Background technology
Gac has flourishing pore texture and huge specific surface area (500-3000 ㎡/g), absorption property is good, organic or inorganic material in gas, solution and colloidal solid etc. there is very strong adsorptive power, have enough chemical stabilities, physical strength, acidproof, alkaline-resisting, heat-resisting, water insoluble and organic solvent, use the superperformances such as the rear easily regeneration of losing efficacy, have purposes widely in various fields such as foodstuffs industry, sugaring, medicine, chemical industry, environmental protection, national defence, agricultural, fuel gas storage, gas delivery, catalyzed reactions.The raw material of preparation gac has timber, coke, refinery coke, various nutshell, spent pulping liquor, straw, synthon, waste or used plastics etc.
China's population is more, and every day, diet all be unable to do without meat-based food.Animal bone is boiled soup and is namely thrown away as waste later on, and the rotten animal bone that goes out of use is seen everywhere, and has not only polluted environment but also has wasted resource.How the animal bone resource is used fully, become in current people's life and bite the problem that needs solution.
Summary of the invention
The objective of the invention is the defective for the prior art existence, a kind of preparation method who takes full advantage of animal bone and have the high-performance bone black that cost is low, the adsorption cleaning ability is strong is provided.
The objective of the invention is to solve by the following technical programs:
A kind of preparation method of high-performance bone black is characterized in that described preparation method carries out in the steps below:
(1) will be broken into through the animal bone that degreasing is come unstuck the particle of 1-5 ㎜;
(2) the particulate state animal bone is sent in carbonized activating furnace, added composite activating agent after with the temperature rise rate of 5-10 ℃/min, furnace temperature being warming up to 500 ℃-550 ℃, kept constant temperature 1-3 hour after then continuing to be warming up to 650 ℃-750 ℃;
(3) stop inputting composite activating agent after continuing to pass into composite activating agent and make furnace temperature be quickly cooled to 150 ℃-180 ℃ after constant temperature finishing, then continue to make furnace temperature to be cooled to rear discharging below 100 ℃;
(4) bone black after carbonization-activation is added in alkaline aqueous solution, then pass into steam and boil and wash 5-10 time;
(5) will boil bone black after washing puts into the aqueous solution rinsing that is dissolved with carbonic acid gas and 5-10 time the ph value is adjusted into 7.0-8.0;
(6) pull out after rinsing dry or dry after the high-performance bone black that gets product.
Composite activating agent in described step (2) and step (3) is the mixture of carbonic acid gas and water vapor.
In the ratio input carbonized activating furnace of composite activating agent in described step (2) according to 0.1-1 kilogram composite activating agent/kilogram animal bone per hour.
In the ratio input carbonized activating furnace of composite activating agent in described step (3) according to 0.5-2 kilogram composite activating agent/kilogram animal bone per hour.
Alkaline aqueous solution in described step (4) is the aqueous solution of potassium hydroxide or sodium hydroxide.
Alkaline aqueous solution concentration in described step (4) is 2-15%.
Alkaline aqueous solution in described step (4) boils when washing at every turn and the weight ratio of bone black is 5-10:1.
In described step (5) be dissolved with the each rinsing of the aqueous solution of carbonic acid gas the time and the weight ratio of bone black be 8-15:1.
The present invention has the following advantages compared to existing technology:
The present invention adopts the animal bones such as common ox bone, sheep bone, horse bone, camel bone to prepare bone black, the input of composite activating agent is conducive to accelerate the generation of carbon geochemistry composition and the specific surface area that improves bone black, be conducive to the discharge of volatile matter soot gas in the carbonization-activation process under temperature constant state, and fully adopt in preparation process boil wash, the mode of rinsing removes the peculiar smell in bone black and adjusts the ph value of bone black, has the strong characteristics of bone black adsorption cleaning ability that technique is simple, cost is low and make.
Calcium phosphate powder in the bone black that the present invention makes can with water in heavy metal, fluorion etc. the chemical replacement reaction occurs, heavy metal in Adsorption water (arsenic, chromium, cadmium, rubidium etc.) ion, fluorion etc., reach the purpose of purifying waste water, because the adsorption cleaning ability of this bone black is strong, the water quality after therefore purifying can reach the standard of tap water.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
at first will be broken into through the animal bone (as ox bone, sheep bone, horse bone, camel bone etc.) that degreasing is come unstuck the particle of 1-5 ㎜, then the particulate state animal bone is delivered in carbonized activating furnace, temperature rise rate with 5 ℃/min is warming up to 500 ℃ with furnace temperature, then will carbonic acid gas and the composite activating agent made after mixing of water vapor input in carbonized activating furnace according to the ratio of 0.4 kilogram of composite activating agent/kilogram animal bone per hour, then continue to be warming up to and keep constant temperature to be beneficial to the discharge of volatile matter soot gas in 1.5 hours after 720 ℃, wherein the input of composite activating agent is conducive to accelerate the generation of carbon geochemistry composition and the specific surface area that improves bone black, be conducive to the discharge of volatile matter soot gas in the carbonization-activation process under temperature constant state, continue after constant temperature finishes will carbonic acid gas and the composite activating agent made after mixing of water vapor input in carbonized activating furnace according to the ratio of 0.5 kilogram of composite activating agent/kilogram animal bone per hour, and stop inputting composite activating agent after making furnace temperature be quickly cooled to 150 ℃, then continue to make furnace temperature to be cooled to rear discharging below 100 ℃, it is in 8% alkaline aqueous solution that bone black after carbonization-activation is added concentration that potassium hydroxide or sodium hydroxide are made, then passes into steam and boils and wash 8 times to remove the peculiar smell in bone black, boils at every turn wherein that when washing, the weight ratio of alkaline aqueous solution and bone black is 7:1, put into the aqueous solution rinsing that is dissolved with carbonic acid gas and 9 times the ph value is adjusted into 7.0-8.0 boiling bone black after washing, be dissolved with the aqueous solution of carbonic acid gas during each rinsing and the weight ratio of bone black is 10:1, pull out after rinsing dry or dry after the high-performance bone black that gets product, this high-performance bone black also can be broken into required particle diameter as required.
Embodiment 2
at first will be broken into through the animal bone (as ox bone, sheep bone, horse bone, camel bone etc.) that degreasing is come unstuck the particle of 1-5 ㎜, then the particulate state animal bone is delivered in carbonized activating furnace, temperature rise rate with 5 ℃/min is warming up to 520 ℃ with furnace temperature, then will carbonic acid gas and the composite activating agent made after mixing of water vapor input in carbonized activating furnace according to the ratio of 1 kilogram of composite activating agent/kilogram animal bone per hour, then continue to be warming up to and keep constant temperature to be beneficial to the discharge of volatile matter soot gas in 2 hours after 680 ℃, wherein the input of composite activating agent is conducive to accelerate the generation of carbon geochemistry composition and the specific surface area that improves bone black, be conducive to the discharge of volatile matter soot gas in the carbonization-activation process under temperature constant state, continue after constant temperature finishes will carbonic acid gas and the composite activating agent made after mixing of water vapor input in carbonized activating furnace according to the ratio of 1.8 kilograms of composite activating agent/kilogram animal bones per hour, and stop inputting composite activating agent after making furnace temperature be quickly cooled to 170 ℃, then continue to make furnace temperature to be cooled to rear discharging below 100 ℃, it is in 12% alkaline aqueous solution that bone black after carbonization-activation is added concentration that potassium hydroxide or sodium hydroxide are made, then passes into steam and boils and wash 6 times to remove the peculiar smell in bone black, boils at every turn wherein that when washing, the weight ratio of alkaline aqueous solution and bone black is 9:1, put into the aqueous solution rinsing that is dissolved with carbonic acid gas and 6 times the ph value is adjusted into 7.0-8.0 boiling bone black after washing, be dissolved with the aqueous solution of carbonic acid gas during each rinsing and the weight ratio of bone black is 13:1, pull out after rinsing dry or dry after the high-performance bone black that gets product, this high-performance bone black also can be broken into required particle diameter as required.
Embodiment 3
at first will be broken into through the animal bone (as ox bone, sheep bone, horse bone, camel bone etc.) that degreasing is come unstuck the particle of 1-5 ㎜, then the particulate state animal bone is delivered in carbonized activating furnace, temperature rise rate with 10 ℃/min is warming up to 550 ℃ with furnace temperature, then will carbonic acid gas and the composite activating agent made after mixing of water vapor input in carbonized activating furnace according to the ratio of 0.6 kilogram of composite activating agent/kilogram animal bone per hour, then continue to be warming up to and keep constant temperature to be beneficial to the discharge of volatile matter soot gas in 3 hours after 650 ℃, wherein the input of composite activating agent is conducive to accelerate the generation of carbon geochemistry composition and the specific surface area that improves bone black, be conducive to the discharge of volatile matter soot gas in the carbonization-activation process under temperature constant state, continue after constant temperature finishes will carbonic acid gas and the composite activating agent made after mixing of water vapor input in carbonized activating furnace according to the ratio of 2 kilograms of composite activating agent/kilogram animal bones per hour, and stop inputting composite activating agent after making furnace temperature be quickly cooled to 160 ℃, then continue to make furnace temperature to be cooled to rear discharging below 100 ℃, it is in 2% alkaline aqueous solution that bone black after carbonization-activation is added concentration that potassium hydroxide or sodium hydroxide are made, then passes into steam and boils and wash 10 times to remove the peculiar smell in bone black, boils at every turn wherein that when washing, the weight ratio of alkaline aqueous solution and bone black is 5:1, put into the aqueous solution rinsing that is dissolved with carbonic acid gas and 10 times the ph value is adjusted into 7.0-8.0 boiling bone black after washing, be dissolved with the aqueous solution of carbonic acid gas during each rinsing and the weight ratio of bone black is 8:1, pull out after rinsing dry or dry after the high-performance bone black that gets product, this high-performance bone black also can be broken into required particle diameter as required.
Embodiment 4
at first will be broken into through the animal bone (as ox bone, sheep bone, horse bone, camel bone etc.) that degreasing is come unstuck the particle of 1-5 ㎜, then the particulate state animal bone is delivered in carbonized activating furnace, temperature rise rate with 8 ℃/min is warming up to 540 ℃ with furnace temperature, then will carbonic acid gas and the composite activating agent made after mixing of water vapor input in carbonized activating furnace according to the ratio of 0.1 kilogram of composite activating agent/kilogram animal bone per hour, then continue to be warming up to and keep constant temperature to be beneficial to the discharge of volatile matter soot gas in 1 hour after 750 ℃, wherein the input of composite activating agent is conducive to accelerate the generation of carbon geochemistry composition and the specific surface area that improves bone black, be conducive to the discharge of volatile matter soot gas in the carbonization-activation process under temperature constant state, continue after constant temperature finishes will carbonic acid gas and the composite activating agent made after mixing of water vapor input in carbonized activating furnace according to the ratio of 0.6 kilogram of composite activating agent/kilogram animal bone per hour, and stop inputting composite activating agent after making furnace temperature be quickly cooled to 180 ℃, then continue to make furnace temperature to be cooled to rear discharging below 100 ℃, it is in 15% alkaline aqueous solution that bone black after carbonization-activation is added concentration that potassium hydroxide or sodium hydroxide are made, then passes into steam and boils and wash 5 times to remove the peculiar smell in bone black, boils at every turn wherein that when washing, the weight ratio of alkaline aqueous solution and bone black is 10:1, put into the aqueous solution rinsing that is dissolved with carbonic acid gas and 5 times the ph value is adjusted into 7.0-8.0 boiling bone black after washing, be dissolved with the aqueous solution of carbonic acid gas during each rinsing and the weight ratio of bone black is 15:1, pull out after rinsing dry or dry after the high-performance bone black that gets product, this high-performance bone black also can be broken into required particle diameter as required.
Embodiment 5
at first will be broken into through the animal bone (as ox bone, sheep bone, horse bone, camel bone etc.) that degreasing is come unstuck the particle of 1-5 ㎜, then the particulate state animal bone is delivered in carbonized activating furnace, temperature rise rate with 6 ℃/min is warming up to 530 ℃ with furnace temperature, then will carbonic acid gas and the composite activating agent made after mixing of water vapor input in carbonized activating furnace according to the ratio of 0.3 kilogram of composite activating agent/kilogram animal bone per hour, then continue to be warming up to and keep constant temperature to be beneficial to the discharge of volatile matter soot gas in 1 hour after 700 ℃, wherein the input of composite activating agent is conducive to accelerate the generation of carbon geochemistry composition and the specific surface area that improves bone black, be conducive to the discharge of volatile matter soot gas in the carbonization-activation process under temperature constant state, continue after constant temperature finishes will carbonic acid gas and the composite activating agent made after mixing of water vapor input in carbonized activating furnace according to the ratio of 1.5 kilograms of composite activating agent/kilogram animal bones per hour, and stop inputting composite activating agent after making furnace temperature be quickly cooled to 150 ℃, then continue to make furnace temperature to be cooled to rear discharging below 100 ℃, it is in 5% alkaline aqueous solution that bone black after carbonization-activation is added concentration that potassium hydroxide or sodium hydroxide are made, then passes into steam and boils and wash 8 times to remove the peculiar smell in bone black, boils at every turn wherein that when washing, the weight ratio of alkaline aqueous solution and bone black is 7:1, put into the aqueous solution rinsing that is dissolved with carbonic acid gas and 8 times the ph value is adjusted into 7.0-8.0 boiling bone black after washing, be dissolved with the aqueous solution of carbonic acid gas during each rinsing and the weight ratio of bone black is 11:1, pull out after rinsing dry or dry after the high-performance bone black that gets product, this high-performance bone black also can be broken into required particle diameter as required.
Part attribute to the made high-performance bone black of above embodiment 1-embodiment 5 is tested, and compares with the every corresponding test data of Brazilian bone black and American-European import bone black, obtains the content shown in following table.
Attribute |
Brazil's bone black |
American-European import bone black |
The high-performance bone black |
Carbon content |
9-11% |
9-11% |
10-11% |
Water-soluble ass in acidity |
<3% |
<3% |
<2% |
Tricalcium phosphate |
70-76% |
70-76% |
>75% |
Calcium carbonate |
7-9% |
7-9% |
8-9% |
Calcium sulfate |
0.1-0.2% |
0.1-0.2% |
<0.1% |
True density (g/cm
3)
|
2.86 |
2.81 |
2.80 |
Specific surface area (BET) |
129.4m
2/g
|
123.2m
2/g
|
125-150m
2/g
|
Iron |
<0.3% |
<0.3% |
<0.2%% |
Moisture content |
5% |
5% |
5% |
As seen from the above table, the part attribute of the high-performance bone black of the present invention's preparation and Brazilian bone black and American-European import bone black maintain an equal level, and the part attribute is better than Brazilian bone black and American-European import bone black.The present invention adopts the animal bones such as common ox bone, sheep bone, horse bone, camel bone to prepare bone black, due to the calcium phosphate powder in bone black can with water in heavy metal, fluorion etc. the chemical replacement reaction occurs, heavy metal in Adsorption water (arsenic, chromium, cadmium, rubidium etc.) ion, fluorion etc., reach the purpose of purifying waste water, and the water quality after purifying can reach the standard of tap water; This preparation method has the advantages that technique is simple, cost is low, and the bone black adsorption cleaning ability that makes is strong.
Above embodiment only for explanation technological thought of the present invention, can not limit protection scope of the present invention with this, every technological thought that proposes according to the present invention, and any change of doing on the technical scheme basis is within all falling into protection domain of the present invention; The technology that the present invention does not relate to all can be realized by prior art.