CN106861111A - A kind of apatite solidification and stabilization method of chrome leather scrap - Google Patents
A kind of apatite solidification and stabilization method of chrome leather scrap Download PDFInfo
- Publication number
- CN106861111A CN106861111A CN201710079033.3A CN201710079033A CN106861111A CN 106861111 A CN106861111 A CN 106861111A CN 201710079033 A CN201710079033 A CN 201710079033A CN 106861111 A CN106861111 A CN 106861111A
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- solidification
- apatite
- chrome leather
- warming
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Classifications
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
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- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of apatite solidification and stabilization method of chrome leather scrap, the apatite solidification and stabilization method of the chrome leather scrap is inserted in sintering furnace using hydroxyapatite and forms height mineralization product with collagen and chromium ion, prepares the solid-state mineralizing material containing chromic salts；Inflated with nitrogen 5min in sintering furnace, is warming up to 100~120 DEG C, is incubated 30~40min, then be warming up to 400~600 DEG C, 30~60min of insulation.Pulverized particles warp after present invention sintering《Solid waste Leaching leaching method sulfonitric method》(HJ/T 299-2007) (pH=3.20 ± 0.05) determines total cr content≤15mg/kg, Cr (VI) content≤0.5mg/kg.
Description
Technical field
It is steady the invention belongs to apatite solidification and stabilization technical field, more particularly to a kind of apatite solidification of chrome leather scrap
Surely method is changed.
Background technology
Curing/stabilizing technology is to process one of main method of poisonous and harmful waste in the world, and the solidification of sludge/steady
Determining treatment is to study more material in poisonous waste is processed both at home and abroad over nearly 20 years.EPA is by cement
Sill solidification is referred to as processing the best-of-breed technology of poisonous and harmful waste.The core of the technology is by waste and cement mixing, through water
Hard solidified cement body is formed after changing reaction, the purpose of hazard component leaching in waste is reduced so as to reach.Leather-making waste contains
Chrome shavinge from rawhide in process hides by horn scraps under chrome tanning rear panel, the remnants for cutting, grinding, be it is a kind of with containing based on collagen,
Next to that the poisonous and harmful waste containing chromium, is referred to as dangerous waste solid, largely discharged in leather making process.It is for many years this containing chrome leather
Bits discarded object has following three kinds of main methods：
1) bury.It is simple method that leather-making waste chrome leather scrap directly is carried out into burial, but because chromic salts easily oozes out, and
Cr VI is oxidized to microorganism and air effect part, not only land occupation, and toxicity increases, contaminated soil and periphery water
Domain, finally goes out of use.
2) burn.Leather-making waste chrome leather scrap is burned as rubbish, but due to burning process in aerobic burning
Cause Cr (III) to be more oxidized to Cr (VI), ash or dust containing Cr (VI) are polluted into environment, method also by
Forbid.
3) albumen is extracted.The collagen in discarded chrome leather scrap is separated using chemical method and regenerated resources are mesh
Preceding most processing method.But, the waste water that separation and Extraction collagen brings therewith is also difficult to process.Remaining body refuse still into
To need poisonous and harmful waste to be processed.If Low fire ceramic particle also needs to highly energy-consuming and treatment limited amount.
In sum, it is always the problem for needing to inquire into find a kind of suitable chrome leather scrap refuse processing method.
The content of the invention
It is an object of the invention to provide a kind of apatite solidification and stabilization method of chrome leather scrap, it is intended to solve existing
The refuse processing method of chrome leather scrap.
The present invention is achieved in that a kind of apatite solidification and stabilization method of chrome leather scrap, the chrome leather scrap
Apatite solidification and stabilization method is：Inserted in sintering furnace using hydroxyapatite and form height mineralising with collagen and chromium ion
Product, prepares the solid-state mineralizing material (phosphorus-calcium-chromium-collagen carbide) containing chromic salts, not only controls chromium (III) to be changed into
Chromium (VI), is difficult to be flooded out even if forming chromium (VI) and also assisting in compound, reaches standard discarded or useful industrially.In order to anti-
Only excessive oxygen participation effect, adds stabilizer and accelerator ferrous sulfate, inflated with nitrogen 5min in sintering furnace to be warming up to 100
~120 DEG C, 30~40min is incubated, albumen is dehydrated denaturation, chromium and hydroxyapatite in close proximity leather, then be warming up to 400
~600 DEG C, 30~60min is incubated, each material is carbonized and be fused to a kind of composite parts material, the material is black gray expandable, its
In chromium (III) and chromium (VI) be all difficult to be leached by acid and neutral water, it is ensured that the stability of heavy metal in compound.
Further, the apatite solidification and stabilization method of the chrome leather scrap is specifically included：
(1) in horizontal mixer, 100 parts of chrome leather scraps of addition, 20~30 parts of water, 5~7 part of 7 aqueous ferrous sulfate, 10~
15 parts of ratio mixtures by different Ca/P, are heated to 35~45 DEG C, stir 30min；
(2) adjusted to pH=9.0~10.0 with 20%NaOH solution, stir 30min, be pressed into 10~20t cargo jacks solid
Setting shape, inserts in sintering furnace, inflated with nitrogen 5min, is warming up to 100~120 DEG C, is incubated 30~40min, then it is warming up to 400~
600 DEG C, it is incubated 30~60min；
(3) come out of the stove, be cooled to normal temperature, be ground into particle as a kind of inorganic-organic hybrid hardened material；Its granularity can be with
Determined as the ingredient requirement of soil-burial, floor tile or plastic floor filler according to inorganic-organic hybrid hardened material.
(4) it is Ca (OH) according to the Ca in the mixture of (1) Ca/P2、CaCl2、Ca(NO3)2, the P in mixture is
NaH2PO4、Na2HPO4、Na3PO4, than the quantity ratio for Ca and P element, ratio is 2.0 to the Ca/P in the mixture of the Ca/P
~4.0, wherein using Ca (OH)2When Ca/P ratios be 2.0~3.0, using CaCl2、Ca(NO3)2When Ca/P ratios be 3.0~4.0.
Further, the Ca in the mixture of the Ca/P is Ca (OH)2、CaCl2、Ca(NO3)2, the P in mixture is
NaH2PO4、Na2HPO4、Na3PO4。
Further, than the quantity ratio for Ca and P element, wherein Ca elements need height to the Ca/P in the mixture of the Ca/P
In apatite proportion of composing, wherein using Ca (OH)2When Ca/P ratios be 2.0~3.0, using CaCl2、Ca(NO3)2When Ca/P ratios
It is 3.0~4.0.
Another object of the present invention is to provide a kind of apatite solidification and stabilization method preparation by the chrome leather scrap
Inorganic-organic hybrid hardened material, be adapted to soil-burial, for cement floor tile filler or plastic floor filler.
The apatite solidification and stabilization method of the chrome leather scrap that the present invention is provided, hydroxyapatite (HAP, Ca10(PO4)6
(OH)2) there is good biocompatibility, it is the ceramic material for having bioactivity.HAP is the main inorganic composition of skeleton,
Not only there is good biocompatibility, and can be formed and be firmly bonded with induction of bone growth and with biological tissue, it is main to use
In human body bone, the replacement of tooth and reparation.When HAP forms hollow-core construction, protein ashing composition and slaine etc. are loaded into
In its cavity and form compound, it becomes possible to oozing out for metal is effectively prevented, as soil and the raw material of construction material.In order to protect
Sour gas and material that card high temperature degradation albumen occurs, it is desirable to the Calcium treatment of excess, it is ensured that phosphorus ash is formed under alkaline environment pH
Stone, pulverized particles warp after sintering《Solid waste Leaching leaching method sulfonitric method》(HJ/T 299-2007) (pH=
3.20 ± 0.05) determine total cr content≤15mg/kg, Cr (VI) content≤0.5mg/kg.
Brief description of the drawings
Fig. 1 is the apatite solidification and stabilization method flow chart of chrome leather scrap provided in an embodiment of the present invention.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The present invention forms height mineralization product, manufacture one with collagen and chromium ion at a certain temperature using hydroxyapatite
Plant containing chromic salts but be difficult to solid-state mineralizing material (the dissolution total cr content≤15mg/kg, Cr (VI) content≤0.5mg/ for oozing out
Kg), it is that process hides waste solid containing chromium seeks a kind of poisonous and harmful waste processing method.
Application principle of the invention is explained in detail below in conjunction with the accompanying drawings.
As shown in figure 1, the apatite solidification and stabilization method of chrome leather scrap provided in an embodiment of the present invention includes following step
Suddenly：
S101：In horizontal mixer, 100 parts of chrome leather scraps, 20~30 parts of water, 5~7 part of 7 aqueous ferrous sulfate, 10 are added
~15 parts of ratio mixtures by different Ca/P, are heated to 35~45 DEG C, stir 30min；
S102：Adjusted to pH=9.0~10.0 with 20%NaOH solution, stir 30min, be pressed into 10~20t cargo jacks
Solid shape, inserts in sintering furnace (high temperature furnace), inflated with nitrogen 5min, is warming up to 100~120 DEG C, is incubated 30~40min, then rise
Temperature is incubated 30~60min to 400~600 DEG C；
S103：Come out of the stove, be cooled to normal temperature, be ground into particle as inorganic-organic hybrid hardened material as soil-burial,
The raw material of floor tile or plastic floor filler.
Chrome leather scrap essentially from process hides shaving waste solid, containing Cr2O3≤ 3.0%, aqueous 35%~45%.
Ca in the mixture of Ca/P is Ca (OH)2、CaCl2、Ca(NO3)2, the P in mixture is NaH2PO4、Na2HPO4、
Na3PO4。
Than the quantity ratio for Ca and P element, ratio is 2.0~4.0 to Ca/P in the mixture of Ca/P, wherein using Ca
(OH)2When Ca/P ratios be 2.0~3.0, using CaCl2、Ca(NO3)2When Ca/P ratios be 3.0~4.0.
Application principle of the invention is further described with reference to specific embodiment.
Embodiment 1
In horizontal mixer, 100 parts are added to contain Cr2O3=1.55% shavings, 20 parts of water, 5 part of 7 aqueous ferrous sulfate, 15 parts
By the Ca (OH) that the ratio of Ca/P is 2.02With Na2HPO4Mixture, is heated to 35 DEG C, stirs 30min, uses 20%NaOH solution
Regulation stirs 30min to pH=9.0~10.0, and solid shape is pressed into 10t cargo jacks, inserts in sintering furnace (high temperature furnace), fills
Nitrogen 5min, is warming up to 100 DEG C, is incubated 30~40min, then is warming up to 500~550 DEG C, is incubated 40min, comes out of the stove, and is cooled to often
Temperature, is ground into particle as the suitable soil-burial of inorganic-organic hybrid hardened material, for cement floor tile filler or plastic floor
Filler.
Pulverized particles warp after sintering《Solid waste Leaching leaching method sulfonitric method》(HJ/T 299—2007)
(pH=3.20 ± 0.05) determines total cr content≤15mg/kg, Cr (VI) content≤0.5mg/kg.
Embodiment 2
In horizontal mixer, 100 parts are added to contain Cr2O3=2.72% shavings, 30 parts of water, 7 part of 7 aqueous ferrous sulfate, 15 parts
By the CaCl that the ratio of Ca/P is 4.02With NaH2PO4Mixture, is heated to 35 DEG C, stirs 30min, is adjusted with 20%NaOH solution
Section stirs 30min to pH=9.0, and solid shape is pressed into 10t cargo jacks, inserts in sintering furnace (high temperature furnace), inflated with nitrogen
5min, is warming up to 100 DEG C, is incubated 40min, then is warming up to 400~450 DEG C, is incubated 60min, comes out of the stove, and is cooled to normal temperature, crushes
Into particle as inorganic-organic hybrid hardened material, be adapted to soil-burial, for cement floor tile filler or plastic floor filler.
Pulverized particles warp after sintering《Solid waste Leaching leaching method sulfonitric method》(HJ/T 299—2007)
(pH=3.20 ± 0.05) determines total cr content≤15mg/kg, Cr (VI) content≤0.5mg/kg.
Embodiment 3
In horizontal mixer, 100 parts are added to contain Cr2O3=2.22% shavings, 30 parts of water, 6 part of 7 aqueous ferrous sulfate, 12 parts
By the Ca (NO that the ratio of Ca/P is 4.03)2With NaH2PO4Mixture, is heated to 35 DEG C, stirs 30min, uses 20%NaOH solution
Regulation stirs 30min to pH=10.0, and solid shape is pressed into 10t cargo jacks, inserts in sintering furnace (high temperature furnace), inflated with nitrogen
5min, is warming up to 120 DEG C, is incubated 40min, then is warming up to 450~500 DEG C, is incubated 60min, comes out of the stove, and is cooled to normal temperature, crushes
Into particle as inorganic-organic hybrid hardened material, be adapted to soil-burial, for cement floor tile filler or plastic floor filler.
Pulverized particles warp after sintering《Solid waste Leaching leaching method sulfonitric method》(HJ/T 299—2007)
(pH=3.20 ± 0.05) determines total cr content≤15mg/kg, Cr (VI) content≤0.5mg/kg.
Application effect of the invention is explained in detail with reference to experiment.
Test result analysis：
Tannery's 10kg chrome leather scraps are taken, according to embodiment 1~3, after being deposited 3 months to pulverized particles after sintering, warp《Gu
Body waste Leaching leaching method sulfonitric method》(HJ/T299-2007) (pH=3.20 ± 0.05) comparative determination result
It is shown in Table 1.
After the solidification stabilization of table 1 in material granule chromium dissolution
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (2)
1. a kind of apatite solidification and stabilization method of chrome leather scrap, it is characterised in that the apatite solidification of the chrome leather scrap
Stabilization method is inserted in sintering furnace using hydroxyapatite and forms height mineralization product with collagen and chromium ion, prepare containing
The solid-state mineralizing material of chromic salts；Inflated with nitrogen 5min in sintering furnace, is warming up to 100 DEG C~120 DEG C, is incubated 30min~40min, then
400 DEG C~600 DEG C are warming up to, 30min~60min is incubated.
2. the apatite solidification and stabilization method of chrome leather scrap as claimed in claim 1, it is characterised in that the chrome leather scrap
Apatite solidification and stabilization method specifically include：
(1) in horizontal mixer, 100 parts of chrome leather scraps, 20 parts of water~30 part water, 5 parts~7 parts aqueous ferrous sulfates, 10 are added
Part~15 parts of ratio mixtures by different Ca/P, and 35 DEG C~45 DEG C are heated to, stir 30min；
(2) adjusted to pH=9.0~10.0 with 20%NaOH solution, stir 30min, fixed shape is pressed into 10t~20t cargo jacks
Shape, inserts in sintering furnace, inflated with nitrogen 5min, is warming up to 100 DEG C~120 DEG C, is incubated 30min~40min, then be warming up to 400 DEG C
~600 DEG C, it is incubated 30min~60min；
(3) come out of the stove, be cooled to normal temperature, be ground into particle；
(4) it is Ca (OH) according to the Ca in the mixture of (1) Ca/P2、CaCl2、Ca(NO3)2, the P in mixture is
NaH2PO4、Na2HPO4、Na3PO4, than the quantity ratio for Ca and P element, ratio is 2.0 to the Ca/P in the mixture of the Ca/P
~4.0, wherein using Ca (OH)2When Ca/P ratios be 2.0~3.0, using CaCl2、Ca(NO3)2When Ca/P ratios be 3.0~4.0.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710079033.3A CN106861111B (en) | 2017-02-14 | 2017-02-14 | Method for solidifying and stabilizing apatite containing chrome leather scraps |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710079033.3A CN106861111B (en) | 2017-02-14 | 2017-02-14 | Method for solidifying and stabilizing apatite containing chrome leather scraps |
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| CN106861111A true CN106861111A (en) | 2017-06-20 |
| CN106861111B CN106861111B (en) | 2021-03-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115068876A (en) * | 2022-07-05 | 2022-09-20 | 徐州鸿丰高分子材料有限公司 | Solid hazardous waste conversion method for chrome-containing leather scraps in tannery |
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|---|---|---|---|---|
| JP2002316172A (en) * | 2001-04-19 | 2002-10-29 | Taiheiyo Cement Corp | Wastewater treatment method |
| JP2007216069A (en) * | 2005-10-28 | 2007-08-30 | Sumikon Serutekku Kk | Treating method of contaminated soil |
| CN105537260A (en) * | 2015-12-11 | 2016-05-04 | 上海交通大学 | Synchronous soil heavy-metal Zn and Cr stabilizing remediation method |
| CN106244155A (en) * | 2015-12-29 | 2016-12-21 | 广西汇泰环保科技有限公司 | A kind of soil Cr pollution amelioration agent |
| CN106277456A (en) * | 2016-08-30 | 2017-01-04 | 浙江奇彩环境科技股份有限公司 | A kind of waste electroplating liquor containing chromium resource prepares the method that ferrochrome is black |
-
2017
- 2017-02-14 CN CN201710079033.3A patent/CN106861111B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002316172A (en) * | 2001-04-19 | 2002-10-29 | Taiheiyo Cement Corp | Wastewater treatment method |
| JP2007216069A (en) * | 2005-10-28 | 2007-08-30 | Sumikon Serutekku Kk | Treating method of contaminated soil |
| CN105537260A (en) * | 2015-12-11 | 2016-05-04 | 上海交通大学 | Synchronous soil heavy-metal Zn and Cr stabilizing remediation method |
| CN106244155A (en) * | 2015-12-29 | 2016-12-21 | 广西汇泰环保科技有限公司 | A kind of soil Cr pollution amelioration agent |
| CN106277456A (en) * | 2016-08-30 | 2017-01-04 | 浙江奇彩环境科技股份有限公司 | A kind of waste electroplating liquor containing chromium resource prepares the method that ferrochrome is black |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115068876A (en) * | 2022-07-05 | 2022-09-20 | 徐州鸿丰高分子材料有限公司 | Solid hazardous waste conversion method for chrome-containing leather scraps in tannery |
| CN115068876B (en) * | 2022-07-05 | 2023-08-18 | 徐州鸿丰高分子材料有限公司 | Solid dangerous waste conversion method for chrome-containing leather scraps in tannery |
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| CN106861111B (en) | 2021-03-23 |
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