CN106861111B - Method for solidifying and stabilizing apatite containing chrome leather scraps - Google Patents
Method for solidifying and stabilizing apatite containing chrome leather scraps Download PDFInfo
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- CN106861111B CN106861111B CN201710079033.3A CN201710079033A CN106861111B CN 106861111 B CN106861111 B CN 106861111B CN 201710079033 A CN201710079033 A CN 201710079033A CN 106861111 B CN106861111 B CN 106861111B
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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
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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
- 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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Abstract
The invention discloses a method for solidifying and stabilizing apatite containing chrome leather scraps, which comprises the steps of placing hydroxyapatite into a sintering furnace to form a highly mineralized product with collagen and chromium ions so as to prepare a solid mineralized material containing chromium salt; and (3) filling nitrogen into the sintering furnace for 5min, heating to 100-120 ℃, preserving heat for 30-40 min, heating to 400-600 ℃, and preserving heat for 30-60 min. The sintered crushed particles are measured by a sulfuric acid-nitric acid method (HJ/T299-2007) (pH is 3.20 +/-0.05) of a solid waste leaching toxicity leaching method, and the total Cr content is less than or equal to 15mg/kg, and the Cr (VI) content is less than or equal to 0.5 mg/kg.
Description
Technical Field
The invention belongs to the technical field of apatite solidification and stabilization, and particularly relates to an apatite solidification and stabilization method for chrome-containing leather scraps.
Background
The solidification/stabilization technology is one of the main international methods for treating toxic and harmful wastes, and the solidification/stabilization treatment of sludge is a material which is researched for treating toxic and harmful wastes at home and abroad for about 20 years. The united states environmental protection agency sets cement-based materials as the best technology for the disposal of hazardous and noxious waste. The core of the technology is that the waste and the cement are mixed and form a hard cement solidified body after hydration reaction, thereby achieving the purpose of reducing leaching of dangerous components in the waste. The chrome-containing leather scraps in the tanning process are residual waste in the lower corner of leather-making raw leather subjected to chrome tanning, cutting and grinding, are toxic and harmful wastes mainly containing collagen and secondarily containing chrome, are called hazardous waste solids, and are discharged in a large quantity in the tanning process. For years, the chromium-containing leather scrap waste has the following three main treatment methods:
1) and (7) burying. The method is simple, but chromium salt is easy to seep out and is partially oxidized into hexavalent chromium along with the action of microorganisms and air, so that the method occupies land, increases toxicity, pollutes soil and surrounding water areas, and is finally discarded.
2) And (5) burning. Chromium-containing leather scraps of tannery wastes are incinerated as wastes, but aerobic incineration in the incineration process causes a large amount of Cr (III) to be oxidized into Cr (VI), and ash or dust containing Cr (VI) enters the environment to cause pollution, and the method is prohibited.
3) And (4) extracting protein. The most treatment method at present is to separate collagen from the waste chrome-containing leather scraps by a chemical method and regenerate and recycle the collagen. However, the waste water associated with the separation and extraction of collagen is also difficult to treat. The remaining sludge still becomes toxic and harmful waste to be treated. High energy consumption and limited amount of processing are also required to fire the ceramic particles.
In view of the above, it is a problem to be studied to find a suitable method for treating chrome-containing leather scraps waste.
Disclosure of Invention
The invention aims to provide a method for solidifying and stabilizing apatite containing chrome leather scraps, and aims to solve the problem of the existing method for treating wastes containing chrome leather scraps.
The invention is realized by the method for stabilizing the solidification of the apatite containing chrome leather scraps, which comprises the following steps: hydroxyapatite is placed in a sintering furnace to form a highly mineralized product with collagen and chromium ions, so that a solid mineralized material (phosphorus-calcium-chromium-collagen carbide) containing chromium salt is prepared, chromium (III) is controlled to be converted into chromium (VI), even if the chromium (VI) is formed, the compound is not easy to leach out by water, and the waste or industrial use standard is reached. In order to prevent excessive oxygen participation, a stabilizer and an accelerant ferrous sulfate are added, nitrogen is filled in a sintering furnace for 5min, the temperature is raised to 100-120 ℃, the temperature is kept for 30-40 min, protein is dehydrated and denatured and closely approaches to chromium and hydroxyapatite in leather, the temperature is raised to 400-600 ℃, the temperature is kept for 30-60 min, all substances are carbonized and fused into a composite component substance, the substance is black gray, chromium (III) and chromium (VI) are not easy to be leached out by acidic and neutral water, and the stability of heavy metal in the composite is ensured.
Further, the method for curing and stabilizing the apatite containing the chrome leather scraps specifically comprises the following steps:
(1) adding 100 parts of chromium-containing leather scraps, 20-30 parts of water, 5-7 parts of ferrous sulfate hydrate and 10-15 parts of mixture according to different Ca/P ratios into a horizontal stirrer, heating to 35-45 ℃, and stirring for 30 min;
(2) adjusting the pH value to 9.0-10.0 by using a 20% NaOH solution, stirring for 30min, pressing into a fixed shape by using a press for 10-20 t, placing into a sintering furnace, filling nitrogen for 5min, heating to 100-120 ℃, preserving heat for 30-40 min, heating to 400-600 ℃, and preserving heat for 30-60 min;
(3) discharging, cooling to normal temperature, and crushing into particles as an inorganic-organic composite hardening material; the granularity of the inorganic-organic composite hardening material can be determined according to the raw material requirement of the inorganic-organic composite hardening material as a filling material for soil landfill, floor tiles or plastic floors.
(4) The Ca in the Ca/P mixture according to (1) is Ca (OH)2、CaCl2、Ca(NO3)2P in the mixture is NaH2PO4、Na2HPO4、Na3PO4The Ca/P ratio in the Ca/P mixture is the quantity ratio of Ca to P, the ratio is 2.0-4.0, wherein Ca (OH) is adopted2The Ca/P ratio is 2.0-3.0, CaCl is adopted2、Ca(NO3)2The Ca/P ratio is 3.0 to 4.0.
Further, Ca in the Ca/P mixture is Ca (OH)2、CaCl2、Ca(NO3)2P in the mixture is NaH2PO4、Na2HPO4、Na3PO4。
Further, the Ca/P ratio of the Ca/P mixture is the quantity ratio of Ca and P, wherein Ca element needs to be higher than the composition ratio of apatite, and Ca (OH) is adopted2The Ca/P ratio is 2.0-3.0, CaCl is adopted2、Ca(NO3)2The Ca/P ratio is 3.0 to 4.0.
Another object of the present invention is to provide an inorganic-organic composite hardening material prepared by the method for curing and stabilizing apatite containing chrome leather scraps, which is suitable for soil landfill, and can be used as a cement floor tile filler or a plastic floor filler.
The present invention provides a method for stabilizing solidification of apatite containing chrome leather scraps, hydroxyapatite (HAP, Ca)10(PO4)6(OH)2) Has good biocompatibility and is a ceramic material with bioactivity. HAP is the main inorganic component of human skeleton, not only has good biocompatibility, but also can induce bone growth and form firm bonding with biological tissues, and is mainly used for replacing and repairing human bone and teeth. When HAP forms a hollow structure, and a protein ashing component, a metal salt, and the like are loaded into the hollow cavity to form a complex, the metal leaching can be effectively prevented, and the HAP can be used as a raw material for soil and building materials. In order to ensure that acidic gases and substances generated by high-temperature degradation of protein are generated, excessive calcium treatment is required, apatite is formed under the condition of alkaline environment pH, and the total Cr content of the sintered crushed particles is less than or equal to 15mg/kg and the Cr (VI) content is less than or equal to 0.5mg/kg through a sulfuric acid-nitric acid method (HJ/T299-2007) (pH is 3.20 +/-0.05) of a solid waste leaching toxicity leaching method.
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FIG. 1 is a flow chart of a method for stabilizing and curing a chrome-containing leather shavings-containing apatite provided in accordance with an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention utilizes hydroxyapatite to form a highly mineralized product with collagen and chromium ions at a certain temperature to manufacture a solid mineralized material containing chromium salt but difficult to exude (the total dissolved Cr content is less than or equal to 15mg/kg, and the Cr (VI) content is less than or equal to 0.5mg/kg), and a method for treating toxic and harmful waste is sought for the chrome-containing waste solids in tanning.
The following detailed description of the principles of the invention is provided in connection with the accompanying drawings.
As shown in FIG. 1, the method for stabilizing and curing apatite containing chrome leather scraps according to the embodiment of the present invention comprises the following steps:
s101: adding 100 parts of chromium-containing leather scraps, 20-30 parts of water, 5-7 parts of ferrous sulfate hydrate and 10-15 parts of mixture according to different Ca/P ratios into a horizontal stirrer, heating to 35-45 ℃, and stirring for 30 min;
s102: adjusting the pH value to 9.0-10.0 by using a 20% NaOH solution, stirring for 30min, pressing into a fixed shape by using a 10-20 t press, placing into a sintering furnace (high temperature furnace), filling nitrogen for 5min, heating to 100-120 ℃, keeping the temperature for 30-40 min, heating to 400-600 ℃, and keeping the temperature for 30-60 min;
s103: taking out of the furnace, cooling to normal temperature, and crushing into particles as the raw material of the inorganic-organic composite hardening material as the filler of the soil landfill, the floor tile or the plastic floor.
The chrome-containing leather scraps are mainly from leather-making shaving waste solids, and contain Cr2O3Less than or equal to 3.0 percent and water content of 35 to 45 percent.
Ca in the Ca/P mixture is Ca (OH)2、CaCl2、Ca(NO3)2P in the mixture is NaH2PO4、Na2HPO4、Na3PO4。
The ratio of Ca/P in the mixture of Ca/P is the quantity ratio of Ca to P, the ratio is 2.0-4.0, wherein Ca (OH) is adopted2The Ca/P ratio is 2.0-3.0, CaCl is adopted2、Ca(NO3)2The Ca/P ratio is 3.0 to 4.0.
The application of the principles of the present invention will now be described in further detail with reference to specific embodiments.
Example 1
100 portions of Cr are added into a horizontal stirrer2O31.55% leather shavings, 20 parts of water, 5 parts of 7 parts of ferrous sulphate hydrate, 15 parts of Ca (OH) in a Ca/P ratio of 2.02With Na2HPO4Heating the mixture to 35 ℃, stirring for 30min, adjusting the pH value to 9.0-10.0 by using a 20% NaOH solution, stirring for 30min, pressing into a fixed shape by using a 10t press, placing the fixed shape into a sintering furnace (high temperature furnace), filling nitrogen for 5min, heating to 100 ℃, preserving heat for 30-40 min, heating to 500-550 ℃, preserving heat for 40min, discharging, cooling to normal temperature, and crushing into particles serving as an inorganic-organic composite hardening material suitable for soil landfill and used as a cement floor tile filler or plastic floor filler.
The content of Cr (Cr) (VI) in the sintered crushed particles is less than or equal to 15mg/kg and less than or equal to 0.5mg/kg by a sulfuric acid-nitric acid method (HJ/T299-2007) (pH is 3.20 +/-0.05) of a solid waste leaching toxicity leaching method.
Example 2
100 portions of Cr are added into a horizontal stirrer2O32.72% leather scraps, 30 parts of water, 7 parts of ferrous sulfate hydrate, and 15 parts of CaCl with a Ca/P ratio of 4.02With NaH2PO4Heating the mixture to 35 ℃, stirring for 30min, adjusting the pH value to 9.0 by using a 20% NaOH solution, stirring for 30min, pressing the mixture into a fixed shape by using a 10t press, placing the fixed shape into a sintering furnace (high temperature furnace), filling nitrogen for 5min, heating to 100 ℃, preserving heat for 40min, heating to 400-450 ℃, preserving heat for 60min, discharging the mixture out of the furnace, cooling to normal temperature, and crushing the mixture into particles serving as an inorganic-organic composite hardening material, wherein the inorganic-organic composite hardening material is suitable for soil landfill and is used for cement floor tile filler or plastic floor filler.
The content of Cr (Cr) (VI) in the sintered crushed particles is less than or equal to 15mg/kg and less than or equal to 0.5mg/kg by a sulfuric acid-nitric acid method (HJ/T299-2007) (pH is 3.20 +/-0.05) of a solid waste leaching toxicity leaching method.
Example 3
100 portions of Cr are added into a horizontal stirrer2O32.22% leather scraps, 30 parts of water, 6 parts of 7 parts of ferrous sulfate hydrate, and 12 parts of Ca (NO) with a Ca/P ratio of 4.03)2With NaH2PO4Heating the mixture to 35 ℃, stirring for 30min, adjusting the pH value to 10.0 by using a 20% NaOH solution, stirring for 30min, pressing the mixture into a fixed shape by using a 10t press, placing the fixed shape into a sintering furnace (high temperature furnace), filling nitrogen for 5min, heating to 120 ℃, preserving heat for 40min, heating to 450-500 ℃, preserving heat for 60min, discharging the mixture out of the furnace, cooling to normal temperature, and crushing the mixture into particles serving as an inorganic-organic composite hardening material, wherein the inorganic-organic composite hardening material is suitable for soil landfill and is used for cement floor tile filler or plastic floor filler.
The content of Cr (Cr) (VI) in the sintered crushed particles is less than or equal to 15mg/kg and less than or equal to 0.5mg/kg by a sulfuric acid-nitric acid method (HJ/T299-2007) (pH is 3.20 +/-0.05) of a solid waste leaching toxicity leaching method.
The effects of the present invention will be described in detail with reference to the following experiments.
And (3) analyzing test results:
the results of comparative measurements on sintered crushed grains stored for 3 months in tannery containing 10kg of chromium leather scraps according to examples 1 to 3 by the sulfuric acid-nitric acid method (HJ/T299-2007) (pH 3.20 ± 0.05) of leaching toxicity of solid wastes are shown in table 1.
TABLE 1 dissolution of chromium from material particles after solidification stabilization
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (1)
1. The method for curing and stabilizing the apatite containing the chrome leather scraps is characterized by comprising the following steps of:
(1) adding 100 parts of chrome-containing leather scraps, 20-30 parts of water, 5-7 parts of water ferrous sulfate and 10-15 parts of mixture according to different Ca/P ratios into a horizontal stirrer, heating to 35-45 ℃, and stirring for 30 min;
(2) adjusting the pH value to 9.0-10.0 by using a 20% NaOH solution, stirring for 30min, pressing into a fixed shape by using a 10 t-20 t press, placing into a sintering furnace, filling nitrogen for 5min, heating to 100-120 ℃, preserving heat for 30-40 min, heating to 400-600 ℃, and preserving heat for 30-60 min;
(3) discharging, cooling to normal temperature, and pulverizing into granules;
the Ca in the Ca/P mixture according to (1) is Ca (OH)2、CaCl2、Ca(NO3)2P in the mixture is NaH2PO4、Na2HPO4、Na3PO4The Ca/P ratio in the Ca/P mixture is the quantity ratio of Ca to P, the ratio is 2.0-4.0, wherein Ca (OH) is adopted2The Ca/P ratio is 2.0-3.0, CaCl is adopted2、Ca(NO3)2The Ca/P ratio is 3.0 to 4.0.
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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 |
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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 |
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