CN109504390A - A kind of reparation medicament and preparation method thereof of high leaded soil - Google Patents

Abstract

The invention discloses a kind of reparation medicaments of high leaded soil, including following component (by mass percentage): cement 18-22%, quick lime 15-20%, natural chelators 8.5-12.5%, calcium phosphate 5.5-7.2%, calcium magnesium phosphate 4.8-6.3%, hydrated manganese oxide 3.4-4.8%, reducing agent 10-15%, zirconium oxide microballoons 2.28-3.34%, polyvinyl pyrrolidone 1.25-1.45%, isopropanol 1.12-1.23%, polyethylene glycol 0.95-1.27%, compatilizer are surplus；The invention also discloses a kind of preparation methods of the reparation medicament of high leaded soil, comprising the following steps: heating stirring, vacuum drying, centrifugal filtration and mixing；The reparation medicament is stronger for the repair ability of high leaded soil, it can be good at incorporating in soil, repair difficulty is smaller, activation capacity is strong, easily voluntarily decomposes, secondary pollution will not be caused to soil, and preparation method of the invention is more simple, equipment requirement is low, has good promotion effect.

Description

A kind of reparation medicament and preparation method thereof of high leaded soil

Technical field

The present invention relates to technical field of soil remediation, the reparation medicament of specially a kind of high leaded soil and its preparation side Method.

Background technique

Soil remediation is the technical measures for making to restore by contaminated soil normal function.In soil remediation industry, have Soil restoring technology reach more than 100 kinds, common technology also has more than ten kinds, is broadly divided into physics, chemistry and biological three kinds of sides Method, for high leaded soil, repair mode in the prior art is generally existing repair difficulty greatly and repairing effect be not added it is scarce It falls into, the phenomenon that heavy metal ion causes secondary pollution to soil after repairing easily occurs, for this purpose, it is proposed that a kind of high leaded soil Reparation medicament and preparation method thereof.

Summary of the invention

The purpose of the present invention is to provide a kind of reparation medicaments and preparation method thereof of high leaded soil, to solve background skill The problem of art proposes.

To achieve the above object, the invention provides the following technical scheme: a kind of reparation medicament of high leaded soil, including with Lower ingredient (by mass percentage): cement 18-22%, quick lime 15-20%, natural chelators 8.5-12.5%, calcium phosphate 5.5- 7.2%, calcium magnesium phosphate 4.8-6.3%, hydrated manganese oxide 3.4-4.8%, reducing agent 10-15%, zirconium oxide microballoons 2.28-3.34%, poly- It is surplus that vinyl, which adjoins pyrrolidone 1.25-1.45%, isopropanol 1.12-1.23%, polyethylene glycol 0.95-1.27%, compatilizer,.

Preferably, including following component (by mass percentage): cement 22%, quick lime 15%, natural chelators 8.5%, Calcium phosphate 5.5%, calcium magnesium phosphate 4.8%, hydrated manganese oxide 3.4%, reducing agent 10%, zirconium oxide microballoons 2.28%, polyvinyl, which adjoin, to be coughed up Alkanone 1.25%, isopropanol 1.12%, polyethylene glycol 0.95%, compatilizer are surplus.

Preferably, including following component (by mass percentage): cement 20%, quick lime 18%, natural chelators 11%, Calcium phosphate 6.5%, calcium magnesium phosphate 5.8%, hydrated manganese oxide 4.2%, reducing agent 14%, zirconium oxide microballoons 2.85%, polyvinyl, which adjoin, to be coughed up Alkanone 1.37%, isopropanol 1.18%, polyethylene glycol 1.16%, compatilizer are surplus.

Preferably, including following component (by mass percentage): cement 19%, quick lime 16%, natural chelators 10%, Calcium phosphate 6.2%, calcium magnesium phosphate 5.2%, hydrated manganese oxide 3.8%, reducing agent 11%, zirconium oxide microballoons 2.56%, polyvinyl, which adjoin, to be coughed up Alkanone 1.3%, isopropanol 1.14%, polyethylene glycol 1.05%, compatilizer are surplus.

Preferably, including following component (by mass percentage): cement 18%, quick lime 20%, natural chelators 12.5%, calcium phosphate 7.2%, calcium magnesium phosphate 6.3%, hydrated manganese oxide 4.8%, reducing agent 15%, zirconium oxide microballoons 3.34%, polyethylene It is surplus that base, which adjoins pyrrolidone 1.45%, isopropanol 1.23%, polyethylene glycol 1.27%, compatilizer,.

Preferably, the natural chelators are the mixture by oxalic acid, tartaric acid and citric acid.

Preferably, the reducing agent is any one of ferrous sulfate, sulphite, sodium thiosulfate or sodium hydrogensulfite Kind；The compatilizer is any one of styrene, acrylonitrile or metering system sour water glyceride.

A kind of preparation method of the reparation medicament of the leaded soil of height as described above, comprising the following steps:

Step 1: weighing both quantitative cement and quick lime, and the water that 35-45% is added is mixed evenly, and it is standby that mixture A is made With；

Step 2: weighing calcium phosphate, calcium magnesium phosphate and hydrated manganese oxide and sequentially add in Mixer pot, and natural chelators and phase is added Hold agent, is extremely dissolved in the at a temperature of stirring of 25-30 degree, then Mixer pot is placed in 60-70 DEG C of thermostatic chamber, and at a high speed Blender is stirred continuously 60-70 minutes, stands 10-15 minutes after stirring；Obtain mixture B；

Step 3: zirconium oxide microballoons are added in dry toluene magnetic agitation 60-120 minutes, and KH570 is added after logical nitrogen, Back flow reaction 3-7 hours at a temperature of 65-75 DEG C, product successively uses toluene, methanol, ethanol washing 1-4 times respectively, then sets In vacuum desiccator, vacuum desiccator valve is opened, at 80-95 DEG C, drying time controls at 2-6 hours, very control temperature Empty drier obtains modified zirconia microballoon；

Step 4: taking polyvinyl pyrrolidone, isopropanol and polyethylene glycol to filter 5-10 minutes by centrifugal filter respectively, It takes three's filtered fluid to be mixed evenly, and mixed liquor is heated to 45-65 degree, obtain mixture C；

Step 5: mixture C, mixture B and modified zirconia microballoon are added sequentially in mixture A, with 160-200r/ The mixing speed of min stirs 30-60 minute, and temperature control divides 3-6 times in 65-85 degrees Celsius, whipping process when stirring is added Reducing agent is cooled to 21-25 DEG C after stirring, obtains reparation medicament.

Compared with prior art, the beneficial effects of the present invention are: formula of the invention is more reasonable, the leaded soil of the height Reparation medicament, by can incorporate well in the leaded soil of large area using cement and quick lime as raw material, cooperation is added natural The activity and biological effectiveness of lead in soil can be improved in chelating agent, makes it easier to flow and absorb, natural chelators activation capacity Relatively strong and easily decomposition, not will form secondary pollution；By the way that reducing agent is added, heavy metal ion can be changed by redox reaction Valence state, to reduce the activity and toxicity of heavy metal in soil；By the way that calcium phosphate, calcium magnesium phosphate and hydrated manganese oxide is added, It can promote the precipitating of lead, reduce the exchangeable species lead in soil；The reparation medicament is stronger for the repair ability of high leaded soil, It can be good at incorporating in soil, repair difficulty is smaller, activation capacity is strong, easily voluntarily decomposes, and will not cause two to soil Secondary pollution, and preparation method of the invention is more simple, and equipment requirement is low, has good promotion effect.

Specific embodiment

Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described, Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all Belong to the scope of protection of the invention.

Embodiment one:

A kind of reparation medicament of high leaded soil, including following component (by mass percentage): cement 22%, quick lime 15%, Natural chelators 8.5%, calcium phosphate 5.5%, calcium magnesium phosphate 4.8%, hydrated manganese oxide 3.4%, reducing agent 10%, zirconium oxide microballoons 2.28%, polyvinyl pyrrolidone 1.25%, isopropanol 1.12%, polyethylene glycol 0.95%, compatilizer are surplus.

Further, natural chelators are the mixture by oxalic acid, tartaric acid and citric acid.

Further, reducing agent is ferrous sulfate；Compatilizer is styrene.

A kind of preparation method of the reparation medicament of high leaded soil, comprising the following steps:

Step 1: weighing both quantitative cement and quick lime, and 35% water is added and is mixed evenly, and it is spare that mixture A is made；

Step 2: weighing calcium phosphate, calcium magnesium phosphate and hydrated manganese oxide and sequentially add in Mixer pot, and natural chelators and phase is added Hold agent, is extremely dissolved in 25 degree of at a temperature of stirring, then Mixer pot is placed in 60 DEG C of thermostatic chamber, and use high speed agitator It is stirred continuously 60 minutes, stands 10 minutes after stirring；Obtain mixture B；

Step 3: zirconium oxide microballoons are added in dry toluene magnetic agitation 60 minutes, KH570 are added after logical nitrogen, at 65 DEG C At a temperature of back flow reaction 3 hours, product successively respectively use toluene, methanol, ethanol washing 1 time, be subsequently placed in vacuum desiccator In, vacuum desiccator valve is opened, control temperature is at 80 DEG C, and at 2 hours, vacuum desiccator obtained modified oxygen for drying time control Change zirconium microballoon；

Step 4: it takes polyvinyl pyrrolidone, isopropanol and polyethylene glycol to filter 5 minutes by centrifugal filter respectively, takes Three's filtered fluid is mixed evenly, and mixed liquor is heated to 45 degree, obtains mixture C；

Step 5: mixture C, mixture B and modified zirconia microballoon are added sequentially in mixture A, with 160r/min's Mixing speed stirs 30 minutes, and temperature control is added three times reducing agent, stirring knot at 65 degrees Celsius in whipping process when stirring It is cooled to 21 DEG C after beam, obtains reparation medicament.

Embodiment two:

A kind of reparation medicament of high leaded soil, including following component (by mass percentage): cement 20%, quick lime 18%, Natural chelators 11%, calcium phosphate 6.5%, calcium magnesium phosphate 5.8%, hydrated manganese oxide 4.2%, reducing agent 14%, zirconium oxide microballoons 2.85%, polyvinyl pyrrolidone 1.37%, isopropanol 1.18%, polyethylene glycol 1.16%, compatilizer are surplus.

Further, natural chelators are the mixture by oxalic acid, tartaric acid and citric acid.

Further, reducing agent is sulphite；Compatilizer is acrylonitrile.

A kind of preparation method of the reparation medicament of high leaded soil, comprising the following steps:

Step 1: weighing both quantitative cement and quick lime, and 38% water is added and is mixed evenly, and it is spare that mixture A is made；

Step 2: weighing calcium phosphate, calcium magnesium phosphate and hydrated manganese oxide and sequentially add in Mixer pot, and natural chelators and phase is added Hold agent, is extremely dissolved in 26 degree of at a temperature of stirring, then Mixer pot is placed in 63 DEG C of thermostatic chamber, and use high speed agitator It is stirred continuously 65 minutes, stands 12 minutes after stirring；Obtain mixture B；

Step 3: zirconium oxide microballoons are added in dry toluene magnetic agitation 80 minutes, KH570 are added after logical nitrogen, at 70 DEG C At a temperature of back flow reaction 4 hours, product successively respectively use toluene, methanol, ethanol washing 2 times, be subsequently placed in vacuum desiccator In, vacuum desiccator valve is opened, control temperature is at 85 DEG C, and at 3 hours, vacuum desiccator obtained modified oxygen for drying time control Change zirconium microballoon；

Step 4: it takes polyvinyl pyrrolidone, isopropanol and polyethylene glycol to filter 7 minutes by centrifugal filter respectively, takes Three's filtered fluid is mixed evenly, and mixed liquor is heated to 50 degree, obtains mixture C；

Step 5: mixture C, mixture B and modified zirconia microballoon are added sequentially in mixture A, with 170r/min's Mixing speed stirs 40 minutes, and at 75 degrees Celsius, point 4 additions reducing agents in whipping process, stirring is tied for temperature control when stirring It is cooled to 22 DEG C after beam, obtains reparation medicament.

Embodiment three:

A kind of reparation medicament of high leaded soil, including following component (by mass percentage): cement 19%, quick lime 16%, Natural chelators 10%, calcium phosphate 6.2%, calcium magnesium phosphate 5.2%, hydrated manganese oxide 3.8%, reducing agent 11%, zirconium oxide microballoons 2.56%, polyvinyl pyrrolidone 1.3%, isopropanol 1.14%, polyethylene glycol 1.05%, compatilizer are surplus.

Further, natural chelators are the mixture by oxalic acid, tartaric acid and citric acid.

Further, reducing agent is sodium thiosulfate；Compatilizer is metering system sour water glyceride.

A kind of preparation method of the reparation medicament of high leaded soil, comprising the following steps:

Step 1: weighing both quantitative cement and quick lime, and 42% water is added and is mixed evenly, and it is spare that mixture A is made；

Step 2: weighing calcium phosphate, calcium magnesium phosphate and hydrated manganese oxide and sequentially add in Mixer pot, and natural chelators and phase is added Hold agent, is extremely dissolved in 29 degree of at a temperature of stirring, then Mixer pot is placed in 68 DEG C of thermostatic chamber, and not with high speed agitator Disconnected stirring 60-70 minutes, stands 14 minutes after stirring；Obtain mixture B；

Step 3: zirconium oxide microballoons are added in dry toluene magnetic agitation 100 minutes, KH570 are added after logical nitrogen, at 72 DEG C At a temperature of back flow reaction 6 hours, product successively respectively use toluene, methanol, ethanol washing 3 times, be subsequently placed in vacuum desiccator In, vacuum desiccator valve is opened, control temperature is at 90 DEG C, and at 5 hours, vacuum desiccator obtained modified oxygen for drying time control Change zirconium microballoon；

Step 4: it takes polyvinyl pyrrolidone, isopropanol and polyethylene glycol to filter 8 minutes by centrifugal filter respectively, takes Three's filtered fluid is mixed evenly, and mixed liquor is heated to 55 degree, obtains mixture C；

Step 5: mixture C, mixture B and modified zirconia microballoon are added sequentially in mixture A, with 190r/min's Mixing speed stirs 50 minutes, and temperature control point 5 additions reducing agents in 65-85 degrees Celsius, whipping process, are stirred when stirring After be cooled to 24 DEG C, obtain reparation medicament.

Example IV:

A kind of reparation medicament of high leaded soil, including following component (by mass percentage): cement 18%, quick lime 20%, Natural chelators 12.5%, calcium phosphate 7.2%, calcium magnesium phosphate 6.3%, hydrated manganese oxide 4.8%, reducing agent 15%, zirconium oxide microballoons 3.34%, polyvinyl pyrrolidone 1.45%, isopropanol 1.23%, polyethylene glycol 1.27%, compatilizer are surplus.

Further, natural chelators are the mixture by oxalic acid, tartaric acid and citric acid.

Further, reducing agent is sodium hydrogensulfite；Compatilizer is acrylonitrile.

A kind of preparation method of the reparation medicament of high leaded soil, comprising the following steps:

Step 1: weighing both quantitative cement and quick lime, and 45% water is added and is mixed evenly, and it is spare that mixture A is made；

Step 2: weighing calcium phosphate, calcium magnesium phosphate and hydrated manganese oxide and sequentially add in Mixer pot, and natural chelators and phase is added Hold agent, is extremely dissolved in 30 degree of at a temperature of stirring, then Mixer pot is placed in 70 DEG C of thermostatic chamber, and not with high speed agitator Disconnected stirring 70 minutes, stands 15 minutes after stirring；Obtain mixture B；

Step 3: zirconium oxide microballoons are added in dry toluene magnetic agitation 120 minutes, KH570 are added after logical nitrogen, at 75 DEG C At a temperature of back flow reaction 7 hours, product successively respectively use toluene, methanol, ethanol washing 4 times, be subsequently placed in vacuum desiccator In, vacuum desiccator valve is opened, control temperature is at 95 DEG C, and at 6 hours, vacuum desiccator obtained modified oxygen for drying time control Change zirconium microballoon；

Step 4: it takes polyvinyl pyrrolidone, isopropanol and polyethylene glycol to filter 10 minutes by centrifugal filter respectively, takes Three's filtered fluid is mixed evenly, and mixed liquor is heated to 65 degree, obtains mixture C；

Step 5: mixture C, mixture B and modified zirconia microballoon are added sequentially in mixture A, with 200r/min's Mixing speed stirs 60 minutes, and at 85 degrees Celsius, point 6 additions reducing agents in whipping process, stirring is tied for temperature control when stirring It is cooled to 25 DEG C after beam, obtains reparation medicament.

Reparation medicament can be made in above four groups of embodiments, and formula of the invention is more reasonable, the leaded soil of the height The reparation medicament of earth, by that can incorporate well in the leaded soil of large area using cement and quick lime as raw material, day is added in cooperation The activity and biological effectiveness of lead in soil can be improved in right chelating agent, makes it easier to flow and absorb, natural chelators activation energy Power is relatively strong and easily decomposes, and not will form secondary pollution；By be added reducing agent, can by redox reaction change heavy metal from The valence state of son, to reduce the activity and toxicity of heavy metal in soil；By the way that calcium phosphate, calcium magnesium phosphate and aqua oxidation is added Manganese can promote the precipitating of lead, reduce the exchangeable species lead in soil；The reparation medicament for high leaded soil repair ability compared with By force, can be good at incorporating in soil, repair difficulty is smaller, activation capacity is strong, easily voluntarily decomposes, and will not cause soil Secondary pollution, and preparation method of the invention is more simple, and equipment requirement is low, has good promotion effect.

It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding And modification, the scope of the present invention is defined by the appended.

Claims (8)

1. a kind of reparation medicament of high leaded soil, which is characterized in that including following component (by mass percentage): cement 18-22%, quick lime 15-20%, natural chelators 8.5-12.5%, calcium phosphate 5.5-7.2%, calcium magnesium phosphate 4.8-6.3%, hydration Manganese oxide 3.4-4.8%, reducing agent 10-15%, zirconium oxide microballoons 2.28-3.34%, polyvinyl pyrrolidone 1.25-1.45%, Isopropanol 1.12-1.23%, polyethylene glycol 0.95-1.27%, compatilizer are surplus.

2. a kind of reparation medicament of high leaded soil according to claim 1, which is characterized in that (pressed including following component Mass percent meter): cement 22%, quick lime 15%, natural chelators 8.5%, calcium phosphate 5.5%, calcium magnesium phosphate 4.8%, hydration oxygen Change manganese 3.4%, reducing agent 10%, zirconium oxide microballoons 2.28%, polyvinyl pyrrolidone 1.25%, isopropanol 1.12%, polyethylene glycol 0.95%, compatilizer is surplus.

3. a kind of reparation medicament of high leaded soil according to claim 1, which is characterized in that (pressed including following component Mass percent meter): cement 20%, quick lime 18%, natural chelators 11%, calcium phosphate 6.5%, calcium magnesium phosphate 5.8%, hydration oxygen Change manganese 4.2%, reducing agent 14%, zirconium oxide microballoons 2.85%, polyvinyl pyrrolidone 1.37%, isopropanol 1.18%, polyethylene glycol 1.16%, compatilizer is surplus.

4. a kind of reparation medicament of high leaded soil according to claim 1, which is characterized in that (pressed including following component Mass percent meter): cement 19%, quick lime 16%, natural chelators 10%, calcium phosphate 6.2%, calcium magnesium phosphate 5.2%, hydration oxygen Change manganese 3.8%, reducing agent 11%, zirconium oxide microballoons 2.56%, polyvinyl pyrrolidone 1.3%, isopropanol 1.14%, polyethylene glycol 1.05%, compatilizer is surplus.

5. a kind of reparation medicament of high leaded soil according to claim 1, which is characterized in that (pressed including following component Mass percent meter): cement 18%, quick lime 20%, natural chelators 12.5%, calcium phosphate 7.2%, calcium magnesium phosphate 6.3%, hydration Manganese oxide 4.8%, reducing agent 15%, zirconium oxide microballoons 3.34%, polyvinyl pyrrolidone 1.45%, isopropanol 1.23%, poly- second two Alcohol 1.27%, compatilizer are surplus.

6. a kind of reparation medicament of high leaded soil described in -5 any one according to claim 1, it is characterised in that: the day Right chelating agent is the mixture by oxalic acid, tartaric acid and citric acid.

7. a kind of reparation medicament of high leaded soil described in -5 any one according to claim 1, it is characterised in that: described to go back Former agent is any one of ferrous sulfate, sulphite, sodium thiosulfate or sodium hydrogensulfite；The compatilizer be styrene, Any one of acrylonitrile or metering system sour water glyceride.

8. a kind of preparation method of the reparation medicament of the leaded soil of height as described in claim 1-7 any one, feature exist In, comprising the following steps:

Step 1: weighing both quantitative cement and quick lime, and the water that 35-45% is added is mixed evenly, and it is standby that mixture A is made With；

Step 2: weighing calcium phosphate, calcium magnesium phosphate and hydrated manganese oxide and sequentially add in Mixer pot, and natural chelators and phase is added Hold agent, is extremely dissolved in the at a temperature of stirring of 25-30 degree, then Mixer pot is placed in 60-70 DEG C of thermostatic chamber, and at a high speed Blender is stirred continuously 60-70 minutes, stands 10-15 minutes after stirring；Obtain mixture B；

Step 3: zirconium oxide microballoons are added in dry toluene magnetic agitation 60-120 minutes, and KH570 is added after logical nitrogen, Back flow reaction 3-7 hours at a temperature of 65-75 DEG C, product successively uses toluene, methanol, ethanol washing 1-4 times respectively, then sets In vacuum desiccator, vacuum desiccator valve is opened, at 80-95 DEG C, drying time controls at 2-6 hours, very control temperature Empty drier obtains modified zirconia microballoon；

Step 4: taking polyvinyl pyrrolidone, isopropanol and polyethylene glycol to filter 5-10 minutes by centrifugal filter respectively, It takes three's filtered fluid to be mixed evenly, and mixed liquor is heated to 45-65 degree, obtain mixture C；

Step 5: mixture C, mixture B and modified zirconia microballoon are added sequentially in mixture A, with 160-200r/ The mixing speed of min stirs 30-60 minute, and temperature control divides 3-6 times in 65-85 degrees Celsius, whipping process when stirring is added Reducing agent is cooled to 21-25 DEG C after stirring, obtains reparation medicament.