CN112194131A - Method for preparing papermaking sludge carbonaceous adsorbent by chemical activation method and application - Google Patents
Method for preparing papermaking sludge carbonaceous adsorbent by chemical activation method and application Download PDFInfo
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- 239000010802 sludge Substances 0.000 title claims abstract description 116
- 239000003463 adsorbent Substances 0.000 title claims abstract description 91
- 230000004913 activation Effects 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000000126 substance Substances 0.000 title claims abstract description 23
- 238000001179 sorption measurement Methods 0.000 claims abstract description 62
- 239000002245 particle Substances 0.000 claims abstract description 43
- 238000005406 washing Methods 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001994 activation Methods 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 33
- 238000000197 pyrolysis Methods 0.000 claims abstract description 22
- 238000000227 grinding Methods 0.000 claims abstract description 21
- 238000007873 sieving Methods 0.000 claims abstract description 21
- 238000002791 soaking Methods 0.000 claims abstract description 21
- 238000003763 carbonization Methods 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 230000003213 activating effect Effects 0.000 claims abstract description 12
- 230000007935 neutral effect Effects 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- AXDJCCTWPBKUKL-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]aniline;hydron;chloride Chemical compound Cl.C1=CC(=N)C(C)=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 AXDJCCTWPBKUKL-UHFFFAOYSA-N 0.000 claims description 18
- 239000011592 zinc chloride Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 3
- 102000018779 Replication Protein C Human genes 0.000 claims description 2
- 108010027647 Replication Protein C Proteins 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 21
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000010000 carbonizing Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 34
- 238000002156 mixing Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 15
- 239000012190 activator Substances 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000004927 clay Substances 0.000 description 6
- 238000000643 oven drying Methods 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 238000013329 compounding Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005285 chemical preparation method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
- C01B32/378—Purification
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
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Abstract
The invention belongs to the technical field of sewage treatment, and particularly discloses a paper mill sludge carbon adsorbent, which is prepared by taking residual activated sludge of a paper mill as a raw material and adopting a chemical activation method, and the paper mill sludge is concentrated, squeezed, dried, ground and sieved to obtain sludge particles; adding an activating agent into the papermaking sludge particles, soaking and drying; putting the mixture into a muffle furnace, and carbonizing and pyrolyzing the mixture; and (3) carrying out acid washing or alkali washing on the sludge particles subjected to carbonization and pyrolysis, washing the sludge particles to be neutral, drying, crushing, grinding and sieving to obtain the papermaking sludge carbonaceous adsorbent. When ZnCl is present2/KOH1/1, the solid-liquid ratio is 1g/4ml, the pyrolysis temperature is 550 ℃, the washing mode is 80 ℃ alkali washing, the adsorption value is 164.04mg/g, and the yield is 52.38%; the cost performance is highest when the adding amount of the sludge carbon-containing adsorbent is 0.2502 g/L. The invention explores a new way for the diversification of the resource utilization of the sludge, realizes the continuous utilization of the sludge resource and has important significance for the sustainable improvement of the urban environment.
Description
Technical Field
The invention relates to the technical field of activating agents and wastewater treatment, and particularly relates to a papermaking sludge carbonaceous adsorbent and a preparation method and application thereof.
Background
The activated carbon is microcrystalline carbon with a special structure, has a large number of pores and a large specific surface area, and has strong selective adsorption capacity. In recent years, the demand for activated carbon has increased dramatically and the cost has increased, so the search for producing activated carbon with low price by using carbonaceous materials such as agricultural and forestry waste, pulp waste, liquid waste and organic waste has been more and more emphasized. Since the 70 s of the 20 th century, reports and researches on using activated sludge as a raw material of activated carbon have appeared at home and abroad. At present, the preparation methods of the sludge carbon adsorbent at home and abroad are mainly divided into four types: carbonization, physical activation, chemical activation, and physicochemical activation. Although the preparation process of the carbonization method is simple, convenient and quick, the prepared carbonized product has uneven pores, unsatisfactory adsorption effect and poor quality because the step of activation is not carried out; the physical activation method requires high temperature and large energy consumption, the carbon loss in the raw materials is large, and the prepared activated carbon has poor adsorption performance; although the activated carbon prepared by the physical and chemical activation method has good adsorption performance, the physical and chemical activation method has strict requirements on production equipment and is difficult to operate.
Disclosure of Invention
The invention aims to overcome the problems, and selects a chemical preparation method which has relatively good effect, but has the greatest advantages that the conditions of an activating agent and an activating process are easy to control, and the preparation process is mature. A new way is explored for the diversification of the resource utilization of the sludge, and the way problem of the sludge is promoted and solved to a certain extent, so that the continuous utilization of the sludge resource is realized, and the method has important significance for the sustainable improvement of the urban environment.
The technical scheme adopted for realizing the purpose of the invention is as follows: a chemical activation method for preparing a papermaking sludge carbonaceous adsorbent comprises the following steps:
(1) concentrating, squeezing and drying the paper making sludge until the water content is 5%, and grinding and sieving by a 200-mesh sieve to obtain sludge particles;
(2) adding an activating agent into the papermaking sludge particles, soaking for 0.5-3h at the soaking temperature of 10-35 ℃, and drying;
(3) putting the treated sludge particles into a muffle furnace, and performing carbonization and pyrolysis;
(4) and (3) carrying out acid washing or alkali washing on the sludge particles after carbonization and pyrolysis, washing with water to be neutral, drying, crushing and grinding, and sieving with a 200-mesh sieve to obtain the papermaking sludge carbonaceous adsorbent.
In the step 2), the activating agent is KOH or ZnCl2A mixture of (a).
In the step 2), the KOH/ZnCl is added according to the mass ratio2＝1/1。
In the step 2), the carbon adsorbent of the papermaking sludge is prepared by a chemical activation method, wherein in the step, the carbon adsorbent of the papermaking sludge is prepared by the following steps of: activator 1 g: 4ml, and the concentration of the activating agent is 5-10 mol/L.
The preparation of the papermaking sludge carbonaceous adsorbent by the chemical activation method comprises the following steps of 3), wherein the temperature of carbonization and pyrolysis is 450-700 ℃ and the time of carbonization and pyrolysis is 50 min.
In the step 3) of preparing the carbonaceous adsorbent from the papermaking sludge by the chemical activation method, the pyrolysis temperature is 550 ℃.
In the step 4) of preparing the papermaking sludge carbonaceous adsorbent by the chemical activation method, the washing temperature is 20-90 ℃, and the time of acid washing or alkali washing is 10 min.
The application of the carbonaceous adsorbent for papermaking sludge prepared by the chemical activation method in treating the sludge carbon of the papermaking wastewater.
The application and the method are as follows: adding the paper sludge carbonaceous adsorbent into a fuchsin solution, standing for adsorption, and allowing adsorption for 30 min.
For the above application, the concentration of the fuchsin solution was 5%.
The invention has the beneficial effects that:
(1) the sludge carbon adsorbent prepared by the chemical method has strong adsorption capacity, and the activated carbon prepared by activating the sludge in the paper mill has larger proportion of micropores, mainly has a micropore structure and relatively larger specific surface areaLarge specific surface area of 476m3The average pore diameter is small, the diffusion time is short during liquid phase adsorption, organic matters can be adsorbed, and the performance is superior to that of common granular activated carbon;
(2) the sludge carbonaceous adsorbent prepared by the chemical method is suitable for adsorbing macromolecular organic matters, and can better treat papermaking sludge wastewater;
(3) the capacity of the sludge carbon adsorbent prepared by the chemical method is superior to that of commercial activated carbon;
drawings
FIG. 1 is a graph showing the effect of immersion temperature on product yield and magenta adsorption number in the examples.
FIG. 2 is a graph showing the effect of immersion time on product yield and magenta adsorption number in the examples.
FIG. 3 is a graph showing the effect of solid-liquid ratio on product yield and magenta adsorption number in examples.
FIG. 4 is a graph of the effect of activator formulation on product yield and magenta adsorption value in the examples.
FIG. 5 is a graph showing the effect of activation temperature on product yield and magenta adsorption number in the examples.
FIG. 6 is a graph showing the effect of washing temperature on product yield and magenta adsorption number in the examples.
FIG. 7 shows the effect of washing on product yield and magenta adsorption number in the examples.
Detailed Description
Example 1 paper sludge carbonaceous sorbent
(1) Concentrating, squeezing and drying the paper making sludge until the water content is 5%, grinding and sieving by a 200-mesh sieve to obtain sludge particles.
(2) 2 parts of ZnCl with the mass concentration of 5mol/L according to the solid-to-liquid ratio2Mixing the solution with 2 parts of KOH solution with the mass concentration of 5mol/L, uniformly mixing, adding 1 part of papermaking sludge particles, soaking for 1 hour at the soaking temperature of 20 ℃, and drying;
(3) putting the treated sludge particles into a muffle furnace, heating to 550 ℃, and performing carbonization and pyrolysis for 50 min;
(4) and heating a KOH solution containing the product with the concentration of 2mol/L in a water bath at 80 ℃ for 10min, washing the KOH solution to be neutral, drying, crushing and grinding the KOH solution, and sieving the KOH solution with a 200-mesh sieve to obtain the papermaking sludge carbonaceous adsorbent.
Example 2 Effect of impregnation temperature on product yield and Clay adsorbent Pair adsorption number
1. Paper sludge carbon adsorbent obtained at different impregnation temperatures
(1) Concentrating, squeezing and drying the paper making sludge until the water content is 5%, grinding and sieving by a 200-mesh sieve to obtain sludge particles.
(2) 2 parts of ZnCl with the mass concentration of 5mol/L according to the solid-to-liquid ratio2Mixing the solution with 2 parts of KOH solution with the mass concentration of 5mol/L, uniformly mixing, adding 1 part of papermaking sludge particles, soaking for 1 hour at the soaking temperature of 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃ and 35 ℃, and drying;
(3) putting the treated sludge particles into a muffle furnace, heating to 550 ℃, and performing carbonization and pyrolysis for 50 min;
(4) and heating a KOH solution containing the product with the concentration of 2mol/L in a water bath at 80 ℃ for 10min, washing the KOH solution to be neutral, drying, crushing and grinding the KOH solution, and sieving the KOH solution with a 200-mesh sieve to obtain the papermaking sludge carbonaceous adsorbent.
2. Influence of impregnation temperature on adsorption effect of argillaceous adsorbent
The product yield was calculated and the results are shown in figure 1. The product yield is equal to m/m0*100％
Wherein m is0: raw sludge particle weight; m: the weight of the argillaceous adsorbent.
Respectively putting 1g of papermaking sludge carbonaceous adsorbent with different impregnation temperatures into 100mL of 5% fuchsin solution, adsorbing for 30min, filtering, drying, weighing, and calculating the fuchsin adsorption value. The results are shown in FIG. 1.
Magenta adsorption number ═ m-m0)/m0
Wherein m is0: the weight of the original argillaceous adsorbent; m: the weight of the existing argillaceous adsorbent.
Activation time 1.0h, ZnCl2The concentration is 5mol/L, the KOH concentration is 5mol/L, ZnCl2The KOH is 1/1, adsorption time is 30min, and the effect of the impregnation temperature is shown in FIG. 1. Overall product yieldAnd the adsorption effect of the argillaceous adsorbent, and the optimal impregnation temperature is 20 ℃.
Example 3 Effect of immersion time on the Red adsorption value of a Clay adsorbent
1. Paper sludge carbon adsorbent obtained in different immersion time
(1) Concentrating, squeezing and drying the paper making sludge until the water content is 5%, grinding and sieving by a 200-mesh sieve to obtain sludge particles.
(2) 2 parts of ZnCl with the mass concentration of 5mol/L according to the solid-to-liquid ratio2Mixing the solution with 2 parts of KOH solution with the mass concentration of 5mol/L, adding 1 part of papermaking sludge particles for soaking for 0.5h, 1h, 1.5h, 2h and 3h respectively after uniform mixing, and drying at the soaking temperature of 20 ℃;
(3) putting the treated sludge particles into a muffle furnace, heating to 550 ℃, and performing carbonization and pyrolysis for 50 min;
(4) and heating a KOH solution containing the product with the concentration of 2mol/L in a water bath at 80 ℃ for 10min, washing the KOH solution to be neutral, drying, crushing and grinding the KOH solution, and sieving the KOH solution with a 200-mesh sieve to obtain the papermaking sludge carbonaceous adsorbent.
2. Influence of impregnation time on adsorption effect of argillaceous adsorbent
The product yield was calculated and the results are shown in figure 2. The product yield is equal to m/m0*100％
Wherein m is0: raw sludge particle weight; m: the weight of the argillaceous adsorbent.
The adsorption method comprises measuring 100ml of 5% fuchsin solution, adding 1g of argillaceous adsorbent, standing for 30min, filtering, oven drying, weighing, and calculating fuchsin adsorption value.
Magenta adsorption number ═ m-m0)/m0
Wherein m is0: the weight of the original argillaceous adsorbent; m: the weight of the existing argillaceous adsorbent.
The solid-liquid ratio is 1g/4ml, the dipping temperature is 20 ℃, and ZnCl is added2The concentration is 5mol/L, the KOH concentration is 5mol/L, ZnCl2The effect of immersion time under adsorption conditions of 30 min/KOH 1/1 is shown in FIG. 2. The product yield and the adsorption effect of the argillaceous adsorbent are integrated, and the optimal impregnation is realizedThe time is 1 h.
Example 4 influence of solid-liquid ratio of sludge activator on red adsorption value of argillaceous adsorbent
1. Papermaking sludge carbon adsorbent obtained by different solid-to-liquid ratios of sludge activators
(1) Concentrating, squeezing and drying the paper making sludge until the water content is 5%, grinding and sieving by a 200-mesh sieve to obtain sludge particles.
(2) 1 part of ZnCl with the mass concentration of 5mol/L according to the solid-to-liquid ratio2Mixing the solution with 1 part of KOH solution with the mass concentration of 5mol/L, respectively adding 2 parts, 1 part, 0.8 part, 0.5 part and 0.4 part of papermaking sludge particles after uniformly mixing, soaking for 1h at the soaking temperature of 20 ℃, and drying;
(3) putting the treated sludge particles into a muffle furnace, heating to 550 ℃, and performing carbonization and pyrolysis for 50 min;
(4) and heating a KOH solution containing the product with the concentration of 2mol/L in a water bath at 80 ℃ for 10min, washing the KOH solution to be neutral, drying, crushing and grinding the KOH solution, and sieving the KOH solution with a 200-mesh sieve to obtain the papermaking sludge carbonaceous adsorbent.
2. Influence of solid-liquid ratio of different sludge activators on adsorption effect of argillaceous adsorbent
The product yield was calculated and the results are shown in figure 3. The product yield is equal to m/m0*100％
Wherein m is0: raw sludge particle weight; m: the weight of the argillaceous adsorbent.
The adsorption method comprises measuring 100ml of 5% fuchsin solution, adding 1g of argillaceous adsorbent with different solid-to-liquid ratios, standing for adsorption for 30min, filtering, oven drying, weighing, and calculating fuchsin adsorption value.
Magenta adsorption number ═ m-m0)m0
Wherein m is0: the weight of the original argillaceous adsorbent; m: the weight of the existing argillaceous adsorbent.
Activating for 1.0h at the dipping temperature of 20 ℃, ZnCl2The concentration is 5mol/L, the KOH concentration is 5mol/L, ZnCl2The solid-liquid ratio of the sludge activator is influenced by 3/1 of KOH under the condition of adsorbing for 30min as shown in figure 3. The optimal solid-liquid ratio is 1g/4ml (0.25)g/ml)。
Example 5 Effect of activator compounding ratio on Clay adsorbent Red adsorption value
1. Papermaking sludge carbon adsorbent prepared by different activator compound ratios
(1) Concentrating, squeezing and drying the paper making sludge until the water content is 5%, grinding and sieving by a 200-mesh sieve to obtain sludge particles.
(2) ZnCl with the mass concentration of 5mol/L is added according to the solid-to-liquid ratio2Mixing the solution with 5mol/L KOH solution according to the mixing proportion of 3/1, 2/1, 1/1, 1/2 and 1/3 respectively, adding 1 part of papermaking sludge particles after uniformly mixing, soaking for 1h at the soaking temperature of 20 ℃, and drying;
(3) putting the treated sludge particles into a muffle furnace, heating to 550 ℃, and performing carbonization and pyrolysis for 50 min;
(4) and heating a KOH solution containing the product with the concentration of 2mol/L in a water bath at 80 ℃ for 10min, washing the KOH solution to be neutral, drying, crushing and grinding the KOH solution, and sieving the KOH solution with a 200-mesh sieve to obtain the papermaking sludge carbonaceous adsorbent.
2. Influence of different activator compounding ratios on adsorption effect of argillaceous adsorbent
The product yield was calculated and the results are shown in figure 4. The product yield is equal to m/m0*100％
Wherein m is0: raw sludge particle weight; m: the weight of the argillaceous adsorbent.
The adsorption method comprises measuring 100ml 5% fuchsin solution, adding 1g argillaceous adsorbent, standing for 30min, filtering, oven drying, weighing, and calculating fuchsin adsorption value.
Magenta adsorption number ═ m-m0)/m0
Wherein m is0: the weight of the original argillaceous adsorbent; m: the weight of the existing argillaceous adsorbent.
The solid-liquid ratio is 1/4, the dipping temperature is 20 ℃, the activation time is 1.0h, ZnCl2The effect of the compounding ratio of the activator under the conditions of 5mol/L concentration and 5mol/L KOH concentration and 30min adsorption is shown in FIG. 4. The optimal compound ratio is ZnCl by integrating the product yield and the adsorption effect of the argillaceous adsorbent2/KOH＝1/1。
EXAMPLE 6 Effect of activation temperature on Clay adsorbent product Red adsorption number
1. Paper sludge carbon adsorbent obtained at different activation temperatures
(1) Concentrating, squeezing and drying the paper making sludge until the water content is 5%, grinding and sieving by a 200-mesh sieve to obtain sludge particles.
(2) 2 parts of ZnCl with the mass concentration of 5mol/L according to the solid-to-liquid ratio2Mixing the solution with 2 parts of KOH solution with the mass concentration of 5mol/L, uniformly mixing, adding 1 part of papermaking sludge particles, soaking for 1 hour at the soaking temperature of 20 ℃, and drying;
(3) putting the treated sludge particles into a muffle furnace, respectively heating to 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, carbonizing and pyrolyzing for 50 min;
(4) and heating a KOH solution containing the product with the concentration of 2mol/L in a water bath at 80 ℃ for 10min, washing the KOH solution to be neutral, drying, crushing and grinding the KOH solution, and sieving the KOH solution with a 200-mesh sieve to obtain the papermaking sludge carbonaceous adsorbent.
2. Influence of different activation temperatures on the adsorption effect of the argillaceous adsorbent
The product yield was calculated and the results are shown in figure 5. The product yield is equal to m/m0*100％
Wherein m is0: raw sludge particle weight; m: the weight of the argillaceous adsorbent.
The adsorption method comprises measuring 100ml 5% fuchsin solution, adding 1g argillaceous adsorbent at different activation temperatures, standing for 30min, filtering, oven drying, weighing, and calculating fuchsin adsorption value.
Magenta adsorption number ═ m-m0)/m0
Wherein m is0: the weight of the original argillaceous adsorbent; m: the weight of the existing argillaceous adsorbent.
The solid-liquid ratio is 1/4, the dipping temperature is 20 ℃, the dipping time is 1.0h, ZnCl2The concentration is 5mol/L, the KOH concentration is 5mol/L, ZnCl2The effect of activation temperature under the conditions of 1/1 KOH/KOH is shown in FIG. 5. The product yield and the adsorption effect of the argillaceous adsorbent are integrated, and the optimal activation temperature is 550 ℃.
Example 7 Effect of washing temperature on the Red adsorption value of a Clay adsorbent
1. Paper sludge carbon adsorbent obtained at different washing temperatures
(1) Concentrating, squeezing and drying the paper making sludge until the water content is 5%, grinding and sieving by a 200-mesh sieve to obtain sludge particles.
(2) 2 parts of ZnCl with the mass concentration of 5mol/L according to the solid-to-liquid ratio2Mixing the solution with 2 parts of KOH solution with the mass concentration of 5mol/L, uniformly mixing, adding 1 part of papermaking sludge particles, soaking for 1 hour at the soaking temperature of 20 ℃, and drying;
(3) putting the treated sludge particles into a muffle furnace, heating to 550 ℃, and performing carbonization and pyrolysis for 50 min;
(4) and (3) heating a KOH solution containing the product with the concentration of 2mol/L in a water bath at the temperature of 20 ℃, 40 ℃, 60 ℃, 80 ℃ and 90 ℃ respectively, washing the KOH solution to be neutral, drying, crushing and grinding the KOH solution, and sieving the KOH solution with a 200-mesh sieve to obtain the papermaking sludge carbonaceous adsorbent.
2. Influence of different washing temperatures on the adsorption effect of the argillaceous adsorbent
The product yield was calculated and the results are shown in figure 6. The product yield is equal to m/m0*100％
Wherein m is0: raw sludge particle weight; m: the weight of the argillaceous adsorbent.
The adsorption method comprises measuring 100ml 5% fuchsin solution, adding 1g argillaceous adsorbent, standing for adsorption for 30min, filtering, oven drying, weighing, and calculating fuchsin adsorption value.
Magenta adsorption number ═ m-m0)/m0
Wherein m is0: the weight of the original argillaceous adsorbent; m: the weight of the existing argillaceous adsorbent.
The solid-liquid ratio is 1/4, the activation temperature is 20 ℃, the activation time is 1.0h, ZnCl2The concentration is 5mol/L, the KOH concentration is 5mol/L, ZnCl2The effect of the washing temperature at a KOH of 1/1 and a pyrolysis temperature of 550 ℃ is shown in FIG. 6. The product yield and the adsorption effect of the argillaceous adsorbent are integrated, and the optimal washing temperature is 80 ℃.
EXAMPLE 8 Effect of washing on the Red adsorption value of the Clay adsorbent
1. Paper sludge carbon adsorbent obtained by different washing modes
(1) Concentrating, squeezing and drying the paper making sludge until the water content is 5%, grinding and sieving by a 200-mesh sieve to obtain sludge particles.
(2) 2 parts of ZnCl with the mass concentration of 5mol/L according to the solid-to-liquid ratio2Mixing the solution with 2 parts of KOH solution with the mass concentration of 5mol/L, uniformly mixing, adding 1 part of papermaking sludge particles, soaking for 1 hour at the soaking temperature of 20 ℃, and drying;
(3) putting the treated sludge particles into a muffle furnace, heating to 550 ℃, and performing carbonization and pyrolysis for 50 min;
(4) and (3) carrying out acid washing (5mol/L HCl solution) or alkali washing (5mol/L KOH solution) on the sludge particles subjected to carbonization and pyrolysis, washing at the washing temperature of 20-90 ℃ to be neutral, drying, crushing and grinding, and sieving with a 200-mesh sieve to obtain the papermaking sludge carbonaceous adsorbent. .
2. Influence of different washing modes on adsorption effect of argillaceous adsorbent
The product yield is equal to m/m0*100％
The adsorption method comprises measuring 100ml 5% fuchsin solution, adding 1g of argillaceous adsorbent, standing for 30min, filtering, oven drying, weighing, and calculating fuchsin adsorption value.
Magenta adsorption number ═ m-m0)/m0
Wherein m is0: the weight of the original argillaceous adsorbent; m: the weight of the existing argillaceous adsorbent.
The solid-liquid ratio is 1/4, the activation temperature is 20 ℃, the activation time is 1.0h, ZnCl2The concentration is 5mol/L, the KOH concentration is 5mol/L, ZnCl2The effect of the washing pattern under the conditions of 1/1 for KOH, 550 ℃ for pyrolysis and 80 ℃ for washing is shown in FIG. 7. The product yield and the adsorption effect of the argillaceous adsorbent are integrated, and the alkaline washing mode is optimal.
Claims (10)
1. The preparation method of the papermaking sludge carbonaceous adsorbent by the chemical activation method is characterized by comprising the following steps:
(1) concentrating, squeezing and drying the paper making sludge until the water content is 5%, and grinding and sieving by a 200-mesh sieve to obtain sludge particles;
(2) adding an activating agent into the papermaking sludge particles, soaking for 0.5-3h at the soaking temperature of 10-35 ℃, and drying;
(3) putting the treated sludge particles into a muffle furnace, and performing carbonization and pyrolysis;
(4) and (3) carrying out acid washing or alkali washing on the sludge particles after carbonization and pyrolysis, washing with water to be neutral, drying, crushing and grinding, and sieving with a 200-mesh sieve to obtain the papermaking sludge carbonaceous adsorbent.
2. The chemical activation process for preparing paper sludge carbonaceous adsorbent according to claim 1, wherein in the step 2), the activating agent is KOH or ZnCl2A mixture of (a).
3. The chemical activation process for preparing paper sludge carbonaceous adsorbent according to claim 2, wherein in the step 2), the KOH/ZnCl is adopted according to the mass ratio2＝1/1。
4. The chemical activation method for preparing the paper sludge carbonaceous adsorbent according to claim 3, wherein in the step 2), the ratio of sludge: activator 1 g: 4ml, and the concentration of the activating agent is 5-10 mol/L.
5. The chemical activation method for preparing the paper sludge carbonaceous adsorbent according to claim 4, wherein the temperature of the carbonization pyrolysis in the step 3) is 450-700 ℃ and the time of the carbonization pyrolysis is 50 min.
6. The chemical activation process for preparing the paper sludge carbonaceous adsorbent according to claim 5, wherein in the step 3), the pyrolysis temperature is 550 ℃.
7. The chemical activation method for preparing the paper sludge carbonaceous adsorbent according to claim 6, wherein in the step 4), the washing temperature is 20-90 ℃, and the acid washing or alkali washing time is 10 min.
8. Use of the carbonaceous adsorbent for papermaking sludge prepared by the chemical activation method according to any one of claims 1 to 7 for treating sludge carbon in papermaking wastewater.
9. Use according to claim 8, characterized in that the method is as follows: adding the paper sludge carbonaceous adsorbent of any one of claims 1-7 into the fuchsin solution, standing for adsorption for 30 min.
10. The use of claim 9, wherein said fuchsin solution is at a concentration of 5%.
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