WO2020119020A1 - 一种炭基载硫含铁脱汞吸附剂的制备方法 - Google Patents

一种炭基载硫含铁脱汞吸附剂的制备方法 Download PDF

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WO2020119020A1
WO2020119020A1 PCT/CN2019/086835 CN2019086835W WO2020119020A1 WO 2020119020 A1 WO2020119020 A1 WO 2020119020A1 CN 2019086835 W CN2019086835 W CN 2019086835W WO 2020119020 A1 WO2020119020 A1 WO 2020119020A1
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iron
sulfur
carbon
mercury
containing mercury
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PCT/CN2019/086835
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French (fr)
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王建成
霍启煌
陈慧君
韩丽娜
常丽萍
鲍卫仁
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太原理工大学
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Priority to US16/833,545 priority Critical patent/US11420183B2/en
Publication of WO2020119020A1 publication Critical patent/WO2020119020A1/zh
Priority to ZA2021/03092A priority patent/ZA202103092B/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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3071—Washing or leaching
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • 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
    • 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
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active 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
    • B01D2253/102—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
    • B01D2253/25—Coated, impregnated or composite adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition

Definitions

  • the invention belongs to the technical field of coal chemical industry application, and specifically relates to a preparation method of a carbon-based sulfur-containing iron-containing mercury-removing adsorbent.
  • high-sulfur coal is usually treated by washing and other methods to remove some of the sulfur-containing substances before being used, but the remaining sulfur can only be removed (solid) during the combustion process or the flue gas is desulfurized. emission.
  • Coal liquefaction residues can be used for hydro-liquefaction, gasification, pyrolysis coking, etc., but the technology is not mature enough and is still being studied and explored.
  • the main utilization method is combustion, and the same problems as high-sulfur coal will be encountered during combustion. .
  • petroleum coke After increasing the sulfur content, petroleum coke has encountered many challenges such as the decline in the quality of petroleum coke products, excessive flue gas emissions and equipment corrosion. Even the country has begun to restrict the trading of high sulfur petroleum coke.
  • the extensive use of these heavy organic sulfur-rich substances may aggravate the environmental pollution situation in my country, such as smog and acid rain. To fundamentally solve the problem of environmental pollution caused by the use of heavy organic sulfur-rich substances, a different approach must be taken.
  • the mercury in the atmosphere mainly exists in the form of particulate mercury (Hg), gaseous divalent mercury (Hg2+) and elemental mercury (Hg)0.
  • Hg particulate mercury
  • Hg2+ gaseous divalent mercury
  • Hg elemental mercury
  • researchers have developed a variety of effective technologies to prevent and control atmospheric mercury pollution, mainly including mercury removal technology for dust removal equipment, mercury removal technology for adsorbents, catalytic oxidation technology, and other mercury removal technologies.
  • particulate mercury can be collected by dust removal facilities; according to the characteristics of being easily soluble in water and easily adhering to particulate matter, gaseous divalent mercury can also be used with conventional pollutant control equipment (such as wet flue gas desulfurization devices, electrostatic precipitators (ESP), inertial dust collectors and bag dust collectors, etc.) for collection and removal; however, because elemental mercury has the characteristics of being difficult to dissolve in water, chemically stable and volatile, the current existing pollutant control equipment has the effect of removing it Not good. But if elemental mercury can be oxidized to divalent mercury ions, the problem of elemental mercury removal will also be solved.
  • pollutant control equipment such as wet flue gas desulfurization devices, electrostatic precipitators (ESP), inertial dust collectors and bag dust collectors, etc.
  • the mercury removal technology of dust removal equipment (including bag dust collector and electrostatic dust collector) is very mature; the mercury removal technology of adsorbent (including activated carbon, fly ash, calcium-based adsorbent and mineral adsorbent, etc.) and catalytic oxidation technology are scientific research workers The research focus is to obtain high-performance, low-cost adsorbent preparation technology.
  • CN107051391A discloses a bromine-loaded sulfur-rich activated carbon flue gas mercury removal adsorbent and a preparation method thereof.
  • the technical scheme uses petroleum coke as a raw material and KOH as an activator, which is activated in a mixed atmosphere of N2 and H2, and then performs it NH4Br chemical modification to improve the chemical adsorption of mercury.
  • the adsorbent needs to be activated and impregnated with NH4Br during the preparation process, which increases the filtration and drying steps, which undoubtedly increases the cost of preparation of the adsorbent; in addition, although there is no vulcanization process, NH4Br transportation and storage conditions are more stringent
  • the solution is slightly toxic and can pollute waters. Undiluted or large amounts of products cannot be contacted with groundwater, water channels or sewage systems, and cannot be discharged into the surrounding environment without government permission.
  • CN105148840A discloses a fly ash flue gas demercury adsorbent made of the following parts by weight of raw materials: fly ash 40-50, ferric nitrate 4-5, manganese acetate 3-4, glass fiber 13- 15. Sodium silicate 5-7, sodium tartrate 3-4, calcium oxide 5-6, chitin 5-6, borate coupling agent 0.3-0.5, appropriate amount of deionized water.
  • the technical scheme adopted is: firstly washing the fly ash, then mixing and roasting with iron nitrate and manganese acetate, and finally adding glass fiber, sodium tartrate, calcium oxide, etc. into a slurry and spray drying to obtain an adsorbent.
  • the technical process of the technical solution is complicated and complicated, especially the water washing of the fly ash, the acid leaching process, the glass fiber pretreatment process and the pulping spray process, thereby greatly increasing the manufacturing cost of the adsorbent.
  • CN104888713A discloses a volcanic rock adsorbent for flue gas mercury removal and its preparation method, characterized in that the adsorbent is made of the following parts by weight of raw materials: calcium carbonate fiber 8-15, tetrabutyl titanate 20-40, silicon Sol 3-5, calcium aluminate 6-8, volcanic rock 60-80, PA6 nylon powder 6-9, gelatin 3-4, ammonium bicarbonate 1-3, polyacrylamide 3-5, 13x molecular sieve 5-8, go Appropriate amount of ionized water.
  • the technical scheme adopted includes the preparation of calcium carbonate glass fiber gel, volcanic acid sulfuric acid leaching for 12h, pelletizing and two-step roasting. The process takes a long time to increase the manufacturing cost, and there is no specific example to illustrate the demercuration of the adsorbent effect.
  • the present invention is to solve the technical problems of low utilization value and difficulty of utilization of heavy organic sulfur-rich substances, and difficulty in removing elemental mercury from existing mercury removal agents or low removal efficiency in the prevention and control of atmospheric mercury pollution.
  • the invention provides a method for preparing a carbon-based sulfur-bearing iron-containing mercury-removing adsorbent, which abandons the traditional heavy organic sulfur-rich substance utilization method and uses chemical activation to make it into a carbon-based sulfur-bearing iron-bearing iron-containing desorption Mercury adsorbent to increase its added value and remove elemental mercury in coal-fired flue gas.
  • a method for preparing a carbon-based sulfur-bearing iron-containing mercury-removing adsorbent includes the following steps:
  • the heavy organic sulfur-rich material with sulfur content> 1% is dried, crushed, and sieved to obtain heavy organic sulfur-rich material particles;
  • the second step is to weigh the heavy organic sulfur-rich material particles and inorganic iron salt according to the ratio of the molar ratio of iron atoms to sulfur atoms ⁇ 1;
  • the third step is to dissolve the inorganic iron salt weighed in the second step in water and mix it evenly with the heavy organic sulfur-rich substance particles weighed in the second step. After drying, the iron salt-loaded heavy organic sulfur-rich substance is obtained ;
  • the KOH weighed in the fourth step and the heavy organic sulfur-rich substance loaded with iron salt are mixed evenly to obtain a mixture, and an aqueous ethanol solution is dropped into the mixture to make the mixture infiltrate;
  • the infiltrated mixture obtained in the fifth step is placed in a tube furnace and fired and activated under the protection of N2 to obtain an activated product;
  • the activated product is repeatedly washed with hot water and filtered until the pH of the filtrate is 7, and dried to obtain a carbon-based sulfur-containing iron-containing mercury-removing adsorbent.
  • the heavy organic sulfur-rich substance in the first step includes any one of high sulfur coal, high sulfur petroleum coke or coal liquefaction residue.
  • the drying temperature in the first step is 60 ⁇ 110°C.
  • the number of meshes in the first step is ⁇ 20 mesh.
  • the inorganic iron salt in the second step includes any one of ferric nitrate, ferric chloride, ferric phosphate or ferric citrate.
  • the drying temperature in the third step is 50 ⁇ 110°C.
  • the ethanol aqueous solution in the fifth step is a solution in which ethanol and water are mixed in a volume ratio of 2:8, and the mass ratio of the volume of the ethanol aqueous solution added and the heavy organic sulfur-rich substance carrying iron salts is 0.4 to 1.5 ml/g .
  • the firing activation temperature in the sixth step is 400-1000°C, and the firing activation time is 1-5 hours.
  • the temperature of the hot water is 50-100°C, and the drying temperature is 110°C.
  • the preparation method of the mercury-removing adsorbent of the present invention is simple, the raw materials are wide, and the feasibility is high.
  • the carbonization activation is completed in one step, and the problem of atmospheric mercury pollution can be prevented while increasing the added value of heavy organic sulfur-rich substances.
  • the mercury removal test of the adsorbent prepared by the present invention is carried out in a fixed-bed mercury removal test device. The results show that under the conditions of 120°C, 150°C and 180°C, the mercury-removing adsorbent of the present invention shows good mercury-removing performance in N 2 + O 2 and simulated coal-fired flue gas atmosphere.
  • the mercury removal technology provides new ideas for the high value-added utilization of heavy organic sulfur-rich substances.
  • the carbon-based sulfur-containing iron-containing mercury-removing sorbent is prepared by using sulfur in the heavy organic sulfur-rich material and its own or external iron elements, which improves the heavy organic richness while treating the mercury pollution of coal-burning flue gas
  • the added value of sulfur substances is not only opens a new way for the clean and high value-added utilization of heavy organic sulfur-rich substances, but also provides a new type of adsorbent for the treatment of mercury pollution of coal-fired gas, and at the same time has both efficient use of resources and environmentally friendly development.
  • Figure 1 is a graph of the effect of alkali-carbon ratio on adsorption and mercury removal activity.
  • Figure 2 is a graph of the effect of activation temperature on the activity of adsorption mercury removal.
  • Figure 3 is a graph of the effect of atmosphere on the mercury removal activity.
  • Figure 4 is a graph of the effect of bed temperature on the adsorption and mercury removal activity.
  • Figure 5 is a graph of mercury removal activity of an adsorbent made from LF coal and SD petroleum coke.
  • ZY high-sulfur coal with a sulfur content of 6.4% was selected as the experimental raw material, and its iron content was 3.5%.
  • the ZY high-sulfur coal is placed in a blast oven at 110°C for 8 hours, then grinded, and 40-60 mesh ZY coal particles are sieved for use.
  • the above mixture was placed in a tube furnace with a set program for roasting and activation.
  • the activation temperature was 800°C, and the constant temperature was 2h after reaching the maximum temperature.
  • the roasted and activated sample was repeatedly washed with 50°C hot water and suction filtered until the pH of the filtrate was 7, and finally the filter cake was dried to obtain a carbon-based sulfur-containing iron-containing mercury-removing adsorbent.
  • the raw material is SH coal liquefaction residue with sulfur content of 1.22% and iron content of 2.24%. Put the SH coal liquefaction residue in a 60°C blast oven for 12 hours, then grind it, and screen out 60-80 mesh coal liquefaction residue particles for use.
  • the weighed SH coal liquefaction residue particles and KOH are uniformly mixed, and the mixed solution with ethanol:water of 2:8 is dropped into the solid mixture with a dropper, and the solid mixture is completely infiltrated.
  • the activation temperature is 400, 500, 600, 700, 800 °C, after reaching the highest temperature, the temperature is constant for 2h, which are respectively denoted as T400, T600, T600, T700, T800 .
  • the raw material for the experiment is LF high-sulfur coal with a sulfur content of 4.27% and an iron content of 0.16%. Place the LF high-sulfur coal in a 90°C blast oven for 12 hours, then grind it, and screen out 40-60 mesh LF coal particles for use.
  • the above mixture is placed in a tube furnace with a set program for roasting and activation.
  • the activation temperature is 800°C
  • the constant temperature is 2h after reaching the highest temperature, which is recorded as LF+Fe.
  • the sample after roasting and activation was repeatedly washed with hot water at 80° C. and filtered until the pH of the filtrate was 7, and finally the filter cake was dried to obtain a carbon-based sulfur-containing iron-containing mercury-removing adsorbent.
  • LF adsorbent prepared by using LF coal
  • the selected SD high-sulfur petroleum coke has a sulfur content of 7.02% and an iron content of ⁇ 0.1%. Place the SD high sulfur petroleum coke in a 105°C blast oven for 12 hours, then grind it, and screen out 20 to 60 mesh SD petroleum coke particles for use.
  • the SD petroleum coke particles loaded with ferric sulfate and KOH were evenly mixed, and the mixed solution with ethanol:water of 2:8 was dropped into the solid mixture with a dropper, and the solid mixture was completely infiltrated.
  • the above mixture was put into a tube furnace with a set program for roasting and activation.
  • the activation temperature was 800°C, and the constant temperature was 5h after reaching the highest temperature, which was recorded as SD+Fe.
  • the sample after roasting and activation was repeatedly washed with hot water at 80° C. and filtered until the pH of the filtrate was 7, and finally the filter cake was dried to obtain a carbon-based sulfur-containing iron-containing mercury-removing adsorbent.
  • SD adsorbent prepared with SD petroleum coke
  • the carbon-based sulfur-bearing iron-containing mercury-removing adsorbents prepared in Examples 1, 2, 3, and 4 of the present invention were placed in a fixed-bed mercury-removal experiment device for two consecutive hours of mercury-removal tests.
  • Reaction conditions fixed bed
  • the reaction temperature is 120 or 150 or 180°C
  • the atmosphere is N2+2+O2+Hg0 (40 ⁇ g/m3) or simulated coal-fired flue gas, which consists of N2, O2, SOX, NOX, Hg0 (40 ⁇ g) /m3)
  • the total gas volume is 1L/min (balance gas uses N2).
  • the simulated gas is passed into the reaction tube to contact with the adsorbent.
  • the loading volume of the adsorbent is 1.5 ⁇ 0.1mL
  • the particle size is 0.25 ⁇ 0.42mm (40 ⁇ 60 mesh).
  • the following methods were used to evaluate the mercury removal performance of carbon-based sulfur-bearing iron-containing sorbents.
  • the mercury removal performance was defined by the mercury removal efficiency of zero-valent mercury.
  • Detection method conduct mercury adsorption experiments on a fixed-bed reactor to evaluate the performance of the mercury-removing adsorbent, use a LUMEX 915M mercury measuring instrument to measure the concentration of Hg 0, record a data every 1 min, and take an average every five minutes to make a dotted line Figure.
  • the mercury removal performance of the samples under specific test conditions is shown in Figures 1 to 5.
  • test conditions of Figure 1, Figure 2, Figure 4 and Figure 5 are: 150°C, 40 ⁇ 2 ⁇ g/m3 Hg0, N2+4%O2, airspeed: 40000h-1.
  • Figure 3 is the test chart of sample T800, the test conditions are: 40 ⁇ 2 ⁇ g/m 3Hg 0, airspeed: 40000h-1.
  • Figure 4 is a test chart of sample R0.5-1.
  • the raw material for the experiment is LF high-sulfur coal with a sulfur content of 4.27% and an iron content of 0.16%. Place the LF high-sulfur coal in a 90°C blast oven for 12 hours, then grind it, and screen out 200-400 mesh LF coal particles for use.
  • the above mixture was put into a tube furnace with a set program for roasting and activation.
  • the activation temperature was 1000°C, and the constant temperature was 1h after reaching the maximum temperature, which were recorded as LF+Fe2, LF+Fe3, and LF+Fe4.
  • the sample after roasting and activation was repeatedly washed with hot water at 60° C. and filtered until the pH of the filtrate was 7, and finally the filter cake was dried to obtain a carbon-based sulfur-containing iron-containing mercury-removing adsorbent.
  • the mercury removal adsorbent prepared above was subjected to a mercury removal experiment on a jet mercury removal device.
  • the temperature was 120°C
  • the residence time was 1.5s
  • the carbon/mercury ratio was 20,000
  • the mercury removal efficiency of the four adsorbents was above 70%. .
  • the adsorbent prepared by the present invention has high mercury removal activity under various atmospheres.
  • the T800 adsorbent prepared in Example 2 has high mercury removal activity in N2-O2 atmosphere, and the average mercury removal efficiency within two hours is above 90%.
  • the mercury removal activity of adsorbents such as R3-1, T500 and SD+Fe is relatively low, compared with the mercury removal activity of ZY coal without KOH activation and SD petroleum coke without iron source activation, the mercury removal performance It has also been improved many times.

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Abstract

一种炭基载硫含铁脱汞吸附剂的制备方法，通过对自身富铁以及外加铁源的重质有机富硫物质进行化学活化等步骤原位制备具有丰富孔结构的炭基载硫含铁脱汞吸附剂，并且制得的吸附剂在模拟烟气气氛中有很好的脱汞性能。

Description

一种炭基载硫含铁脱汞吸附剂的制备方法 技术领域
本发明属于煤化工应用技术领域，具体涉及一种炭基载硫含铁脱汞吸附剂的制备方法。
背景技术
我国的高硫煤资源丰富，是一种重要的煤炭资源，高硫的特点是它清洁高效利用最大的挑战。从基本国情来看，煤炭在可预见的未来仍是中国最主要的一次能源。在煤炭高效清洁利用过程中煤的液化技术被视为重要的手段之一，但在煤液化过程中会产生大量残渣，由于残渣富硫的特点限制了它的开发和利用。目前主要用于燃烧，但燃烧会产生大量硫氧化合物导致污染大气。近年来，随着我国从中东等地进口的高硫原油量不断升高和延迟焦化技术的大力推广，石油焦中的硫含量也随之不断增高，硫含量的升高使石油焦在后续利用中受到了巨大的限制。以上几种物质均可视为富硫的重质有机物。
目前高硫煤在利用之前，通常会经过洗选等方式进行处理脱除其中的部分含硫物质，但剩余部分的硫只能在燃烧过程中脱(固)硫或对烟气进行脱硫处理再排放。煤液化残渣可用作加氢液化、气化、热解焦化等，但技术不够成熟还在进一步研究探索中，现在主要的利用方式为燃烧，在燃烧时与会遇到与高硫煤相同的问题。石油焦在硫含量升高后遇到了石油焦制品质量下降、烟气排放超标和设备腐蚀等众多挑战，甚至国家已经开始限制高硫石油焦的交易。这些重质有机富硫物质的粗放型利用可能会加剧我国的环境污染状况，比如雾霾和酸雨等。要从根本上解决重质有机富硫物质利用造成的环境污染问题，须另辟蹊径。
现今，环境问题不断凸显，我们关注的不再仅仅是SO X、NO X的问题，重金属污染逐渐成为全球关注的焦点。其中汞污染问题日益突出，引起了密切关注，在2017年《水俣病公约》正式生效。据美国环保局的调查结果显示，燃煤烟气是全球最大的汞污染源，汞排放占比超过了总排放量的30％。我国大片国土处于北温带，冬季寒冷需要燃煤供暖，而且电厂大多数为火力发电厂。我国每年大约消耗20亿吨煤炭，工业锅炉和发电机组所排放的烟气是极大的汞污染源。因此，对燃煤烟气进行脱汞处理是防治大气汞污染的一个重要举措。
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CN104888713A公开了一种烟气脱汞用火山岩吸附剂及其制备方法，其特征在于，吸附剂由以下重量份的原料制成：碳酸钙纤维8-15、钛酸四丁酯20-40、硅溶胶3-5、铝酸钙6-8、火山岩60-80、PA6尼龙粉6-9、明胶3-4、碳酸氢铵1-3、聚丙烯酰胺3-5、13x分子筛5-8、去离子水适量。所采用的的技术方案包括制备碳酸钙玻璃纤维凝胶，火山岩硫酸浸12h、制球和两步焙烧，工艺流程耗时较长增加了制造成本，并且没有具体实施例以说明该吸附剂的脱汞效果。
发明内容
本发明所要解决的是重质有机富硫物质利用价值较低和利用困难，以及大气汞污染防治工作中元素汞难以被现有脱汞剂脱除或脱除效率不高的技术问题。本发明提供一种炭基载硫含铁脱汞吸附剂的制备方法，摒弃了传统的重质有机富硫物质利用方式，用化学活化的方式，将其制成炭基载硫含铁的脱汞吸附剂来提高它的附加值和脱除燃煤烟气中的单质汞。
本发明采用如下技术方案：
一种炭基载硫含铁脱汞吸附剂的制备方法，包括如下步骤：
第一步，将含硫量＞1％的重质有机富硫物质烘干，粉碎，过筛，得到重质有机富硫物质颗粒；
第二步，按照铁原子和硫原子的摩尔比≤1的比例，分别称量重质有机富硫物质颗粒和无机铁盐；
第三步，将第二步称取的无机铁盐溶于水，并与第二步称取的重质有机富硫物质颗粒混合均匀，干燥后，得到负载铁盐的重质有机富硫物质；
第四步，按照KOH和第三步所得的负载铁盐的重质有机富硫物质的质量比≤3:1的比例，分别称取KOH和负载铁盐的重质有机富硫物质；
第五步，将第四步称取的KOH和负载铁盐的重质有机富硫物质混合均匀，得到混合物，向混合物中滴入乙醇水溶液，使混合物呈浸润状；
第六步，将第五步所得的呈浸润状的混合物置于管式炉中，在N 2保护下焙烧活化，得到活化产物；
第七步，将活化产物用热水反复洗涤并过滤，直至滤液pH为7，烘干后得到炭基载硫含铁脱汞吸附剂。
第一步中所述重质有机富硫物质包括高硫煤、高硫石油焦或煤液化残渣中的任意一种。
第一步中烘干温度为60～110℃。
第一步中所述过筛的目数为≤20目。
第二步中所述无机铁盐包括硝酸铁、氯化铁、磷酸铁或柠檬酸铁中的任意一种。
第三步中干燥温度为50～110℃。
第五步中所述乙醇水溶液为乙醇和水按体积比2:8的比例混合的溶液，乙醇水溶液添加的体积和负载铁盐的重质有机富硫物质的质量比为0.4～1.5ml/g。
第六步中所述焙烧活化温度为400～1000℃，焙烧活化时间为1～5h。
第七步中所述热水的温度为50～100℃，烘干温度为110℃。
本发明的有益效果如下：
(1)本发明所述脱汞吸附剂的制备方法简单、原料广泛、可行性高，炭化活化一步完成，而且能在提高重质有机富硫物质的附加值的同时防治大气汞污染的问题。
(2)在固定床脱汞实验装置中对本发明制得的吸附剂进行脱汞试验。结果显示：在120℃、150℃和180℃条件下，本发明所述脱汞吸附剂在N 2+O 2和模拟燃煤烟气气氛中显示出良好的脱 汞性能。
(3)该脱汞技术为重质有机富硫物质的高附加值利用提供了新思路。本发明中利用重质有机富硫物质中的硫和自身的或外加的铁元素制备了炭基载硫含铁脱汞吸附剂，在治理燃煤烟气汞污染的同时提高了重质有机富硫物质的附加值。本发明既为重质有机富硫物质的清洁高附加值利用开辟了新途径，也为燃煤燃气汞污染的治理提供了新型吸附剂，同时兼备资源高效利用和环境友好发展。
附图说明
图1为碱碳比对吸附脱汞活性的影响图。
图2为活化温度对吸附脱汞活性的影响图。
图3为气氛对吸附脱汞活性的影响图。
图4为床层温度对吸附脱汞活性的影响图。
图5为LF煤和SD石油焦制得的吸附剂的脱汞活性图。
具体实施方式
实施例1
选用含硫量为6.4％的ZY高硫煤作为实验原料，其铁含量为3.5％。将ZY高硫煤置于110℃的鼓风烘箱中烘干8h，然后磨碎，筛分出40～60目的ZY煤颗粒备用。
用天平分别称取10g筛分出的ZY煤颗粒、0g硝酸铁和0g、5g、7.5g、10g、30g的KOH。
再将称好的ZY煤颗粒和KOH均匀混合，用滴管将按乙醇:水为2:8的混合溶液滴入固体混合物中，并使固体混合物呈浸润状，分别记作：R0-1、R0.5-1、R0.75-1、R1-1、R3-1。
将上述混合物放入设置好程序的管式炉中进行焙烧活化，活化温度为800℃，达到最高温后恒温2h。
将焙烧活化后的样品用50℃热水反复洗涤抽滤，直至滤液pH为7，最后将滤饼干燥得到炭基载硫含铁脱汞吸附剂。
实施例2
原料选用含硫量为1.22％，含铁量为2.24％的SH煤液化残渣。将SH煤液化残渣置于60℃的鼓风烘箱中烘干12h，然后磨碎，筛分出60～80目的煤液化残渣颗粒备用。
用天平分别称取5g筛分出的SH煤液化残渣颗粒、0g硝酸铁和10g的KOH，准备4份。
再将称好的SH煤液化残渣颗粒和KOH均匀混合，用滴管将按乙醇:水为2:8的混合溶液滴入固体混合物中，并使固体混合物完全浸润。
将上述混合物放入设置好程序的管式炉中进行焙烧活化，活化温度为400、500、600、700、 800℃，达到最高温后恒温2h，分别记作T400、T600、T600、T700、T800。
将焙烧活化后的样品用100℃热水反复洗涤抽滤，直至滤液pH为7，最后将滤饼干燥得到炭基载硫含铁脱汞吸附剂。
实施例3
实验用原料为含硫量4.27％，含铁量0.16％的LF高硫煤。将LF高硫煤置于90℃的鼓风烘箱中烘干12h，然后磨碎，筛分出40～60目的LF煤颗粒备用。
用天平分别称取10g筛分出的LF煤颗粒和按照铁原子和硫原子个数比为0.8的硝酸铁，并将硝酸铁溶于适量水，然后与LF煤均匀混合并干燥。
用天平分别称取10g上述负载硝酸铁的LF煤颗粒和5g的KOH。
再将称好的负载柠檬酸铁的LF煤颗粒和KOH均匀混合，用滴管将按乙醇:水为2:8的混合溶液滴入固体混合物中，并使固体混合物完全浸润。
将上述混合物放入设置好程序的管式炉中进行焙烧活化，活化温度为800℃，达到最高温后恒温2h，记作LF+Fe。
将焙烧活化后的样品用80℃热水反复洗涤抽滤，直至滤液pH为7，最后将滤饼干燥得到炭基载硫含铁脱汞吸附剂。
为活性评价时作对比，在制备吸附剂时除不掺杂铁外其他条件不变，将利用LF煤制得的吸附剂记作LF。
实施例4
选用的SD高硫石油焦含硫量为7.02％、含铁量＜0.1％。将SD高硫石油焦置于105℃的鼓风烘箱中烘干12h，然后磨碎，筛分出20～60目的SD石油焦颗粒备用。
用天平分别称取10g筛分出的SD石油焦颗粒和按照铁原子和硫原子个数比为0.5的硫酸铁，并将硫酸铁溶于适量水，然后与SD石油焦均匀混合并干燥。
用天平分别称取10g上述负载硫酸铁的SD石油焦颗粒和5g的KOH。
再将称好的负载硫酸铁的SD石油焦颗粒和KOH均匀混合，用滴管将按乙醇:水为2:8的混合溶液滴入固体混合物中，并使固体混合物完全浸润。
将上述混合物放入设置好程序的管式炉中进行焙烧活化，活化温度为800℃，达到最高温后恒温5h，记作SD+Fe。
将焙烧活化后的样品用80℃热水反复洗涤抽滤，直至滤液pH为7，最后将滤饼干燥得到炭基载硫含铁脱汞吸附剂。
为活性评价时作对比，在制备吸附剂时除不掺杂铁外其他条件不变，将利用SD石油焦制得的 吸附剂记作SD。
实施例5
将本发明实施例1、2、3、4制得的炭基载硫含铁脱汞吸附剂分别置于固定床脱汞实验装置中进行连续两个小时的脱汞试验，反应条件：固定床反应温度为120或150或180℃；气氛为N 2+O 2+Hg 0(40μg/m 3)或模拟燃煤烟气，由N 2、O 2、SO X、NO X、Hg 0(40μg/m 3)组成，总气量为1L/min(平衡气使用N 2)。将模拟气体通入反应管与吸附剂接触，吸附剂的装填量为1.5±0.1mL，粒径大小为0.25～0.42mm(40～60目)。
具体步骤：取石英棉平铺在反应管中，标定空白值作为入口汞浓度值；标定完空白值后，量取1.5mL的吸附剂装入固定床反应器中，待固定床反应温度稳定后通入气氛进行吸附剂脱汞性能测试。
用以下方法评价炭基载硫含铁吸附剂的脱汞性能，其脱汞性能通过对零价汞的脱汞效率来定义，具体的定义如下：η(％)＝(1-C 1/C 0)×100％，其中，η代表吸附剂的脱汞效率，C 1和C 0分别代表的是反应器入口汞浓度和出口汞浓度，其单位为μg/m 3或ppm。
检测方法：在固定床反应器上进行汞吸附实验，评价脱汞吸附剂的性能，采用LUMEX 915M测汞仪来测量Hg 0的浓度，每1min记录一个数据，每五分钟取平均值做点线图。具体测试条件下样品的脱汞性能如图1至图5所示。
图1、图2、图4和图5的测试条件为：150℃，40±2μg/m 3 Hg 0，N 2+4％O 2，空速：40000h-1。
图3为样品T800的测试图，测试条件为：40±2μg/m 3 Hg 0，空速：40000h-1。
图4为样品R0.5-1的测试图。
实施例6
实验用原料为含硫量4.27％，含铁量0.16％的LF高硫煤。将LF高硫煤置于90℃的鼓风烘箱中烘干12h，然后磨碎，筛分出200～400目的LF煤颗粒备用。
用天平分别称取10g筛分出的LF煤颗粒4份和按照铁原子和硫原子个数比为0.6的硫酸铁、氯化铁和磷酸铁各一份，并将各铁盐溶于适量水，然后与LF煤均匀混合并干燥。
用天平分别称取10g上述负载铁盐的LF煤颗粒各一份和5g的KOH三份。
再将称好的负载铁盐的LF煤颗粒和KOH均匀混合，用滴管将按乙醇:水为2:8的混合溶液滴入固体混合物中，并使固体混合物完全浸润。
将上述混合物放入设置好程序的管式炉中进行焙烧活化，活化温度为1000℃，达到最高温后恒温1h，分别记作LF+Fe2、LF+Fe3、LF+Fe4。
将焙烧活化后的样品用60℃热水反复洗涤抽滤，直至滤液pH为7，最后将滤饼干燥得到炭基载硫含铁脱汞吸附剂。
上述制得的脱汞吸附剂在喷射脱汞装置上进行脱汞实验，温度为120℃，停留时间为1.5s，炭/汞比为20000，四种吸附剂的脱汞效率均在70％以上。
实验结果：在120～180℃温度条件下，本发明所制得的吸附剂在各气氛下均有较高的脱汞活性，其中实施例1中制得的R0.5-1吸附剂和实施例2中制得的T800吸附剂在N 2-O 2气氛中脱汞活性很高，两小时内的平均脱汞效率在90％以上。虽然R3-1、T500和SD+Fe等吸附剂的脱汞活性相对较低，但与不加KOH活化的ZY煤、不加铁源活化的SD石油焦的脱汞活性相比，脱汞性能也提高了很多倍，可预见地通过调变所用KOH用量、重质有机富硫物质种类、铁源用量以及活化过程中的条件制备出脱汞性能更优异的吸附剂。这表明本发明制得的炭基载硫含铁脱汞吸附剂在燃煤烟气气氛下有较好的脱汞效果，意味着利用重质有机富硫物质制备炭基载硫含铁脱汞吸附剂是可行的，在燃煤烟气脱汞方面具有不可估量的工业应用前景。

Claims (9)

  1. 一种炭基载硫含铁脱汞吸附剂的制备方法，其特征在于：包括如下步骤：
    第一步，将含硫量＞1％的重质有机富硫物质烘干，粉碎，过筛，得到重质有机富硫物质颗粒；
    第二步，按照铁原子和硫原子的摩尔比≤1的比例，分别称量重质有机富硫物质颗粒和铁盐；
    第三步，将第二步称取的铁盐溶于水，并与第二步称取的重质有机富硫物质颗粒混合均匀，干燥后，得到负载铁盐的重质有机富硫物质；
    第四步，按照KOH和第三步所得的负载铁盐的重质有机富硫物质的质量比≤3:1的比例，分别称取KOH和负载铁盐的重质有机富硫物质；
    第五步，将第四步称取的KOH和负载铁盐的重质有机富硫物质混合均匀，得到混合物，向混合物中滴入乙醇水溶液，使混合物呈浸润状；
    第六步，将第五步所得的呈浸润状的混合物置于管式炉中，在N 2保护下焙烧活化，得到活化产物；
    第七步，将活化产物用热水反复洗涤并过滤，直至滤液pH为7，烘干后得到炭基载硫含铁脱汞吸附剂。
  2. 根据权利要求1所述的一种炭基载硫含铁脱汞吸附剂的制备方法，其特征在于：第一步中所述重质有机富硫物质包括高硫煤、高硫石油焦或煤液化残渣中的任意一种。
  3. 根据权利要求1所述的一种炭基载硫含铁脱汞吸附剂的制备方法，其特征在于：第一步中烘干温度为60～110℃。
  4. 根据权利要求1所述的一种炭基载硫含铁脱汞吸附剂的制备方法，其特征在于：第一步中所述过筛的目数为≤20目。
  5. 根据权利要求1所述的一种炭基载硫含铁脱汞吸附剂的制备方法，其特征在于：第二步中所述铁盐包括硝酸铁、硫酸铁、氯化铁、磷酸铁或柠檬酸铁中的任意一种。
  6. 根据权利要求1所述的一种炭基载硫含铁脱汞吸附剂的制备方法，其特征在于：第三步中干燥温度为50～110℃。
  7. 根据权利要求1所述的一种炭基载硫含铁脱汞吸附剂的制备方法，其特征在于：第五步中所述乙醇水溶液为乙醇和水按体积比2:8的比例混合的溶液，乙醇水溶液添加的体积和负载铁盐的重质有机富硫物质的质量比为0.4～1.5ml/g。
  8. 根据权利要求1所述的一种炭基载硫含铁脱汞吸附剂的制备方法，其特征在于：第六步中所述焙烧活化温度为400～1000℃，焙烧活化时间为1～5h。
  9. 根据权利要求1所述的一种炭基载硫含铁脱汞吸附剂的制备方法，其特征在于：第七步中所述热水的温度为50～100℃，烘干温度为110℃。
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