CN109126698A - A method of demercuration adsorbent is prepared using sulphur coal - Google Patents

A method of demercuration adsorbent is prepared using sulphur coal Download PDF

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CN109126698A
CN109126698A CN201811072656.9A CN201811072656A CN109126698A CN 109126698 A CN109126698 A CN 109126698A CN 201811072656 A CN201811072656 A CN 201811072656A CN 109126698 A CN109126698 A CN 109126698A
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coal
sulphur
sulphur coal
demercuration
demercuration adsorbent
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王建成
王雅慧
霍启煌
韩丽娜
常丽萍
鲍卫仁
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Taiyuan University of Technology
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Taiyuan University of Technology
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Priority to PCT/CN2019/086818 priority patent/WO2020052251A1/en
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0262—Compounds of O, S, Se, Te
    • B01J20/0266—Compounds of S
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1128—Metal sulfides
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character

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Abstract

A method of demercuration adsorbent is prepared using sulphur coal, belong to the clean efficient technique of rainwater utilization field of sulphur coal, it can solve problem of environmental pollution caused by sulphur coal utilizes, and element mercury is difficult to by existing mercury removal agent removes or removal efficiency is not high technical problem in Mercury In The Air prevention and cure of pollution work, the present invention by the way that sulphur coal is mixed with metal salt solution, destructive distillation roasting and activation and etc. porous charcoal base demercuration adsorbent is made, and demercuration adsorbent obtained is in N2‑H2There is good demercuration activity in S atmosphere.The preparation method had both been that the clean utilization of sulphur coal opened up a new way, and also the prevention and treatment for atmosphere mercury pollution provides new possibility, has a very important significance in terms of environmental protection.

Description

A method of demercuration adsorbent is prepared using sulphur coal
Technical field
The invention belongs to the clean efficient technique of rainwater utilization fields of sulphur coal, and in particular to a kind of to prepare demercuration using sulphur coal The method of adsorbent.
Background technique
From the fundamental realities of the country in China, in a foreseeable future coal will be the most important non-renewable energy of China, but It is significantly exploited and using the sharply reduction for having caused high-quality coal resource, has intensified the lance between energy security and environmental protection Shield.The high sulfur coal resource in China is abundant, and 7.80% in national coal mine under the unified-allocation system and emphasis coal mine is all sulphur coal, is a kind of important Coal resources.But the high-sulfur feature of sulphur coal itself hinders its development and utilization.
Sulphur coal can remove most of pyrite and ash content by washing, be conducive to improve, stablize coal quality, but thermal coal Washing is there are also to be developed, and coal washing not only causes a large amount of water pollutions, and fine particle shape pyrite and organic sulfur therein are nothings Method is removed by physical method, only can be only achieved reduction SO by taking off (solid) sulphur or flue gas removing in combustion process2Discharge Purpose.At present both at home and abroad development and application flue gas desulfurization technique and technology category it is various, desulfuration efficiency generally can reach 90% with On, taken off in combustion process (Gu) sulphur efficiency also can reach 80%~90%.If the sulphur coal for using sulfur-bearing 3%~4% passes through above-mentioned If method realizes 90% desulfuration efficiency, then SO2Discharge amount just corresponds to exploit and use the special low-sulfur of sulfur-bearing 0.3%~0.4% Coal, though by 80% desulfurization degree calculate, be also equivalent to exploitation and use 0.6%~0.8% low-sulfur coal.Removing SO at present2, it is net Changing flue gas is the main path for utilizing and administering sulphur coal.
It is well known that the sulphur (especially organic sulfur) in sulphur coal cannot effectively be pre-processed by physical method, The sulphur coal in China is still directly used in combustion power generation at present, this exacerbates the environmental situation in China, such as haze and acid rain. Once sulphur coal has been banned for some time, but has been driven by interests, and substantial portion of sulphur coal still circulates in market, continues to pollute The home of our human survivals.Fundamentally to solve problem of environmental pollution caused by sulphur coal, it is necessary to open up new utilize on the way Diameter.
In addition, today increasingly strict in environmental requirement, mercury pollution problem become increasingly conspicuous, world community is gradually caused It pays close attention to.The investigation result of U.S.EPA shows that about 31% mercury is derived from coal-burning power plant in atmosphere, is the largest emission source. As a coal big country, China consumes about 2,000,000,000 tons of coals every year, wherein about 70% is directly used in power generation.Therefore, prevention and treatment is big One key measure of bicycle pump pollution is exactly the mercury emissions of strict control coal-burning power plant.
Mercury in atmosphere is mainly with particulate Hg (HgP), gaseous state bivalent mercury (Hg2+) and element mercury (Hg0) 3 kinds of forms exist. The characteristics of for mercury and atmosphere Status of mercury, researcher develop the effective technology of a variety of prevention and treatment atmosphere mercury pollution, mainly Including cleaner demercuration technology, adsorbent demercuration technology, catalytic oxidation technologies and some other demercuration technology.Wherein, Grain state mercury can be collected with dust removal installation；According to the soluble easily in water and easy feature being attached on particulate matter, gaseous state bivalent mercury Conventional pollutant catabolic gene equipment (such as wet type fume sweetening device, electrostatic precipitator (ESP), inertial dust separator and cloth can also be used Bag dust collector etc.) it is collected and removes；However element mercury is insoluble in water and highly volatile, current pollutant catabolic gene equipment is not It can effectively be handled.But if can be dimercurion by elemental mercury, then the removing problem of element mercury also will It is readily solved.For demercuration technology, cleaner demercuration technology (including bag filter and electrostatic precipitator) has been approached top Peak, substantially without improved space；Adsorbent demercuration technology (including active carbon, flying dust, Ca-base adsorbent and mineral substance absorption Agent) research space it is also less big, the work of researcher in this respect is concentrated mainly on study on the modification.Mercury catalysis oxidation skill Art is a kind of emerging Elemental Mercury removing sulfuldioxide, is of great significance to the emission control of gas mercury.The technology is intended to It is bivalent mercury by elemental mercury, to solve the problems, such as that element mercury is difficult to remove, but the research for the demercuration technology at present Also in the exploratory stage at initial stage, demercuration mechanism is also unclear, thus the technology have in terms of Mercury In The Air prevention and cure of pollution it is particularly significant Research significance and very huge research space.
Summary of the invention
Element mercury in problem of environmental pollution caused by the present invention is utilized for sulphur coal and Mercury In The Air prevention and cure of pollution work It is difficult to by the technical problem that existing mercury removal agent removes or removal efficiency is not high, provides and a kind of prepare demercuration adsorbent using sulphur coal Method, the present invention abandoned at present using sulphur coal as a kind of Main Viewpoints of energy, handle sulphur coal with metal salt solution, The organic sulfur for being difficult to remove in metal and sulphur coal is coupled, metal sulfide carbon-supported catalyst is made and is used to oxidation removal Hg in atmosphere0。
The present invention adopts the following technical scheme:
A method of demercuration adsorbent being prepared using sulphur coal, is included the following steps:
The first step dries sulphur coal coal sample, and sieving obtains high-sulfur coal particle；
Second step is weighed respectively in ratio of the molar ratio less than 1 of the sulphur in the metal and high-sulfur coal particle in metal nitrate High-sulfur coal particle and metal nitrate；
Third step, by weighed metal nitrate and ethyl alcohol mixed preparing metal salt ethanol solution, wherein ethyl alcohol and sulphur coal The volume mass ratio of grain is 0.5-1mL/1g；
4th step is poured into weighed high-sulfur coal particle in the metal salt ethanol solution of third step preparation, mixed by ultrasonic vibration It closes uniformly and ethyl alcohol evaporates into after no longer oozing out, it is dry, obtain prepreg；
The prepreg that 4th step obtains is put into progress destructive distillation roasting in tube furnace, obtains the suction containing metal sulfide by the 5th step Attached dose of precursor；
6th step, the adsorbent precursors containing metal sulfide that the 5th step is obtained are activated, and obtain porous metal vulcanization Object charcoal base demercuration adsorbent.
The drying temperature of sulphur coal coal sample described in the first step is 80-100 DEG C, and drying time 8-11h, sieving obtains The high-sulfur coal particle of 40-60 mesh.
Metal nitrate described in second step is one of Cu, Zn and Fe or a variety of nitrate.
Preferably, the volume mass ratio of ethyl alcohol and high-sulfur coal particle is 0.7mL/1g in third step.
Drying temperature is 30-70 DEG C in 4th step, drying time 5-10h.
Heating rate in 5th step in destructive distillation roasting is 3-8 DEG C/min, and it is 700-800 DEG C that destructive distillation, which roasts final temperature, After reaching final temperature, constant temperature 3-5h.
Activation is steam activation or CO in 6th step2Activation, activation time 2-4.5h, activation temperature 850-950 ℃。
Preferably, activation is steam activation in the 6th step.
Beneficial effects of the present invention are as follows:
The present invention has abandoned at present using sulphur coal as a kind of Main Viewpoints of energy, handles sulphur coal with metal salt solution, will The organic sulfur for being difficult to remove in metal and sulphur coal is coupled, and it is big for oxidation removal that metal sulfide carbon-supported catalyst is made Hg in gas0。
(1) preparation method of demercuration adsorbent of the present invention is simple, feasibility is high, and can solve simultaneously sulphur coal without Method with atmosphere mercury pollution rationally using being difficult to administer two hang-ups.
(2) in an embodiment of the present invention, adsorbent produced by the present invention is carried out in fixed bed demercuration experimental provision Demercuration test.As the result is shown: under the conditions of 150 DEG C, demercuration adsorbent of the present invention is in N2-H2It is shown in S atmosphere good Demercuration activity.
(3) the demercuration technology provides new approach for the clean utilization of sulphur coal.Using in sulphur coal in the present invention Sulphur realizes the removing to the Elemental Mercury in atmosphere, is the idea of a good treatment of wastes with processes of wastes against one another.The present invention utilizes sulphur coal and gold Belong to salt couple to form metal sulfide charcoal base demercuration adsorbent, new approach is both opened for the clean utilization of sulphur coal, also for The prevention and treatment of atmosphere mercury pollution provides new possibility.
Detailed description of the invention
Fig. 1 is preparation flow figure of the present invention.
Specific embodiment
Embodiment 1
Sulfur content > 3wt% high-sulfur Linfen coal is dried into 10 h in 80 DEG C of convection oven, is then ground, screen out 40~ The high-sulfur coal particle of 60 mesh is spare.
Weigh the Cu (NO of high-sulfur coal particle and 1.30 g that 10 g are screened out respectively with balance3)2▪10H2O sample.
The ethanol solution of 7 ml, the Cu (NO that will be weighed up are measured with liquid-transfering gun3)2▪10H2O pours into ethanol solution In, so that copper nitrate is completely dissolved in ethanol solution in stirring on magnetic stirring apparatus.
The high-sulfur coal particle weighed up is poured into the small beaker for filling copper nitrate ethanol solution again, is placed in ultrasonator It is uniformly mixed it and evaporates into solvent no longer to ooze out, be finally putting into 45 DEG C of baking ovens dry 8 hours and obtain prepreg.
Prepreg obtained is put into in the tube furnace for set program progress destructive distillation roasting, heating rate be set as 5 DEG C/ Min, roasting final temperature are set as 750 DEG C, reach 5 h of constant temperature calcining after final temperature.
Sample after roasting is activated, porous copper bearing sulphide charcoal base demercuration adsorbent is made.Activate item Part are as follows: activation phenomenon is the vapor (N that volume fraction is 40%2It is Balance Air), activation time 3h, activation temperature 900 ℃。
Embodiment 2
Sulfur content > 3wt% high-sulfur Linfen coal is dried into 8 h in 100 DEG C of convection oven, is then ground, screen out 40~ The high-sulfur coal particle of 60 mesh is spare.
Weigh the Cu (NO of high-sulfur coal particle and 3.86 g that 20 g are screened out respectively with balance3)2▪10H2O sample.
The ethanol solution of 15 ml, the Cu (NO that will be weighed up are measured with liquid-transfering gun3)2▪10H2O pours into ethanol solution In, so that copper nitrate is completely dissolved in ethanol solution in stirring on magnetic stirring apparatus.
The high-sulfur coal particle weighed up is poured into the small beaker for filling copper nitrate ethanol solution again, is placed in ultrasonator It is uniformly mixed it and evaporates into solvent no longer to ooze out, be finally putting into 30 DEG C of baking ovens dry 10 hours and obtain prepreg.
Prepreg obtained is put into in the tube furnace for set program progress destructive distillation roasting, heating rate be set as 3 DEG C/ Min, roasting final temperature are set as 700 DEG C, reach 3 h of constant temperature after roasting final temperature.
Sample after roasting is activated, porous copper bearing sulphide charcoal base demercuration adsorbent is made.Activate item Part are as follows: activation phenomenon is the vapor (N that volume fraction is 40%2It is Balance Air), activation time is 3 h, activation temperature 850 ℃。
Embodiment 3
Sulfur content > 3wt% high-sulfur Linfen coal is dried into 10 h in 100 DEG C of convection oven, is then ground, screen out 40~ The high-sulfur coal particle of 60 mesh is spare.
Weigh the Zn (NO of high-sulfur coal particle and 2.40 g that 10 g are screened out respectively with balance3)2▪6H2O sample.
The ethanol solution of 8 ml, the Zn (NO that will be weighed up are measured with liquid-transfering gun3)2▪6H2O pours into ethanol solution In, so that zinc nitrate is completely dissolved in ethanol solution in magnetic agitation on magnetic stirring apparatus.
The high-sulfur coal particle weighed up is poured into the small beaker for filling zinc nitrate ethanol solution again, is placed in ultrasonator It is uniformly mixed it and evaporates into solvent no longer to ooze out, be finally putting into 60 DEG C of baking ovens dry 8 hours and obtain prepreg.
Prepreg obtained is put into in the tube furnace for set program progress destructive distillation roasting, heating rate be set as 8 DEG C/ Min, roasting final temperature are set as 800 DEG C, reach 4 h of constant temperature after roasting final temperature.
Sample after roasting is activated, the porous charcoal of sulfide containing zinc base demercuration adsorbent is made.Activate item Part are as follows: activation phenomenon is the vapor (N that volume fraction is 40%2It is Balance Air), activation time is 4.5 h, and activation temperature is 900 ℃。
Embodiment 4
Sulfur content > 3wt% high-sulfur Linfen coal is dried into 11 h in 80 DEG C of convection oven, is then ground, screen out 40~ The high-sulfur coal particle of 60 mesh is spare.
Weigh the Zn (NO of high-sulfur coal particle and 1.56 g that 20 g are screened out respectively with balance3)2▪6H2O sample.
The ethanol solution of 10 ml, the Zn (NO that will be weighed up are measured with liquid-transfering gun3)2▪6H2O pours into ethanol solution In, so that zinc nitrate is completely dissolved in ethanol solution in magnetic agitation on magnetic stirring apparatus.
The high-sulfur coal particle weighed up is poured into the small beaker for filling zinc nitrate ethanol solution again, is placed in ultrasonator It is uniformly mixed it and evaporates into solvent no longer to ooze out, be finally putting into 50 DEG C of baking ovens dry 10 hours and obtain prepreg.
Prepreg obtained is put into in the tube furnace for set program progress destructive distillation roasting, heating rate be set as 8 DEG C/ Min, roasting final temperature are set as 750 DEG C, reach 5 h of constant temperature after final temperature.
Sample after roasting is activated, the porous charcoal of sulfide containing zinc base demercuration adsorbent is made.Activate item Part are as follows: activation phenomenon is the vapor (N that volume fraction is 40%2It is Balance Air), activation time is 2.5 h, and activation temperature is 950 ℃。
Embodiment 5
Sulfur content > 3wt% high-sulfur Linfen coal is dried into 8 h in 90 DEG C of convection oven, then grinds, screens out 40~60 Purpose high-sulfur coal particle is spare.
Weigh the Fe (NO of high-sulfur coal particle and 1.41 g that 10 g are screened out respectively with balance3)3▪9H2O sample.
The ethanol solution of 10 ml, the Fe (NO that will be weighed up are measured with liquid-transfering gun3)3▪9H2O pours into ethanol solution In, so that ferric nitrate is completely dissolved in ethanol solution in magnetic agitation on magnetic stirring apparatus.
The high-sulfur coal particle weighed up is poured into the small beaker for filling ferric nitrate ethanol solution again, is placed in ultrasonator It is uniformly mixed it and evaporates into solvent no longer to ooze out, be finally putting into 70 DEG C of baking ovens dry 5 hours and obtain prepreg.
Prepreg obtained is put into in the tube furnace for set program progress destructive distillation roasting, heating rate be set as 5 DEG C/ Min, roasting final temperature are set as 800 DEG C, reach 5 h of constant temperature after roasting final temperature.
Sample after roasting is activated, the porous base of charcoal containing iron sulfide demercuration adsorbent is made.Activate item Part are as follows: activation phenomenon is the vapor (N that volume fraction is 40%2It is Balance Air), activation time is 2 h, activation temperature 900 ℃。
Comparative example 1
In order to compare, the carbon-supported catalyst of metal salt is not added in preparation under roasting same as Example 1 and activation condition. Specifically the preparation method is as follows: sulfur content > 3wt% high-sulfur Linfen coal is dried 10 h in 80 DEG C of convection oven, then grind Broken, the high-sulfur coal particle for screening out 40~60 mesh is spare.
It weighs the high-sulfur coal particle that 10 g are screened out respectively with balance and is put into the tube furnace for set program and carry out destructive distillation Roasting, heating rate are set as 5 DEG C/min, and roasting final temperature is set as 750 DEG C, reaches 5 h of constant temperature calcining after final temperature.
Sample after roasting is activated, porous charcoal base demercuration adsorbent is made.Activation condition are as follows: activation phenomenon Vapor (the N for being 40% for volume fraction2It is Balance Air), activation time 3h, activation temperature is 900 DEG C.
Embodiment 6
The metal salt only carbon-supported catalyst as made from high-sulfur coal carbonization and the embodiment of the present invention 1 will be not added made from comparative example 1, Metal sulfide charcoal base demercuration adsorbent made from 2,3,4,5, which is respectively placed in fixed bed demercuration experimental provision, carries out continuous two The demercuration test of hour, reaction condition: fixed bed reaction temperature is 150 DEG C；Simulated atmosphere is simulation coal gas, by Hg0(40 μ g/m3), H2The ppm of S(150~200), high-purity N2Carrier gas (600 ml/min) composition, total tolerance are the use of 1 L/min(Balance Air Nitrogen).Simulation gas is passed through reaction tube to contact with demercuration adsorbent, the loadings of demercuration adsorbent are 500 ± 2 mg, partial size Size is the mesh of 0.25~0.42 mm(40~60).
Specific steps: taking silica wool to be laid in reaction tube, demarcates blank value as entrance mercury concentration value；Blank is demarcated After value, the adsorbent for weighing 500 mg is placed on reaction bed, and bed reaction temperature to be fixed is switched to main road after stablizing and is adsorbed Agent demercuration performance test.
The demercuration performance of metal sulfide carbon-supported catalyst is evaluated using the following method, and demercuration performance passes through the demercuration to nonvalent mercury Efficiency defines, and is specifically defined as follows:
In formula, η represents the demercuration efficiency of adsorbent, n0And n1What is respectively represented is that reactor inlet mercury concentration and outlet mercury are dense Degree, unit are μ g/m3Or pp.
Detection method: carrying out mercury adsorption experiment on fixed bed reactors, evaluate the performance of demercuration adsorbent, uses LUMEX 915M mercury vapourmeter measures Hg0Concentration, every 2 min records a data.
Given in table 1 comparative example 1 preparation be not added metal salt only the carbon-supported catalyst as made from high-sulfur coal carbonization and The demercuration experimental data of the adsorbent of 1-5 of embodiment of the present invention preparation.Sample number into spectrum be 0#~5#(0# be when being not added metal salt by Carbon-supported catalyst made from high-sulfur coal carbonization, 1#~5# are followed successively by adsorbent made from 1-5 of the embodiment of the present invention).
Each embodiment of table 1 and the demercuration rate for not adding adsorbent made from metal salt
Experimental result: under the conditions of 150 DEG C of temperature, demercuration adsorbent obtained by the present invention has in the case where simulating coal gas atmosphere Higher demercuration activity, the demercuration adsorbent that wherein prepared by embodiment 1 and embodiment 2 is in N2-H2Demercuration activity is very high in S atmosphere, Starting demercuration rate can reach 95% or more, and two hours average demercuration rates also can reach 90% or more.Although the demercuration of 3#, 4# and 5# Very high, but compared with the adsorbent 0# made from the raw coal for not adding metal salt, demercuration performance is also respectively increased as 0# activity 8 times, 5 times and 3 times, it is believed that by metal salt type or ratio used in modulation, demercuration can be prepared by adjusting preparation condition It can more excellent adsorbent.This shows charcoal base demercuration adsorbent produced by the present invention containing H2There is preferable demercuration under S atmosphere Effect, it is meant that using sulphur coal prepare metal sulfide carbon-supported catalyst be it is feasible, in terms of coal gas demercuration have it is huge Prospects for commercial application.

Claims (8)

1. a kind of method for preparing demercuration adsorbent using sulphur coal, characterized by the following steps:
The first step dries sulphur coal coal sample, and sieving obtains high-sulfur coal particle；
Second step is weighed respectively in ratio of the molar ratio less than 1 of the sulphur in the metal and high-sulfur coal particle in metal nitrate High-sulfur coal particle and metal nitrate；
Third step, by weighed metal nitrate and ethyl alcohol mixed preparing metal salt ethanol solution, wherein ethyl alcohol and sulphur coal The volume mass ratio of grain is 0.5-1mL/1g；
4th step is poured into weighed high-sulfur coal particle in the metal salt ethanol solution of third step preparation, mixed by ultrasonic vibration It closes uniformly and ethyl alcohol evaporates into after no longer oozing out, it is dry, obtain prepreg；
The prepreg that 4th step obtains is put into progress destructive distillation roasting in tube furnace, obtains the suction containing metal sulfide by the 5th step Attached dose of precursor；
6th step, the adsorbent precursors containing metal sulfide that the 5th step is obtained are activated, and obtain porous metal vulcanization Object charcoal base demercuration adsorbent.
2. a kind of method for preparing demercuration adsorbent using sulphur coal according to claim 1, it is characterised in that: the first step Described in sulphur coal coal sample drying temperature be 80-100 DEG C, drying time 8-11h, sieving obtain the sulphur coal of 40-60 mesh Particle.
3. a kind of method for preparing demercuration adsorbent using sulphur coal according to claim 1, it is characterised in that: second step Described in metal nitrate be one of Cu, Zn and Fe or a variety of nitrate.
4. a kind of method for preparing demercuration adsorbent using sulphur coal according to claim 1, it is characterised in that: third step The volume mass ratio of middle ethyl alcohol and high-sulfur coal particle is 0.7mL/1g.
5. a kind of method for preparing demercuration adsorbent using sulphur coal according to claim 1, it is characterised in that: the 4th step Middle drying temperature is 30-70 DEG C, drying time 5-10h.
6. a kind of method for preparing demercuration adsorbent using sulphur coal according to claim 1, it is characterised in that: the 5th step Heating rate in middle destructive distillation roasting is 3-8 DEG C/min, and it is 700-800 DEG C, after reaching final temperature that destructive distillation, which roasts final temperature, Constant temperature 3-5h.
7. a kind of method for preparing demercuration adsorbent using sulphur coal according to claim 1, it is characterised in that: the 6th step Middle activation is steam activation or CO2Activation, activation time 2-4.5h, activation temperature are 850-950 DEG C.
8. a kind of method for preparing demercuration adsorbent using sulphur coal according to claim 7, it is characterised in that: the 6th step Middle activation is steam activation.
CN201811072656.9A 2018-09-14 2018-09-14 A method of demercuration adsorbent is prepared using sulphur coal Pending CN109126698A (en)

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CN114570341A (en) * 2022-01-20 2022-06-03 河南理工大学 Application of high-sulfur coal and recovery of Au (S) by using roasted product of high-sulfur coal2O3)23-Method (2)

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CN103608086A (en) * 2011-03-25 2014-02-26 阿尔比马尔公司 Compositions and methods to sequester flue gas mercury in concrete
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WO2020052251A1 (en) * 2018-09-14 2020-03-19 太原理工大学 Method for preparing mercury removal adsorbent using high sulfur coal
CN114570341A (en) * 2022-01-20 2022-06-03 河南理工大学 Application of high-sulfur coal and recovery of Au (S) by using roasted product of high-sulfur coal2O3)23-Method (2)
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