CN105905898B - A kind of preparation method of the coal base agglomerated activated carbon of high methylene blue number - Google Patents

Abstract

The invention discloses a kind of preparation method of the coal base agglomerated activated carbon of high methylene blue number, including：Coal blending is carried out for raw material using jet coal, gas rich coal and pitch and mixed with zinc chloride, crush to obtain feed coal；It by the feed coal compound stalk forming, is granulated, obtains coal particle；Oxidation processes, charing process are carried out to the coal particle, obtain carbonized material；The carbonized material is impregnated using liquor zinci chloridi, is dried after separation of solid and liquid, obtained dipping carbonized material is subjected to activation process, activated carbon is made.The present invention prepares activated carbon using a certain amount of jet coal, gas rich coal and pitch coal blending, the property of above-mentioned raw materials and mutual mating reaction are combined well, compared with traditional coal base agglomerated activated carbon, under the action of chlorination zinc compound additive, the methylene blue number of activated carbon product can be effectively promoted, solves the problems, such as that the methylenum careuleum adsorptivity of generally existing in the production of traditional coal base agglomerated activated carbon is poor.

Description

A kind of preparation method of the coal base agglomerated activated carbon of high methylene blue number

Technical field

The invention belongs to activated carbon preparation field, the preparation of the coal base agglomerated activated carbon of more particularly to a kind of high methylene blue number Method.

Background technology

Since activated carbon has highly developed pore structure and great specific surface area, application range is from for food Decoloration and taste removal, breathing mask with medicine develop to net for solvent refining and recycling, water depth processing, flue gas on a large scale Change, blood purification etc. propose the absorption property of activated carbon new, higher requirement.

Activated carbon can be divided into active carbon from coal, petroleum coke activated carbon, wood activated charcoal and shell activity according to raw material difference Charcoal etc., wherein, petroleum coke activated carbon, wood activated charcoal and active fruit shell carbon etc. are easily limited due to raw material sources, it is difficult to long-term Large-scale production, simultaneously as coal resources in China enriches, yield is big, from the horse's mouth, and the yield of active carbon from coal increases year by year Add, and its utilization scope is more and more wider.Dividing according to form, activated carbon includes pressed active carbon and powdered activated carbon, wherein Powdered activated carbon has larger adsorptivity (iodine number and/or methylene blue number) compared to pressed active carbon, but due to its powdery Form limits application field.

More than reason is based on, the production of coal base agglomerated activated carbon is increasingly taken seriously.With the development of society, water pollution Ingredient is also increasingly complicated, and macromolecular chemical industry organic pollution gradually increases.This requires activated carbon products in absorption tradition pollution On the basis of object, also chemical industry organic pollution can be adsorbed.The active carbon from coal micropore of common process production is flourishing, to traditional dirty Dye object adsorptivity is very strong, but adsorbs macromolecular chemical industry organic pollution or do not sent out then as the mesoporous that biological high-area carbon needs It reaches, it is relatively low to show as methylene blue number, it is impossible to full macromolecular chemical industry pollutant and charcoal carrier media, and traditional pass through increase Soak time obtains method to promote methylene blue number, reduces yield iodine sorption value and intensity.

CN1248962C discloses a kind of preparation method of agglomerated activated carbon, wherein, it will be by weakly caking coal, coking coal and coal tar pitch After the raw material of composition is mixed with alkali metal hydroxide, crushed, briquetting is granulated, through carbonizing and activated carbon is made in activation, however, whole Apparently, the methylene blue number and iodine number of activated carbon product are still relatively low for body, and also need to using highly basic, big to environment hidden danger.

Invention content

The purpose of the present invention is to provide a kind of preparation method of the coal base agglomerated activated carbon of high methylene blue number, to solve to pass The problem of methylenum careuleum adsorptivity is poor during coal base agglomerated activated carbon of uniting produces.

To achieve the above object, the present invention uses following technical scheme：

A kind of preparation method of the coal base agglomerated activated carbon of high methylene blue number, includes the following steps：

A, coal blending is carried out for raw material using jet coal, gas rich coal and pitch and mixed with zinc chloride, crush to obtain raw material Coal, wherein, with the total weight of the feed coal, the dosage of the jet coal is 65wt%-80wt%, and the dosage of gas rich coal is 15wt%-25wt%, the dosage of pitch is 3wt%-7wt%, and the dosage of zinc chloride is 2wt-5wt%；

B, by the feed coal compound stalk forming, granulation, coal particle is obtained；

C, oxidation processes, charing process are carried out to the coal particle, obtains carbonized material；

D, the carbonized material is impregnated using liquor zinci chloridi, is dried after separation of solid and liquid, obtained dipping carbonized material is carried out Activation process, activated carbon is made.

In the preparation process in accordance with the present invention, step a be using jet coal, gas rich coal and pitch be raw material carry out coal blending and with Zinc chloride mixing is crushed to obtain feed coal, and specific coal blending and crushing process are known in the art, can make a certain amount of length Flame coal, gas rich coal, pitch and zinc chloride are uniformly mixed and are crushed to smaller particle size, such as cross 170 mesh, 180 mesh or 200 Mesh sieves (Taylor standard sieve).The study found that when using above-mentioned raw materials and with aforementioned proportion coal blending, be conducive to be promoted last made The methylene blue number of the agglomerated activated carbon obtained, it is preferable that the dosage of jet coal is 70wt%-75wt% in the feed coal, such as 72wt%, the dosage of gas rich coal are 15wt%-20wt%, such as 18wt%.

The jet coal is young coal, used for this invention, as the basic material for realizing activated carbon basic performance, is ground Study carefully discovery, when the gas rich coal with the present invention is used cooperatively, the introducing of the jet coal is conducive to the life of activated carbon product hole Into convenient for follow-up reaming, so as to promote the methylene blue number of activated carbon product.Preferably, the volatile matter of the jet coal is not less than 37%, such as 40%, light transmittance is not less than 50, such as 55, and vitrinite's content is not less than 70%, preferably not less than 75%, such as 80% or 85% etc., to further improve the pore structure of activated carbon；For example, the jet coal can be selected from Toksun Black Hills coal Or Qitai Beishan Mountain raw coal.

Long bituminous coal is very young, and internal degree of coalification is low, and activity is high, subsequently easy reaming.But due to its degree of coalification Low, intensity is relatively low, and without caking property, intensity can be reduced further in carbonization process, therefore produced and led in conventional carbon Domain, few people are produced with long bituminous coal.The gas rich coal is the coal of strong cohesive property, and addition gas rich coal can not only add Using its caking property during work, the caking ability between pulverized coal particle is promoted, meanwhile, it is used cooperatively in the jet coal with the present invention When, the introducing of the gas rich coal also helps formation and the strength enhancing of follow-up charcoal skeleton, and due in follow-up carbonization process In can easily shrink, the introducing of the gas rich coal, which additionally aids, to be prevented from causing to be unfavorable for Initial Crack due to hypersystole Formation and influence the progress of subsequent activation reaming.Preferably, the caking index of the gas rich coal not less than 85, for example, 90 or 95 etc., cuticle thickness is not less than 25, for example, 27 or 30 etc., so as to also have while adhesion strength between pulverized coal particle Conducive to the absorption property for promoting activated carbon product；For example, the gas rich coal can be selected from Qitai Red Hill low-lying area coal or Citroen zx along logical coal.

In the present invention, it adds in pitch and then can guarantee that there is certain initial strength, such as the pitch in briquetting workshop section Can be coal tar asphalt, asphalt, DCL/Direct coal liquefaction pitch or High softening-point modified pitch etc.；Preferably, the pitch is soft Change point>105 DEG C, more preferably High softening-point modified pitch.In the present invention, the solid for 2-5wt% being added in the raw coal prepared Zinc chloride, since zinc chloride has the function of stronger dehydroxylation and dehydration, at a certain temperature, the zinc chloride of addition can be with Hydrogen and oxygen in raw material is made to be released in the form of water, and is conducive to make empty reaction from inside.

In a preferred embodiment of the present invention, feed coal is crushed to obtain having specified particle size distribution Coal dust, wherein, the average grain diameter of the feed coal after crushing is not less than 20 μm, wherein, coal dust content of the grain size no more than 80 μm is not Less than 90wt%；The coal dust content that grain size is 40 μm -80 μm is not less than 10wt%.The study found that when the coal dust is with above-mentioned When dynamics is distributed, the rational gradation composition of different-grain diameter coal dust can be realized in forming process, ensures have while shaping strength Good initial void distribution.Preferably, in the feed coal, coal dust content of the grain size no more than 80 μm is not less than 95wt%； Coal dust content of the grain size no more than 40 μm is not less than 70wt%；It is further preferred that the average grain diameter of the coal dust is 20 μm -40 μm, such as 30 μm；It is highly preferred that the grain size of the coal dust is not more than 200 μm, such as no more than 150 μm or no more than 100 μ m.It it will be appreciated by those skilled in the art that can be by the way that corresponding standard screen be selected to sieve the feed coal after crushing, so as to obtain To the coal dust with above-mentioned size distribution.

It should be noted that if above-mentioned anthracite and/or long flame pit ash are exceeded so that final activated carbon product When ash content is undesirable, those skilled in the art are readily apparent that before coal blending to above-mentioned anthracite and/or long flame pit ash It is controlled, such as the smokeless ash content is made to be less than 3% by processing such as washing delimings, certainly specific controlling extent is with most It is, for example, less than 10% subject to the ash content of whole activated carbon product can meet the requirements.This point is known in the art, here no longer It repeats.

In the present invention, step b is that compound stalk forming is carried out to above-mentioned raw materials coal, is granulated, to obtain coal particle.In coal base pressure In the preparation of block activated carbon, conventional process of the processing being granulated for this field is molded and crushed to coal dust, such as Pulverized coal forming is carried out using two pairs of rollers briquetting forming machine, is crushed for example, by using crusher, then screening obtains certain grain size model The coal particle enclosed, detailed process is known in the art, in one embodiment, the compound stalk forming pressure of the feed coal For 10-15t/cm；The granulation includes broken and screening, to obtain grain size between 1mm-10mm, more preferable 3mm-8mm Coal particle.Preferably, in step b, the heap of the briquetting coal obtained by compound stalk forming again than for 660g/L-720g/L, such as 670 or 700g/L, can by the way that briquetting pressure, temperature or the heap that preferably controls briquetting coal by the molding mode of returning charge is controlled to compare again, Described in returning charge molding mode be that partial briquetting briquetting coal after molding is broken for grain size no more than 3mm, preferably 0.5- 2.5mm, such as the coal particle of 1mm or 2mm, and the raw material coal quality 10wt%-30wt%, preferably 15wt%- will be accounted for The coal particle return of 25wt% is uniformly mixed with the feed coal, for compound stalk forming.The study found that above-mentioned coal particle with When after feed coal mixing for the compound stalk forming in step b, it can preferably become the core of briquetting coal skeleton in briquetting process The heart so as to which on the basis of briquetting coal intensity is ensured, the optimization collection for being further conducive to activated carbon internal particle is matched, keeps abundant Gap, be conducive to the entrance of subsequent activation agent.

In the present invention, step c is to carry out oxidation processes, charing process to the coal particle, obtains carbonized material；To being granulated Gained coal particle carries out oxidation processes, charing process is the common processing step in process for preparing active carbon, is art technology Known to personnel.In the present invention, the condition of the oxidation processes can be：At 200 DEG C -250 DEG C, such as 220-250 DEG C Under, oxidation processes 3-6 hour are carried out to material, oxygen content is 6-12vol% in oxidizing atmosphere, such as mixing with nitrogen and air Gas is closed as oxidant formation oxidizing atmosphere, so that the oxidation control of material in lighter degree, makes part oxygen be incorporated into coal, Accelerate priming reaction rate.

The condition of the charing process can be：600-650 DEG C of temperature, Carbonization Atmospheres oxygen content are no more than 5vol%, charcoal Change processing time 15min-40min, such as 20min or 30min, after charing, the charcoal atom combination in carbon compound can shape Into the carbon structure in some cracks, there is certain adsorption capacity, these cracks will form more flourishing in activation procedure Microcellular structure；Preferably, during charing, material is warming up to 600 DEG C from 250 DEG C with 8-10 DEG C/min heating rates.It is relatively traditional It the characteristics of carbonization reaction, the present invention preferably combines feed coal, is rapidly heated and carbonizes, be more advantageous to subsequent activation pore-creating, and Immersion solvent is facilitated to enter inside.

In the present invention, step d is to impregnate the carbonized material using liquor zinci chloridi, dries, will obtain after separation of solid and liquid Dipping carbonized material carry out activation process, be made activated carbon.In dipping process, liquor zinci chloridi can well into/ooze In the crack and/or the microcellular structures that enter carbon structure, further the activated positions of the zinc chloride in feed coal are formed and are supplemented, Effect is that solid phase mixing is difficult to realize, so as to follow-up fully activation.Preferably, the liquor zinci chloridi is a concentration of 10wt%-20wt%, dip time 1-2h.Carbonized material after dipping through separation of solid and liquid, wherein, remaining liquor zinci chloridi is also Next group carbonized material can be impregnated, utilization ratio is high.Carbonized material drying after separation, until the water content of carbonized material is not more than 8wt%, such as 3wt% or 5wt% (can be used for activation process) obtain dipping carbonized material.In the present invention, zinc chloride is impregnated It can be uniformly adhered on the inner wall of crack or micropore, there is no need to excess, certainly very few to be also unfavorable for fully activating.

Activation process is carried out to carbonized material as the common processing step in process for preparing active carbon, is those skilled in the art It is known.In the present invention, the condition of the activation process is preferably：Using vapor as activated media, in 700 DEG C -850 DEG C Under, such as 800 DEG C or 840 DEG C, carry out priming reaction, the reaction time is 5-7 hours, such as 5.5 or 6.5 hours；Preferably, will Dipping carbonized material to be not more than 20 DEG C/min, such as 10-15 DEG C/min heating rate be warming up to 700 DEG C -800 DEG C after, start It is passed through vapor to be activated, continues to heat up, and at 800-850 DEG C stablize and activate 5.5-6 hours.It lives with respect to traditional coal base Property charcoal activation, the characteristics of present invention preferably combines feed coal, suitably reduce activation temperature, improve activation effect, increase absorption Ability, while prevent excessive surface activation.

Compared with prior art, preparation method of the invention has the following advantages：

1st, the present invention prepares activated carbon using a certain amount of jet coal, gas rich coal and pitch coal blending, combines well The property of raw material and mutual mating reaction are stated, compared with traditional coal base agglomerated activated carbon, in chlorination zinc compound Under the action of additive, the methylene blue number of activated carbon product can be effectively promoted, solves the production of traditional coal base agglomerated activated carbon The problem of methylenum careuleum adsorptivity of middle generally existing is poor；Coal base agglomerated activated carbon produced by the invention, iodine number> During 1000mg/g, it is ensured that ensure that adsorptive value methylene blue number is more than 220mg/g while intensity and yield is not reduced.

2nd, the present invention matches and zinc chloride is introduced in material by raw material solid phase mixing and carbonized material dipping respectively, to carry Overactivity effect, particularly methylenum careuleum adsorptive value；In addition, the present invention is good for the environment without using strongly alkaline compound.

Specific embodiment

The present invention is described in detail with reference to embodiments, but the present invention is not limited to this.

The characterizing method of the relevant parameter of activated carbon is described as follows：

Iodine sorption value-be measured according to GB/T7702.3-2008；

Methylenum careuleum adsorptive value-be measured according to GB/T7702.6-2008；

Intensity-be measured according to GB/T7072.3-2008.

Remaining parameter is characterized using national standard or this field conventional characterization mode.

In following embodiment/comparative example, chemical reagent used is pure to analyze；

Example 1

The jet coal is Urumchi Black Hills coal mine raw coal, and gas rich coal is the accurate eastern Red Hill low-lying area gas rich coal in Xinjiang.

The High softening-point modified pitch that the pitch is produced for the precious sharp chemical industry in Hebei Handan, softening point is 113-118 DEG C.

In feed coal, jet coal content is 75wt%, gas rich coal content is 17wt%, bitumen content 5wt%, zinc chloride Content is 3wt%.Feed coal is crushed, is sized to the coal dust that average grain diameter is 29 μm, wherein, coal dust of the grain size more than 80 μm contains It measures as 2.5wt%；Coal dust content of the grain size more than 40 μm is 28wt%.

Compound stalk forming is carried out to feed coal using briquetting forming machine, briquetting pressure is about 13t/cm, by returning to material mode The coal particle return briquetting that the grain size that will be about feed coal weight 30% is 1mm-3mm, the material bulk density 690g/l suppressed, Intensity 92.8.

Obtained briquetting material sieves after primary breakup and secondary breakup, and qualified pellet carries out oxidation processes and charcoal successively Change processing activation process, wherein oxidation processes condition is：With the air and day of oxygen content 11% in electrical heating external-heat converter Tail gas mixed gas after right gas burning as oxidant at 230-250 DEG C to pellet into the oxidation processes of 3h during behavior；Charcoal Changing treatment conditions is：Material is warming up to 650 from 250 DEG C with 8-10 DEG C/min heating rates in electrical heating external-heat converter DEG C, heat preservation 15min carries out charing process, and oxygen concentration control is less than 5vol% in furnace atmosphere.

After obtained carbonized material impregnates 80min with 15% solder(ing)acid, (wherein water content is about for separation of solid and liquid, drying It for 4wt%, is then fed into activation furnace and activates, activation process condition is：Using vapor as activated media, with 10-15 DEG C/ After the heating rate of min is warming up to 700 DEG C, starts to be passed through vapor and activated, continue to heat up, it is living at 815 DEG C -825 DEG C Change 7 hours, obtain activated carbon product.The indices of manufactured activated carbon are as follows：Product iodine number 1087, intensity 97.11, heap ratio 442 are weighed, methylene blue number 272.

Embodiment 2

With embodiment 1 the difference lies in：The jet coal is Qitai Beishan Mountain raw coal, and gas rich coal is Citroen zx along logical coal mine Producing coal.In feed coal, jet coal content is 70wt%, gas rich coal content is 20%, bitumen content 5%, chlorination Zn content are 5%.The material bulk density 670g/l suppressed, intensity 93.3.

Charing process condition is：3h charing process is carried out to material with 530-550 DEG C in electrical heating external-heat converter.It is living Changing treatment conditions is：In activated media, i.e., in the presence of flowing steam of the flow velocity for 1.5 kilogram of steam/kilogram charing particle, make to turn Charing particle in stove activates 4.5 hours at 889-900 DEG C, obtains activated carbon product.The indices of manufactured activated carbon It is as follows：Product iodine number 1091, intensity 96.87, bulk density 457, methylene blue number 252.

Embodiment 3

With embodiment 1 the difference lies in：Before briquetting, the feed coal after crushing is sized to the coal that average grain diameter is 22 μm Powder, wherein, coal dust content of the grain size more than 80 μm is 2wt%；Coal dust content of the grain size more than 40 μm is 15wt%.It suppresses Material bulk density 700g/l, intensity 93.1.

The indices of manufactured activated carbon are as follows：Product iodine number 1096, intensity 96.32, bulk density 439, methylene blue number 276。

Embodiment 4

With embodiment 1 the difference lies in：After feed coal after crushing crosses 180 mesh sieve, briquetting is sent into as feed coal Compound stalk forming in machine.

The indices of manufactured activated carbon are as follows：Product iodine number 1082, intensity 96.11, bulk density 447, methylene blue number 249。

Comparative example 1

The difference lies in the content of zinc chloride is 8wt% in feed coal, and carbonized material no longer impregnates with embodiment 1 Liquor zinci chloridi.

The indices of manufactured activated carbon are as follows：Product iodine number 1079, intensity 96.7, bulk density 422, methylene blue number 223。

Comparative example 2

The difference lies in feed coal does not add zinc chloride, is impregnated using the liquor zinci chloridi of 40wt% with embodiment 2 Carbonized material 3 hours.

The indices of manufactured activated carbon are as follows：Product iodine number 1084, intensity 97.8, bulk density 452, methylene blue number 214。

Comparative example 3

With embodiment 1 difference lies in, the jet coal in feed coal is replaced with into the weakly caking coal from Hami Poly coal mine, Gas rich coal is replaced with into the coking coal from Dahuangshan Coal Mine.

The indices of manufactured activated carbon are as follows：Product iodine number 1065, intensity 97.6, bulk density 475, methylene blue number 246。

Claims (11)

1. a kind of preparation method of the coal base agglomerated activated carbon of high methylene blue number, includes the following steps：

A, coal blending is carried out for raw material using jet coal, gas rich coal and pitch and is mixed with zinc chloride, crush to obtain feed coal, In, with the total weight of the feed coal, the dosage of the jet coal is 65wt%-80wt%, and the dosage of gas rich coal is 15wt%-25wt%, the dosage of pitch is 3wt%-7wt%, and the dosage of zinc chloride is 2wt-5wt%；

B, by the feed coal compound stalk forming, granulation, coal particle is obtained；

C, oxidation processes, charing process are carried out to the coal particle, obtains carbonized material；

D, the carbonized material is impregnated using liquor zinci chloridi, is dried after separation of solid and liquid, obtained dipping carbonized material is activated Processing, activated carbon is made.

2. preparation method according to claim 1, which is characterized in that in step d, the liquor zinci chloridi it is a concentration of 10wt%-20wt%, dip time 1-2h.

3. preparation method according to claim 1, which is characterized in that in step a, the average grain diameter of the feed coal after crushing Not less than 20 μm, wherein, coal dust content of the grain size no more than 80 μm is not less than 90wt%；Grain size is that 40 μm -80 μm of coal dust contains Amount is not less than 10wt%.

4. preparation method according to claim 3, which is characterized in that in the coal dust obtained by step a, grain size is not more than 80 μm Coal dust content be not less than 95wt%；Coal dust content of the grain size no more than 40 μm is not less than 70wt%.

5. preparation method according to claim 1, which is characterized in that in step b, the heap of the briquetting coal obtained by compound stalk forming Again than for 660g/L-720g/L.

6. preparation method according to any one of claims 1-5, which is characterized in that the volatile matter of the jet coal is not small In 37%, light transmittance is not less than 50, and vitrinite's content is not less than 70%；The caking index of the gas rich coal is not less than 85, cutin Layer thickness is not less than 25；The pitch is selected from coal tar asphalt, asphalt, DCL/Direct coal liquefaction pitch and High softening-point modified pitch In one or more, softening point>105℃.

7. preparation method according to claim 6, which is characterized in that vitrinite's content of the jet coal is not less than 75%；The pitch is High softening-point modified pitch.

8. preparation method according to any one of claims 1-5, which is characterized in that the use of jet coal in the feed coal It measures as 70wt%-75wt%, the dosage of gas rich coal is 15wt%-20wt%.

9. preparation method according to any one of claims 1-5, which is characterized in that in step c, oxidation processes condition For：Oxidation processes are carried out 3-6 hours to material at 200 DEG C -250 DEG C, oxygen content is 6-12% in oxidizing atmosphere.

10. preparation method according to any one of claims 1-5, which is characterized in that in step c, charing process condition For：600-650 DEG C of temperature, Carbonization Atmospheres oxygen content are not more than 5vol%, charing process time 20min-40min.

11. preparation method according to any one of claims 1-5, which is characterized in that in step d, activation process condition For：Using vapor as activated media, priming reaction is carried out at 800 DEG C -850 DEG C, soak time is 5-7 hours.