CN110182804A - The preparation method of coal base vinyl acetate Carbon supports - Google Patents

The preparation method of coal base vinyl acetate Carbon supports Download PDF

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Publication number
CN110182804A
CN110182804A CN201910509599.4A CN201910509599A CN110182804A CN 110182804 A CN110182804 A CN 110182804A CN 201910509599 A CN201910509599 A CN 201910509599A CN 110182804 A CN110182804 A CN 110182804A
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coal
vinyl acetate
activation
carbon supports
base vinyl
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CN110182804B (en
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李静伟
霍焕儒
贺彬艳
冀有俊
杨钊
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China Energy Investment Corp Ltd
Shenhua Ningxia Coal Industry Group Co Ltd
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China Energy Investment Corp Ltd
Shenhua Ningxia Coal Industry Group Co Ltd
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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/02—Solids
    • B01J35/10—Solids characterised by their surface properties or porosity
    • B01J35/1004—Surface area
    • B01J35/1028—Surface area more than 1000 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/02—Solids
    • B01J35/10—Solids characterised by their surface properties or porosity
    • B01J35/1033—Pore volume
    • B01J35/1042—0.5-1.0 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/02—Solids
    • B01J35/10—Solids characterised by their surface properties or porosity
    • B01J35/1052—Pore diameter
    • B01J35/1061—2-50 nm
    • 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
    • C01B32/318—Preparation characterised by the starting materials
    • 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
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
    • 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
    • C01B32/336—Preparation characterised by gaseous activating agents
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds

Abstract

The present invention provides a kind of coal base vinyl acetate Carbon supports and preparation method.The raw material for preparing coal base vinyl acetate Carbon supports includes the substance of following parts by weight: anthracite 100, water 5-10, coal tar 30-40, coal tar pitch 4-10；Anthracite is the anchracite duff after milling, and partial size is 75 μm of D90 <, ash content < 3.5wt%, volatile matter < 9wt%；In coal tar, ash content < 0.5wt%, bitumen content 50-60wt%；In coal tar pitch, ash content < 1wt%, softening temperature is 95-120 DEG C.Preparation method is the following steps are included: kneading press strip, charing, primary activation, re-activation, washing and drying.The intensity of the coal base vinyl acetate Carbon supports is high, and the adsorbance of Dichlorodiphenyl Acetate zinc is high；The preparation method can be improved activation yield and properties of product.

Description

The preparation method of coal base vinyl acetate Carbon supports
Technical field
The invention belongs to field of material preparation, the especially preparation method of coal base vinyl acetate Carbon supports.
Background technique
The synthesis of China's vinyl acetate is mainly based on acetylene method.The method is to prepare acetylene by calcium carbide, and zinc acetate is born It is loaded on solid carrier charcoal, acetylene and acetic acid generate vinyl acetate under the catalytic action of zinc acetate.Active carbon has Gao Bibiao Area, electronic property are special, surface functional group is adjustable, can accommodate the features such as active metal and auxiliary agent, are by active carbon (AC) Carrier prepares all kinds of load type metal catalysts, can prepare multiple catalysts Carbon supports, in recent years answering in catalytic field With presentation growth trend.However, need to have low ash, high-specific surface area, high intensity, harmful metal ion few etc. for catalyst carrier charcoal Feature.Currently, industrially generalling use coconut husk, shell, sawdust etc. is that raw material produces solid carrier charcoal, technical maturity, but cost Higher, catalyst consumption is larger.And common coal active carbon is unable to satisfy to catalyst carrier charcoal aforementioned claim, and due to coal Activated carbon is difficult to activate relative to wood activated charcoal, and the charcoal wear-resistant strength and acetic acid adsorbance prepared are lower, use process Middle loss is larger.
Summary of the invention
The first purpose of this invention is to provide a kind of coal base vinyl acetate Carbon supports, the coal base vinyl acetate Carbon supports Intensity it is high, the adsorbance of Dichlorodiphenyl Acetate zinc is high；
Second object of the present invention is to provide a kind of preparation method of coal base vinyl acetate Carbon supports, the preparation method It can be improved activation yield and properties of product.
First purpose to realize the present invention, the following technical solution is employed:
A kind of coal base vinyl acetate Carbon supports, the raw material for preparing the coal base vinyl acetate Carbon supports includes following parts by weight Several substances:
The anthracite is the anchracite duff after milling, and partial size is 75 μm of D90 <, preferably 60 μm of D90 <, preferably D90 50 μm of <；Ash content < 3.5wt%, preferably ash content < 2.5wt%, preferably ash content < 2wt%, for example, for 1.8wt%, 1.5wt%, 1.2wt%, 1wt%, 0.8wt% or 0.6wt%；Volatile matter < 9wt%, preferably volatile matter < 8wt%, for example, for 7wt%, 6wt%, 5wt% or 4wt%；Preferably, in the anthracite, moisture < 5wt%；
In the coal tar, ash content < 0.5wt%, for example be 0.4wt%, 0.3wt%, 0.2wt%, 0.1wt%；Pitch Content is 50-60wt%, preferably 52-58wt%, for example is 53wt%, 54wt%, 55wt%, 56wt% or 57wt%；
In the coal tar pitch, ash content < 1wt%, for example be 0.8wt%, 0.6wt%, 0.4wt% or 0.2wt%；Softening Temperature is 95-120 DEG C, preferably 100-110 DEG C, such as 103 DEG C, 106 DEG C or 108 DEG C.
Coal base vinyl acetate Carbon supports of the invention, by adding coal tar and coal tar pitch in the feed, and by coal tar It is mixed according to a certain percentage with coal tar pitch with anthracite and water, to improve the mouldability of coal cream, and improves the molding of sketching charcoal Property and appearance, make its surface it is smooth, without crackle in length and breadth, without block material, not conglomeration；And bone can be generated after losing using coal tar pitch burning The characteristics of frame structure, improves the intensity of coal base vinyl acetate Carbon supports product；The adsorbance of Dichlorodiphenyl Acetate zinc is high.
Preferably, the anthracite is Taixi anthracite.
The ash content of Taixi anthracite is small, and volatile matter is also small, and the content of wherein trace meter is higher, especially silicon and aluminium Content is more, and wherein the total content of silica, alchlor and calcium oxide accounts for 70wt% or more, to facilitate after charing The skeleton structure with coordinate bond is generated, improves the quantity of active site, and the hole of 3-5nm compares in product obtained It is more, be conducive to the intensity and catalytic activity that improve obtained coal base vinyl acetate Carbon supports；And iron, manganese in Taixi anthracite Equal poisonous metals oxide content is low, can remove poisonous metal oxide therein by pickling.
Preferably, prepare the coal base vinyl acetate Carbon supports raw material further include parts by weight be 0.5-2 catalyst, Preferably 1-1.5, for example be 1.1,1.2,1.3,1.4,1.5；The catalyst is potassium carbonate class composite catalyst or sodium carbonate Class composite catalyst, preferably potassium carbonate class composite catalyst.
Sylvite or sodium salt facilitate the priming reaction of sketching charcoal.Especially sylvite, since it is with combustion-supporting effect, effect is more It is good.
Coal base vinyl acetate Carbon supports of the invention keep active principle therein equal by adding catalyst in the feed It is even to be distributed in inside material, increase its active site；Since priming reaction is catalyst mechanism from inside to outside, when activation, material Internal energy barrier reduces, and the difference of inside and outside activation environment reduces, and internal capillary mushrooms out in a relatively short period of time, makes entire work Change reaction time shortening, reduces external burn-off phenomenon, so that the micropore of final products is evenly distributed, absorption property significantly improves.Cause This can control the pore development in activation process, including hole life by adding catalyst in the feed in activation process Long speed and pore size improve pore structure, and then obtained coal base vinyl acetate Carbon supports is made to have more active sites Point, meanwhile, also make it have higher intensity.
Preferably, the catalyst is the catalyst fines after milling, and partial size is 75 μm of D90 <.
Preferably, the potassium carbonate class composite catalyst is the mixture of potassium carbonate and potassium hydroxide, and potassium carbonate and hydrogen The mass ratio of potassium oxide is 10:(1-5), preferably 10:(1.5-4), such as 10:2,10:2.5,10:3 or 10:3.5.
Preferably, the sodium carbonate class composite catalyst is the mixture of sodium carbonate and sodium hydroxide, and sodium carbonate and hydrogen The mass ratio of sodium oxide molybdena is 10:(1-5), preferably 10:(1.5-4), such as 10:2,10:2.5,10:3 or 10:3.5.
Preferably, prepare the coal base vinyl acetate Carbon supports raw material further include parts by weight be 3-5 bituminous coal, it is described Bituminous coal is the bituminous coal powder after milling, and partial size is 75 μm of D90 <, ash content < 6wt%, preferably ash content < 5wt%, such as 4wt%, 3wt%, 2.5wt%, 2wt%, 1.5wt%, 1.2wt%, 1wt%, 0.8wt% or 0.5wt%；Volatile matter < 28wt%, preferably volatile matter < 26wt%, for example be 23wt%, 22wt%.Bituminous coal is the coal of volatile matter > 20wt% a kind of, because Although this present invention merely defines its volatile matter < 28wt%, due to the characteristic of its own, volatile matter is in 20-28wt% Between.
Preferably, the bituminous coal is that meager lean coal, coking coal and 1/3 coking coal are any one or more of.
Preferably, the meager lean coal is weakly caking coal.
Preferably, the bituminous coal is the Mixture Density Networks of weakly caking coal and coking coal, and the mass ratio of weakly caking coal and coking coal is (0.5- 2): 1, such as 0.8:1,1:1,1.3:1,1.5:1 or 1.8:1.
Preferably, the meager lean coal is Lingwu coal, and the coking coal is 1/3 coking coal
In the present invention, partial size is 75 μm of D90 <, is referred to by mass, 75 μm of D90 <.Partial size is obtained by sieve method.
Second purpose to realize the present invention, the following technical solution is employed:
A kind of preparation method of foregoing coal base vinyl acetate Carbon supports, comprising the following steps:
(1) kneading press strip
The raw material is mixed according to corresponding parts by weight, and by mixed material kneading coal-forming cream, then By coal cream extrusion forming, sketching charcoal is obtained；
Usually in the middle kneading that carries out of kneading mixing plant (such as Double shaft stirring kneading machine) to obtain uniform coal cream, Extrusion forming is higher to obtain compactness on hydraulic forming machine or screw extruder；
(2) it carbonizes
Under anaerobic state, the sketching charcoal obtained to step (1) carries out heating charing, obtains carbonized material；
Charing is that lower-molecular substance is waved in the thermal decomposition and solidification and coal tar for carry out at low temperature coal and coal tar pitch Hair；Carbonization process can remove the volatile matter in sketching charcoal, and harden sketching charcoal, to increase its intensity, and form preliminary hole In favor of effective pore structure carried out and determine final products to a certain extent of subsequent activation process；
(3) it activates
The carbonized material that step (2) obtains once is activated, carries out secondary work again after then an activated material cools down Change, obtains re-activation material；
Activation is carried out in activation furnace, and when activation should also be passed through activator (such as vapor) to work into activation furnace The carbonized material changed in furnace carries out activation pore-creating；
Echelon activation is carried out using re-activation technique, activation yield and properties of product can be greatly improved；
(4) it washs and dry
The re-activation material that step (3) obtains successively is subjected to pickling, washing and drying, obtains final products；
Pickling can reduce ash content therein, wash away harmful metal ion therein, for example reduces copper ion therein and contain Amount and iron ion content.Acid washing method can be to be rinsed or impregnated with acid solution, preferably soak acid-cleaning, to re-activation material Pickling is more evenly.
Preferably, in the step (4), pickling be the re-activation material is placed in concentration be 5-15wt% (preferably 7-12wt%, for example be 9wt%, 10wt% or 11wt%) acid solution in impregnate 5-20h (preferably 8-15h, such as 10h Or 12h), the volume ratio of the acid solution and the re-activation material is (2-3): 1, such as 2.1:1,2.3:1,2.5:1, 2.7:1 or 2.9:1；Acid used is any one of sulfuric acid, nitric acid and hydrochloric acid, preferably hydrochloric acid.
Above-mentioned restriction is carried out to soak acid-cleaning, helps to be rinsed soak acid-cleaning to re-activation material, to sufficiently go Except harmful metal ion therein.
Washing can wash to rinse or impregnating, and preferably wash, in favor of taking off the metal ion not removed after wherein pickling It removes.
Preferably, in the step (4), washing is to be rinsed with water 1-5 times, rinses 3-10h, such as 5h or 7h every time.
Drying can be naturally dry or drying.
It will be understood by those skilled in the art that step (1) resulting sketching charcoal can be carbonized again after sunning solidification.
Preferably, in the step (1), kneading temperature be 70-90 DEG C, preferably 75-85 DEG C, for example, 78 DEG C, 80 DEG C or 82 DEG C of person；The kneading time is 8-20min, such as 12min or 16min, to obtain the coal that material is uniformly mixed, processability is good Cream.
Preferably, in the step (2), carbonization temperature be 650-750 DEG C, preferably 680-730 DEG C, for example, 690 DEG C, 700 DEG C, 710 DEG C or 720 DEG C, the volatilization of gained carbonized material is divided into 8-12wt% after charing；It is preferred that carbonization time is 25- 50min, further preferably 30-45min, such as 34min, 38min, 40min or 42min, to obtain intensity height and have There is the carbonized material of preliminary hole, so that subsequent activation step obtains preferable activated material；The intensity of gained carbonized material after charing Reach 95%.
Preferably, in the step (3), activation temperature is 900-950 DEG C, preferably 915-930 DEG C, such as 920 DEG C or 925 DEG C；Activation time is 10-25min, preferably 20-25min, such as 22min.
Preferably, in the step (3), carry out re-activation is sent to after an activated material is cooled to 30-100 DEG C, two Secondary activation temperature is 910-960 DEG C, preferably 940-960 DEG C, such as 940 DEG C, 945 DEG C or 950 DEG C；The re-activation time is 20-30min, preferably 20-25min, such as 21min.In the step (3), using re-activation technique, gained re-activation The loading density of material is 370~450g/mL.
The present invention also provides a kind of coal base vinyl acetate Carbon supports obtained using preparation method above-mentioned.
Coal base vinyl acetate Carbon supports of the invention and preparation method, have the advantages that
(1) coal base vinyl acetate Carbon supports of the invention, by adding coal tar and coal tar pitch in the feed, and by coal tar Oil and coal tar pitch mix according to a certain percentage with anthracite and water, to improve the mouldability of coal cream, and improve sketching charcoal at Type and appearance, make its surface it is smooth, without crackle in length and breadth, without block material, not conglomeration；And it can be generated after being lost using coal tar pitch burning The characteristics of skeleton structure, improves the intensity of coal base vinyl acetate Carbon supports product；The adsorbance of Dichlorodiphenyl Acetate zinc is high；
(2) by adding catalyst in the feed, so as to control the pore development in activation process, and then guaranteeing While obtained coal base vinyl acetate Carbon supports have preferably activity, it may have higher intensity；
(3) preparation method of the invention, the molding direct high temperature carbonization of sketching charcoal, without roasting hard and etc.；Using secondary work Chemical industry skill carries out echelon activation, can greatly improve activation yield and properties of product；Only need an acid cleaning process that can effectively wash away Harmful metal ion therein reduces harmful metal ion content therein, and obtained coal base vinyl acetate is effectively avoided to carry Catalyst poisoning occurs in use for body charcoal；
(4) using coal base vinyl acetate Carbon supports made from aforementioned preparation process, catalytic activity and intensity are high, Dichlorodiphenyl Acetate zinc Absorption property it is good, adsorbance is high；
(5) general coal base vinyl acetate Carbon supports, intensity are only capable of reaching 90wt%, coal base vinyl acetate of the invention Carbon supports, intensity can reach 95wt%.
Specific embodiment
Technical solution of the present invention and its effect are described further below by way of specific embodiment.Following embodiment party Formula is merely to illustrate the contents of the present invention, and invention is not limited in following embodiments or embodiment.Using design of the invention All within the scope of the claimed invention to the simple change of the invention carried out.
In following embodiment, raw materials used is that analysis is pure, is purchased from Tianjin Zhi Yuan chemical reagent Co., Ltd.Nothing used Bituminous coal is Taixi anthracite.
Embodiment 1
Taixi anthracite by ash content less than 3wt% is milled to 75 μm of D90 <, and Taixi anthracite, water, coal tar and coal drip Blueness uniform coal-forming cream of kneading in Double shaft stirring kneading machine by the weight ratio of 100:6:33:6, then squeezes on hydraulic forming machine At sketching charcoal；Sketching charcoal is carbonized into retort in 650 DEG C after sunning solidification；Gained carbonized material is sent into activation furnace, and is passed through High-temperature water vapor carries out primary activation 15min at 910 DEG C, obtains an activated material, an activated material is then cooled to 30 DEG C, it is then re-fed into activation furnace again, and be passed through high-temperature water vapor, re-activation, re-activation time is carried out at 950 DEG C For 25min, re-activation material is obtained；Gained re-activation material with concentration is 5wt%, volume is its 2.5 times hydrochloric acid (that is, two The volume ratio of secondary activated material and hydrochloric acid be 2.5:1) impregnate 5h, after be rinsed with water 2 times, rinse 5h every time, then drying, screening After obtain coal base vinyl acetate Carbon supports, be denoted as product A, the ash content of product A is 5.6wt%, and acetic acid adsorbance is 511mg/g, The adsorbance of zinc acetate is 5.15g/100ml, intensity 93wt%.
Embodiment 2
Compared with Example 1, only following difference:
Taixi anthracite, water, coal tar and coal tar pitch weight ratio be 100:6:33:10.
Its obtained coal base vinyl acetate Carbon supports, is denoted as product B, and the ash content of product B is 5.1wt%, acetic acid adsorbance For 535mg/g, the adsorbance of zinc acetate is 5.29g/100ml, intensity 95wt%.
Embodiment 3
Compared with Example 1, only following difference:
Activation time is 20min, and the re-activation time is 30min.
Its obtained coal base vinyl acetate Carbon supports, is denoted as products C, and the ash content of products C is 5.1wt%, acetic acid adsorbance For 548mg/g, the adsorbance of zinc acetate is 5.39g/100ml, intensity 94wt%.
Embodiment 4
Compared with Example 1, only following difference:
Raw material is Taixi anthracite, water, coal tar, coal tar pitch and catalyst, and Taixi anthracite, water, coal tar, coal drip Green and catalyst weight ratio is 100:6:33:10:1, and catalyst is the mixture of potassium carbonate and potassium hydroxide, wherein potassium carbonate Mass ratio with potassium hydroxide is 10:2.
Its obtained coal base vinyl acetate Carbon supports, is denoted as product D, and the ash content of product D is 5.1wt%, acetic acid adsorbance For 589mg/g, the adsorbance of zinc acetate is 5.78g/100ml, intensity 94wt%.
Embodiment 5
Compared with Example 4, only following difference:
Raw material is Taixi anthracite, water, coal tar, coal tar pitch, catalyst and coking coal, and Taixi anthracite, water, coal tar Oil, coal tar pitch, catalyst and coking coal weight ratio be 100:6:33:10:1:5.
Its obtained coal base vinyl acetate Carbon supports, is denoted as product E, and the ash content of product E is 5.3wt%, acetic acid adsorbance For 581mg/g, the adsorbance of zinc acetate is 5.84g/100ml, intensity 95wt%.
Embodiment 6
Compared with Example 5, only following difference:
Raw material be Taixi anthracite, water, coal tar, coal tar pitch, catalyst, Lingwu coal and coking coal, and Taixi anthracite, Water, coal tar, coal tar pitch, catalyst and Lingwu coal weight ratio be 100:6:33:10:1:2.5:2.5.
Its obtained coal base vinyl acetate Carbon supports, is denoted as product F, and the ash content of product F is 5.7wt%, acetic acid adsorbance For 587mg/g, the adsorbance of zinc acetate is 5.89g/100ml, intensity 96wt%.
Embodiment 7
Compared with Example 4, only following difference:
Taixi anthracite, water, coal tar, coal tar pitch and catalyst weight ratio be 100:6:33:10:2, catalyst is carbon The mixture of sour sodium and sodium hydroxide, wherein the mass ratio of sodium carbonate and sodium hydroxide is 10:5.
Its obtained coal base vinyl acetate Carbon supports, is denoted as product G, and the ash content of product G is 5.1wt%, acetic acid adsorbance For 562mg/g, the adsorbance of zinc acetate is 5.81g/100ml, intensity 95wt%.
Comparative example 1
Compared with Example 2, only following difference:
Activated material is without pickling.
Its obtained coal base vinyl acetate Carbon supports, is denoted as product H, and the ash content of product H is 11.8wt%, acetic acid adsorbance For 556mg/g, the adsorbance of zinc acetate is 4.95g/100ml, intensity 95wt%.
As a result compare
The comparison for the product F that the product B and comparative example 1 that embodiment 2 obtains are obtained is as shown in table 1.
The comparison of table 1 product B and product F
According to table 1 as can be seen that pickling can reduce the ash content of obtained coal base vinyl acetate Carbon supports product, increase Its external surface area and the hole 3-5nm hold ratio, increase the adsorptive value of its Dichlorodiphenyl Acetate zinc, improve its catalytic performance；Although pickling Afterwards in obtained coal base vinyl acetate Carbon supports product, heaping weight and intensity are slightly reduced, but can satisfy requirement, It does not influence to use.
Generally require activated carbon capillary diameter total not less than zinc acetate, acetic acid, acetylene and vinyl acetate molecule average diameter 1-2 times of sum, optimum aperture distribution beThat is 3-5nm, the aperture within the scope of this is more, right The absorption of zinc acetate etc. and De contamination are easier, and enabling it, it is recycled, and are more suitable for carrier use.And according to table The hole 3-5nm holds the numerical value of ratio (v%) it is found that after pickling in 1, and the hole 3-5nm holds ratio (v%) and increases, and is made after illustrating pickling Coal base vinyl acetate Carbon supports product it is more excellent.

Claims (10)

1. a kind of coal base vinyl acetate Carbon supports, which is characterized in that the raw material for preparing the coal base vinyl acetate Carbon supports includes The substance of following parts by weight:
The anthracite is the anchracite duff after milling, and partial size is 75 μm of D90 <, ash content < 3.5wt%, volatile matter < 9wt%；
In the coal tar, ash content < 0.5wt%, bitumen content 50-60wt%；
In the coal tar pitch, ash content < 1wt%, softening temperature is 95-120 DEG C.
2. coal base vinyl acetate Carbon supports according to claim 1, which is characterized in that prepare the coal base vinyl acetate and carry The raw material of body charcoal further includes the catalyst that parts by weight are 0.5-2, and the catalyst is potassium carbonate class composite catalyst or carbonic acid Sodium class composite catalyst；Preferably, the catalyst is the catalyst fines after milling, and partial size is 75 μm of D90 <.
3. coal base vinyl acetate Carbon supports according to claim 2, which is characterized in that the potassium carbonate class composite catalyst For the mixture of potassium carbonate and potassium hydroxide, and the mass ratio of potassium carbonate and potassium hydroxide is 10:(1-5)；The sodium carbonate class Composite catalyst is the mixture of sodium carbonate and sodium hydroxide, and the mass ratio of sodium carbonate and sodium hydroxide is 10:(1-5).
4. coal base vinyl acetate Carbon supports according to any one of claim 1-3, which is characterized in that prepare the coal base The raw material of vinyl acetate Carbon supports further includes the bituminous coal that parts by weight are 3-5, and the bituminous coal is the bituminous coal powder after milling, partial size It is 75 μm of D90 <, ash content < 6wt%, volatile matter < 28wt%.
5. coal base vinyl acetate Carbon supports according to claim 4, which is characterized in that the bituminous coal is meager lean coal, coking coal It is any one or more of with 1/3 coking coal；Preferably, the meager lean coal is weakly caking coal；Preferably, the bituminous coal be weakly caking coal and The Mixture Density Networks of coking coal, and the mass ratio of weakly caking coal and coking coal is (0.5-2): 1.
6. a kind of preparation method of coal base vinyl acetate Carbon supports according to any one of claims 1 to 5, which is characterized in that The preparation method comprises the following steps:
(1) kneading press strip
The raw material is mixed according to corresponding parts by weight, and by mixed material kneading coal-forming cream, then by coal Cream extrusion forming, obtains sketching charcoal；
(2) it carbonizes
Under anaerobic state, the sketching charcoal obtained to step (1) carries out heating charing, obtains carbonized material；
(3) it activates
The carbonized material that step (2) obtains once is activated, re-activation is carried out again after then an activated material cools down, obtains To re-activation material；
(4) it washs and dry
The re-activation material that step (3) obtains successively is subjected to pickling, washing and drying, obtains final products.
7. preparation method according to claim 6, which is characterized in that in the step (2), carbonization temperature 650-750 DEG C, the volatilization of gained carbonized material is divided into 8-12wt% after charing, and preferably carbonization time is 25-50min.
8. preparation method according to claim 6 or 7, which is characterized in that in the step (3), one time activation temperature is 900-950 DEG C, an activation time is 10-25min.
9. preparation method according to claim 8, which is characterized in that in the step (3), an activated material is cooled to Carry out re-activation is sent to after 30-100 DEG C, re-activation temperature is 910-960 DEG C, and the re-activation time is 20-30min.
10. the preparation method according to any one of claim 6-9, which is characterized in that in the step (4), pickling is The re-activation material is placed in the acid solution that concentration is 5-15wt% and impregnates 5-20h, the acid solution and the secondary work The volume ratio of material is (2-3): 1；Acid used is any one of sulfuric acid, nitric acid and hydrochloric acid.
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