WO2023000523A1 - 铜基硫化物脱汞剂载体及其制备方法 - Google Patents

铜基硫化物脱汞剂载体及其制备方法 Download PDF

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Publication number
WO2023000523A1
WO2023000523A1 PCT/CN2021/125031 CN2021125031W WO2023000523A1 WO 2023000523 A1 WO2023000523 A1 WO 2023000523A1 CN 2021125031 W CN2021125031 W CN 2021125031W WO 2023000523 A1 WO2023000523 A1 WO 2023000523A1
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copper
mercury removal
agent carrier
removal agent
based sulfide
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PCT/CN2021/125031
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English (en)
French (fr)
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许龙龙
张振国
赵少丹
黄迪
王文幼
薛春珍
吕克
罗圆
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西安向阳航天材料股份有限公司
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Priority to JP2022552496A priority Critical patent/JP7419559B2/ja
Priority to US17/939,936 priority patent/US20230030866A1/en
Publication of WO2023000523A1 publication Critical patent/WO2023000523A1/zh

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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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • 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
    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • 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
    • B01D2253/104—Alumina
    • 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
    • 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

Definitions

  • the invention belongs to the technical field of preparation methods of mercury removal agents, and relates to a copper-based sulfide mercury removal agent carrier and a preparation method thereof.
  • mercury is highly volatile, highly toxic and corrosive, it will cause serious harm to the environment and process equipment, and directly affect the development and utilization of mercury-containing natural gas. security.
  • the mercury content in raw gas is generally required to be less than 0.01 ⁇ g/m 3 , because a large number of aluminum plate-fin heat exchangers are used in natural gas liquefaction and natural gas condensate recovery devices, mercury It will condense and enrich in the heat exchanger, form amalgam with aluminum and cause the dense aluminum oxide film on the aluminum surface to fall off, resulting in corrosion and perforation of equipment.
  • the mercury content in China's natural gas fields is usually between 1 ⁇ g/m 3 and 200 ⁇ g/m 3 , and some even as high as 2000 ⁇ g/m 3 , and with the development of gas fields, the mercury content shows an upward trend.
  • people pay more and more attention to environmental issues, how to effectively remove mercury has become an urgent problem to be solved.
  • mercury removal technology is to develop efficient mercury removal agents.
  • metal sulfides represented by copper-based sulfides have shown excellent mercury removal effects.
  • copper-based sulfide can fix Hg 0 in the form of HgS, with strong binding force and high mercury removal accuracy.
  • the reaction mechanism of mercury removal is shown in the following formula:
  • the research focus of copper-based sulfide mercury removal agents usually focuses on the modification and loading process of the active component copper sulfide, and there is less research on the modification of the carrier, and the carrier also plays a role in the mercury removal effect of the mercury removal agent. It plays a crucial role.
  • a suitable carrier must be used.
  • mercury removal agents based on hydrated alumina still have the disadvantage of decreasing mercury capacity during use or storage, which needs to be overcome. Therefore, in order to prepare metal sulfide-type mercury removal agents with high mercury capacity and high precision, the development of suitable carriers is one of the key technologies, and it is also one of the bottlenecks restricting the development of mercury removal technology in my country.
  • One of the objectives of the present invention is to provide a method for preparing a copper-based sulfide mercury removal agent carrier, which uses alumina hydrate as the basic raw material, and can prepare a mercury removal agent with high mercury content through acid modification and addition of silicon additives .
  • the second object of the present invention is to provide a copper-based sulfide mercury removal agent carrier.
  • the technical solution adopted in the present invention is a preparation method of a copper-based sulfide mercury removal agent carrier, comprising the following steps:
  • Step 1 mixing alumina hydrate with an organic acid to obtain a mixed solution A;
  • Step 2 adding tetraalkylsiloxane to the mixed solution A obtained in Step 1, stirring under airtight conditions, spraying atomized water, and continuing to stir to obtain a mercury removal agent carrier.
  • the aluminum oxide hydrate and the organic acid are mixed at -10°C to 40°C.
  • the mass of the organic acid in the mixed solution A obtained in the step 1 is 1% to 10% of the mass of the alumina hydrate.
  • the mass of the organic acid in the mixed solution A obtained in the step 1 is 6% of the mass of the alumina hydrate.
  • the organic acid in step 1 is any one of oxalic acid, ethylenediaminetetraacetic acid or citric acid.
  • the mass of tetraalkylsiloxane added in step 2 is 3%-15% of the mass of alumina hydrate.
  • the tetraalkylsiloxane is tetramethylsiloxane or tetraethylsiloxane.
  • the mass of the atomized water sprayed in step 2 is 3 to 8 times the mass of the tetraalkylsiloxane.
  • step 2 after spraying atomized water in step 2, stirring is continued for 1 h to 24 h to obtain a mercury removal agent carrier.
  • the technical solution adopted in the present invention is that a copper-based sulfide mercury removal agent carrier is prepared by the above-mentioned method.
  • the mercury removal agent prepared by adopting the copper-based sulfide mercury removal agent carrier provided by the present invention has the same preparation process and the same content of active copper sulfide, and the mercury removal ability is increased by at least 10% .
  • the mercury removal agent prepared by using the copper-based sulfide mercury removal agent carrier provided by the present invention will not decrease in mercury removal ability during use or storage, and can be stored for a long time.
  • the principle of the present invention is to avoid the cross-linking of the hydrous oxide carrier during use.
  • the carrier of copper-based sulfide mercury removal agent provided by the present invention is based on hydrated alumina, which is modified during the preparation process.
  • the addition of organic acid can effectively inhibit the dehydration of hydrated alumina;
  • the addition of silicon additive tetraalkylsiloxane can form a protective film on the surface of the carrier, reduce the contact between the hydrated alumina particles, and also slow down the dehydration process.
  • the groups contained in the organic acid have a certain complex adsorption capacity for mercury, which can accelerate the surface adsorption process of mercury and promote the increase of mercury capacity, thereby increasing the mercury content of the copper-based sulfide mercury removal agent carrier provided by the present invention. Allow.
  • the preparation steps of the mercury removal agent carrier provided by the present invention are simple and low in cost.
  • Step 1 mixing alumina hydrate and organic acid at -10°C to 40°C to obtain mixed solution A, wherein the amount of organic acid added is 1% to 10% of the mass of alumina hydrate, and the organic acid is oxalic acid, ethyl One of diaminetetraacetic acid or citric acid;
  • Step 2 add tetraalkylsiloxane with a mass of 3% to 15% of the mass of alumina hydrate to the mixed solution A obtained in step 1, and the tetraalkylsiloxane is tetramethylsiloxane or tetraethylsiloxane
  • the oxane is continuously stirred under airtight conditions, and sprayed with atomized water.
  • the amount of atomized water is 3 to 8 times the mass of the tetraalkylsiloxane, and the mercury removal agent carrier is obtained after continuing to stir for 1 to 24 hours.
  • the preparation method of the copper-based sulfide mercury removal agent carrier provided by the embodiment of the present invention has simple steps and low cost.
  • Step 1 Mechanically mix 100g quick-release powder and 1g oxalic acid at 40°C for 10 minutes;
  • Step 2 continue to add 3g of tetramethylsiloxane
  • Step 3 Stir the above materials continuously under airtight conditions, spray 24 g of atomized water, and continue stirring for 5 hours to obtain a mercury removal agent carrier.
  • Step 1 Mechanically mix 100g of aluminum hydroxide and 5g of ethylenediaminetetraacetic acid at 30°C for 20min;
  • Step 2 continue to add 5g tetraethylsiloxane
  • Step 3 Stir the above materials continuously under airtight conditions, spray 15 g of atomized water, and continue stirring for 1 hour to obtain a mercury removal agent carrier.
  • Step 1 Mechanically mix 100g quick-release powder and 10g citric acid at 0°C for 20min;
  • Step 2 continue to add 10g tetraethylsiloxane
  • Step 3 Stir the above materials continuously under airtight conditions, spray 40 g of atomized water, and continue stirring for 24 hours to obtain a mercury removal agent carrier.
  • Step 1 Mechanically mix 100g of pseudoboehmite and 6g of citric acid at -10°C for 30min;
  • Step 2 continue to add 6g tetraethylsiloxane
  • Step 3 Stir the above materials continuously under airtight conditions, spray 30 g of atomized water, and continue stirring for 12 hours to obtain a mercury removal agent carrier.
  • Step 1 Mechanically mix 100g quick-release powder with 6g citric acid at 25°C for 30min;
  • Step 2 continue to add 6g tetraethylsiloxane
  • Step 3 Stir the above materials continuously under airtight conditions, spray 30 g of atomized water, and continue stirring for 12 hours to obtain a mercury removal agent carrier.
  • the comparative example and Examples 1-5 were used as the mercury removal agent carrier, and the metal sulfide mercury removal agent was prepared by conventional molding technology in the field, so that the metal sulfide content in the finished product was 35%. Since the technology for preparing the metal sulfide mercury removal agent is an existing technology, it will not be repeated here.
  • the prepared mercury removal agent was tested for performance within 1 day after preparation, after 3 months of storage, and after 6 months of storage.
  • the test conditions are: loading volume: 0.1ml; particle size: 0.25 ⁇ 0.45mm; pressure: normal pressure; reaction temperature: 50°C; room temperature: 30°C; space velocity: 1.5 ⁇ 105h -1 ; raw material gas composition: 1:2 methane and nitrogen; mercury content: 20-25mg/m 3 .
  • Example 1 sample number Mercury content (%) Mercury content after storage for 3 months (%) Mercury content after storage for 6 months (%) comparative example 12.5 10.5 8.4 Example 1 14.1 13.9 13.5 Example 2 14.3 14.2 14.0 Example 3 15.6 15.5 15.5 Example 4 17.1 17.1 17.0 Example 5 16.8 16.6 16.6
  • the carrier prepared by the method for preparing the copper-based sulfide mercury removal agent carrier provided by the present invention can make the finished mercury removal agent have higher
  • the mercury capacity is at least 10% higher than that of the unmodified carrier.
  • the mercury content does not decrease significantly, while the mercury content of the unmodified carrier decreases continuously during the storage process. It shows that the carrier provided by the present invention has a good improvement effect on the metal sulfide mercury removal agent.
  • Step 1 mixing alumina hydrate and oxalic acid at -10°C to obtain mixed solution A, wherein the amount of organic acid added is 1% of the mass of alumina hydrate;
  • Step 2 add tetramethylsiloxane with 3% alumina hydrate quality to the mixed solution A in step 1, stir continuously under airtight conditions, and spray atomized water, the amount of atomized water is tetraalkylsiloxane 3 times the mass of oxane, and continue stirring for 1 hour to obtain a mercury removal agent carrier.
  • Step 1 mixing alumina hydrate and ethylenediaminetetraacetic acid at 20°C to obtain a mixed solution A, wherein the amount of organic acid added is 6% of the mass of alumina hydrate;
  • Step 2 add tetraethylsiloxane with 9% alumina hydrate quality to the mixed solution A in step 1, stir continuously under airtight conditions, and spray atomized water, the amount of atomized water is tetraalkylsiloxane 5 times the mass of oxane, and continue to stir for 15 hours to obtain a mercury removal agent carrier.
  • Step 1 mixing alumina hydrate and citric acid at 40°C to obtain a mixed solution A, wherein the amount of citric acid added is 10% of the mass of alumina hydrate;
  • Step 2 add tetraethylsiloxane with 15% alumina hydrate mass to the mixed solution in step 1, stir continuously under airtight conditions, and spray atomized water, the amount of atomized water is tetraalkylsiloxane 8 times the mass of alkane, and continue to stir for 24 hours to obtain a mercury removal agent carrier.
  • the principle of the present invention is to avoid cross-linking of the hydrous oxide support during use.
  • the mercury removal ability of the same mass metal sulfide was seriously reduced.
  • the mercury removal ability of raw copper sulfide can be very strong, and the mercury removal ability of 1 part of copper sulfide can absorb more than 0.6 parts of mercury in terms of mass.
  • 1 part of copper sulfide can absorb 0.4 part of mercury at most, and the longer the time of storage, the worse the mercury removal ability of the sample.
  • hydrated alumina will continue to dehydrate to form a cross-linked structure during use or storage, resulting in continuous changes in pore volume and pore structure. It is difficult for the water under the product to escape, which also prevents the contact of mercury with copper sulfide. Therefore, during use or storage, the mercury content of the mercury removal agent will decrease.
  • the carrier of copper-based sulfide mercury removal agent provided by the present invention is based on hydrated alumina, which is modified during the preparation process.
  • the addition of organic acid can effectively inhibit the dehydration of hydrated alumina;
  • the addition of silicon additive tetraalkylsiloxane can form a protective film on the surface of the carrier, reduce the contact between the hydrated alumina particles, and also slow down the dehydration process.
  • the groups contained in the organic acid have a certain ability to complex and adsorb mercury, which can accelerate the surface adsorption process of mercury and promote the increase of the mercury capacity of the carrier.

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Abstract

本发明公开了一种铜基硫化物脱汞剂载体及其制备方法，其中，铜基硫化物脱汞剂载体的制备方法包括如下步骤：步骤1，将水合氧化铝与有机酸混合，得到混合溶液A；步骤2，向步骤1得到的混合溶液A中加入四烷基硅氧烷，在密闭条件下进行搅拌，并喷入雾化水，继续搅拌后得到脱汞剂载体。本发明提供的铜基硫化物脱汞剂载体的制备方法，以水合氧化铝为基础原材料，通过酸改性及添加硅助剂，能制备出高汞容的脱汞剂。

Description

铜基硫化物脱汞剂载体及其制备方法 技术领域
本发明属于脱汞剂制备方法技术领域，涉及一种铜基硫化物脱汞剂载体及其制备方法。
背景技术
在天然气开发中发现，大部分的天然气气田中都含有微量的汞，由于汞具有高挥发性、高毒性及腐蚀性，会对环境和工艺设备造成严重的危害，直接影响含汞天然气开发和利用的安全性。在天然气液化及凝液回收装置中，一般要求原料气中汞含量低于0.01μg/m 3，因为天然气液化及天然气凝液回收等装置中采用了大量的铝制板翅式换热器，汞会在换热器部位冷凝富集，与铝形成汞齐并使铝表面的致密氧化铝膜脱落，导致设备腐蚀穿孔。我国天然气田中汞含量通常在1μg/m 3～200μg/m 3之间，有的甚至高达2000μg/m 3，并且随着气田的开发，汞含量呈现上升趋势。随着我国社会经济的不断发展，人们对环境问题日益重视，如何有效脱汞成为当前亟待解决的问题。
目前脱汞技术的重点在于开发高效的脱汞剂。其中，以铜基硫化物为代表的金属硫化物表现出了优越的脱汞效果。铜基硫化物在脱汞过程中，可以使Hg 0以HgS的形式固定下来，结合力强，脱汞精度高，其脱汞反应机理如下式所示：
Hg+Cu XS y→HgS+Cu XS y-1
目前，铜基硫化物脱汞剂的研究重点通常集中在活性组分硫化铜的改性及负载工艺上，对载体改性的研究较少，而载体同样对脱汞剂的脱汞效果起着至关重要的作用，要制备脱汞性能好的脱汞剂，必须采用合适的载体。另外，以水合氧 化铝为载体的脱汞剂在使用或保存过程中还存在汞容不断降低的缺点，需要进行克服。因此，要制备高汞容、高精度的金属硫化物型脱汞剂，开发合适的载体是技术关键之一，也是制约我国脱汞技术发展的瓶颈之一。
发明内容
本发明的目的之一是提供一种铜基硫化物脱汞剂载体的制备方法，以水合氧化铝为基础原材料，通过酸改性及添加硅助剂，能制备出高汞容的脱汞剂。
本发明的目的之二是提供一种铜基硫化物脱汞剂载体。
为达到第一个目的，本发明所采用的技术方案是，一种铜基硫化物脱汞剂载体的制备方法，包括如下步骤：
步骤1，将水合氧化铝与有机酸混合，得到混合溶液A；
步骤2，向步骤1得到的混合溶液A中加入四烷基硅氧烷，在密闭条件下进行搅拌，并喷入雾化水，继续搅拌后得到脱汞剂载体。
作为一种实施方式，所述步骤1中水合氧化铝与有机酸在-10℃～40℃下混合。
作为一种实施方式，所述步骤1得到的混合溶液A中有机酸的质量为水合氧化铝的质量的1％～10％。
作为一种实施方式，所述步骤1得到的混合溶液A中有机酸的质量为水合氧化铝的质量的6％。
作为一种实施方式，所述步骤1中的有机酸为草酸、乙二胺四乙酸或柠檬酸中的任意一种。
作为一种实施方式，步骤2中加入的四烷基硅氧烷的质量为水合氧化铝的质量的3％～15％。
作为一种实施方式，所述四烷基硅氧烷为四甲基硅氧烷或四乙基硅氧烷。
作为一种实施方式，所述步骤2中喷入的雾化水的质量为四烷基硅氧烷的质量的3～8倍。
作为一种实施方式，步骤2中喷入雾化水后继续搅拌1h～24h得到脱汞剂载体。
为达到第二个目的，本发明所采用的技术方案是，一种铜基硫化物脱汞剂载体，采用上述的方法制备得到。
本发明提供的铜基硫化物脱汞剂载体的制备方法具有以下有益效果：
1、采用本发明提供的铜基硫化物脱汞剂载体制得的脱汞剂与现有技术相比，在制备工艺相同，活性硫化铜含量相同的情况下，脱汞能力至少提升10％以上。
2、采用本发明提供的铜基硫化物脱汞剂载体制得的脱汞剂，在使用或放置过程中，脱汞能力不会下降，可以长时间保存。
3、本发明的原理是避免了水合氧化物载体在使用过程中的交联。本发明提供的铜基硫化物脱汞剂载体以水合氧化铝为基础材料，在制备过程中，对其进行了改性，首先，有机酸的加入能对水合氧化铝的脱水进行有效的抑制；其次，硅助剂四烷基硅氧烷的加入可以在载体表面形成保护膜，减少水合氧化铝颗粒之间的项目接触，同样可以减缓脱水过程的进行。
4、有机酸中所含基团对汞有一定的络合吸附能力，可以加速汞的表面吸附过程，促进汞容增加，从而增加了本发明所提供的铜基硫化物脱汞剂载体的汞容。
5、本发明所提供的脱汞剂载体制备步骤简单，成本低廉。
具体实施方式
下面结合具体实施方式对本发明进行详细说明。
本发明实施例提供的铜基硫化物脱汞剂载体的制备方法，包括如下步骤：
步骤1，将水合氧化铝与有机酸在-10℃～40℃下混合，得到混合溶液A，其中， 有机酸的加入量为水合氧化铝质量的1％～10％，有机酸为草酸、乙二胺四乙酸或柠檬酸中的一种；
步骤2，向步骤1获得的混合溶液A中加入质量为水合氧化铝质量3％～15％的四烷基硅氧烷，四烷基硅氧烷为四甲基硅氧烷或四乙基硅氧烷，在密闭条件下不断搅拌，并喷入雾化水，雾化水的用量为四烷基硅氧烷质量的3～8倍，继续搅拌1～24h后得到脱汞剂载体。
本发明实施例提供的铜基硫化物脱汞剂载体制备方法步骤简单、成本低廉。
对比例
直接在市场购买快脱粉。
实施例1
本发明实施例提供的铜基硫化物脱汞剂载体的制备方法，包括以下步骤：
步骤一、将100g快脱粉与1g草酸在40℃下机械混合10min；
步骤二、继续加入3g四甲基硅氧烷；
步骤三、将上述物料在密闭条件下不断搅拌，并喷入24g雾化水，继续搅拌5h后得脱汞剂载体。
实施例2
本发明实施例提供的铜基硫化物脱汞剂载体的制备方法，包括以下步骤：
步骤一、将100g氢氧化铝与5g乙二胺四乙酸在30℃下机械混合20min；
步骤二、继续加入5g四乙基硅氧烷；
步骤三、将上述物料在密闭条件下不断搅拌，并喷入15g雾化水，继续搅拌1h后得脱汞剂载体。
实施例3
本发明实施例提供的铜基硫化物脱汞剂载体的制备方法，包括以下步骤：
步骤一、将100g快脱粉与10g柠檬酸在0℃下机械混合20min；
步骤二、继续加入10g四乙基硅氧烷；
步骤三、将上述物料在密闭条件下不断搅拌，并喷入40g雾化水，继续搅拌24h后得脱汞剂载体。
实施例4
本发明实施例提供的铜基硫化物脱汞剂载体的制备方法，包括以下步骤：
步骤一、将100g拟薄水铝石与6g柠檬酸在-10℃下机械混合30min；
步骤二、继续加入6g四乙基硅氧烷；
步骤三、将上述物料在密闭条件下不断搅拌，并喷入30g雾化水，继续搅拌12h后得脱汞剂载体。
实施例5
本发明实施例提供的铜基硫化物脱汞剂载体的制备方法，包括以下步骤：
步骤一、将100g快脱粉与6g柠檬酸在25℃下机械混合30min；
步骤二、继续加入6g四乙基硅氧烷；
步骤三、将上述物料在密闭条件下不断搅拌，并喷入30g雾化水，继续搅拌12h后得脱汞剂载体。
将对比例及实施例1～5作为脱汞剂载体，以本领域常规成型技术制备金属硫化物脱汞剂，使成品中金属硫化物含量为35％。由于制备金属硫化物脱汞剂的技术为现有技术，在此不再赘述。将所制备的脱汞剂在制备后1天内、放置3月后、放置6月后进行性能测试。测试条件为：装量：0.1ml；粒度：0.25～0.45mm；压力：常压；反应温度：50℃；室内温度：30℃；空速：1.5×105h -1；原料气组成： 1:2的甲烷气与氮气；汞含量：20～25mg/m 3。进口气与尾气含量采用《GB/T16781.2-1997天然气中汞含量的测定冷原子荧光分光光度法》进行测定，当出口汞浓度连续三次测定超过2mg/m 3时认为穿透。脱汞剂取出后，采用《GB/T17136-1997土壤质量总汞的测定冷原子吸收分光光度法》进行测定。结果如表1所示。
表1
样品号 汞容(％) 放置3月后汞容(％) 放置6月后汞容(％)
对比例 12.5 10.5 8.4
实施例1 14.1 13.9 13.5
实施例2 14.3 14.2 14.0
实施例3 15.6 15.5 15.5
实施例4 17.1 17.1 17.0
实施例5 16.8 16.6 16.6
从脱汞剂活性测定结果可以看出，采用本发明提供的铜基硫化物脱汞剂载体的制备方法所制备的载体用于制备金属硫化物脱汞剂时可以使成品脱汞剂具有较高的汞容，比未改性的载体汞容至少提高10％以上。而且长期放置后，其汞容没有明显下降，而使用未改性的载体在放置过程中其汞容有不断降低的现象。说明本发明所提供的载体对金属硫化物脱汞剂有很好的改进效果。
实施例6
本发明实施例提供的铜基硫化物脱汞剂载体的制备方法，包括如下步骤：
步骤1，将水合氧化铝与草酸在-10℃下混合，得到混合溶液A，其中，有机酸的加入量为水合氧化铝质量的1％；
步骤2，向步骤1的混合溶液A中加入水合氧化铝质量3％的四甲基硅氧烷，在密闭条件下不断搅拌，并喷入雾化水，雾化水的用量为四烷基硅氧烷质量的3倍，继续搅拌1h后得脱汞剂载体。
实施例7
本发明实施例提供的铜基硫化物脱汞剂载体的制备方法，包括如下步骤：
步骤1，将水合氧化铝与乙二胺四乙酸在20℃下混合，得到混合溶液A，其中，有机酸的加入量为水合氧化铝质量的6％；
步骤2，向步骤1的混合溶液A中加入水合氧化铝质量9％的四乙基硅氧烷，在密闭条件下不断搅拌，并喷入雾化水，雾化水的用量为四烷基硅氧烷质量的5倍，继续搅拌15h后得脱汞剂载体。
实施例8
本发明实施例提供的铜基硫化物脱汞剂载体的制备方法，包括如下步骤：
步骤1，将水合氧化铝与柠檬酸在40℃下混合，得到混合溶液A，其中，柠檬酸的加入量为水合氧化铝质量的10％；
步骤2，向步骤1的混合溶液中加入水合氧化铝质量15％的四乙基硅氧烷，在密闭条件下不断搅拌，并喷入雾化水，雾化水的用量为四烷基硅氧烷质量的8倍，继续搅拌24h后得脱汞剂载体。
本发明的原理是避免了水合氧化物载体在使用过程中的交联。在脱汞剂研究过程中，发现金属硫化物活性组分在与水合氧化铝载体混合成型后，相同质量的金属硫化物脱汞能力严重下降。例如，原料硫化铜脱汞能力可以很强，以质量计， 1份硫化铜脱汞能力可以吸收0.6份以上的汞。但负载成型后，1份硫化铜最多吸收0.4份的汞，而且放置时间越久的样品脱汞能力越差。其原因是，成型过程中使用的水合氧化铝载体是快脱粉或拟薄水铝石，经烘干后得成品。但水合氧化铝在使用或放置过程中会继续脱水形成交联结构，导致孔容、孔道结构持续变化，一方面使汞的扩散更为困难，另一方面使硫化铜包裹的更加严实，而且脱下的水在产品内部难于逸出，同样阻止了汞与硫化铜的接触。因此，在使用或存放过程中，会导致脱汞剂汞容有所下降。本发明提供的铜基硫化物脱汞剂载体以水合氧化铝为基础材料，在制备过程中，对其进行了改性，首先，有机酸的加入能对水合氧化铝的脱水进行有效的抑制；其次，硅助剂四烷基硅氧烷的加入可以在载体表面形成保护膜，减少水合氧化铝颗粒之间的项目接触，同样可以减缓脱水过程的进行。另外，有机酸中所含基团对汞有一定的络合吸附能力，可以加速汞的表面吸附过程，促进载体的汞容增加。
上述实施方式仅为本发明的优选实施方式，不能以此来限定本发明保护的范围，本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。

Claims (10)

  1. 一种铜基硫化物脱汞剂载体的制备方法，其特征在于，包括如下步骤：
    步骤1，将水合氧化铝与有机酸混合，得到混合溶液A；
    步骤2，向步骤1得到的混合溶液A中加入四烷基硅氧烷，在密闭条件下进行搅拌，并喷入雾化水，继续搅拌后得到脱汞剂载体。
  2. 根据权利要求1所述的铜基硫化物脱汞剂载体的制备方法，其特征在于，所述步骤1中水合氧化铝与有机酸在-10℃～40℃下混合。
  3. 根据权利要求1所述的铜基硫化物脱汞剂载体的制备方法，其特征在于，所述步骤1得到的混合溶液A中有机酸的质量为水合氧化铝的质量的1％～10％。
  4. 根据权利要求4所述的铜基硫化物脱汞剂载体的制备方法，其特征在于，所述步骤1得到的混合溶液A中有机酸的质量为水合氧化铝的质量的6％。
  5. 根据权利要求1-4任意一项所述的铜基硫化物脱汞剂载体的制备方法，其特征在于，所述步骤1中的有机酸为草酸、乙二胺四乙酸或柠檬酸中的任意一种。
  6. 根据权利要求1-4任意一项所述的铜基硫化物脱汞剂载体的制备方法，其特征在于，所述步骤2中加入的四烷基硅氧烷的质量为所述步骤1中水合氧化铝的质量的3％～15％。
  7. 根据权利要求1-4任意一项所述的铜基硫化物脱汞剂载体的制备方法，其特征在于，所述四烷基硅氧烷为四甲基硅氧烷或四乙基硅氧烷。
  8. 根据权利要求1-4任意一项所述的铜基硫化物脱汞剂载体的制备方法，其特征在于，所述步骤2中喷入的雾化水的质量为四烷基硅氧烷的质量的3～8倍。
  9. 根据权利要求1-4任意一项所述的一种铜基硫化物脱汞剂载体的制备方法，其特征在于，所述步骤2中喷入雾化水后继续搅拌1h～24h得到脱汞剂载体。
  10. 一种铜基硫化物脱汞剂载体，其特征在于，采用如权利要求1-9任意一项所述的方法制备得到。
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