CN101428790A - Method for producing carbon molecular sieve with waste printed circuit board as raw material - Google Patents
Method for producing carbon molecular sieve with waste printed circuit board as raw material Download PDFInfo
- Publication number
- CN101428790A CN101428790A CNA2008102325021A CN200810232502A CN101428790A CN 101428790 A CN101428790 A CN 101428790A CN A2008102325021 A CNA2008102325021 A CN A2008102325021A CN 200810232502 A CN200810232502 A CN 200810232502A CN 101428790 A CN101428790 A CN 101428790A
- Authority
- CN
- China
- Prior art keywords
- temperature
- destructive distillation
- wiring board
- waste printed
- molecular sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for preparing a carbon molecular sieve through taking a waste printed-wiring board as raw material, which comprises the following steps: separating non-metallic substances from the waste printed-wiring board, purifying the non-metallic separating substances of the waste printed-wiring board, carrying out resin carbonization, crushing, forming, carbonizing, weakly activating, and carrying out vapor deposition. The method further comprises the steps of testing performance index. Through testing, the prepared carbon molecular sieve in the invention has 10 to 5.0 percent of ash content, the loading density of 0.44 to 0.65 g/cm<3>, the micro-bore volume of 0.45 to 0.66 cm<3>/g, and the selective adsorption coefficient of 2.1 to 5.5 to N2O2. The invention has the advantages of reasonable design, stable process, low ash content of the prepared carbon molecular sieve, high density, large bore volume of a micro-bore, large adsorptive capacity of the N2O2, and the like; and the waste printed-wiring board is prepared into the carbon molecular sieve by adopting the invention. The invention can be used for nitrogen gas enriched with air, thereby solving the problem of the environmental contamination of the waste printed-wiring board.
Description
Technical field
The invention belongs to the carbonaceous molecular sieve technical field, being specifically related to waste printed wiring board is the method for feedstock production carbonaceous molecular sieve.
Background technology
Carbonaceous molecular sieve is a kind of novel non-polar adsorbent, it mainly acts on is the nitrogen of separation of air enrichment at normal temperatures, is widely used in industries such as chemical industry, petrochemical industry, chemical fibre, medicine, glasswork, coal, thermal treatment, metallurgy, refrigeration and air-conditioning, beer and food fresh keeping.
The raw material of preparation carbonaceous molecular sieve is very extensive, and natural product or high molecular polymer are arranged, and specifically can be divided three classes: a class is various coals and coal-based derivative; Another kind of is organic high molecular polymer, as saran, resol; Also having a class is the plant class, mainly is nutshell or the nuclear that utilizes plant, as nut-shell, almond, coconut husk etc.Material choice is the best with low ash content, high carbon content and alap volatile component generally.Resol is owing to have higher carbon residue rate and low-volatile, its three-dimensional netted crosslinking structure easily forms the micropore about 1nm in further pyrolytic process, providing very favorable condition for further preparing carbonaceous molecular sieve, is the good persursor material of preparation carbonaceous molecular sieve.
Nonmetal isolate in the waste printed wiring board mainly is resol or Resins, epoxy, also has some glass fibre and remaining metal in addition.Speed up along with electronic product updates, produce a large amount of waste printed wiring boards, its resource utilization research is the hot issue that current electronic waste is handled.Existing recovery method stresses the recovery of metal in the wiring board more, and shorter mention accounts for the resource utilization of the nonmetal composition of total amount more than 50% and innoxious.At present, in the non-metallic material except minority as the filler, mostly is as garbage loading embeading, and not only valuable substance such as resin and glass fibre is not fully utilized and runs off, and also easy contaminate environment by all means of objectionable impurities such as fire retardant wherein, residual metal.Also handle the research report of the nonmetal isolate of waste printed wiring board relevant for pyrolytic technique, the nonmetal isolate that utilizes pyrolytic technique to handle waste printed wiring board mainly is to be used for reclaiming pyrolysis oil, the solid phase residue can not get recycling preferably as a kind of refuse or rudimentary weighting material.The nonmetal isolate that if can the degree of depth separates waste printed wiring board, obtain the higher resin of purity, and through further processing treatment acquisition carbonaceous molecular sieve, the nonmetal isolate of waste printed wiring board will be reasonably and effectively used, and this technology will have application promise in clinical practice.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of reasonable in design, process stabilizing, and prepared carbonaceous molecular sieve ash content is low, density is high, the micropore pore volume is big, to N
2And O
2Adsorptive capacity big be the method for feedstock production carbonaceous molecular sieve with the waste printed wiring board.
Solving the problems of the technologies described above the technical scheme that is adopted is that it comprises the steps:
1, from waste printed wiring board, separates nonmetal thing
With impactor, knife mill, rotary crusher, ball mill the waste printed circuit board plate is ground into particulate less than 1mm according to this, with low intensive magnetic separator separating ferrum magnetic substance, again by the metal except that ferromagnetic material in the breakdown products of electrostatic separation split circuit plate, residue is the nonmetal isolate of waste printed wiring board, and resin content is more than 50%.
2, the purifying of the nonmetal isolate of waste printed wiring board
With mass concentration 43.5%～67.7% KI or NaI or ZnCl
2Or ZnBr
2Or NH
4NO
3The nonmetal isolate of the aqueous solution and waste printed wiring board compares uniform mixing by the quality of 1:0.2～1, centrifugal 10～20 minutes with 5000 rev/mins of centrifuge separators, the residual metal of separation resin, glass fibre and trace, separated resin is with 100 ℃ deionized water wash 2～3 times, and 100 ℃ of dryings are 1～2 hour in loft drier.
3, resin destructive distillation
Resin is placed vacuum oven, and 200～600 ℃ of constant temperature destructive distillation 0.5～4.5 hour naturally cool to room temperature, obtain the destructive distillation product.
4, pulverize
With ball mill the destructive distillation product is crushed to the fine powder that particle diameter is 5～15 μ m.
5, moulding
The interpolation softening temperature is 75 ℃ a coal-tar middle oil in the destructive distillation product powder, the mass ratio of destructive distillation product powder and coal-tar middle oil is 100:25～45, mediate repeatedly for 60～90 ℃, be squeezed into the cylindrical particle that diameter is 2.5mm, place in the loft drier in 80 ℃ of dryings 6 hours with screw extruder.
6, carbonization
With the above-mentioned forming composition carbide furnace of packing into, at N
2Be warming up to 650～950 ℃ of carbonizations 0.5～3.5 hour under the protection, naturally cool to room temperature, make carbide.
7, weak activation
The carbide of step 6 preparation is packed in the activation furnace, in 650～950 ℃, the water vapor of 0.08～0.20MPa, activate 0.5～2.5 hour.
8, vapour deposition
Nitrogen is carried propylene enter the carbon laydown device, carry out the gas-phase carbon deposition process, be prepared into carbonaceous molecular sieve, the carbon laydown temperature is 650～950 ℃, and depositing time is 0.5～3.5 hour, and nitrogen flow rate is 20～100ml/min.
Above-mentioned carbon laydown device is to add a container that propylene is housed before activation furnace.
9, testing performance index
Prepared carbonaceous molecular sieve is adopted CO with physical adsorption appearance
2Its micropore pore volume and specific surface area of test under 298K, the packing density of carbonaceous molecular sieve adopts GB/T7702.4-1997, and the ash content of carbonaceous molecular sieve is measured according to GB9345-88.
Estimate the sieving capacity of carbonaceous molecular sieve with single tower pressure-swing absorption apparatus.Single tower transformation absorption column length 30cm, internal diameter 12mm can load about 30g carbonaceous molecular sieve in the post.Main operating parameters is during test: adsorption temp is a room temperature, adsorptive pressure 4 * 10
5Pa, desorption pressure 4 * 10
3Pa, desorption time 2 minutes.Product nitrogen-rich gas oxygen level is measured with KY22B type oxygen measuring instrument.
In the purifying process step 2 of the nonmetal isolate of waste printed wiring board of the present invention, KI or NaI or ZnCl
2Or ZnBr
2Or NH
4NO
3The preferred mass concentration of the aqueous solution is 50.1%～57.1%, KI or NaI or ZnCl
2Or ZnBr
2Or NH
4NO
3The aqueous solution is 1:0.4～0.7 with the preferred mass ratio of activator; In resin destructive distillation processing step 3, preferred pyrolysis temperature is that 300～500 ℃, destructive distillation time are 2.5～3.5 hours; In disintegrating process step 4, destructive distillation product powder particle diameter is preferably 8～12 μ m; In moulding process step 5, the destructive distillation product mixes than for 100:30～40 with the preferred mass of coal-tar middle oil, and preferred mixing temperature is 70～80 ℃; In carbonization technique step 6, preferred carbonization temperature is 750～850 ℃, carbonization 1.5～2.5 hours; In weak activating process step 7, preferred activation temperature is 750～850 ℃, activates 1.0～2.0 hours, and preferred water vapor pressure is 0.12～0.16MPa; In gas-phase deposition step 8, preferred carbon laydown temperature is that 750～850 ℃, depositing time are 1.5～2.5 hours, and preferred carrier gas N2 flow velocity is 50～70ml/min.
In the purifying process step 2 of the nonmetal isolate of waste printed wiring board of the present invention, KI or NaI or ZnCl
2Or ZnBr
2Or NH
4NO
3The best in quality concentration of the aqueous solution is 53.5%, KI or NaI or ZnCl
2Or ZnBr
2Or NH
4NO
3The aqueous solution and optimum quality ratio activator are 1:0.55; In resin destructive distillation processing step 3, best pyrolysis temperature is 400 ℃, destructive distillation 2.5 hours; In disintegrating process step 4, best powder particle diameter is 9 μ m; In moulding process step 5, the destructive distillation product is that 100:35 mixes with the optimum quality ratio of coal-tar middle oil, and best mixing temperature is 75 ℃; In carbonization technique step 6, best carbonization temperature is 800 ℃, carbonization 2.0 hours; In weak activating process step 7, the optimal activation temperature is 800 ℃, activates 1.5 hours, and best water vapor pressure is 0.14MPa; In gas-phase deposition step 8, best carbon laydown temperature is 800 ℃, deposits 2.0 hours, and best carrier gas nitrogen flow velocity is 60ml/min.
The present invention utilizes in the waste printed wiring board difference of each density of fraction in the non-metallic material, by being mixed with certain density solution, in conjunction with centrifugal separation technique, resin in the non-metallic material is separated with glass fibre, isolating resin is through destructive distillation, moulding, pulverizing, carbonization, weak activation and vapor deposition step thereof, the carbonaceous molecular sieve of preparation is used for the nitrogen of enriched air By.Adopt the prepared carbonaceous molecular sieve of the present invention after tested, ash content is 1.0%～5.0, packing density is 0.44～0.65g/cm
3, the micropore pore volume is 0.45～0.66cm
3/ g, to N
2And O
2The selection adsorption index be 2.1～5.5.The present invention has reasonable in design, process stabilizing, prepared carbonaceous molecular sieve ash content is low, density is high, the micropore pore volume big, to N
2And O
2Advantages such as adsorptive capacity is big, adopt the present invention that waste printed wiring board is prepared into carbonaceous molecular sieve, solved the problem of environmental pollution of waste printed wiring board.
Embodiment
The present invention is described in more detail below in conjunction with embodiment, but the invention is not restricted to these embodiment.
Embodiment 1
With used mass concentration is that 53.5% KI aqueous solution 100g is an example, other used raw material and to prepare the method for carbonaceous molecular sieve as follows:
1, from waste printed wiring board, separates nonmetal thing
With impactor, knife mill, rotary crusher, ball mill the waste printed circuit board plate is ground into particulate less than 1mm according to this, with low intensive magnetic separator separating ferrum magnetic substance, again by the metal except that ferromagnetic material in the breakdown products of electrostatic separation split circuit plate, residue is the nonmetal isolate of waste printed wiring board, and resin content is more than 50%.
2, the purifying of the nonmetal isolate of waste printed wiring board
With mass concentration is 53.5% the KI aqueous solution 100g and the nonmetal isolate 55g uniform mixing of waste printed wiring board, mass concentration is that the mass ratio of the nonmetal isolate of 53.5% the KI aqueous solution and waste printed wiring board is 1:0.55, centrifugal 10～20 minutes with 5000 rev/mins of centrifuge separators, separation resin, glass fibre and residual metal, separated resin is with 100 ℃ deionized water wash 2～3 times, and 100 ℃ of dryings are 1～2 hour in loft drier.
3, resin destructive distillation
Resin is placed vacuum oven, and 400 ℃ of constant temperature destructive distillation 2.5 hours naturally cool to room temperature, obtain the destructive distillation product.
4, pulverize
With ball mill the destructive distillation product is crushed to the fine powder that particle diameter is 9 μ m.
5, moulding
Get destructive distillation product powder 30g, the interpolation softening temperature is 75 ℃ coal-tar middle oil 10.5g in the destructive distillation product powder, the mass ratio of destructive distillation product powder and coal-tar middle oil is 100:35, mediate repeatedly for 75 ℃, be squeezed into the cylindrical particle that diameter is 2.5mm with screw extruder, place in the loft drier in 80 ℃ of dryings 6 hours.
6, carbonization
With the above-mentioned forming composition carbide furnace of packing into, at N
2Be warming up to 800 ℃ of carbonizations 2.0 hours under the protection, naturally cool to room temperature, make carbide.
7, weak activation
The carbide of step 6 preparation is changed in the carbide furnace, and activation is 1.5 hours in 800 ℃, the water vapor of 0.14MPa.
8, vapour deposition
Nitrogen is carried industrial propylene enter the carbon laydown device, carry out the gas-phase carbon deposition process, be prepared into carbonaceous molecular sieve, the carbon laydown temperature is 800 ℃, and depositing time is 2.0 hours, and nitrogen flow rate is 60ml/min; Above-mentioned carbon laydown device is to add a container that industrial propylene is housed before activation furnace,
9, testing performance index
Carbonaceous molecular sieve to prepared adopts CO with physical adsorption appearance
2Its micropore pore volume of test is 0.66cm under 298K
3/ g, specific surface area 1500m
2/ g, the packing density of carbonaceous molecular sieve adopts " mensuration of packing density " GB/T7702.4-1997, and the ash content of carbonaceous molecular sieve is measured according to GB9345-88.
Embodiment 2
With used mass concentration is that 53.5% KI aqueous solution 100g is an example, other used raw material and to prepare the method for carbonaceous molecular sieve as follows:
In the nonmetal isolate purifying process step 1 of waste printed wiring board, be 53.5% the KI aqueous solution 100g and the nonmetal isolate 20g uniform mixing of waste printed wiring board with mass concentration, other step of this processing step is identical with embodiment 1.In resin destructive distillation processing step 2, pyrolysis temperature is 200 ℃, destructive distillation 4.5 hours, naturally cools to room temperature and obtains the destructive distillation product; In disintegrating process step 3, the destructive distillation product is crushed to the fine powder that particle diameter is 5 μ m with ball mill.In moulding process step 4, get destructive distillation product powder 10g, the interpolation softening temperature is 75 ℃ coal-tar middle oil 2.5g in the destructive distillation product powder, mediates repeatedly for 60 ℃, other step of this processing step is identical with embodiment 1, makes cylindrical particle.In carbonization technique step 5, the cylindrical particle thing of the moulding carbide furnace of packing into is at N
2Be warming up to 650 ℃ of carbonizations 3.5 hours under the protection, naturally cool to room temperature, make carbide.In weak activating process step 6, carbide is packed in the activation furnace, activation is 2.5 hours in 650 ℃, the water vapor of 0.20MPa.In gas-phase deposition step 7, nitrogen is carried industrial propylene enter the carbon laydown device, carry out the gas-phase carbon deposition process, be prepared into carbonaceous molecular sieve, the carbon laydown temperature is 650 ℃, and depositing time is 3.5 hours, and nitrogen flow rate is 20ml/min.
Embodiment 3
With used mass concentration is that 53.5% KI aqueous solution 100g is an example, other used raw material and to prepare the method for carbonaceous molecular sieve as follows:
In the nonmetal isolate purifying process step 1 of waste printed wiring board, be 53.5% the KI aqueous solution 100g and the nonmetal isolate 100g uniform mixing of waste printed wiring board with mass concentration, other step of this processing step is identical with embodiment 1.In resin destructive distillation processing step 2, pyrolysis temperature is 600 ℃, destructive distillation 0.5 hour, naturally cools to room temperature and obtains the destructive distillation product; In disintegrating process step 3, the destructive distillation product is crushed to the fine powder that particle diameter is 15 μ m with ball mill.In moulding process step 4, get destructive distillation product powder 50g, the interpolation softening temperature is 75 ℃ coal-tar middle oil 22.5g in the destructive distillation product powder, mediates repeatedly for 90 ℃, other step of this processing step is identical with embodiment 1, makes cylindrical particle.In carbonization technique step 5, the cylindrical particle thing of the moulding carbide furnace of packing into is at N
2Be warming up to 950 ℃ of carbonizations 0.5 hour under the protection, naturally cool to room temperature, make carbide.In weak activating process step 6, carbide is packed in the activation furnace, activation is 0.5 hour in 950 ℃, the water vapor of 0.08MPa.In gas-phase deposition step 7, nitrogen is carried industrial propylene enter the carbon laydown device, carry out the gas-phase carbon deposition process, be prepared into carbonaceous molecular sieve, the carbon laydown temperature is 950 ℃, and depositing time is 0.5 hour, and nitrogen flow rate is 100ml/min.
Embodiment 4
With used mass concentration is that 43.53% KI aqueous solution 100g is an example, other used raw material and to prepare the method for carbonaceous molecular sieve as follows:
In above embodiment 1～3, used mass concentration is that 53.5% KI aqueous solution mass concentration is that 43.5% the KI aqueous solution is replaced, and consumption is identical.Other processing step is identical with respective embodiments.
Embodiment 5
With used mass concentration is that 67.7% NaI aqueous solution 100g is an example, other used raw material and to prepare the method for carbonaceous molecular sieve as follows:
In above embodiment 1～3, used mass concentration is that 53.5% KI aqueous solution mass concentration is that 67.7% the KI aqueous solution is replaced, and consumption is identical.Other processing step is identical with respective embodiments.
Embodiment 6
With used mass concentration is that 43.5%～67.7% NaI aqueous solution 100g is an example, other used raw material and to prepare the method for carbonaceous molecular sieve as follows:
In above embodiment 1～5, used mass concentration is that 43.5%～67.7% the KI aqueous solution is replaced with the NaI aqueous solution of equal in quality concentration, and consumption is identical.Other processing step is identical with respective embodiments.
Embodiment 7
With used mass concentration 43.5%～67.7% ZnCl
2Aqueous solution 100g is an example, other used raw material and to prepare the method for carbonaceous molecular sieve as follows:
In above embodiment 1～5, used mass concentration is 43.5%～67.7% the KI aqueous solution ZnCl with equal in quality concentration
2The aqueous solution is replaced, and consumption is identical.Other processing step is identical with respective embodiments.
Embodiment 8
With used mass concentration 43.5%～67.7% ZnBr
2Aqueous solution 100g is an example, other used raw material and to prepare the method for carbonaceous molecular sieve as follows:
In above embodiment 1～5, used mass concentration is 43.5%～67.7% the KI aqueous solution ZnBr with equal in quality concentration
2The aqueous solution is replaced, and consumption is identical.Other processing step is identical with respective embodiments.
Embodiment 9
With used mass concentration 43.5%～67.7% NH4NO
3Aqueous solution 100g is an example, other used raw material and to prepare the method for carbonaceous molecular sieve as follows:
In above embodiment 1～5, used mass concentration is 43.5%～67.7% the KI aqueous solution NH with equal in quality concentration
4NO
3The aqueous solution is replaced, and consumption is identical.Other processing step is identical with respective embodiments.
In order to determine the processing step of the best of the present invention, the contriver has carried out a large amount of laboratory study tests, and various test situation are as follows:
The test raw material: the nonmetal isolate of waste printed wiring board, by contriver's self-control, the preparation method is as follows:
Get waste printed wiring board 10kg, with rotary crusher, ball mill the waste printed circuit board plate is ground into particulate less than 1mm, with low intensive magnetic separator separating ferrum magnetic substance, again by the metal except that ferromagnetic material in the breakdown products of electrostatic separation split circuit plate, residue is the nonmetal isolate of waste printed wiring board, resin content uses for experiment more than 50%.
1, determines the used strength of solution of separation resin and glass fibre
Be mixed with the KI aqueous solution of mass concentration 43.5%～67.7% according to a conventional method.Get the KI aqueous solution of 100g different concns, the nonmetal isolate that adds the waste printed wiring board of 55g, be that 1:0.55 mixes promptly by the KI aqueous solution and the mass ratio of the nonmetal isolate of waste printed wiring board, mixed solution stirs with the electromagnetism stirrer, abundant mixing, place centrifuge separator, the sedimentator rotating speed is 5000 rev/mins, centrifugal 15～20 minutes, be separated into two kinds of major ingredient resins and glass fibre solid, take out two kinds of isolates respectively, with deionized water wash 2～3 times, be washed till no KI, with two kinds of solid isolates, 100 ℃ of dryings 1～2 hour in loft drier, analyze respectively with scanning electron microscope.Analytical results sees Table 1.
The influence that table 1 strength of solution is elementary composition to sample separation
By table 1 as seen, the mass concentration of the KI aqueous solution is 50.1%～57.1% o'clock, and principal element consists of C, O, Br in the upper strata separation article, and principal element consists of C, O, Al, Si, Br, Ca in lower floor's separation article.Show that the mass concentration of the KI aqueous solution is at 50.1%～57.1% o'clock, resin can access good the separation with glass fibre and residual metal.It is 43.5%～67.7% that the present invention selects the mass concentration of the KI aqueous solution, and wherein the preferred mass concentration of the aqueous solution is 50.1%～57.1%, and the mass concentration of the best KI aqueous solution is 54.0%.
2, determine the nonmetal isolate proportioning of the KI aqueous solution and waste printed wiring board
Get mass concentration and be 54.0% KI aqueous solution 100g, the nonmetal isolate that adds the waste printed wiring board of 20～100g also mixes, and promptly the mass ratio of the nonmetal isolate of the KI aqueous solution and waste printed wiring board is 1:0.2～1.Other step is identical with experiment 1.The gained sample is analyzed with scanning electron microscope and corresponding electron diffraction pattern.Analytical results sees Table 2.
The separating obtained sample of nonmetal isolate proportioning of table 2 different solutions and waste printed wiring board elementary composition
By table 2 as seen, the nonmetal isolate quality of the KI aqueous solution and waste printed wiring board is than being 1:0.4～0.7 o'clock, and principal element consists of in the sample of upper strata: C, O, Br, principal element consists of in lower floor's sample: C, O, Al, Si, Br, Ca.When the nonmetal isolate proportioning that the KI aqueous solution and waste printed wiring board be described was used in this scope, by centrifugal, resin can access good the separation with fiber and residual metal.The present invention selects the KI aqueous solution and the nonmetal isolate quality ratio of waste printed wiring board to be 1:0.2～1.0, and preferred mass is than being 1:0.4～0.7, and optimum quality ratio is 1:0.55.
3, determine the resin pyrolysis temperature
Get mass concentration and be 54.0% KI solution 100g, add the nonmetal isolate of the waste printed wiring board of 55g, with the abundant mixing of magnetic stirrer, place centrifuge separator, 5000 rev/mins centrifugal 20 minutes.Centrifugation, upper strata are resin, and lower floor is glass fibre and residual metal.Solid sample in the upper and lower two layers of solution is taken out, after cleaning with deionized water, drying.
The 30g resin is placed vacuum oven, 200～600 ℃ of destructive distillation 2 hours, reaction is cooled to room temperature after finishing naturally.The resin pyrolysis temperature sees Table 3 to the influence of its cut.
Table 3 resin pyrolysis temperature is to the influence of its cut
| Pyrolysis temperature (℃) | 200 | 300 | 400 | 500 | 600 |
| Destructive distillation cut (%) | 45 | 54 | 58 | 64 | 65 |
By table 3 as seen, under the situation that only changes the resin pyrolysis temperature, when pyrolysis temperature during at 300～500 ℃, the cut of resin is higher.It is 200～600 ℃ that the present invention selects the resin pyrolysis temperature, and wherein preferred pyrolysis temperature is that 300～500 ℃, optimum temps are 400 ℃.
4, determine the resin destructive distillation time
The separation resin step is identical with experiment 3.
The 30g resin is placed vacuum oven, 400 ℃ of constant temperature 0.5～4.5 hour, reaction is cooled to room temperature after finishing naturally.The relation of gained destructive distillation cut and pyrolysis temperature is listed in table 4.
The table 4 resin destructive distillation time is to the influence of its cut
| The destructive distillation time (hour) | 0.5 | 1.0 | 1.5 | 2.0 | 2.5 | 3.0 | 3.5 | 4.0 | 4.5 |
| Destructive distillation cut (%) | 45 | 48 | 50 | 53 | 60 | 62 | 63 | 64 | 65 |
By table 4 as seen, under the situation that only changes the resin destructive distillation time, when the destructive distillation time greater than 2.5 hours after, the cut of resin is higher, and changes little.It is 0.5～4.5 hour that the present invention selects the resin destructive distillation time, and wherein the preferred resin destructive distillation time is 2.5～3.5 hours, and the optimum resin destructive distillation time is 2.5 hours.
5, determine destructive distillation product powder particle diameter
The separation resin step is identical with experiment 3.
The 30g resin is placed vacuum oven, 400 ℃ of constant temperature 2.5 hours, reaction is cooled to room temperature after finishing naturally.Gained destructive distillation product is ground into the particle of 5,7,9,11,13,15,17 μ m with ball mill, adds softening temperature and be 75 ℃ coal-tar middle oil, and the mass ratio of destructive distillation product and coal-tar middle oil is 100:35, kneading repeatedly under 75 ℃ of temperature.Be squeezed into the cylindrical particle that diameter is 2.5mm with screw extruder, in loft drier in 80 ℃ of dryings 6 hours.With the above-mentioned cylindrical particle carbide furnace of packing into, at N
2Be warming up to 800 ℃ of carbonizations 2.0 hours under the protection, naturally cool to room temperature, obtain carbide.A destructive distillation material footpath sees Table 5 to the influence of carbide density.
Table 5 footpath is to the influence of carbonized product density.
| Destructive distillation material particular diameter (μ m) | 5 | 7 | 9 | 11 | 13 | 15 | 17 |
| Density (g/cm 3) | 0.45 | 0.49 | 0.55 | 0.47 | 0.44 | 0.41 | 0.39 |
By table 5 as seen, under the situation that only changes the destructive distillation material particular diameter, after particle diameter was less than 11 μ m, the density of carbonized product was higher.It is 5～15 μ m that the present invention selects destructive distillation product powder particle diameter, and wherein preferable particle size is 5～11 μ m, and optimum grain-diameter is 9 μ m.
6, determine the mixing temperature of destructive distillation product and coal tar
The separation resin step is identical with experiment 3.
The 30g resin is placed vacuum oven, 400 ℃ of constant temperature 2.5 hours, reaction is cooled to room temperature after finishing naturally.Gained destructive distillation product is ground into the particle of 9 μ m with mortar, adds softening temperature and be 75 ℃ coal-tar middle oil, and the mass ratio of destructive distillation product and coal-tar middle oil is 100:35,60～90 ℃ of kneadings repeatedly of temperature.Be squeezed into the cylindrical particle that diameter is 2.5mm with screw extruder, 80 ℃ of dryings are 6 hours in loft drier.With the above-mentioned forming composition carbide furnace of packing into, at N
2Be warming up to 800 ℃ of carbonizations 2.0 hours under the protection, naturally cool to room temperature, obtain carbide.Destructive distillation product and coal tar mixing temperature see Table 6 to the influence of carbide density.
Table 6 destructive distillation product and coal tar mixing temperature are to the influence of carbonized product density.
| Mixing temperature (℃) | 60 | 65 | 70 | 75 | 80 | 85 | 90 |
| Density (g/cm 3) | 0.25 | 0.31 | 0.43 | 0.49 | 0.45 | 0.36 | 0.28 |
By table 6 as seen, under the situation that only changes destructive distillation product and coal tar mixing temperature, when mixing temperature was in 70～80 ℃ of scopes, the density of carbonized product was higher.It is 60～90 ℃ that the present invention selects destructive distillation product and coal tar mixing temperature, and wherein preferred mixing temperature is 70～80 ℃, and best mixing temperature is 75 ℃.
7, determine destructive distillation product and coal-tar middle oil proportioning
The separation resin step is identical with experiment 3.
The 30g resin is placed vacuum oven, and 400 ℃ of constant temperature 2.5 hours, question response was cooled to room temperature after finishing naturally.Gained destructive distillation product is ground into the particle of 9 μ m with mortar, adds softening temperature then and be 75 ℃ coal-tar middle oil, and the mass ratio of destructive distillation product and coal-tar middle oil is 100:25～45, mediates repeatedly under 75 ℃.Be squeezed into the cylindrical particle that diameter is 2.5mm with screw extruder, in loft drier in 80 ℃ of dryings 6 hours.With the above-mentioned forming composition carbide furnace of packing into, at N
2Be warming up to 800 ℃ of carbonizations 2.0 hours under the protection, naturally cool to room temperature, obtain carbide.Destructive distillation product and coal tar proportioning see Table 7 to the influence of carbide micropore pore volume.
Table 7 destructive distillation product and coal tar proportioning are to the influence of carbonized product micropore pore volume.
| Destructive distillation product and coal tar proportioning | 100：25 | 100：30 | 100：35 | 100：40 | 100：45 |
| Micropore pore volume (cm 3/g) | 0.31 | 0.44 | 0.54 | 0.47 | 0.36 |
By table 7 as seen, under the situation that only changes destructive distillation product and coal tar proportioning, when destructive distillation product and coal tar proportioning during at 100:30～40, the micropore pore volume of carbonized product is higher.It is 100:25～45 that the present invention selects destructive distillation product and coal tar proportioning, and wherein optimum ratio is 100:30～40, and best proportioning is 100:35.
8, determine carbonization temperature
The separation resin step is identical with experiment 3.
The 30g resin is placed vacuum oven, 400 ℃ of constant temperature 2.5 hours, reaction is cooled to room temperature after finishing naturally.Gained destructive distillation product is ground into the particle of 9 μ m with mortar, adds softening temperature and be 75 ℃ coal-tar middle oil, and the mass ratio of destructive distillation product and coal-tar middle oil is 100:35, in 75 ℃ of kneadings repeatedly of temperature.Be squeezed into the cylindrical particle that diameter is 2.5mm with screw extruder, place in the loft drier, 80 ℃ of dryings 6 hours.With the above-mentioned forming composition carbide furnace of packing into, at N
2Be warming up to 650～950 ℃ of constant temperature 2.0 hours under the protection, naturally cool to room temperature, obtain carbide.Carbonization temperature sees Table 8 to the carbide structure Effect on Performance.
Table 8 carbonization temperature is to the carbide structure Effect on Performance.
| Carbonization temperature (℃) | 650 | 700 | 750 | 800 | 850 | 900 |
| Micropore pore volume (cm 3/g) | 0.31 | 0.39 | 0.49 | 0.54 | 0.50 | 0.41 |
| Select adsorption index | 0.7 | 1.6 | 2.1 | 2.8 | 2.4 | .2 |
By table 8 as seen, under the situation that only changes carbonization temperature, when carbonization temperature was in 750～850 ℃ of scopes, the micropore pore volume of carbonized product was higher, selected adsorption index bigger.It is 650～950 ℃ that the present invention selects carbonization temperature, and wherein preferred carbonization temperature is 750～850 ℃, and best carbonization temperature is 800 ℃.
9, determine carbonization time
The separation resin step is identical with experiment 3.
The 30g resin is placed vacuum oven, constant temperature is 2.5 hours under 400 ℃ the temperature, after reaction finishes, naturally be cooled to room temperature, gained destructive distillation product is ground into the particle of 9 μ m with mortar, the interpolation softening temperature is 75 ℃ a coal-tar middle oil, and the mass ratio of destructive distillation product and coal-tar middle oil is 100:35, and temperature is mediated for 75 ℃ repeatedly.Be squeezed into the cylindrical particle that diameter is 2.5mm with screw extruder, place in the loft drier, 80 ℃ of dryings 6 hours.With the above-mentioned forming composition carbide furnace of packing into, at N
2Be warming up to 800 ℃ of constant temperature 0.5～3.5 hour under the protection, naturally cool to room temperature, obtain carbide.Carbonization time sees Table 9 to the carbide structure Effect on Performance.
Table 9 carbonization time is to the carbide structure Effect on Performance.
| Carbonization time (hour) | 0.5 | 1.0 | 1.5 | 2.0 | 2.5 | 3.0 | 3.5 |
| Micropore pore volume (cm 3/g) | 0.31 | 0.38 | 0.48 | 0.54 | 0.51 | 0.45 | 0.34 |
| Select adsorption index | 1.9 | 2.5 | 2.8 | 3.2 | 2.7 | 2.1 | 1.6 |
By table 9 as seen, under the situation that only changes carbonization time, when carbonization time during at 1.5～2.5 hours, the micropore pore volume of carbonized product is higher, selects adsorption index bigger.It is 0.5～3.5 hour that the present invention selects carbonization time, and wherein preferred carbonization time is 1.5～2.5 hours, and best carbonization time is 2.0 hours.
10, determine weak activation temperature
Method according to experiment 9 prepares carbide.Take by weighing this carbonization material 10g, this carbide is placed activation furnace, 650～950 ℃ of temperature, activation is 1.5 hours in the water vapor of pressure 0.14MPa.Reaction naturally cools to room temperature after finishing, and obtains activation products.Weak activation temperature sees Table 10 to the activation products Structural Influence.
The weak activation temperature of table 10 is to the activation products Structural Influence.
| Weak activation temperature (℃) | 650 | 700 | 750 | 800 | 850 | 900 |
| Micropore pore volume (cm 3/g) | 0.38 | 0.42 | 0.54 | 0.65 | 0.59 | 0.43 |
| Select adsorption index | 2.4 | 2.6 | 3.1 | 3.4 | 3.2 | 2.4 |
By table 10 as seen, under the situation that only changes activation temperature, when 750～850 ℃ of activation temperatures, the micropore pore volume of activation products is higher, selects adsorption index bigger.It is 650～950 ℃ that the present invention selects activation temperature, and wherein preferred activation temperature is 750～850 ℃, 800 ℃ of optimal activation temperature.
11, determine water vapor pressure
Method according to experiment 9 prepares carbide.Take by weighing this carbonization material 10g, then this carbide is placed activation furnace, 800 ℃ of temperature, activation is 1.5 hours in the water vapor of pressure 0.08～0.20MPa.Reaction naturally cools to room temperature after finishing, and obtains activation products.Water vapor pressure sees Table 11 to the activation products Structural Influence.
Table 11 water vapor pressure is to the activation products Structural Influence.
| Water vapor pressure (MPa) | 0.08 | 0.10 | 0.12 | 0.14 | 0.16 | 0.18 | 0.20 |
| Micropore pore volume (cm 3/g) | 0.38 | 0.43 | 0.56 | 0.65 | 0.58 | 0.41 | 0.32 |
| Select adsorption index | 1.8 | 2.1 | 2.8 | 3.1 | 2.6 | 2.3 | 1.5 |
By table 11 as seen, under the situation that only changes water vapor pressure, when water vapor pressure was in 0.08～0.20MPa scope, the micropore pore volume of activation products was higher, selected adsorption index bigger.Water vapor pressure of the present invention is 0.08～0.20MPa, and wherein water vapor pressure is preferably 0.12～0.16MPa, the best 0.14MPa of being of water vapor pressure.
12, determine soak time
Method according to experiment 9 prepares carbide.Take by weighing this carbonization material 10g, this carbide is placed activation furnace, in 800 ℃, the water vapor of 0.14MPa, activate 0.5～2.5 hour.Reaction naturally cools to room temperature after finishing, and obtains activation products.Soak time sees Table 12 to the activation products Structural Influence.
Table 12 soak time is to the activation products Structural Influence
| Soak time (hour) | 0.5 | 1.0 | 1.5 | 2.0 | 2.5 |
| Micropore pore volume (cm 3/g) | 0.38 | 0.53 | 0.65 | 0.55 | 0.40 |
| Select adsorption index | 2.3 | 2.8 | 3.5 | 2.9 | 2.1 |
By table 12 as seen, under the situation that only changes soak time, when soak time during at 1.0～2.0 hours, the micropore pore volume of activation products is higher, selects adsorption index bigger.It is 0.5～2.5 hour that the present invention selects soak time, and wherein preferred soak time is 1.0～2.0 hours, and optimum activating time is 1.5 hours.
13, the carbon laydown temperature determines
After priming reaction finishes a little less than the method for experiment 12, water vapor is switched to the propylene steam that is carried by nitrogen carry out vapor deposition reaction, the carbon laydown temperature is 650～950 ℃, and depositing time is 2.0 hours, and carrier gas N2 flow velocity is 60ml/min.Reaction naturally cools to room temperature after finishing, and obtains carbonaceous molecular sieve.The carbon laydown temperature sees Table 13 to the product structure Effect on Performance.
Table 13 carbon laydown temperature is to the product structure Effect on Performance.
| The carbon laydown temperature (℃) | 650 | 700 | 750 | 800 | 850 | 900 | 950 |
| Micropore pore volume (cm 3/g) | 0.36 | 0.43 | 0.56 | 0.68 | 0.59 | 0.44 | 0.32 |
| Select adsorption index | 2.8 | 3.4 | 4.8 | 5.2 | 4.9 | 3.2 | 2.6 |
By table 13 as seen, under the situation that only changes the carbon laydown temperature, when the carbon laydown temperature was in 750～850 ℃ of scopes, the micropore pore volume of product was higher, selected adsorption index bigger.It is 650～950 ℃ that the present invention selects the carbon laydown temperature, and wherein excellent carbon laydown temperature is 750～850 ℃, and best carbon laydown temperature is 800 ℃.
14, the carbon laydown time determines
After priming reaction finishes a little less than the method for experiment 12, water vapor is switched to the propylene steam that is carried by nitrogen carry out vapor deposition reaction, the carbon laydown temperature is 800 ℃, depositing time is 0.5～3.5 hour, carrier gas N
2Flow velocity is 60ml/min.Reaction naturally cools to room temperature after finishing, and obtains carbonaceous molecular sieve.The carbon laydown time sees Table 14 to the product structure Effect on Performance.
The table 14 carbon laydown time is to the product structure Effect on Performance
| The carbon laydown time (hour) | 0.5 | 1.0 | 1.5 | 2.0 | 2.5 | 3.0 | 3.5 |
| Micropore pore volume (cm 3/g) | 0.45 | 0.48 | 0.56 | 0.64 | 0.58 | 0.47 | 0.41 |
| Select adsorption index | 2.8 | 3.6 | 4.1 | 4.8 | 4.5 | 3.8 | 2.3 |
By table 14 as seen, under the situation that only changes the carbon laydown time, when carbon laydown time during at 1.5～2.5 hours, the micropore pore volume of product is higher, selects adsorption index bigger.It is 0.5～3.5 hour that the present invention selects the carbon laydown time, and the wherein preferred carbon laydown time is 1.5～2.5 hours, Best Times 2.0 hours.
15, carrier gas flux determines
After priming reaction finishes a little less than the method for experiment 12, water vapor is switched to the propylene steam that is carried by nitrogen carry out vapor deposition reaction, 800 ℃ of carbon laydowns of carbon laydown temperature 2.0 hours, carrier gas N
2Flow is 20～100ml/min.Reaction naturally cools to room temperature after finishing, and obtains carbonaceous molecular sieve.Carrier gas N2 flow sees Table 15 to the product structure Effect on Performance.
Table 15 carrier gas N
2Flow is to the product structure Effect on Performance.
| Carrier gas N2 flow (ml/min) | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 | 100 |
| Micropore pore volume (cm 3/g) | 0.48 | 0.52 | 0.58 | 0.64 | 0.66 | 0.63 | 0.57 | 0.53 | 0.45 |
| Select adsorption index | 2.4 | 3.1 | 4.8 | 5.0 | 5.5 | 5.2 | 4.6 | 3.3 | 2.1 |
By table 15 as seen, only changing carrier gas N
2Under the situation of flow, as carrier gas N
2Flow is when 50～70ml/min, and the micropore pore volume of product is higher, selects adsorption index bigger.The present invention selects carbon carrier gas N
2Flow is 20～100ml/min, wherein preferred carrier gas N
2Flow is 50～70ml/min, best carrier gas N
2Flow is 60ml/min.
In order to verify beneficial effect of the present invention, the contriver adopts the carbonaceous molecular sieve of the embodiment of the invention 1 preparation to carry out testing performance index, and various test case are as follows:
Get prepared carbonaceous molecular sieve 0.2g, test its micropore pore volume, specific surface area with physical adsorption appearance.The packing density of carbonaceous molecular sieve adopts GB/T7702.4-1997, and the ash content of carbonaceous molecular sieve is measured according to GB9345-88.Adopt CO with physical adsorption appearance
2Its micropore pore volume of test under 298K.
Test result sees Table 16.
The performance index of table 16 carbonaceous molecular sieve
| Micropore pore volume (cm 3/g) | Specific surface area (m 2/g) | Packing density (g/cm 3) | Ash content (%) |
| 0.66 | 1500 | 0.65 | 1.00 |
Claims (3)
1, a kind of is the method for feedstock production carbonaceous molecular sieve with the waste printed wiring board, it is characterized in that it comprises the steps:
(1) from waste printed wiring board, separates nonmetal thing
With impactor, knife mill, rotary crusher, ball mill the waste printed circuit board plate is ground into particulate less than 1mm according to this, with low intensive magnetic separator separating ferrum magnetic substance, again by the metal except that ferromagnetic material in the breakdown products of electrostatic separation split circuit plate, residue is the nonmetal isolate of waste printed wiring board, and resin content is more than 50%;
(2) the nonmetal isolate purifying of waste printed wiring board
With mass concentration 43.53%～67.71% KI or NaI or ZnCl
2Or ZnBr
2Or NH
4NO
3The nonmetal isolate of the aqueous solution and waste printed wiring board compares uniform mixing by the quality of 1:0.2～1, centrifugal 10～20 minutes with 5000 rev/mins of centrifuge separators, separation resin, glass fibre and residual metal, separated resin is with 100 ℃ deionized water wash 2～3 times, and 100 ℃ of dryings are 1～2 hour in loft drier;
(3) resin destructive distillation
Resin is placed vacuum oven, and 200～600 ℃ of constant temperature destructive distillation 0.5～4.5 hour naturally cool to room temperature, obtain the destructive distillation product;
(4) pulverize
With ball mill the destructive distillation product is crushed to the fine powder that particle diameter is 5～15 μ m;
(5) moulding
The interpolation softening temperature is 75 ℃ a coal-tar middle oil in the destructive distillation product powder, the mass ratio of destructive distillation product powder and coal-tar middle oil is 100:25～45, mediate repeatedly for 60～90 ℃, be squeezed into the cylindrical particle that diameter is 2.5mm, place in the loft drier in 80 ℃ of dryings 6 hours with screw extruder;
(6) carbonization
With the above-mentioned forming composition carbide furnace of packing into, at N
2Be warming up to 650～950 ℃ of carbonizations 0.5～3.5 hour under the protection, naturally cool to room temperature, make carbide;
(7) weak activation
The carbide of step (6) preparation is packed in the activation furnace, in 650～950 ℃, the water vapor of 0.08～0.20MPa, activate 0.5～2.5 hour;
(8) vapour deposition
Nitrogen is carried industrial propylene enter the carbon laydown device, carry out the gas-phase carbon deposition process, be prepared into carbonaceous molecular sieve, the carbon laydown temperature is 650～950 ℃, and depositing time is 0.5～3.5 hour, and nitrogen flow rate is 20～100ml/min;
Above-mentioned carbon laydown device is to add a container that industrial propylene is housed before activation furnace.
2, described according to claim 1 is the method for feedstock production carbonaceous molecular sieve with the waste printed wiring board, it is characterized in that: in the nonmetal isolate purifying process step (2) of said waste printed wiring board, and KI or NaI or ZnCl
2Or ZnBr
2Or NH
4NO
3The mass concentration of the aqueous solution is 50.1%～57.1%, KI or NaI or ZnCl
2Or ZnBr
2Or NH
4NO
3The mass ratio of the aqueous solution and activator is 1:0.4～0.7; In resin destructive distillation processing step (3), pyrolysis temperature is that 300～500 ℃, destructive distillation time are 2.5～3.5 hours; In disintegrating process step (4), destructive distillation product powder particle diameter is 8～12 μ m; In moulding process step (5), the destructive distillation product is that mix 100:30～40 with the mass ratio of coal-tar middle oil, and mixing temperature is 70～80 ℃; In carbonization technique step (6), carbonization temperature is 750～850 ℃, carbonization 1.5～2.5 hours; In weak activating process step (7), activation temperature is 750～850 ℃, 1.0～2.0 hours, and water vapor pressure is 0.12～0.16MPa; In gas-phase deposition step (8), the carbon laydown temperature is that 750～850 ℃, depositing time are 1.5～2.5 hours, carrier gas N
2Flow velocity is 50～70ml/min.
3, described according to claim 1 is the method for feedstock production carbonaceous molecular sieve with the waste printed wiring board, it is characterized in that: in the nonmetal isolate purifying process step (2) of said waste printed wiring board, and KI or NaI or ZnCl
2Or ZnBr
2Or NH
4NO
3The mass concentration of the aqueous solution is 53.5%, KI or NaI or ZnCl
2Or ZnBr
2Or NH
4NO
3The aqueous solution and mass ratio activator are 1:0.55; In resin destructive distillation processing step (3), pyrolysis temperature is 400 ℃, destructive distillation 2.5 hours; In disintegrating process step (4), powder particle diameter is 9 μ m; In moulding process step (5), the destructive distillation product is that 100:35 mixes with the mass ratio of coal-tar middle oil, and mixing temperature is 75 ℃; In carbonization technique step (6), carbonization temperature is 800 ℃, carbonization 2.0 hours; In weak activating process step (7), activation temperature is 800 ℃, activates 1.5 hours, and water vapor pressure is 0.14MPa; In gas-phase deposition step (8), the carbon laydown temperature is 800 ℃, deposits 2.0 hours, and the carrier gas nitrogen flow velocity is 60ml/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102325021A CN101428790B (en) | 2008-12-01 | 2008-12-01 | Method for producing carbon molecular sieve with waste printed circuit board as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102325021A CN101428790B (en) | 2008-12-01 | 2008-12-01 | Method for producing carbon molecular sieve with waste printed circuit board as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101428790A true CN101428790A (en) | 2009-05-13 |
| CN101428790B CN101428790B (en) | 2011-05-04 |
Family
ID=40644471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102325021A Expired - Fee Related CN101428790B (en) | 2008-12-01 | 2008-12-01 | Method for producing carbon molecular sieve with waste printed circuit board as raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101428790B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105060275A (en) * | 2015-08-13 | 2015-11-18 | 湖州新奥利吸附材料有限公司 | Preparation method of phenolic resin based carbon molecular sieve |
| CN105460933A (en) * | 2015-12-29 | 2016-04-06 | 东莞市青麦田数码科技有限公司 | Preparation method of carbon molecular sieve |
| CN110983031A (en) * | 2019-11-22 | 2020-04-10 | 江西省科学院 | Comprehensive separation and recovery method for electronic waste |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293648B (en) * | 2008-06-06 | 2011-11-16 | 朱海良 | Technique for preparing carbon molecular sieve |
-
2008
- 2008-12-01 CN CN2008102325021A patent/CN101428790B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105060275A (en) * | 2015-08-13 | 2015-11-18 | 湖州新奥利吸附材料有限公司 | Preparation method of phenolic resin based carbon molecular sieve |
| CN105460933A (en) * | 2015-12-29 | 2016-04-06 | 东莞市青麦田数码科技有限公司 | Preparation method of carbon molecular sieve |
| CN105460933B (en) * | 2015-12-29 | 2018-03-23 | 东莞市广信知识产权服务有限公司 | A kind of preparation method of carbon molecular sieve |
| CN110983031A (en) * | 2019-11-22 | 2020-04-10 | 江西省科学院 | Comprehensive separation and recovery method for electronic waste |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101428790B (en) | 2011-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Trazzi et al. | Adsorption and desorption of phosphate on biochars | |
| Santos-Clotas et al. | Sewage biogas efficient purification by means of lignocellulosic waste-based activated carbons | |
| Brown et al. | Production and characterization of synthetic wood chars for use as surrogates for natural sorbents | |
| Sukiran et al. | Production and characterization of bio-char from the pyrolysis of empty fruit bunches | |
| Tsai et al. | A low cost adsorbent from agricultural waste corn cob by zinc chloride activation | |
| US8840817B2 (en) | Preparation method for asphalt-based spherical activated carbon which requires no infusibilization process | |
| Veksha et al. | Pyrolysis of wood to biochar: Increasing yield while maintaining microporosity | |
| CN102674343B (en) | Production method for activated carbon | |
| CN101653721A (en) | Preparation method of coal-based granular activated carbon with molecular sieving effect and application thereof in pressure-transformation adsorption and separation concentrated gas | |
| CN101428790B (en) | Method for producing carbon molecular sieve with waste printed circuit board as raw material | |
| CN101428797B (en) | Method for producing super absorbent charcoal with waste printed circuit board as raw material | |
| Xiang et al. | Study on the Cd (II) adsorption of biochar based carbon fertilizer | |
| CN102417174B (en) | Porous carbon material and its preparation method | |
| Ren et al. | Sintering flue gas desulfurization with different carbon materials modified by microwave irradiation | |
| Cuthbertson | The production of pyrolytic biochar for addition in value-added composite material | |
| CN108689406A (en) | A kind of preparation method of water purification activated carbon | |
| Yasin et al. | Production of activated carbon from bio-waste materials by chemical activation method | |
| Djeridi et al. | Effect of the both texture and electrical properties of activated carbon on the CO2 adsorption capacity | |
| CN113668245B (en) | Preparation method and application of polystyrene-hydroxylated multi-walled carbon nanotube-polypyrrole composite nanofiber | |
| Fang et al. | Effects of free iron oxyhydrates and soil organic matter on copper sorption-desorption behavior by size fractions of aggregates from two paddy soils | |
| Chemerys et al. | Influence of intrinsic properties of lignocellulosic feedstock on adsorptive properties of biochar | |
| Tsui et al. | The potential applications of using compost chars for removing the hydrophobic herbicide atrazine from solution | |
| Wood et al. | Biochars at the molecular level. Part 1--Insights into the molecular structures within biochars | |
| CN106693895B (en) | A kind of technique using low-quality charcoal processing lignite upgrading waste water | |
| Ubaydullayeva et al. | Studying the sorption properties of adsorbents obtained on the basis of plant waste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110504 Termination date: 20131201 |