WO2020258588A1 - 用于重金属吸附的异相凝并吸附剂及其制备方法和应用 - Google Patents

用于重金属吸附的异相凝并吸附剂及其制备方法和应用 Download PDF

Info

Publication number
WO2020258588A1
WO2020258588A1 PCT/CN2019/110747 CN2019110747W WO2020258588A1 WO 2020258588 A1 WO2020258588 A1 WO 2020258588A1 CN 2019110747 W CN2019110747 W CN 2019110747W WO 2020258588 A1 WO2020258588 A1 WO 2020258588A1
Authority
WO
WIPO (PCT)
Prior art keywords
adsorbent
heterogeneous
heavy metal
coagulation
heavy metals
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2019/110747
Other languages
English (en)
French (fr)
Inventor
赵永椿
崔向峥
周煜明
张军营
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huazhong University of Science and Technology
Original Assignee
Huazhong University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huazhong University of Science and Technology filed Critical Huazhong University of Science and Technology
Priority to US16/967,136 priority Critical patent/US11745135B2/en
Publication of WO2020258588A1 publication Critical patent/WO2020258588A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • B01J20/3028—Granulating, agglomerating or aggregating
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • 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
    • 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
    • B01D53/06—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 with moving adsorbents, e.g. rotating beds
    • B01D53/10—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 with moving adsorbents, e.g. rotating beds with dispersed adsorbents
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5209—Regulation methods for flocculation or precipitation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • 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
    • B01D2253/20—Organic adsorbents
    • 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
    • B01D2253/20—Organic adsorbents
    • B01D2253/202—Polymeric 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Definitions

  • the invention belongs to the field of heavy metal adsorbents, and more specifically, relates to a heterogeneous condensing adsorbent for heavy metal adsorption, and a preparation method and application thereof.
  • the fine particles in the atmosphere are usually rich in a large number of toxic trace heavy metals, and they are easily inhaled by the human body, which seriously endangers human health. Due to the difference in morphology, different heavy metals have different characteristics in different chemical reaction intervals during the combustion process: As, Pb, etc. tend to stay in the bottom ash or form sub-micron fine particle fly ash; some gaseous As and Pb have different characteristics on the particle surface
  • the phases condense to form heavy metal aerosols or are adsorbed by fine particles.
  • the particle size distribution of such heavy metal aerosols is quite different from that of traditional dust particles. They can easily penetrate existing dust removal devices and escape; the highly volatile Se compounds can even It exists in gaseous form and is directly discharged into the chimney into the atmosphere. All these have brought huge challenges to the emission control and coordinated removal of heavy metals from coal-fired power plants in my country.
  • the present invention provides a heterogeneous condensing adsorbent for heavy metal adsorption and its preparation method and application, wherein by optimizing its composition and ratio, it can be improved accordingly.
  • the adsorption effect of the adsorbent can effectively promote the adsorption of gaseous heavy metals in the flue gas and the coagulation of fine particulate heavy metals.
  • a heterogeneous condensing and adsorbent for heavy metal adsorption which, in terms of mass percentage, includes the following components: 0.005% to 0.01% polyacrylamide, 0.0005% ⁇ 0.001% calcium chloride, 0.001% ⁇ 0.01% coconut oil fatty acid diethanolamide, the balance is water.
  • the mass percentage of polyacrylamide in the heterogeneous condensation and adsorbent is preferably 0.008% to 0.01%.
  • the concentration of particulate heavy metals is less than 40 mg/m 3
  • the mass percentage of polyacrylamide in the heterogeneous coagulation adsorbent is preferably 0.005% to 0.008%.
  • the mass percentage of calcium chloride in the heterogeneous condensing and adsorbent is preferably 0.0007% to 0.001%, and when the gaseous heavy metal concentration in the flue gas is lower than 3 ⁇ g/g, the mass percentage of calcium chloride in the heterogeneous coagulation adsorbent is preferably 0.0005% to 0.0007%.
  • a method for preparing the above heterogeneous coagulation and adsorbent is proposed, which is characterized in that the method is specifically: adding polyacrylamide to water and stirring uniformly, and adding coconut oil fatty acid after being completely dissolved Diethanolamide and calcium chloride are finally stirred until they are completely dissolved to obtain the heterogeneous coagulation and adsorbent.
  • a method for using the above-mentioned heterogeneous condensing adsorbent for heavy metal adsorption is proposed.
  • the method is specifically: atomizing the heterogeneous condensing adsorbent into droplets, and then atomizing the heterogeneous condensing adsorbent into droplets.
  • the droplets are sprayed into the flue before the dust collector to trap gaseous heavy metals and condensed fine-particle heavy metals, thereby performing heavy metal adsorption.
  • the particle size of the droplets is preferably 50 ⁇ m to 60 ⁇ m.
  • the input amount of the heterogeneous condensation and adsorbent is preferably 1000 kg/h to 2000 kg/h.
  • the heterogeneous condensing and adsorbent provided by the present invention includes polyacrylamide, calcium chloride, coconut oil fatty acid diethanolamide and water, in which calcium ions can react with heavy metals such as arsenic and selenium in the gas phase to promote the generation of gaseous heavy metals
  • the heterogeneous adsorption is fixed on the heterogeneous condensing and adsorbent, thereby improving the removal efficiency of gaseous heavy metals by the dust collector; at the same time, the polyacrylamide dissolved in water has a large number of amide groups on the main chain, which has high chemical activity , It can be electrically neutralized between the fine particles rich in heavy metals, and the long polymer chains adsorbed on the surface of the particles can be adsorbed on the surface of another particle at the same time, and the two or more Condensation of many particles, through electrical neutralization, adsorption bridging effect to promote particle coagulation, thereby improving the removal efficiency of fine particulate heavy metals;
  • the heterogeneous condensing adsorbent provided by the present invention can adjust the proportion of each component in the heterogeneous condensing adsorbent according to the flue gas conditions and heavy metal emission characteristics, and has strong adaptability.
  • the concentration of heavy metals is high, the concentration of calcium chloride can be increased to promote the reaction of calcium ions with heavy metals in the gas phase.
  • the concentration of fine particulate heavy metals in the flue gas is high, the concentration of polyacrylamide can be increased to promote the fine particulate state. Condensation of heavy metals;
  • the preparation method of the heterogeneous coagulation adsorbent provided by the present invention has a wide range of raw materials, low price, simple and fast synthesis process, and no harm to the environment, so it has a good application prospect;
  • the present invention atomizes the heterogeneous condensation and adsorbent and sprays it into the flue before the dust collector. It can fully contact with gaseous heavy metals and fine particulate heavy metals and adsorb and condense, thereby improving the dust collector's heavy metals Removal efficiency.
  • Figure 1 is a diagram of the mechanism of action of the heterogeneous condensation and adsorbent for heavy metal adsorption provided by the present invention
  • Fig. 2 is a flow chart of using heterogeneous condensation and adsorbent to adsorb heavy metals in a preferred embodiment of the present invention.
  • the embodiment of the present invention proposes a heterogeneous coagulation and adsorbent for heavy metal adsorption, which, in terms of mass percentage, includes the following components: 0.005% to 0.01% polyacrylamide, 0.0005% to 0.001 % Calcium chloride, 0.001% to 0.01% coconut oil fatty acid diethanolamide, and the balance is water.
  • calcium chloride is used to provide calcium ions, which then react with heavy metals such as arsenic and selenium in the gas phase to promote heterogeneous condensation of gaseous heavy metals; when the concentration of gaseous heavy metals in the flue gas is higher than 3 ⁇ g/g, heterogeneous condensation and adsorption
  • the mass percentage of calcium chloride in the agent is preferably 0.0007% to 0.001%, so as to promote the heterogeneous condensation of calcium ions and gaseous heavy metals.
  • the mass percentage of calcium is preferably 0.0005% to 0.0007%.
  • polyacrylamide has a large number of amide groups with high chemical activity on the main chain, it can generate electrical neutralization between fine particles rich in heavy metals, and promote particle aggregation through adsorption and bridging. Therefore, when the concentration of fine particulate heavy metals in the flue gas is higher than 40mg/m 3 , the mass percentage of polyacrylamide in the heterogeneous condensation and adsorbent is preferably 0.008% to 0.01%, thereby promoting the adsorption of fine particulate heavy metals.
  • the concentration of fine particulate heavy metals in the gas is less than 40 mg/m 3 , and the mass percentage of polyacrylamide in the heterogeneous condensation and adsorbent is preferably 0.005% to 0.008%.
  • the present invention also proposes a method for preparing the above-mentioned heterogeneous coagulation and adsorbent.
  • the method is specifically as follows: adding polyacrylamide to water and stirring uniformly, adding coconut oil fatty acid diethanolamide and calcium chloride after being completely dissolved, and finally Stir to completely dissolve, so as to obtain heterogeneous condensation and adsorbent.
  • the present invention also proposes a method for using the above-mentioned heterogeneous condensing adsorbent for heavy metal adsorption.
  • the method is specifically: atomizing the heterogeneous condensing adsorbent into droplets, and then atomizing the droplets Sprayed into the flue before the dust collector, used to capture gaseous heavy metals and condensed fine particulate heavy metals, so as to carry out heavy metal adsorption;
  • the different components in the raw materials can be stored separately, and the heterogeneous coagulation and adsorbent can be obtained according to the proportion during use; or the high concentration solution can be prepared according to the proportion for storage, and the industrial water can be diluted in proportion to obtain the heterogeneous phase during use. Condensate adsorbent, but the storage time of the prepared high-concentration solution should not be too long, one week is appropriate.
  • the particle size of the droplets is preferably 50 ⁇ m to 60 ⁇ m, and the droplets within this particle size range can interact with particulate matter in the flue gas to achieve a better adsorption effect;
  • the input amount of the heterogeneous coagulation and adsorbent is preferably 1000kg/h to 2000kg/h, so as to avoid increasing production costs while ensuring the removal efficiency.
  • a heterogeneous coagulation and adsorbent which includes 0.01% polyacrylamide, 0.0005% calcium chloride, 0.008% coconut oil fatty acid diethanolamide, and the balance is water;
  • the heterogeneous condensed and adsorbent is atomized into droplets with a particle size of 60 ⁇ m, and the weight is 1000kg
  • the input amount of /h is sprayed into the reaction chamber, and the two interact in the simulated flue environment of the reaction chamber.
  • the residence time is about 3s.
  • the cloth bag uses conventional chemical fiber filter material, and EPA29 is used to take heavy metal sampling at the outlet of the bag dust removal device to determine the concentration of heavy metal emissions;
  • test results show that the concentration of heavy metal emissions decreased significantly after spraying the formula with heterogeneous condensation and adsorbent, and the gaseous heavy metals and fine particulate heavy metals after the dust removal device were reduced by 48.7% and 48.7% respectively compared with when the heterogeneous condensation and adsorbent was not sprayed. 64.3%.
  • a heterogeneous coagulant and adsorbent which includes 0.005% polyacrylamide, 0.001% calcium chloride, 0.006% coconut oil fatty acid diethanolamide, and the balance is water;
  • the heterogeneous condensate and adsorbent atomized into droplets with a diameter of 55 ⁇ m, and weighed 1100kg The input amount of /h is sprayed into the reaction chamber, and the two interact in the simulated flue environment of the reaction chamber.
  • the residence time is about 3s.
  • the cloth bag adopts conventional chemical fiber filter material, and EPA29 is used to take heavy metal sampling at the rear outlet of the cloth bag dust removal device to determine the concentration of heavy metal emissions;
  • test results show that the concentration of heavy metal emissions decreased significantly after spraying the formula with heterogeneous condensation and adsorbent, and the gaseous heavy metals and fine particulate heavy metals after the dust removal device were reduced by 52.3% and 52.3% respectively compared with when the heterogeneous condensation and adsorbent was not sprayed. 66.7%.
  • a heterogeneous coagulation and adsorbent which includes 0.006% polyacrylamide, 0.0007% calcium chloride, 0.01% coconut oil fatty acid diethanolamide, and the balance is water;
  • the heterogeneous condensate and adsorbent atomized into droplets with a diameter of 58 ⁇ m, and weighed at 1300kg The input amount of /h is sprayed into the reaction chamber, and the two interact in the simulated flue environment of the reaction chamber.
  • the residence time is about 3s.
  • the cloth bag uses conventional chemical fiber filter material, and EPA29 is used to take heavy metal sampling at the outlet of the bag dust removal device to determine the concentration of heavy metal emissions;
  • the test results showed that the heavy metal emission concentration decreased significantly after spraying the formula with heterogeneous condensation and adsorbent, and the gaseous heavy metals and fine particulate heavy metals after the dust removal device were reduced by 55.4% and 55.4% respectively compared with when the heterogeneous condensation and adsorbent was not sprayed. 69.8%.
  • a heterogeneous coagulant and adsorbent which includes 0.008% polyacrylamide, 0.0009% calcium chloride, 0.001% coconut oil fatty acid diethanolamide, and the balance is water;
  • the heterogeneous condensed and adsorbent is atomized into droplets with a particle size of 50 ⁇ m through a liquid distribution pump, compressed air, and dual-flow atomizing nozzles, and sprayed into the vertical at an input amount of 2000kg/h In the flue, it is used for heavy metal adsorption;
  • the gaseous heavy metals and fine-particle heavy metals in the smoke and dust were reduced by 59.6% and 75.2%, respectively, compared with when the heterogeneous condensation and adsorbent was not sprayed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

用于重金属吸附的异相凝并吸附剂及其制备方法和应用。该异相凝并吸附剂按照质量百分比计，包括以下组分：0.005％～0.01％的聚丙烯酰胺，0.0005％～0.001％的氯化钙，0.001％～0.01％的椰子油脂肪酸二乙醇酰胺，余量为水。异相凝并吸附剂中，钙离子可以促进气态重金属发生异相吸附从而固定在异相凝并吸附剂上；同时溶解于水中的聚丙烯酰胺可在富集重金属的细颗粒间发生电性中和作用，并通过架桥方式将两个或更多的颗粒凝并，进而提高细颗粒态重金属的脱除效率；此外，椰子油脂肪酸二乙醇酰胺可以降低水的表面张力，从而提高有机化合物的可溶性。

Description

用于重金属吸附的异相凝并吸附剂及其制备方法和应用 【技术领域】
本发明属于重金属吸附剂领域，更具体地，涉及用于重金属吸附的异相凝并吸附剂及其制备方法和应用。
【背景技术】
我国是目前世界上最大的煤炭生产和消费国，但是我国动力用煤种类繁杂、富含多种重金属，其中砷、硒、铅平均含量分别为3.8μg/g、2.8μg/g、16.9μg/g。同时因高重金属煤(平均值2倍以上)覆盖9大煤炭主产区，占全国煤炭总量的66％，因此燃煤是大气细颗粒物污染的主要来源。
大气中的细颗粒物上通常富集有大量有毒微量重金属，且容易被人体吸入，严重危害人类健康。不同重金属由于形态差异，其在燃烧过程中不同化学反应区间特性迥异：As、Pb等倾向于留在底灰中或形成亚微米级细颗粒飞灰；部分气态的As、Pb在颗粒表面发生异相凝结形成重金属气溶胶或被细颗粒吸附，这类重金属气溶胶的颗粒尺度分布与传统粉尘颗粒有着较大的差异，它们极易穿透现有除尘装置而逃逸；挥发性强的Se化合物甚至以气态形式存在，直接排入烟囱进入大气。这些都对我国燃煤电厂重金属的排放控制和协同脱除带来了巨大的挑战。
我国燃煤电厂在SO 2、NOx、粉尘等污染物方面超低排放控制已处于世界领先水平，但由于砷、硒、铅等为代表的重金属在国内动力煤中的分布富集差异和偏高特性，迫切需要针对典型煤种和高重金属煤种分别开展技术研发。通过抑制气态重金属产物的生成、强化现有装置对重金属的协同捕集、有针对性的控制易逃逸的细颗粒态重金属等这些关键技术问题攻克，促进我国燃煤电厂污染物的近零排放。
【发明内容】
针对现有技术的上述缺点和/或改进需求，本发明提供了一种用于重金属吸附的异相凝并吸附剂及其制备方法和应用，其中通过对其成分和比例进行优化，相应能够提高吸附剂的吸附效果，有效促进烟气中气态重金属的吸附和细颗粒态重 金属的凝并。
为实现上述目的，按照本发明的一个方面，提出了一种用于重金属吸附的异相凝并吸附剂，按照质量百分比计，包括以下组分：0.005％～0.01％的聚丙烯酰胺，0.0005％～0.001％的氯化钙，0.001％～0.01％的椰子油脂肪酸二乙醇酰胺，余量为水。
作为进一步优选地，当烟气中细颗粒态重金属的浓度高于40mg/m 3，所述异相凝并吸附剂中聚丙烯酰胺的质量百分比优选为0.008％～0.01％，当烟气中细颗粒态重金属的浓度低于40mg/m 3，所述异相凝并吸附剂中聚丙烯酰胺的质量百分比优选为0.005％～0.008％。
作为进一步优选地，当烟气中气态重金属浓度高于3μg/g，所述异相凝并吸附剂中氯化钙的质量百分比优选为0.0007％～0.001％，当烟气中气态重金属浓度低于3μg/g，所述异相凝并吸附剂中氯化钙的质量百分比优选为0.0005％～0.0007％。
按照本发明的另一方面，提出了一种制备上述异相凝并吸附剂的方法，其特征在于，该方法具体为：向水中加入聚丙烯酰胺并搅拌均匀，待完全溶解后加入椰子油脂肪酸二乙醇酰胺和氯化钙，最后搅拌至完全溶解，以此获得所述异相凝并吸附剂。
按照本发明的又一方面，提出了一种将上述异相凝并吸附剂用于重金属吸附的方法，该方法具体为：将所述异相凝并吸附剂雾化为液滴，然后将所述液滴喷入除尘器之前的烟道中，用于捕集气态重金属和凝并细颗粒态重金属，从而进行重金属吸附。
作为进一步优选地，所述液滴的粒径优选为50μm～60μm。
作为进一步优选地，所述异相凝并吸附剂的投入量优选为1000kg/h～2000kg/h。
总体而言，通过本发明所构思的以上技术方案与现有技术相比，主要具备以下的技术优点：
1.本发明提供的异相凝并吸附剂包括聚丙烯酰胺、氯化钙、椰子油脂肪酸二乙醇酰胺以及水，其中钙离子可以与气相中的砷、硒等重金属发生反应，促进气 态重金属发生异相吸附从而固定在异相凝并吸附剂上，进而提高除尘器对气态重金属的脱除效率；同时溶解于水中的聚丙烯酰胺的主链上带有大量的酰胺基，其化学活性较高，可在富集重金属的细颗粒间发生电性中和作用，而吸附在颗粒表面上的高分子长链可同时吸附在另一个颗粒的表面上，通过“架桥”方式将两个或更多的颗粒凝并，通过电性中和、吸附架桥作用促进颗粒发生凝并，进而提高除尘器对细颗粒态重金属的脱除效率；此外，椰子油脂肪酸二乙醇酰胺可以降低水的表面张力，从而提高有机化合物的可溶性，有利于凝并的发生，因此本发明提供的异相凝并吸附剂对气态重金属和细颗粒态重金属的团聚作用显著，可使燃煤电厂重金属排放降低50％以上；
2.尤其是，本发明提供的异相凝并吸附剂可以根据烟气条件及重金属排放特性调节异相凝并吸附剂中各组分的比例，具有较强的适应性，当烟气中气态重金属浓度较高时，则可以提高氯化钙的浓度，促进钙离子与气相重金属发生反应，当烟气中细颗粒态重金属的浓度较高时，可以提高聚丙烯酰胺的浓度，促进细颗粒态重金属发生凝并；
3.此外，本发明提供的异相凝并吸附剂的制备方法原料来源广泛，价格低廉，合成过程简单快捷，并且对环境没有危害，因此具有较好的应用前景；
4.同时，本发明将异相凝并吸附剂雾化后喷入除尘器之前的烟道中，能够与气态重金属和细颗粒态重金属充分接触并发生吸附和凝并，从而提高除尘器对重金属的脱除效率。
【附图说明】
图1是本发明提供的用于重金属吸附的异相凝并吸附剂的作用机理图；
图2是本发明优选实施例中利用异相凝并吸附剂吸附重金属的流程图。
【具体实施方式】
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
如图1所示，本发明实施例提出了一种用于重金属吸附的异相凝并吸附剂，按照质量百分比计，包括以下组分：0.005％～0.01％的聚丙烯酰胺，0.0005％～0.001％的氯化钙，0.001％～0.01％的椰子油脂肪酸二乙醇酰胺，余量为水。
进一步，氯化钙用于提供钙离子，进而与气相中的砷、硒等重金属发生反应，促进气态重金属异相凝并；当烟气中气态重金属浓度高于3μg/g，异相凝并吸附剂中氯化钙的质量百分比优选为0.0007％～0.001％，从而促进钙离子与气态重金属发生异相凝并，当烟气中气态重金属浓度低于3μg/g，异相凝并吸附剂中氯化钙的质量百分比优选为0.0005％～0.0007％。
进一步，由于聚丙烯酰胺的主链上带有大量具有高化学活性的酰胺基，其可在富集重金属的细颗粒间发生电性中和作用，并通过吸附架桥作用促进颗粒的凝并，因此当烟气中细颗粒态重金属的浓度高于40mg/m 3，异相凝并吸附剂中聚丙烯酰胺的质量百分比优选为0.008％～0.01％，从而促进细颗粒态重金属的吸附，当烟气中细颗粒态重金属的浓度低于40mg/m 3，异相凝并吸附剂中聚丙烯酰胺的质量百分比优选为0.005％～0.008％。
本发明还提出了一种制备上述异相凝并吸附剂的方法，该方法具体为：向水中加入聚丙烯酰胺并搅拌均匀，待完全溶解后加入椰子油脂肪酸二乙醇酰胺和氯化钙，最后搅拌至完全溶解，以此获得异相凝并吸附剂。
如图2所示，本发明还提出了一种将上述异相凝并吸附剂用于重金属吸附的方法，该方法具体为：将异相凝并吸附剂雾化为液滴，然后将液滴喷入除尘器之前的烟道中，用于捕集气态重金属和凝并细颗粒态重金属，从而进行重金属吸附；
在使用前可将原料中不同组分独立储存，使用时按照比例进行配比获得异相凝并吸附剂；或者按比例配成高浓度溶液进行储存，使用时按比例添加工业水稀释获得异相凝并吸附剂，但配得的高浓度溶液储存时间不宜过久，以一周为宜。
进一步，液滴的粒径优选为50μm～60μm，该粒径范围内的液滴能够在烟道内与烟气中的颗粒物相互作用实现较好的吸附效果；
异相凝并吸附剂的投入量优选为1000kg/h～2000kg/h，从而在保证脱除效率的同时避免增加生产成本。
可以针对燃煤电厂、水泥厂、冶炼厂等工业系统的除尘设备进行异相凝并技术改造，根据不同烟气条件及燃煤重金属排放浓度特性调节异相凝并吸附剂不同组分的比例，确定异相凝并吸附剂用量，在除尘器之前的烟道中布置双流雾化喷嘴，将异相凝并吸附剂以微米级液滴喷入，促进气态重金属捕集和细颗粒态重金属凝并，提高除尘器对气态重金属和细颗粒态重金属的脱除效率，降低重金属排放浓度，保护大气环境。
下面根据具体实施例对本发明作进一步说明。
实施例1
配制一种异相凝并吸附剂，其中包括0.01％的聚丙烯酰胺、0.0005％的氯化钙、0.008％的椰子油脂肪酸二乙醇酰胺，余量为水；
采用某电厂静电除尘器五电场细灰与含砷、硒的预热空气混合作为模拟烟气通入反应室，将该异相凝并吸附剂雾化为粒径60μm的液滴，并以1000kg/h的投入量喷入反应室中，两者在反应室内模拟烟道环境中发生相互作用，停留时间约3s，异相凝并吸附剂促使细颗粒物团聚长大，进而被后续的布袋除尘器捕获，布袋采用常规化纤滤料，采用EPA29在布袋除尘装置后部出口处进行重金属取样，测定重金属排放浓度；
测试结果表明，喷入该配方异相凝并吸附剂后重金属排放浓度明显下降，除尘装置后气态重金属和细颗粒态重金属与未喷入异相凝并吸附剂时相比分别降低了48.7％和64.3％。
实施例2
配制一种异相凝并吸附剂，其中包括0.005％的聚丙烯酰胺、0.001％的氯化钙、0.006％的椰子油脂肪酸二乙醇酰胺，余量为水；
采用某电厂静电除尘器五电场细灰与含砷、硒的预热空气混合作为模拟烟气通入反应室，将该异相凝并吸附剂雾化为粒径55μm的液滴，并以1100kg/h的投入量喷入反应室中，两者在反应室内模拟烟道环境中发生相互作用，停留时间约3s，异相凝并吸附剂促使细颗粒物团聚长大，进而被后续的布袋除尘器捕获，布袋采用常规化纤滤料，采用EPA29在布袋除尘装置后部出口处进行重金属取样， 测定重金属排放浓度；
测试结果表明，喷入该配方异相凝并吸附剂后重金属排放浓度明显下降，除尘装置后气态重金属和细颗粒态重金属与未喷入异相凝并吸附剂时相比分别降低了52.3％和66.7％。
实施例3
配制一种异相凝并吸附剂，其中包括0.006％的聚丙烯酰胺、0.0007％的氯化钙、0.01％的椰子油脂肪酸二乙醇酰胺，余量为水；
采用某电厂静电除尘器五电场细灰与含砷、硒的预热空气混合作为模拟烟气通入反应室，将该异相凝并吸附剂雾化为粒径58μm的液滴，并以1300kg/h的投入量喷入反应室中，两者在反应室内模拟烟道环境中发生相互作用，停留时间约3s，异相凝并吸附剂促使细颗粒物团聚长大，进而被后续的布袋除尘器捕获，布袋采用常规化纤滤料，采用EPA29在布袋除尘装置后部出口处进行重金属取样，测定重金属排放浓度；
测试结果表明，喷入该配方异相凝并吸附剂后重金属排放浓度明显下降，除尘装置后气态重金属和细颗粒态重金属与未喷入异相凝并吸附剂时相比分别降低了55.4％和69.8％。
实施例4
配制一种异相凝并吸附剂，其中包括0.008％的聚丙烯酰胺、0.0009％的氯化钙、0.001％的椰子油脂肪酸二乙醇酰胺，余量为水；
在某300MW锅炉静电除尘器前，通过配液泵、压缩空气、双流雾化喷嘴将该异相凝并吸附剂雾化为粒径50μm的液滴，并以2000kg/h的投入量喷入垂直烟道中，用于进行重金属吸附；
烟尘中气态重金属和细颗粒态重金属与未喷入异相凝并吸附剂时相比分别降低了59.6％和75.2％。
本领域的技术人员容易理解，以上仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (7)

  1. 一种用于重金属吸附的异相凝并吸附剂，其特征在于，按照质量百分比计，包括以下组分：0.005％～0.01％的聚丙烯酰胺，0.0005％～0.001％的氯化钙，0.001％～0.01％的椰子油脂肪酸二乙醇酰胺，余量为水。
  2. 如权利要求1所述的用于重金属吸附的异相凝并吸附剂，其特征在于，当烟气中细颗粒态重金属的浓度高于40mg/m 3，所述异相凝并吸附剂中聚丙烯酰胺的质量百分比优选为0.008％～0.01％，当烟气中细颗粒态重金属的浓度低于40mg/m 3，所述异相凝并吸附剂中聚丙烯酰胺的质量百分比优选为0.005％～0.008％。
  3. 如权利要求1或2所述的用于重金属吸附的异相凝并吸附剂，其特征在于，当烟气中气态重金属浓度高于3μg/g，所述异相凝并吸附剂中氯化钙的质量百分比优选为0.0007％～0.001％，当烟气中气态重金属浓度低于3μg/g，所述异相凝并吸附剂中氯化钙的质量百分比优选为0.0005％～0.0007％。
  4. 一种制备如权利要求1～3任一项所述的异相凝并吸附剂的方法，其特征在于，该方法具体为：向水中加入聚丙烯酰胺并搅拌均匀，待完全溶解后加入椰子油脂肪酸二乙醇酰胺和氯化钙，最后搅拌至完全溶解，以此获得所述异相凝并吸附剂。
  5. 一种将如权利要求1～3任一项所述的异相凝并吸附剂用于重金属吸附的方法，其特征在于，该方法具体为：将所述异相凝并吸附剂雾化为液滴，然后将所述液滴喷入除尘器之前的烟道中，用于捕集气态重金属和凝并细颗粒态重金属，从而进行重金属吸附。
  6. 如权利要求5所述的将异相凝并吸附剂用于重金属吸附的方法，其特征在于，所述液滴的粒径优选为50μm～60μm。
  7. 如权利要求5或6所述的将异相凝并吸附剂用于重金属吸附的方法， 其特征在于，所述异相凝并吸附剂的投入量优选为1000kg/h～2000kg/h。
PCT/CN2019/110747 2019-06-28 2019-10-12 用于重金属吸附的异相凝并吸附剂及其制备方法和应用 Ceased WO2020258588A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US16/967,136 US11745135B2 (en) 2019-06-28 2019-10-12 Heterogeneous agglomeration adsorbent for heavy metal adsorption, method for preparing same, and applications thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910579543.6 2019-06-28
CN201910579543.6A CN110330062B (zh) 2019-06-28 2019-06-28 用于重金属吸附的异相凝并吸附剂及其制备方法和应用

Publications (1)

Publication Number Publication Date
WO2020258588A1 true WO2020258588A1 (zh) 2020-12-30

Family

ID=68144664

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/110747 Ceased WO2020258588A1 (zh) 2019-06-28 2019-10-12 用于重金属吸附的异相凝并吸附剂及其制备方法和应用

Country Status (3)

Country Link
US (1) US11745135B2 (zh)
CN (1) CN110330062B (zh)
WO (1) WO2020258588A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110882619A (zh) * 2019-11-26 2020-03-17 华中科技大学 一种用于捕集燃煤烟气中硒的碱基吸附剂及其制备方法
CN110975411A (zh) * 2019-12-20 2020-04-10 中核二七二铀业有限责任公司 一种萃原液预处理过滤设备
CN112845535A (zh) * 2021-01-28 2021-05-28 中国神华能源股份有限公司国华电力分公司 一种重金属固化剂及其制备方法和应用方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7713421B2 (en) * 2003-12-09 2010-05-11 Separation Design Group, Llc Sorption method, device, and system
JP2014180643A (ja) * 2013-03-21 2014-09-29 Kuraray Co Ltd 金属イオン吸着材、及び金属回収方法
CN105329977A (zh) * 2015-12-10 2016-02-17 广西森合高新科技股份有限公司 一种处理贵金属生产含氰废水的吸附剂及其制备方法
CN105771531A (zh) * 2016-04-11 2016-07-20 武汉天空蓝环保科技有限公司 一种化学团聚促进剂
CN106082415A (zh) * 2016-07-06 2016-11-09 青岛特澳能源检测有限公司 一种高效的用于重金属处理的稳定剂
CN107096350A (zh) * 2017-04-26 2017-08-29 华中科技大学 一种协同去除燃煤烟气污染物的化学团聚促进剂及方法

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4169714A (en) * 1977-01-14 1979-10-02 A.P.T., Inc. Removal of fine particles from a gas stream by solid particle addition in venturi contactor
DE3926169A1 (de) * 1989-08-08 1991-02-14 Basf Ag Verfahren zur verbesserung der wasseraufnahmekapazitaet von vernetzten, wasserquellbaren polymeren
WO1998011992A1 (en) * 1996-09-20 1998-03-26 Philp Sanborn F Removal of respirable particulate matter from flue gases
JP3711229B2 (ja) * 2000-06-30 2005-11-02 株式会社日本触媒 廃液処理方法
CN1231286C (zh) * 2001-04-28 2005-12-14 清华大学 一种添加铁质飞灰的循环流化床烟气净化方法及其装置
US6495504B1 (en) * 2002-07-31 2002-12-17 Colgate-Palmolive Company Unit dose nonaqueous softener disposed in water soluble container
CA2577549C (en) * 2004-08-25 2017-02-21 John Tsavalas Paper manufacturing using agglomerated hollow particle latex
CN101445758A (zh) * 2008-12-19 2009-06-03 华中科技大学 燃烧过程中减少细微颗粒物及金属排放的方法
US8967383B1 (en) * 2012-10-19 2015-03-03 KaMin, LLC Processes for producing high-brightness kaolin in high yields, and kaolin materials produced therefrom
US20150060145A1 (en) * 2013-09-01 2015-03-05 Daryl Breese Drilling Fluid That Fracks While Drilling And Can Be Used In Well Completion
US10576413B2 (en) * 2014-12-10 2020-03-03 Ethan J. Novek Systems and methods for separating gases
CN104474830B (zh) * 2014-12-12 2016-05-11 广东电网有限责任公司电力科学研究院 用于脱除燃煤细颗粒物的化学团聚促进剂及其使用方法
US10793768B2 (en) * 2016-04-29 2020-10-06 PfP Industries LLC Polyacrylamide slurry for fracturing fluids
EP3545055B1 (en) * 2016-11-25 2024-11-13 Commonwealth Scientific and Industrial Research Organisation Particulate material and method for removing one or more contaminants from hydrocarbon gas
CN112996825B (zh) * 2018-11-07 2023-10-03 株式会社日本触媒 颗粒状吸水剂的制造方法及颗粒状吸水剂
WO2023091856A1 (en) * 2021-11-17 2023-05-25 Johnson & Johnson Consumer Inc. Curable absorbent films

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7713421B2 (en) * 2003-12-09 2010-05-11 Separation Design Group, Llc Sorption method, device, and system
JP2014180643A (ja) * 2013-03-21 2014-09-29 Kuraray Co Ltd 金属イオン吸着材、及び金属回収方法
CN105329977A (zh) * 2015-12-10 2016-02-17 广西森合高新科技股份有限公司 一种处理贵金属生产含氰废水的吸附剂及其制备方法
CN105771531A (zh) * 2016-04-11 2016-07-20 武汉天空蓝环保科技有限公司 一种化学团聚促进剂
CN106082415A (zh) * 2016-07-06 2016-11-09 青岛特澳能源检测有限公司 一种高效的用于重金属处理的稳定剂
CN107096350A (zh) * 2017-04-26 2017-08-29 华中科技大学 一种协同去除燃煤烟气污染物的化学团聚促进剂及方法

Also Published As

Publication number Publication date
US20210370225A1 (en) 2021-12-02
CN110330062A (zh) 2019-10-15
US11745135B2 (en) 2023-09-05
CN110330062B (zh) 2020-08-14

Similar Documents

Publication Publication Date Title
CN105126561B (zh) 一种基于脱硫废水蒸发处理的燃煤烟气PM2.5/SO3/Hg联合脱除方法
CN101513583B (zh) 一种燃煤超细颗粒化学团聚促进剂
CN104474830B (zh) 用于脱除燃煤细颗粒物的化学团聚促进剂及其使用方法
CN103432887B (zh) 一种垃圾焚烧烟气净化系统及工艺
CN103721550B (zh) 烟气同时脱硫脱硝脱VOCs吸收剂及其制备和应用
WO2020258588A1 (zh) 用于重金属吸附的异相凝并吸附剂及其制备方法和应用
CN111330427A (zh) 一种金属硫化物脱汞剂在洗涤脱除烟气中汞方面的应用
CN109012091A (zh) 一种协同脱除烟气中Hg0和废液中Hg2+的方法
CN104147890B (zh) 利用凹凸棒粘土悬浊液团聚捕集燃煤pm2.5的方法
CN106512704B (zh) 一种除尘器飞灰改性高效脱汞方法及系统
CN103521052A (zh) 一种利用燃煤电厂的脱硫废水进行烟气脱汞的方法及系统
CN211146501U (zh) 一种污泥喷雾干化焚烧协同脱硫的装置
CN107601570A (zh) 一种可再生循环利用的汞吸附剂及其制备与再生方法
CN107096350A (zh) 一种协同去除燃煤烟气污染物的化学团聚促进剂及方法
CN102657992B (zh) 电气石团聚pm2.5颗粒的烟气净化装置及其净化方法
CN102500208A (zh) 一种湿法烟气脱硫废水的利用方法和装置
CN203437026U (zh) 一种垃圾焚烧烟气净化系统
CN105771531B (zh) 一种化学团聚促进剂
CN106076095A (zh) 基于电袋除尘器去除烟气中汞及三氧化硫的控制方法及装置
CN110449017A (zh) 一种碱液喷射提升wesp脱除砷硒铅重金属的装置
CN203635061U (zh) 一种尾气净化装置
CN102886203B (zh) 一种烟气脱硫脱汞的方法
CN115475596B (zh) 一种有效协同脱除so2和重金属的双氧掺杂氮化硼催化剂的制备方法
CN104258699B (zh) 等离子体与气固或气液分散系协同净化污染物的方法
CN116688745B (zh) 一种组合脱硫剂及其垃圾焚烧系统脱硫提标改造的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19934760

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19934760

Country of ref document: EP

Kind code of ref document: A1