CN107617416A - A kind of preparation method of adsorbable heavy metal anglers bone biological carbon materials - Google Patents

Abstract

The invention provides a kind of preparation method of adsorbable heavy metal anglers bone biological carbon materials to comprise the following steps：The fish-bone after appropriate segment defrosting is taken, boiling water pulverizes and sieves after sloughing the attached meat on fish-bone；Gained fishbone dust obtains adsorbable heavy metal anglers fish-bone biological carbon materials in nitrogen atmosphere high temperature pyrolysis charring again in activator solution after the charing of the step hydro-thermal of autoclave two.Anglers fish-bone biological carbon materials specific surface area is big obtained by the present invention, and absorption heavy metal in waste water effect is good, and the added value of angler fish-bone, green, environmental protection, economy is greatly improved.

Description

A preparation method of an anglerfish bone biochar material capable of adsorbing heavy metals

technical field

The invention relates to a preparation method of a biochar material, in particular to a preparation method of an anglerfish bone biochar material capable of absorbing heavy metals, and belongs to the technical field of fish processing.

Background technique

Fishbone is the general term for the axial bone, appendage bone and fishbone of the fish body. It usually accounts for 10% to 15% of the fish's body weight. It is rich in calcium, collagen, chondroitin and other nutrients. However, as a by-product of the fish processing industry, fish bones are usually discarded together with other processing waste or only used as fertilizer and feed, resulting in a waste of resources. Biochar is a product of waste resource utilization. As a new type of environmental functional material, biochar has become a frontier research topic in environmental science and other disciplines due to its excellent environmental and ecological effects. At present, the research on biochar raw materials mainly focuses on materials with high lignocellulose content, such as plant husks and straws, while there is less research on processing by-products such as fish bones. Anglerfish is commonly known as toad fish and sea toad. It has extremely high nutritional, edible and medicinal values, and is popular all over the world. In recent years, with the increase in demand for anglerfish, its production has also increased significantly. After industrial processing A large amount of fish bones produced by the later anglerfish are all discarded as leftovers, which not only pollutes the environment, but also causes a large waste of resources. Therefore, how to efficiently develop and utilize anglerfish bones into biochar is an urgent problem to be solved by those skilled in the art.

Contents of the invention

Aiming at the problem of insufficient development and utilization of anglerfish bones, the object of the present invention is to provide a preparation method of an anglerfish bone biochar material capable of adsorbing heavy metals, and preparing anglerfish bones into a biochar material capable of adsorbing heavy metals greatly improves the The utilization value of fish bones has been improved.

In order to achieve the above object, the present invention adopts the following technical solutions:

A preparation method of an anglerfish bone biochar material capable of adsorbing heavy metals, characterized in that the specific steps are:

(1) Take the sliced and thawed fish bones, add distilled water until submerged, heat at 100°C and stir for 30 minutes, filter and wash with distilled water, remove the attached meat on the fish bones, crush the fish bones with a grinder, and sieve to obtain fish bone powder .

(2) Disperse the fishbone powder described in step (1) in the activator solution, react in an autoclave, cool naturally, vacuum filter, and dry at 80° C. for 12 hours.

(3) Place the dried fishbone powder in a resistance furnace, pass through nitrogen for pyrolysis, and take out the fishbone charcoal powder after cooling naturally to room temperature after the pyrolysis process is completed.

(4) Take an appropriate amount of fishbone charcoal powder, wash it with hydrochloric acid, then wash it with distilled water until neutral, and dry it in vacuum for 12 hours to obtain a fishbone biochar material that can adsorb heavy metals.

The beneficial effects of the present invention are as follows: the present invention uses waste anglerfish bone as raw material, and obtains anglerfish bone biochar material through activation and pyrolysis process, and the anglerfish bone biochar material has a small average particle size and a high specific surface area , The high efficiency of adsorbing heavy metals improves the utilization rate and economic value of anglerfish bones, and provides a new way for the efficient utilization of fish bones resources.

Preferably, the sieve in step (1) is 20 mesh.

The beneficial effect of adopting the above preferred scheme is that the average particle size of the fish bone powder is guaranteed to be uniform and the dispersion degree of the fish bone powder is ensured.

Preferably, the activator described in step (2) is one of zinc chloride, phosphoric acid, and sodium hydroxide.

Preferably, the concentration range of the activator in step (2) is 4-8 mol/L.

The beneficial effects of adopting the above preferred scheme are: the activator has the function of catalyzing dehydroxylation and dehydration, so that the hydrogen and oxygen in the raw material are released in the form of water vapor to form a porous structure, and the activator vaporizes at high temperature, and the activator molecules enter The interior of the carbon acts as a skeleton, and the high polymer of carbon is deposited on the skeleton after carbonization. After the zinc chloride is removed by acid washing, the carbon becomes a porous structure activated carbon with a high specific surface area, so solution soaking is beneficial to expand the micropores of the material. ;

Preferably, the reaction condition of the high-pressure reactor in step (2) is to first react at 150-180°C for 2-6 hours, and then raise the temperature to 200-250°C for 18-22 hours.

The beneficial effects of adopting the above preferred scheme are: the degradation of each component of waste biomass under hydrothermal and pyrolysis conditions is mainly affected by temperature, and low-molecular organic matter can be extracted to undergo hydrothermal carbonization at 150-180°C; The ether bond is broken at 190°C to form oligosaccharides and monosaccharides, while the hydrolysis and carbonization temperature of cellulose is relatively high, generally above 220°C. The two-step high-pressure hydrothermal carbonization can fully dissolve and carbonize different components to achieve the best Carbonization effect.

Preferably, the flow rate of nitrogen fed into the pyrolysis process in step (3) is 100 mL/min.

Preferably, in step (3), the heating rate of pyrolysis is 3-5° C./min, the pyrolysis temperature is 700-900° C., and the pyrolysis time is 3-5 hours.

The beneficial effect of adopting the above-mentioned preferred scheme is: the nitrogen atmosphere can prevent the carbon-carbon skeleton from being oxidized into _CO in oxygen and collapse into a macroporous structure, and keep the original tiny carbon skeleton structure of the biomass to the greatest extent, so the carbon-carbon skeleton in the nitrogen atmosphere Pyrolysis further increases the specific surface area of fish bone biochar, increases pores and pore volume, provides more adsorption sites for heavy metal adsorption, and controls the nitrogen flow rate and pyrolysis temperature rate to make the reaction more uniform and stable.

Preferably, the concentration of hydrochloric acid described in step (4) is 1mol/L.

detailed description

The specific embodiments of the present invention will be further described below.

Unless otherwise specified, the raw materials used in the present invention can be purchased from the market or commonly used in the field. If not specified, the methods in the following examples are all conventional methods in the field.

Example 1

A preparation method of an anglerfish bone biochar capable of adsorbing heavy metals, comprising the following steps:

(1) Take 100g of sliced and thawed fish bones, add distilled water until submerged, heat on a magnetic heating stirrer at 100°C for 30 minutes, filter and wash with distilled water to remove the attached meat on the fish bones. Crush the fish bones with a pulverizer and pass through a 20-mesh sieve.

(2) Take 20g of fish bone meal and disperse it in 4mol/L ZnCl ₂ solution, put it in the autoclave at 150°C for 6h, then raise the temperature to 250°C for 18h. Cool naturally after the reaction, vacuum filter, and dry at 80°C for 12 hours.

(3) The dried fishbone meal is placed in a tubular resistance furnace, and nitrogen gas with a flow rate of 100mL/min is introduced into the furnace to maintain an oxygen-deficient environment in the furnace; the heating rate is controlled by the program at 3°C/min, and the temperature is continuously raised to the target temperature. 700°C, keep the final temperature for pyrolysis for 5 hours; after the pyrolysis process, the fish bone charcoal powder is naturally cooled to room temperature and then taken out.

(4) Take an appropriate amount of fishbone charcoal powder and wash it with 1mol/L hydrochloric acid and distilled water until it becomes neutral, then dry it in vacuum at 80°C overnight.

Example 2

A preparation method of an anglerfish bone biochar capable of adsorbing heavy metals, comprising the following steps:

(1) Take 150g of sliced and thawed fish bones, add distilled water until submerged, heat on a magnetic heating stirrer at 100°C for 30 minutes, filter and wash with distilled water to remove the attached meat on the fish bones. Crush the fish bones with a pulverizer and pass through a 20-mesh sieve.

(2) Take 30g of fish bone meal and disperse in 6mol/L ZnCl ₂ solution, put it in a high-pressure reactor at 160°C for 4h, then raise the temperature to 220°C for 20h. Cool naturally after the reaction, vacuum filter, and dry at 80°C for 12 hours.

(3) The dried fishbone meal is placed in a tubular resistance furnace, and nitrogen gas with a flow rate of 100mL/min is introduced into the furnace to maintain an oxygen-deficient environment in the furnace; the heating rate is controlled by the program at 3°C/min, and the temperature is continuously raised to the target temperature. 800°C, keep the final temperature for pyrolysis for 4 hours; after the pyrolysis process, the fish bone charcoal powder is naturally cooled to room temperature and then taken out.

(4) Take an appropriate amount of fishbone charcoal powder and wash it with 1mol/L hydrochloric acid and distilled water until it becomes neutral, then dry it in vacuum at 80°C overnight.

Example 3

A preparation method of an anglerfish bone biochar capable of adsorbing heavy metals, comprising the following steps:

(1) Take 200g of sliced and thawed fish bones, add distilled water until submerged, heat on a magnetic heating stirrer at 100°C for 30 minutes, filter and wash with distilled water to remove the attached meat on the fish bones. Crush the fish bones with a pulverizer and pass through a 20-mesh sieve.

(2) Take 30g of fish bone meal and disperse in 8mol/L ZnCl ₂ solution, put it in the autoclave at 180°C for 2h, then raise the temperature to 200°C for 22h. Cool naturally after the reaction, vacuum filter, and dry at 80°C for 12 hours.

(3) The dried fishbone meal is placed in a tubular resistance furnace, and nitrogen gas with a flow rate of 100mL/min is introduced into the furnace to maintain an oxygen-deficient environment in the furnace; the heating rate is controlled by the program at 3°C/min, and the temperature is continuously raised to the target temperature. 900°C, keep the final temperature for 3 hours; after the pyrolysis process, the fish bone charcoal powder is naturally cooled to room temperature and then taken out.

(4) Take an appropriate amount of fishbone charcoal powder and wash it with 1mol/L hydrochloric acid and distilled water until it becomes neutral, then dry it in vacuum at 80°C overnight.

Example 4

A preparation method of an anglerfish bone biochar capable of adsorbing heavy metals, comprising the following steps:

(1) Take 100g of sliced and thawed fish bones, add distilled water until submerged, heat on a magnetic heating stirrer at 100°C for 30 minutes, filter and wash with distilled water to remove the attached meat on the fish bones. Crush the fish bones with a pulverizer and pass through a 20-mesh sieve.

(2) Take 20g of fish bone powder and disperse in 4mol/L H ₃ PO ₄ solution, put it in a high-pressure reactor at 150°C for 4h, then raise the temperature to 200°C for 20h. Cool naturally after the reaction, vacuum filter, and dry at 80°C for 12 hours.

(3) The dried fishbone powder is placed in a tubular resistance furnace, and nitrogen gas with a flow rate of 100mL/min is introduced into the furnace to maintain an oxygen-deficient environment in the furnace; 700°C, keep the final temperature for pyrolysis for 4 hours; after the pyrolysis process, the fish bone charcoal powder is naturally cooled to room temperature and then taken out.

(4) Take an appropriate amount of fishbone charcoal powder and wash it with 1mol/L hydrochloric acid and distilled water until it becomes neutral, then dry it in vacuum at 80°C overnight.

Example 5

A preparation method of an anglerfish bone biochar capable of adsorbing heavy metals, comprising the following steps:

(1) Take 150g of sliced and thawed fish bones, add distilled water until submerged, heat on a magnetic heating stirrer at 100°C for 30 minutes, filter and wash with distilled water to remove the attached meat on the fish bones. Crush the fish bones with a pulverizer and pass through a 20-mesh sieve.

(2) Take 30g of fish bone meal and disperse in 8mol/L H ₃ PO ₄ solution, put it in the autoclave at 150°C for 6h, then raise the temperature to 220°C for 18h. Cool naturally after the reaction, vacuum filter, and dry at 80°C for 12 hours.

(3) The dried fishbone powder is placed in a tubular resistance furnace, and nitrogen gas with a flow rate of 100mL/min is introduced into the furnace to maintain an oxygen-deficient environment in the furnace; 800°C, keep the final temperature for 3h pyrolysis; after the pyrolysis process, wait for the fish bone charcoal powder to cool down to room temperature naturally and take it out.

(4) Take an appropriate amount of fishbone charcoal powder and wash it with 1mol/L hydrochloric acid and distilled water until it becomes neutral, then dry it in vacuum at 80°C overnight.

Example 6

A preparation method of an anglerfish bone biochar capable of adsorbing heavy metals, comprising the following steps:

(1) Take 200g of sliced and thawed fish bones, add distilled water until submerged, heat on a magnetic heating stirrer at 100°C for 30 minutes, filter and wash with distilled water to remove the attached meat on the fish bones. Crush the fish bones with a pulverizer and pass through a 20-mesh sieve.

(2) Take 30g of fish bone meal and disperse it in 4mol/L NaOH solution, put it in the autoclave at 180°C for 4h, then raise the temperature to 250°C for 20h. Cool naturally after the reaction, vacuum filter, and dry at 80°C for 12 hours.

(3) The dried fishbone meal is placed in a tube-type resistance furnace, and nitrogen gas with a flow rate of 100mL/min is introduced into the furnace to maintain an oxygen-deficient environment in the furnace; the heating rate is controlled by the program at 4°C/min, and the temperature is continuously raised to the target temperature. 800°C, keep the final temperature for pyrolysis for 4 hours; after the pyrolysis process, the fish bone charcoal powder is naturally cooled to room temperature and then taken out.

(4) Take an appropriate amount of fishbone charcoal powder and wash it with 1mol/L hydrochloric acid and distilled water until it becomes neutral, then dry it in vacuum at 80°C overnight.

Example 7

A preparation method of an anglerfish bone biochar capable of adsorbing heavy metals, comprising the following steps:

(1) Take 150g of sliced and thawed fish bones, add distilled water until submerged, heat on a magnetic heating stirrer at 100°C for 30 minutes, filter and wash with distilled water to remove the attached meat on the fish bones. Crush the fish bones with a pulverizer and pass through a 20-mesh sieve.

(2) Take 20g of fish bone meal and disperse it in 8mol/L NaOH solution, put it in the autoclave at 180°C for 4h, then raise the temperature to 220°C for 20h. Cool naturally after the reaction, vacuum filter, and dry at 80°C for 12 hours.

(3) The dried fishbone meal is placed in a tube-type resistance furnace, and nitrogen gas with a flow rate of 100mL/min is introduced into the furnace to maintain an oxygen-deficient environment in the furnace; the heating rate is controlled by a program at 4°C/min, and the temperature is continuously raised to the target temperature. 900°C, keep the final temperature for pyrolysis for 5 hours; after the pyrolysis process, the fish bone charcoal powder is naturally cooled to room temperature and then taken out.

(4) Take an appropriate amount of fishbone charcoal powder and wash it with 1mol/L hydrochloric acid and distilled water until it becomes neutral, then dry it in vacuum at 80°C overnight.

Performance Testing

1. Specific surface area test:

The fishbone biochar powders obtained in Examples 1-7 were respectively placed in an Onis 100BET specific surface tester, and the specific surface area was measured after degassing for 12 hours at a temperature of 350°C and a pressure of 10-5 Pa. The results are shown in Table 1.

2. Adsorption heavy metal test:

Pb ²⁺ , Cd ²⁺ , Cu ²⁺ heavy metal wastewater is obtained by artificial preparation method, and the specific operation steps are as follows:

Weigh 1.598g of lead nitrate, 2.745g of cadmium nitrate tetrahydrate, and 3.930g of copper sulfate pentahydrate and dissolve them in deionized water, set the volume to the 1L mark, shake them and refrigerate at 2°C to obtain a solution with a concentration of 1g/L. The Pb ²⁺ , Cd ²⁺ , and Cu ² stock solutions were diluted with deionized water according to the required concentration to obtain the experimental solution. The concentration of heavy metal ions in the solution was 150 mg/L in the experiment. Add 50mg of adsorbent and 25mL of solution into a 50mL sample bottle, the pH of the solution is 5, mix thoroughly with a vortex mixer, place in a constant temperature shaking box and shake overnight at (25±1)°C. After equilibration, filter with a 0.45um filter membrane, and measure the remaining metal ion concentration in the filtrate with an atomic absorption spectrophotometer.

The heavy metal removal rate is calculated according to formula (1):

R=(C ₀ ~C _e )/C ₀ ·100% (1)

The removal capacity of heavy metals is calculated according to formula (2):

Q＝(C ₀ ～C _e )V/m (2)

Where: R is the heavy metal removal rate, %;

C ₀ , C _e are the mass concentrations of heavy metals in the solution before and after equilibrium, mg/L, respectively;

Q is the removal capacity of heavy metals, mg;

V is the solution volume, mL;

m is the mass of the adsorbent, mg.

The adsorption results are shown in Table 1:

Table 1

It can be seen from Table 1 that the average pore diameter of the anglerfish bone biochar prepared by the method of the present invention is 27.32-43.88nm, the pore volume is 0.543-0.835cm ³ /g, and the specific surface area is 290.464-474.532m ² /g. The removal rate of heavy metal Pb ²⁺ reaches over 97%, and the removal capacity is 28-46mg/g; the removal rate of heavy metal Cd ²⁺ reaches 41%-54%, and the removal capacity is 7.41-11.5mg/ ^g ; The removal rate of ⁺ reaches 54%-78%, and the removal capacity is 10.1-24.41mg/g.

The anglerfish bone biochar prepared by the invention has a small average pore size and a large specific surface area, can efficiently remove heavy metal ions, and is suitable for water quality purification treatment of industrial sewage, domestic wastewater, and the like.

The basic principles and main features of the present invention and the advantages of the present invention have been shown and described above. Those skilled in the industry should understand that the present invention is not limited by the above-mentioned embodiments. What are described in the above-mentioned embodiments and the description only illustrate the principle of the present invention. Without departing from the spirit and scope of the present invention, the present invention will also have Variations and improvements are possible, which fall within the scope of the claimed invention.

Claims (9)

1. a preparation method of an anglerfish bone biochar material capable of adsorbing heavy metals, characterized in that, the specific steps are: (1) get the anglerfish bone, remove the attached meat on the fish bone, pulverize the fish bone, and sieve to obtain fish bone meal; (2) Get the fishbone powder obtained in step (1) and disperse in the activator solution, cool after reacting in the autoclave, filter, and dry; (3) Pyrolyzing the dried fishbone powder under nitrogen protection, after pyrolysis, the fishbone charcoal powder is naturally cooled to room temperature; (4) Fishbone charcoal powder was washed with hydrochloric acid and then washed with distilled water until neutral, and dried to obtain a fishbone biochar material capable of absorbing heavy metals. 2. the preparation method of a kind of heavy metal-absorbable anglerfish bone biochar material according to claim 1, is characterized in that, the sieve described in step (1) is 20 orders. 3. the preparation method of a kind of heavy metal-absorbing anglerfish bone biochar material according to claim 1, is characterized in that, the activator described in step (2) is zinc chloride, phosphoric acid, sodium hydroxide A sort of. 4. A method for preparing an anglerfish bone biochar material capable of absorbing heavy metals according to claim 1 or 3, wherein the concentration of the activator is 4 to 8 mol/L. 5. the preparation method of a kind of heavy metal-absorbable anglerfish bone biochar material according to claim 1, is characterized in that, the reaction condition of high-pressure reactor in step (2) is first 150～180 ℃ of reaction 2～6h , and then heated to 200 ~ 250 ° C reaction for 18 ~ 22h. 6. the preparation method of a kind of heavy metal-absorbable anglerfish bone biochar material according to claim 1, is characterized in that, in the step (3), the pyrolysis equipment is a resistance furnace. 7. the preparation method of a kind of heavy metal-absorbable anglerfish bone biochar material according to claim 1, is characterized in that, in step (3), feed nitrogen flow rate and be 100mL/min. 8. the preparation method of a kind of heavy metal-absorbable anglerfish bone biochar material according to claim 1, is characterized in that, in step (3), the pyrolysis heating rate is 3～5 ℃/min, and the pyrolysis temperature is 700～900℃, the pyrolysis time is 3～5h. 9. A method for preparing an anglerfish bone biochar material capable of absorbing heavy metals according to claim 1, wherein the hydrochloric acid concentration in step (4) is 1mol/L.