The method that carbon dioxide absorbing material is manufactured with fast growing wood
Technical field
The present invention relates to a kind of method that carbon dioxide absorbing material is manufactured with fast growing wood, belong to timber processing with
Composite wooden material field.
Background technology
The fast growing woods such as Plantation Poplar, eucalyptus are the primary raw materials of the composite wooden materials such as China's wood-based plate, at present production
Product are single, added value is relatively low, larger to the influence on development of fast growing wood manufacture field.For this reason, it may be necessary to further develop fast-growing wood
Material New Machining Technology, study the new material of high added value.At present, with environment worsening and fossil energy scarcity,
The trapping of carbon dioxide has become current study hotspot with separating, and is base by the nano-cellulose for processing fast growing wood
Material, then by surface-functionalized processing, high performance carbon dioxide absorbing material is prepared, for trapping recovery flue gas, naturally
Carbon dioxide in gas and biogas, the process technology that can improve fast growing wood is horizontal, develop the new material of high added value.
The content of the invention
Proposed by the present invention is a kind of method that carbon dioxide absorbing material is manufactured with fast growing wood, and the purpose is to utilize speed
Green wood processes high value added product, improves the value of fast growing wood;In addition, it is base using reproducible string
Material, carbon dioxide absorbing material is manufactured, reduces the dependence to non-renewable material so that carbon dioxide adsorption process becomes greener
Color, be advantageous to the popularization of carbon dioxide adsorption technique, reduce the discharge of carbon dioxide.
The technical solution of the present invention:The method that carbon dioxide absorbing material is manufactured with fast growing wood, including following work
Skill step:
(1)The fast growing woods such as Plantation Poplar, eucalyptus are crushed to 30-50 mesh;
(2)Under the conditions of 90 DEG C, 8-12% is used(w/w)Sodium hydroxide solution processing step(1)In the plant that has crushed
Fibrous raw material 6-9 hours, filter, washing, obtain solid fiber.Then, then under the conditions of 160-180 DEG C, with 2-6 %(w/w)
Sodium sulfite solution handles these solid fibers 0.5-2 hours, filters, washing, obtains white fiber element;
(3)At a temperature of 4 DEG C, using 20-40% ammonium chloride saturated solutions, precipitated cellulose enzymes soln, at 4 DEG C
3-6 hours are stood, are then centrifuged under the conditions of 4 DEG C, 8000 rpm, take its supernatant, and will wherein ammonium sulfate saturation degree
Regulation is positioned in 4 DEG C of refrigerators and stood overnight, centrifuged under the conditions of 4 DEG C, 8000 rpm, remove supernatant to 60%,
And with distillation water washing gained sediment three times, washed every time with the deionized water isometric with sediment, obtained sediment
As endo cellulase;
(4)Under temperature 50 C, pH=4.8, step is used(3)In isolated endo cellulase processing step(2)In
Cellulose, slurry solid-to-liquid ratio 1:30-60, endo cellulase dosage are 30-45 IU/g paper pulp fibers, processing time 20-
24 hours.After ferment treatment, filtering, and be washed with deionized three times, each deionized water dosage is equal to overall during ferment treatment
Product;
(5)At room temperature, high-pressure homogeneous processing processing step(4)Middle gained cellulose, content of cellulose in slurry during processing
For 1-2% (w/w), operation pressure 800-100bar, circulate 3-5 times, then under the conditions of 4 DEG C, 11000 rpm, centrifugation removes
Remove a certain amount of moisture;
(6)Take step(5)Middle part nano-cellulose, it is 3-5 % nano-cellulose suspension to be configured to concentration, further
Ultrasonic disperse is into colloidal.Instilled in the divalent salt solutions that concentration is 0.20-0.50 mol/L, stand 8-12 hours, obtain
A diameter of 4-8 mm almost spherical granular nanometer cellulose aquagel is obtained, filtering, is respectively placed in twice nanofiber
12-24 hours in 25%, 50%, 95% ethanol solution of hydrogel volume, it is filtrated to get nano-cellulose alcogel particle;
(7)By step(6)The nano-cellulose alcogel particle of middle gained and the ethanol solution of amino containing silane mix, and put
In being modified reaction in the pressure-resistant water heating kettle reactor of rotation.Reaction condition:120 DEG C of reaction temperature, is incubated at such a temperature
10-16 hours, the concentration 2-8% of amino containing silane in the ethanol solution of amino containing silane, the volume of the ethanol solution of amino containing silane is receives
1-3 times of rice cellulose alcogel volume, rotary speed is 1-4 rpm.After the completion of reaction, promptly reacted with originally water cooling
Kettle half an hour, then filter, obtain aminated nanofiber crude granule;
(8)Will be by step(7)In obtained aminated nanofiber crude granule be put into supercritical extraction reactor, in 35-60
DEG C, pressure is under 35-65 MPa, extracts 20-60 minutes, obtains aminated nano-cellulose aerogel particle and is inhaled for carbon dioxide
Enclosure material.
Beneficial effects of the present invention, the aminated nano-cellulose aerogel particle produced using the present invention have following
Characteristic:
1)BET surface area 400-600m2/ g,
2)Average pore size is 15-25 nm,
3)The adsorption capacity of carbon dioxide is 1.5-2.5 mmol/g at 25 DEG C;
4)After carbon dioxide adsorption saturation, 3 regeneration rates of the aeroge are all higher than 90%.
Embodiment
The method that carbon dioxide absorbing material is manufactured with fast growing wood, is comprised the technical steps that:
(1)The fast growing woods such as Plantation Poplar, eucalyptus are crushed to 30-50 mesh;
(2)Under the conditions of 90 DEG C, 8-12% is used(w/w)Sodium hydroxide solution processing step(1)In the plant that has crushed
Fibrous raw material 6-9 hours, filter, washing, obtain solid fiber.Then, then under the conditions of 160-180 DEG C, with 2-6 %(w/w)
Sodium sulfite solution handles these solid fibers 0.5-2 hours, filters, washing, obtains white fiber element;
(3)At a temperature of 4 DEG C, using 20-40% ammonium chloride saturated solutions, precipitated cellulose enzymes soln, at 4 DEG C
3-6 hours are stood, are then centrifuged under the conditions of 4 DEG C, 8000 rpm, take its supernatant, and will wherein ammonium sulfate saturation degree
Regulation is positioned in 4 DEG C of refrigerators and stood overnight, centrifuged under the conditions of 4 DEG C, 8000 rpm, remove supernatant to 60%,
And with distillation water washing gained sediment three times, washed every time with the deionized water isometric with sediment, obtained sediment
As endo cellulase;
(4)Under temperature 50 C, pH=4.8, step is used(3)In isolated endo cellulase processing step(2)In
Cellulose, slurry solid-to-liquid ratio 1:30-60, endo cellulase dosage are 30-45 IU/g paper pulp fibers, processing time 20-
24 hours.After ferment treatment, filtering, and be washed with deionized three times, each deionized water dosage is equal to overall during ferment treatment
Product;
(5)At room temperature, high-pressure homogeneous processing processing step(4)Middle gained cellulose, content of cellulose in slurry during processing
For 1-2% (w/w), operation pressure is 800-100 bar, is circulated 3-5 times, then under the conditions of 4 DEG C, 11000 rpm, centrifugation
Remove a certain amount of moisture;
(6)Take step(5)Middle part nano-cellulose, it is 3-5 % nano-cellulose suspension to be configured to concentration, further
Ultrasonic disperse is into colloidal.Instilled in the divalent salt solutions that concentration is 0.20-0.50 mol/L, stand 8-12 hours, obtain
A diameter of 4-8 mm almost spherical granular nanometer cellulose aquagel is obtained, filtering, is respectively placed in twice nanofiber
12-24 hours in 25%, 50%, 95% ethanol solution of hydrogel volume, it is filtrated to get nano-cellulose alcogel particle;
(7)By step(6)The nano-cellulose alcogel particle of middle gained and the ethanol solution of amino containing silane mix, and put
In being modified reaction in the pressure-resistant water heating kettle reactor of rotation.Reaction condition:120 DEG C of reaction temperature, is incubated at such a temperature
10-16 hours, the concentration 2-8% of amino containing silane in the ethanol solution of amino containing silane, the volume of the ethanol solution of amino containing silane is receives
1-3 times of rice cellulose alcogel volume, rotary speed is 1-4 rpm.After the completion of reaction, promptly reacted with originally water cooling
Kettle half an hour, then filter, obtain aminated nanofiber crude granule;
(8)Will be by step(7)In obtained aminated nanofiber crude granule be put into supercritical extraction reactor, in 35-60
DEG C, pressure is under 35-65 MPa, extracts 20-60 minutes, obtains aminated nano-cellulose aerogel particle and is inhaled for carbon dioxide
Enclosure material.
Embodiment 1
The method that carbon dioxide absorbing material is manufactured with fast growing wood, is comprised the technical steps that:
(1)The fast growing woods such as Plantation Poplar, eucalyptus are crushed to 30 mesh;
(2)Under the conditions of 90 DEG C, with 8%(w/w)Sodium hydroxide solution processing step(1)In the plant that has crushed it is fine
Tie up raw material 6 hours, filter, washing, obtain solid fiber.Then, then under the conditions of 160 DEG C, with 2 %(w/w)Sodium sulfite is molten
Liquid handles these solid fibers 0.5 hour, filters, washing, obtains white fiber element;
(3)It is quiet at 4 DEG C using 20% ammonium chloride saturated solution, precipitated cellulose enzymes soln at a temperature of 4 DEG C
Put 3 hours, then centrifuged under the conditions of 4 DEG C, 8000 rpm, take its supernatant, and wherein ammonium sulfate saturation degree will adjust
To 60%, it is positioned in 4 DEG C of refrigerators and stands overnight, centrifuged under the conditions of 4 DEG C, 8000 rpm, remove supernatant, be used in combination
Distill water washing gained sediment three times, washed every time with the deionized water isometric with sediment, obtained sediment is
Endo cellulase;
(4)Under temperature 50 C, pH=4.8, step is used(3)In isolated endo cellulase processing step(2)In
Cellulose, slurry solid-to-liquid ratio 1:30, endo cellulase dosage is 30-45 IU/g paper pulp fibers, 20 hours processing times.
After ferment treatment, filtering, and be washed with deionized three times, cumulative volume when each deionized water dosage is equal to ferment treatment;
(5)At room temperature, high-pressure homogeneous processing processing step(4)Middle gained cellulose, content of cellulose in slurry during processing
For 1% (w/w), operation pressure is 800 bar, circulates 3-5 times, then under the conditions of 4 DEG C, 11000 rpm, is centrifuged off one
Quantitative moisture;
(6)Take step(5)Middle part nano-cellulose, it is 3-5 % nano-cellulose suspension to be configured to concentration, further
Ultrasonic disperse is into colloidal.Instilled in the divalent salt solutions that concentration is 0.20 mol/L, stand 8 hours, obtain a diameter of 4
Mm almost spherical granular nanometer cellulose aquagel, filtering, is respectively placed in twice nano-cellulose hydrogel volume
25%, 50%, 95% ethanol solution in 12 hours, be filtrated to get nano-cellulose alcogel particle;
(7)By step(6)The nano-cellulose alcogel particle of middle gained and the ethanol solution of amino containing silane mix, and put
In being modified reaction in the pressure-resistant water heating kettle reactor of rotation.Reaction condition:120 DEG C of reaction temperature, is incubated at such a temperature
10 hours, the concentration 2-8% of amino containing silane in the ethanol solution of amino containing silane, the volume of the ethanol solution of amino containing silane was nanometer
1-3 times of cellulose alcogel volume, rotary speed 1rpm.After the completion of reaction, promptly with originally water cooling reactor half
Hour, then filter, obtain aminated nanofiber crude granule;
(8)Will be by step(7)In obtained aminated nanofiber crude granule be put into supercritical extraction reactor, at 35 DEG C,
Pressure is under 35 MPa, is extracted 20 minutes, it is carbon dioxide absorbing material to obtain aminated nano-cellulose aerogel particle.
Embodiment 2
The method that carbon dioxide absorbing material is manufactured with fast growing wood, is comprised the technical steps that:
(1)The fast growing woods such as Plantation Poplar, eucalyptus are crushed to 50 mesh;
(2)Under the conditions of 90 DEG C, with 12%(w/w)Sodium hydroxide solution processing step(1)In the plant that has crushed it is fine
Tie up raw material 9 hours, filter, washing, obtain solid fiber.Then, then under the conditions of 180 DEG C, with 6 %(w/w)Sodium sulfite is molten
Liquid handles these solid fibers 2 hours, filters, washing, obtains white fiber element;
(3)It is quiet at 4 DEG C using 40% ammonium chloride saturated solution, precipitated cellulose enzymes soln at a temperature of 4 DEG C
Put 6 hours, then centrifuged under the conditions of 4 DEG C, 8000 rpm, take its supernatant, and wherein ammonium sulfate saturation degree will adjust
To 60%, it is positioned in 4 DEG C of refrigerators and stands overnight, centrifuged under the conditions of 4 DEG C, 8000 rpm, remove supernatant, be used in combination
Distill water washing gained sediment three times, washed every time with the deionized water isometric with sediment, obtained sediment is
Endo cellulase;
(4)Under temperature 50 C, pH=4.8, step is used(3)In isolated endo cellulase processing step(2)In
Cellulose, slurry solid-to-liquid ratio 1:60, endo cellulase dosage is 45 IU/g paper pulp fibers, 24 hours processing times.Enzyme
After processing, filtering, and be washed with deionized three times, cumulative volume when each deionized water dosage is equal to ferment treatment;
(5)At room temperature, high-pressure homogeneous processing processing step(4)Middle gained cellulose, content of cellulose in slurry during processing
For 2% (w/w), operation pressure is 100 bar, is circulated 5 times, then under the conditions of 4 DEG C, 11000 rpm, is centrifuged off certain
The moisture of amount;
(6)Take step(5)Middle part nano-cellulose, it is 3-5 % nano-cellulose suspension to be configured to concentration, further
Ultrasonic disperse is into colloidal.Instilled in the divalent salt solutions that concentration is 0.50 mol/L, stand 12 hours, obtained a diameter of
8 mm almost spherical granular nanometer cellulose aquagel, filtering, is respectively placed in twice nano-cellulose water gel
24 hours in 25%, 50%, 95% long-pending ethanol solution, nano-cellulose alcogel particle is filtrated to get;
(7)By step(6)The nano-cellulose alcogel particle of middle gained and the ethanol solution of amino containing silane mix, and put
In being modified reaction in the pressure-resistant water heating kettle reactor of rotation.Reaction condition:120 DEG C of reaction temperature, is incubated at such a temperature
16 hours, the concentration 8% of amino containing silane in the ethanol solution of amino containing silane, the volume of the ethanol solution of amino containing silane was Nanowire
Tie up plain alcogel volume 1-3 times, rotary speed are 4 rpm.It is promptly small with originally water cooling reactor half after the completion of reaction
When, then filter, obtain aminated nanofiber crude granule;
(8)Will be by step(7)In obtained aminated nanofiber crude granule be put into supercritical extraction reactor, at 60 DEG C,
Pressure is under 65 MPa, is extracted 60 minutes, it is carbon dioxide absorbing material to obtain aminated nano-cellulose aerogel particle.
Embodiment 3
The method that carbon dioxide absorbing material is manufactured with fast growing wood, is comprised the technical steps that:
(1)The fast growing woods such as Plantation Poplar, eucalyptus are crushed to 40 mesh;
(2)Under the conditions of 90 DEG C, with 10%(w/w)Sodium hydroxide solution processing step(1)In the plant that has crushed it is fine
Tie up raw material 7 hours, filter, washing, obtain solid fiber.Then, then under the conditions of 170 DEG C, with 4%(w/w)Sodium sulfite solution
Handle these solid fibers 1.5 hours, filter, washing, obtain white fiber element;
(3)At a temperature of 4 DEG C, using 20-40% ammonium chloride saturated solutions, precipitated cellulose enzymes soln, at 4 DEG C
4 hours are stood, is then centrifuged under the conditions of 4 DEG C, 8000 rpm, takes its supernatant, and wherein ammonium sulfate saturation degree will adjust
Section is positioned in 4 DEG C of refrigerators and stood overnight, centrifuged under the conditions of 4 DEG C, 8000 rpm, remove supernatant to 60%, and
With distillation water washing gained sediment three times, washed every time with the deionized water isometric with sediment, obtained sediment is i.e.
For endo cellulase;
(4)Under temperature 50 C, pH=4.8, step is used(3)In isolated endo cellulase processing step(2)In
Cellulose, slurry solid-to-liquid ratio 1:45, endo cellulase dosage is 35 IU/g paper pulp fibers, 22 hours processing times.Enzyme
After processing, filtering, and be washed with deionized three times, cumulative volume when each deionized water dosage is equal to ferment treatment;
(5)At room temperature, high-pressure homogeneous processing processing step(4)Middle gained cellulose, content of cellulose in slurry during processing
For 1-2% (w/w), operation pressure 900bar, circulate 4 times, then under the conditions of 4 DEG C, 11000 rpm, be centrifuged off certain
The moisture of amount;
(6)Take step(5)Middle part nano-cellulose, it is 4 % nano-cellulose suspension to be configured to concentration, is further surpassed
Sound is dispersed into colloidal.Instilled in the divalent salt solutions that concentration is 0.30 mol/L, stand 10 hours, obtain a diameter of 6
Mm almost spherical granular nanometer cellulose aquagel, filtering, is respectively placed in twice nano-cellulose hydrogel volume
25%, 50%, 95% ethanol solution in 10 hours, be filtrated to get nano-cellulose alcogel particle;
(7)By step(6)The nano-cellulose alcogel particle of middle gained and the ethanol solution of amino containing silane mix, and put
In being modified reaction in the pressure-resistant water heating kettle reactor of rotation.Reaction condition:120 DEG C of reaction temperature, is incubated at such a temperature
13 hours, the concentration 5% of amino containing silane in the ethanol solution of amino containing silane, the volume of the ethanol solution of amino containing silane was Nanowire
Tie up plain alcogel volume 1-3 times, rotary speed are 3 rpm.It is promptly small with originally water cooling reactor half after the completion of reaction
When, then filter, obtain aminated nanofiber crude granule;
(8)Will be by step(7)In obtained aminated nanofiber crude granule be put into supercritical extraction reactor, at 40 DEG C,
Pressure is under 50 MPa, is extracted 30 minutes, it is carbon dioxide absorbing material to obtain aminated nano-cellulose aerogel particle.