in ball mill grinding again, carry out selecting powder and separation.
Embodiment 2：A kind of preparation method of removal of heavy metal ions agent, comprises the following steps：
1st, choose discarded concrete from building waste, and with small-sized hammer mill carry out just broken control discharging-material size≤
10mm, the discarded concrete after just broken are fitted into corundum crucible and are put into chamber type electric resistance furnace in different temperature schedules
Lower carry out pre-burning, it is 400 DEG C to control calcined temperature.Furnace temperature is taken out after cooling to 100 DEG C, is transferred in drier and is cooled to room
Temperature, then its quality is weighed with electronic scale, take reading.
2nd, appropriate discarded concrete is added every time to be crushed and separated in electromagnetic type shakes pulverizer, and controls shake
The time swung, after concussion separation, pour into square hole screen, carry out the separation of coarse aggregate and waste water mudstone；The concussion time is 10s,
Separated coarse aggregate is caused to crush powdering and be mixed into petrifying water mudstone in order to avoid transition is shaken.
3rd, ball-milling treatment is carried out after separating obtained Behavior of Hardened Cement Paste being added into ball mill, ethylene glycol 0.02 is added in mechanical milling process
~0.08%, the grade of triisopropanolamine 0.03~0.1% surfactant carries out Dispersion on surface processing；The Ball-milling Time is controlled to be simultaneously
20~50min, control out abrasive particle degree≤80um;Discarded mixed mud after ball milling writes down its quality with electronic scale.
4th, the material by air flow grader after grinding carries out selecting powder and separation, and collection cut size≤80um active particle is
It is standby for heavy metal wastewater thereby remover；Rest materials again return in ball mill grinding again, carry out selecting powder and separation.
On the one hand the present invention causes petrifying water mudstone dehydration shrinkage in burn-in process, after there are a large amount of microcracks reductions
Continuous ball milling prepares difficulty；On the other hand petrifying water mudstone can be caused microcrack occur with interfacial transition zone, this causes petrifying water
Mudstone is separated from discarded concrete, is provided for the standby removal of heavy metal ions agent made of stones of hardened cement in discarded concrete
May.The separating effect of waste water mudstone is illustrated in fig. 1 shown below under different calcined temperatures.It will be seen from figure 1 that discarded before pre-burning mixed
Petrifying water mudstone and coarse aggregate are closely cemented together in solidifying soil, are the entirety of more difficult separation.After pre-burning, due to petrifying water
Mudstone dehydration shrinkage generates larger tension, in the presence of tension aggregate is separated with petrifying water mudstone, therefore
It is observed that occurring obvious crack between coarse aggregate and Behavior of Hardened Cement Paste in industrial microscope.This is in follow-up discarded concrete
Hardened cement standby removal of heavy metal ions agent made of stones provides guarantee.
To obtain optimal preheating temperature, precalcining processing, such as Fig. 2 are carried out to discarded concrete at different temperatures
It is shown.Fig. 2 is heat treating regime figure of the discarded concrete in chamber type electric resistance furnace, and it is 8 that heating rate is controlled in temperature-rise period
DEG C/min, constant temperature 20min after predetermined temperature is reached, finally naturally cools to room temperature with stove.
Discarded concrete is cut into a plane using concrete cutting machine before calcining, coarse aggregate in plane is compiled
Number（N=1、2 、3……）, as shown in Figure 3.After numbering using each coarse aggregate of industrial microscope direct measurement and its around
The length in petrifying water mudstone interface area, as the aggregate and the total length at petrifying water mudstone interface, it is designated as L0.Will be useless after numbering
Abandon concrete block and carry out precalcining under said temperature system, and after Observe and measure precalcining in discarded concrete coarse aggregate and its
The length in surrounding hydrated cement paste body interface area crack, is designated as L.Define a dimensionless constant：Φ,
And makeΦ=L / L0×100% (1)
The precalcining temperature of table 1 is the cracking situation in 300 DEG CShi interfaces areas
| NO. | L 0 （mm） | L（mm） | Φi(%） |
| 1 | 29.72 | 2.44 | 8.21 |
| 2 | 13.14 | 1.14 | 8.68 |
| 3 | 19.88 | 1.51 | 7.59 |
| 4 | 15.34 | 0.72 | 4.69 |
| 5 | 17.85 | 0 | 0 |
| 6 | 13.75 | 0 | 0 |
| 7 | 13.57 | 1.12 | 8.25 |
| 8 | 33.49 | 0.14 | 0.41 |
| 9 | 14.14 | 0.21 | 1.48 |
| 10 | 39.76 | 0 | 0 |
| 11 | 18.05 | 0 | 0 |
| 12 | 15.97 | 0.23 | 1.44 |
| 13 | 12.74 | 0.21 | 1.64 |
| 14 | 23.31 | 2.14 | 9.18 |
| 15 | 21.6 | 0.65 | 3.01 |
The precalcining temperature of table 2 is the cracking situation in 350 DEG CShi interfaces areas
| NO. | L 0 （mm） | L（mm） | Φi（%） |
| 1 | 24.69 | 6.10 | 24.70 |
| 2 | 19.47 | 2.23 | 11.45 |
| 3 | 34.49 | 7.21 | 20.90 |
| 4 | 37.67 | 7.11 | 18.87 |
| 5 | 42.79 | 5.82 | 13.60 |
| 6 | 59.01 | 21.95 | 37.19 |
| 7 | 24.58 | 7.31 | 29.73 |
| 8 | 16.7 | 2.56 | 15.33 |
| 9 | 14.03 | 0.98 | 6.99 |
| 10 | 24.65 | 9.37 | 38.01 |
| 11 | 51.10 | 8.54 | 16.71 |
| 12 | 23.88 | 0.63 | 2.64 |
| 13 | 40.82 | 5.86 | 14.36 |
| 14 | 15.18 | 2.89 | 19.03 |
| 15 | 19.23 | 3.27 | 16.70 |
| 16 | 19.58 | 4.47 | 22.83 |
| 17 | 18.26 | 7.39 | 40.47 |
The precalcining temperature of table 3 is the cracking situation in 380 DEG CShi interfaces areas
| NO. | L 0 （mm） | L（mm） | Φi（%） |
| 1 | 66.38 | 41.15 | 61.98 |
| 2 | 28.06 | 17.14 | 61.08 |
| 3 | 23.40 | 14.15 | 60.47 |
| 4 | 36.55 | 22.14 | 60.57 |
| 5 | 15.07 | 10.13 | 67.22 |
| 6 | 11.53 | 4.13 | 35.82 |
| 7 | 9.94 | 4.56 | 45.88 |
| 8 | 16.59 | 9.87 | 59.49 |
| 9 | 39.31 | 24.02 | 61.10 |
| 10 | 29.08 | 3.94 | 13.55 |
| 11 | 57.39 | 36.24 | 63.15 |
| 12 | 33.65 | 13.51 | 40.15 |
| 13 | 27.48 | 26.27 | 95.59 |
| 14 | 32.01 | 16.17 | 50.52 |
| 15 | 29.86 | 20.15 | 67.48 |
| 16 | 29.55 | 3.14 | 10.63 |
| 17 | 14.65 | 8.13 | 55.49 |
| 18 | 16.45 | 6.45 | 39.2 |
| 19 | 12.59 | 7.14 | 56.71 |
The precalcining temperature of table 4 is the cracking situation in 400 DEG CShi interfaces areas
| NO. | L 0 （mm） | L（mm） | Φi（%） |
| 1 | 13.39 | 11.24 | 83.94 |
| 2 | 11.97 | 9.83 | 82.12 |
| 3 | 13.33 | 13.33 | 100 |
| 4 | 13.02 | 7.79 | 59.83 |
| 5 | 11.33 | 10.12 | 83.32 |
| 6 | 28.02 | 26.35 | 94.04 |
| 7 | 25.54 | 23.40 | 91.62 |
| 8 | 33.43 | 27.28 | 81.61 |
| 9 | 16.24 | 16.01 | 98.58 |
| 10 | 18.62 | 14.67 | 78.79 |
| 11 | 36.06 | 30.76 | 85.31 |
| 12 | 67.53 | 54.10 | 80.12 |
| 13 | 15.18 | 3.81 | 25.13 |
| 14 | 14.83 | 5.26 | 35.51 |
| 15 | 21.63 | 1.15 | 5.32 |
| 16 | 20.27 | 18.47 | 91.14 |
| 17 | 19.40 | 18.07 | 93.15 |
| 18 | 14.32 | 13.67 | 95.51 |
When precalcining temperature is 300 DEG C, as known from Table 1, coarse aggregate and petrifying water mudstone interface in discarded concrete after calcining
Ftracture unobvious in area,ΦValue is generally less than 10%, and crack is not observed with petrifying water mudstone interface area in part of coarse aggregates.This says
It is bright 300 DEG C to discarded concrete carry out pre-burning when, petrifying water mudstone drying shrinkage stress is smaller, is not enough to produce wide transition
Area's crackle.Continue to improve treatment temperature for this, to increase coarse aggregate and the crackle of petrifying water mudstone transition region in discarded concrete,
To reduce later separation difficulty.As a result as shown in table 2, table 3 and table 4.Know from table 2, when calcining heat is 350 DEG C, discard
Petrifying water mudstone is generally more than 10% with the increase of Interface Crack length, Φ values in concrete, and Φ values reach 40% around aggregates.
Constantly improve with calcining heat, when calcining heat is 380 DEG C, Φ values are concentrated mainly on 60% or so, illustrate that interface area is micro-
Crackle further generates, grown up, as shown in table 3.As known from Table 4, when precalcining temperature brings up to 400 DEG C, microcrack enters one
Step extension, Φ values have generally reached more than 90%, and interface micro-crack insertion situation occur, have now reached ideal
Separation situation, therefore it is precalcining temperature to select 400 DEG C.
Because the mechanical property of aggregate in discarded concrete is significantly larger than the petrifying water mudstone after pre-burning, will be forged through 400 DEG C
Burn, and petrifying water mudstone and aggregate interface area degree of cracking have reached about 90% discarded concrete and utilized electromagnetic type concussion pulverizer
Carry out concussion processing so that petrifying water mudstone is efficiently separated with aggregate in discarded concrete.Control electricity is needed in separation process
The concussion time of magnetic-type concussion pulverizer is 10s, causes separated coarse aggregate to crush powdering and be mixed into firmly in order to avoid transition is shaken
Change in Behavior of Hardened Cement Paste.
In order to further improve the specific surface area of petrifying water mudstone, increase its surface-active, by the cement for sieving separation
Stone adds ball-milling treatment 20min in ball mill.Lignosulfonates, ethylene glycol, triisopropanolamine group are added in mechanical milling process
Into composite grinding aids to improve mill efficiency, improve the decentralization of particle, and then further increase particle to a huge sum of money in waste water
Belong to the treatment effect of ion.A in the ESEM such as Fig. 4 of particle under different amplification after ball milling）、b）It is shown.
As can be seen from Figure 4, the particle that particle size differs can be observed when amplifying 2000 times, particle size distribution is wider,
But particle diameter is all below 50 microns, most particle diameter is at more than ten micron or even several microns；When being amplified to 20000 times,
Grain surface in irregular sheet stack, and sheet surface simultaneously out-of-flatness, structure is loose, and crystallinity is poor, such laminated structure it
Between can form irregular pore structure.Understand have in X-ray diffraction spectrum in combination with X-ray diffraction material phase analysis shown in Fig. 1
Atomic weak wide C-S-H diffraction maximums, it is mainly the relatively low C-S-H gels of crystallinity to illustrate it.There are some researches show C-S-H
In water-saturated state, its specific surface area reaches 750m2/ Kg, so huge specific surface area, it is higher necessarily make it that it is in energy
State, there is larger Ion release performance and absorption property.Particle after ball milling is carried out using gas flow sizing machine to select powder
And separation, experimental study different-grain diameter d（d≤315um, d≤160um, d≤80um, d≤45um, ）Lower active particle
The ability of variety classes heavy metal particles in waste water is removed, as a result as shown in 5, Fig. 6 and Fig. 7.
As can be seen from Figure 5, it is that 100mg/L contains Zn when initial concentration is put into prepared heavy metals removal agent2+In waste water
When being handled, with the increase of dosage, Zn in waste water2+Concentration gradually reduces.When dosage is 0.7g, after reacting 30min,
Zn in waste water2+Ion concentration has descended to below 0.5mg/L, and clearance reaches more than 99%, and aqueous concentration has reached GB
18918-2002《Urban wastewater treatment firm pollutant emission standard》In emission request, heavy metals removal agent prepared by explanation
There is preferable using effect.
As can be seen from Figure 6, it is that 100mg/L contains Cr when initial concentration is put into prepared heavy metals removal agent3+In waste water
When being handled, with the increase of dosage, Cr in waste water3+Concentration gradually reduces.When dosage is 0.5g, after reacting 30min,
Cr in waste water3+Concentration has descended to below 0.5mg/L, and clearance reaches more than 99%, and aqueous concentration has reached GB
18918-2002《Urban wastewater treatment firm pollutant emission standard》In emission request, heavy metal prepared by explanation goes
Except agent has preferable using effect.
As can be seen from Figure 7, it is that 100mg/L contains Ni when initial concentration is put into prepared heavy metals removal agent2+In waste water
When being handled, with the increase of dosage, Ni in waste water2+Concentration gradually reduces.When dosage is 0.5g, after reacting 30min,
Ni in waste water2+Ion concentration has descended to below 1mg/L, and clearance reaches 99%, and aqueous concentration has basically reached GB
18918-2002《Urban wastewater treatment firm pollutant emission standard》In emission request, heavy metals removal agent prepared by explanation
There is preferable using effect.
As it can be observed in the picture that contain Cu when initial concentration is put into prepared heavy metals removal agent for 100mg/L2+In waste water
When being handled, with the increase of dosage, Cu in waste water2+Concentration gradually reduces.When dosage is 0.3g, after reacting 30min,
Cu in waste water2+Ion concentration has descended to below 0.5mg/L, and clearance reaches more than 99%, and aqueous concentration has reached GB
18918-2002《Urban wastewater treatment firm pollutant emission standard》In emission request, heavy metals removal agent prepared by explanation
There is preferable using effect.
The preferential policies such as national policy subsidy, tax revenue, competitively priced and discount loan of powering are not considered, in units of ton
Prepared removal of heavy metal ions agent is estimated, as shown in table 5
The cost analysis of removal of heavy metal ions agent prepared by table 5
| Project | Human resources | Power consumption | Fuel | Sale | Equipment | Communications and transportation | It is other | Amount to |
| Expense（Yuan/ton） | 1.2 | 2.3 | 4.4 | 3.5 | 1.6 | 10 | 2 | 25 |
It can be seen that raw materials of the present invention are separating obtained Behavior of Hardened Cement Paste in discarded mixed mud, its wide material sources, cost are cheap, this
The recycling that discarding hardened cement for flood tide is provides a new approach；And preparation method cost is relatively low.
The present invention uses discarded hardened cement concrete as raw material, including discarded petrifying water mudstone, cement mortar or/and water
Cement concrete building block, through first broken and pre-burning, crushing and separation, ball milling activation, powder is selected to be isolated.Its essential mineral composition is two
The eakleite that silica synthesizes at high temperature under high pressure with calcium oxide（Xonotite）And tobermorite（Tobermorite）
Deng by calcination, ball milling and crushing.To improve the specific surface area of petrifying water mudstone, increase its surface-active, separated by sieving
Behavior of Hardened Cement Paste add ball-milling treatment in ball mill, lignosulfonates, ethylene glycol or/and three isopropanols are added in mechanical milling process
The composite grinding aids of amine composition improve the decentralization of particle, and then further increase particle in waste water to improve mill efficiency
The treatment effect of heavy metal ion.The present invention provides that an environmental benefit is good, economical adds for discarded hardened cement concrete
The utilization new way that value is high, " can control poison with useless "；Also it is the water containing heavy metal such as China river, lake, industrial and life contaminated water
The improvement of body provides a kind of wide material sources, cheap and easy to get, green new material.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this
Among the right of invention.
Claims (5)
- A kind of 1. preparation method of removal of heavy metal ions agent, it is characterised in that discarded hardened cement concrete is used as raw material, Through first broken and pre-burning, crushing and separation, ball milling activation, select the isolated heavy metals removal agent of powder.
- 2. the preparation method of removal of heavy metal ions agent according to claim 1, it is characterised in that comprise the following steps：1）First broken and pre-burning；Take it is broken at the beginning of discarded hardened cement concrete, control just broken particle size facilitate pre-burning；In temperature control 30-45min is calcined under the conditions of 380 ~ 400 DEG C, then takes out and naturally cools to room temperature；2）Crush and separate：By step 1）Discarded hardened cement concrete after pre-burning, cooling is crushed, then by thick bone Material is separated with particle；3）Ball milling activates：By step 2）Separating obtained particle carries out ball-milling treatment in ball mill and obtains adsorption particle, control Granularity is less than 80 μm；4）Select powder and separation：By step 3）Obtained adsorption particle carries out selecting powder and separation, and collection cut size is not more than 80 μm of suction Attached particle is removal of heavy metal ions agent；Adsorption particle more than 80 μm is selected powder and separation again.
- 3. the preparation method of removal of heavy metal ions agent according to claim 1, it is characterised in that the discarded hardened cement Concrete includes discarded petrifying water mudstone, cement mortar or/and coagulating cement earth building blocks.
- 4. the preparation method of removal of heavy metal ions agent according to claim 2, it is characterised in that the step 3）At ball milling During reason, surfactant is added, Ball-milling Time is 20 ~ 50min.
- 5. the preparation method of removal of heavy metal ions agent according to claim 4, it is characterised in that the surfactant is The one or two of ethylene glycol or triisopropanolamine；Addition presses ethylene glycol 0.02~0.08%, and triisopropanolamine 0.03~ 0.1%, surplus is discarded petrifying water mudstone.
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| CN108654339A (en) * | 2018-05-14 | 2018-10-16 | 南京工业大学 | A kind of fume desulfurizing agent and method using hardening of cement slurry preparation in discarded concrete |
| CN109621925A (en) * | 2019-01-24 | 2019-04-16 | 长江师范学院 | A kind of collecting carbonic anhydride agent and its application |
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| CN111167405A (en) * | 2020-01-03 | 2020-05-19 | 中国科学院武汉岩土力学研究所 | Adsorbing material based on construction waste and preparation method and application thereof |
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| CN109621925A (en) * | 2019-01-24 | 2019-04-16 | 长江师范学院 | A kind of collecting carbonic anhydride agent and its application |
| CN109621925B (en) * | 2019-01-24 | 2021-09-28 | 长江师范学院 | Carbon dioxide trapping agent and application thereof |
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| CN110773117A (en) * | 2019-12-02 | 2020-02-11 | 南京信息工程大学 | Method for preparing glass pumice and adsorbing heavy metals by using waste glass and cement blocks |
| CN111167405A (en) * | 2020-01-03 | 2020-05-19 | 中国科学院武汉岩土力学研究所 | Adsorbing material based on construction waste and preparation method and application thereof |
| CN111167405B (en) * | 2020-01-03 | 2021-04-09 | 中国科学院武汉岩土力学研究所 | Adsorbing material based on construction waste and preparation method and application thereof |
| CN112028661A (en) * | 2020-09-11 | 2020-12-04 | 山东铭城环保新材料科技有限公司 | Preparation method of recyclable cadmium adsorption porcelain powder foam concrete block |
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