CN104549128B - 硫砷净化剂及其用途 - Google Patents
硫砷净化剂及其用途 Download PDFInfo
- Publication number
- CN104549128B CN104549128B CN201310512282.9A CN201310512282A CN104549128B CN 104549128 B CN104549128 B CN 104549128B CN 201310512282 A CN201310512282 A CN 201310512282A CN 104549128 B CN104549128 B CN 104549128B
- Authority
- CN
- China
- Prior art keywords
- grams
- sulphur arsenic
- arsenic cleanser
- cleanser
- sodium carbonate
- 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.)
- Active
Links
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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/0233—Compounds of Cu, Ag, Au
-
- 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
- B01J20/0274—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 characterised by the type of anion
- B01J20/0277—Carbonates of compounds other than those provided for in B01J20/043
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
-
- 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
-
- 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
-
- 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
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing 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
- B01D2253/112—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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Detergent Compositions (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明涉及一种硫砷净化剂及其用途,主要解决现有技术中硫砷净化剂堆密度高,硫容砷容低,工业应用成本高的问题。本发明通过一种硫砷净化剂,以重量百分比计,包括以下组分:a)20~75%的类水滑石;b)20~75%的绿铜锌矿;c)1~10%的碱式碳酸铜的技术方案较好的解决了该问题,可用于天然气、合成气、轻质气液态烃类等的净化中。
Description
技术领域
本发明涉及一种硫砷净化剂及用途。
背景技术
硫砷等杂质广泛存在于天然气、合成气、煤制气、轻质气液态烃类等原料中,这些杂质的存在会导致很多催化剂中毒失活,大大缩短催化剂寿命,甚至导致催化反应无法正常进行;此外,未脱除干净的硫砷杂质会随着生产的进行进入下游合成品中,从而带来一系列的环境健康等方面的问题。因此,高效高精度地脱除硫砷等杂质对于保护下游装置的主催化剂且同时提高下游产品的品质有着非常重要的意义。
一般情况下,在工业原料中存在的含硫物质主要是H2S和COS,对于这些含硫物质的深度脱除效果最好的是氧化锌脱硫剂。氧化锌脱硫以其脱硫精度高、使用便捷、稳妥可靠、硫容量高、起着“把关”和“保护”作用而占据非常重要的地位,它广泛的应用在合成氨、制氢、煤化工、石油精制、饮料生产等行业,以脱除天然气、石油馏分、油田气、炼厂气、合成气、二氧化碳等原料中的硫化氢及某些有机硫。硫化锌脱硫可将原料气中的硫脱除至0.055mg/kg。常温氧化锌脱硫剂中添加CuO以提高其脱硫能力。氧化锌脱硫剂一般用于精脱硫过程,它也能吸收一般的有机硫化合物。工业原料中的砷杂质,通常以AsH3形式存在,工业上使用的脱砷剂大致可分成铜系、铅系、锰系和镍系四类,其中以铜系较为常见。铜系脱砷剂砷容高,可在常温、常压及较高空速下进行。铜系脱砷剂又可分成金属铜、CuO-Al2O3、CuO-ZnO-Al2O3等。当以CuO为活性组分时,AsH3将Cu2+还原为低价或金属态,砷与铜结合或游离成元素态。脱硫剂和脱砷剂的发展趋势是向低堆密度、低使用温度、高强度以及高硫容和砷容的方向发展。
专利CN101591554A公开了一种常温复合硫砷净化剂及其制备方法,该硫砷净化剂由载体和活性组分组成,活性组分为氧化铅、磁性氧化铁及氧化铜,载体为γ-Al2O3,该硫砷净化剂需要在350~650℃活化4~8小时,从其组成及制备方法可以看出,该氧化物硫砷净化剂堆密度高,制备过程复杂,工业应用成本较高。
专利CN102049236A公开了一种铜锌常温脱硫剂及其制备方法,该脱硫剂是由碱式碳酸锌、碱式碳酸铜和粘结剂组成,该脱硫硫剂的制备是将市售的碱式碳酸锌、碱式碳酸铜、粘结剂和水进行捏合、成型、干燥后得到,该脱硫剂通过物理混合得到,因而其中的锌铜活性组分无法发挥协同作用,从而导致其硫容较低。
发明内容
本发明所要解决的技术问题是现有技术中硫砷净化剂堆密度高,工业应用成本较高,硫容砷容低的问题,提供一种新的硫砷净化剂。该硫砷净化剂在用于天然气、合成气、轻质气液态烃类等的净化中时,具有堆密度低,工业应用成本低,硫容砷容高的优点。
为解决上述技术问题,本发明采用的技术方案如下:一种硫砷净化剂,以重量百分比计,包括以下组分:a)20~75%的类水滑石;b)20~75%的绿铜锌矿;c)1~10%的碱式碳酸铜。
上述技术方案中,以硫砷净化剂重量百分比计,所述类水滑石的优选范围为30~65%;所述绿铜锌矿的优选范围为30~65%;所述碱式碳酸铜的优选范围为2~8%;硫砷净化剂的优选方案为堆密度小于0.9kg/m3,侧压强度大于70N/粒。
上述技术方案中,类水滑石为[CuyZn(1-x-y)Alx(OH)2](CO3)x/2 .mH2O),x为Al/(Zn+Cu+Al)的摩尔比,x为0.2~0.33,m为结晶水数目;x优选为0.25;Cu:Zn:Al摩尔比优选为3:3:2或2:4:2。
所述的硫砷净化剂的制备方法,依次包括以下步骤:
(1)将硝酸铜、硝酸锌、硝酸铝的水溶性无机盐和水按摩尔比计:Cu/Zn为0.3~2,;Al/Zn为0.1~0.7;(Cu+Zn+Al)/H2O为0.01~0.04的比例混合,搅拌均匀得到溶液Ⅰ;
(2)将碳酸钠、碳酸氢钠、碳酸铵中的至少一种和水按摩尔比为0.01~0.04的比例混合,搅拌均匀得到溶液Ⅱ;
(3)将溶液Ⅰ和Ⅱ混合均匀,用碳酸钠溶液调节溶液的pH值为6.0~9.0,在40~90℃,反应0.5~3小时得沉淀物,将沉淀物洗涤干燥;
(4)将沉淀物、粘结剂、润滑剂混合碾压均匀,加入10~50重量%的水,造粒、压片成型为硫砷净化剂。
上述技术方案中,所述粘结剂为氧化铝、矾土水泥及纤维素中的至少一种;所述润滑剂为石墨、滑石粉、田菁粉和硬脂酸中的至少一种。
本发明所述硫砷净化剂,活性组分为类水滑石[CuyZn(1-x-y)Alx(OH)2](CO3)x/ 2 .mH2O)与绿铜锌矿((Cu,Zn)5(CO3)2(OH)6)晶相,两组分协同作用,类水滑石结构为Cu、Zn原子提供更大的比表面积,绿铜锌矿结构中氧原子以双层紧密堆积方式排列,二价铜离子在八面体的中心,而二价锌离子位于四面体位置,从而使得Cu、Zn可以在原子水平上互为间隔,从而保证活性中心相对分散。因此,类水滑石和绿铜锌矿相互作用,吸附剂具有较高的比表面积,活性组分相对分散,而具有较高的硫容和砷容。同时,类水滑石和绿铜锌矿体积较大,在堆积过程中会产生较大的孔道,因而其堆密度较低,工业应用成本较低。
本发明所述硫砷净化剂可用于天然气、合成气、轻质气液态烃类等的净化中。在常温、常压、体积空速为1500h-1的条件下,以含不同浓度硫、砷化合物杂质的氮气或合成气通过反应器,吸附剂的硫容可达20%以上。在常温、压力为3.0MPa、质量空速为3.5h-1的条件下,以含不同浓度硫、砷化合物杂质的液态丙烯通过反应器,吸附剂的硫容砷容也可达20%以上。
下面通过实施例对本发明作进一步的阐述。
附图说明
图1是合成吸附剂的XRD衍射谱图。(类水滑石的衍射峰在2θ=11.7±0.2°和23.5±0.2°;绿铜锌矿的特征衍射峰在2θ=13.0±0.2°,24.2±0.2°和32.9±0.2°;碱式碳酸铜的特征衍射峰在2θ=14.8±0.2°,17.6±0.2°和24.1±0.2°)
具体实施方式
【比较例1】
比较例1合成样品为类水滑石。
将硝酸锌55克,硝酸铜45克,硝酸铝60克和水450克混合搅拌均匀得到金属盐溶液,将碳酸钠70克和水550克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液充分混合,在70℃反应1小时,将沉淀物洗涤干燥,而后加入石墨1克混合碾压,以沉淀物和石墨的总重量百分比计,再加入30重量%的水,造粒,干燥,压片成型,得到样品组成见表1。
【比较例2】
比较例2合成样品为绿铜锌矿。
将硝酸锌55克,硝酸铜45克和水490克混合搅拌均匀得到金属盐溶液,将碳酸钠43克和水550克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液充分混合,在70℃反应1小时,将沉淀物洗涤干燥,而后加入氧化铝10克,石墨1克混合碾压,以沉淀物、氧化铝和石墨的总重量百分比计,再加入30重量%的水,造粒,干燥,压片成型,得到样品组成见表1。
【比较例3】
比较例3合成样品为碱式碳酸铜。
将硝酸铜90克和水500克混合搅拌均匀得到金属盐溶液,将碳酸钠45克和水500克份混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液充分混合,在70℃反应1小时,将沉淀物洗涤干燥,而后加入氧化铝10克,石墨1克混合碾压,以沉淀物、氧化铝和石墨的总重量百分比计,再加入30重量%的水,造粒,干燥,压片成型,得到样品组成见表1。
【实施例1】
将硝酸锌55克,硝酸铜45克,硝酸铝12克和水450克混合搅拌均匀得到金属盐溶液,将碳酸钠49克和水550克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液充分混合,用1重量%碳酸钠调节溶液的pH值为7.0,在70℃反应1小时,将沉淀物洗涤干燥,而后加入氧化铝10克,石墨1克混合碾压,以沉淀物和石墨的总重量百分比计,再加入30重量%的水,造粒,干燥,压片成型,得到样品组成见表1。
【实施例2】
将硝酸锌55克,硝酸铜45克,硝酸铝18克和水450克混合搅拌均匀得到金属盐溶液,将碳酸钠52克和水550克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液充分混合,用1重量%碳酸钠调节溶液的pH值为7.0,在70℃反应1小时,将沉淀物洗涤干燥,而后加入氧化铝9克,石墨1克混合碾压,以沉淀物和石墨的总重量百分比计,再加入30重量%的水,造粒,干燥,压片成型,得到样品组成见表1。
【实施例3】
将硝酸锌55克,硝酸铜45克,硝酸铝25克和水450克混合搅拌均匀得到金属盐溶液,将碳酸钠55克和水550克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液充分混合,用1重量%碳酸钠调节溶液的pH值为7.0,在70℃反应1小时,将沉淀物洗涤干燥,而后加入氧化铝8克,石墨1克混合碾压,以沉淀物和石墨的总重量百分比计,再加入30重量%的水,造粒,干燥,压片成型,得到样品组成见表1。
【实施例4】
将硝酸锌55克,硝酸铜45克,硝酸铝32克和水450克混合搅拌均匀得到金属盐溶液,将碳酸钠58克和水550克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液充分混合,用1重量%碳酸钠调节溶液的pH值为7.0,在70℃反应1小时,将沉淀物洗涤干燥,而后加入氧化铝7克,石墨1克混合碾压,以沉淀物和石墨的总重量百分比计,再加入30重量%的水,造粒,干燥,压片成型,得到样品组成见表1。
【实施例5】
将硝酸锌55克,硝酸铜45克,硝酸铝39克和水450克混合搅拌均匀得到金属盐溶液,将碳酸钠62克和水550克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液充分混合,用1重量%碳酸钠调节溶液的pH值为7.0,在70℃反应1小时,将沉淀物洗涤干燥,而后加入氧化铝6克,石墨1克混合碾压,以沉淀物和石墨的总重量百分比计,再加入30重量%的水,造粒,干燥,压片成型,得到样品组成见表1。
【实施例6】
将硝酸锌55克,硝酸铜45克,硝酸铝46克和水450克混合搅拌均匀得到金属盐溶液,将碳酸钠66克和水550克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液充分混合,用1重量%碳酸钠调节溶液的pH值为7.0,在70℃反应1小时,将沉淀物洗涤干燥,而后加入氧化铝5克,石墨1克混合碾压,以沉淀物和石墨的总重量百分比计,再加入30重量%的水,造粒,干燥,压片成型,得到样品组成见表1。
【实施例7】
将硝酸锌55克,硝酸铜45克,硝酸铝12克和水450克混合搅拌均匀得到金属盐溶液,将碳酸钠49克和水550克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液充分混合,用1重量%碳酸钠调节溶液的pH值为6.5,在70℃反应1小时,将沉淀物洗涤干燥,而后加入氧化铝10克,石墨1克混合碾压,以沉淀物和石墨的总重量百分比计,再加入30重量%的水,造粒,干燥,压片成型,得到样品组成见表1。
【实施例8】
将硝酸锌55克,硝酸铜45克,硝酸铝12克和水450克混合搅拌均匀得到金属盐溶液,将碳酸钠49克和水550克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液充分混合,用1重量%碳酸钠调节溶液的pH值为7.5,在70℃反应1小时,将沉淀物洗涤干燥,而后加入氧化铝10克,石墨1克混合碾压,以沉淀物和石墨的总重量百分比计,再加入30重量%的水,造粒,干燥,压片成型,得到样品组成见表1。
【实施例9】
将硝酸锌55克,硝酸铜45克,硝酸铝12克和水450克混合搅拌均匀得到金属盐溶液,将碳酸钠49克和水550克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液充分混合,用1重量%碳酸钠调节溶液的pH值为8.0,在70℃反应1小时,将沉淀物洗涤干燥,而后加入氧化铝10克,石墨1克混合碾压,以沉淀物和石墨的总重量百分比计,再加入30重量%的水,造粒,干燥,压片成型,得到样品组成见表1。
【实施例10】
将硝酸锌55克,硝酸铜45克,硝酸铝12克和水450克混合搅拌均匀得到金属盐溶液,将碳酸钠49克和水550克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液充分混合,用1重量%碳酸钠调节溶液的pH值为6.0,在70℃反应1小时,将沉淀物洗涤干燥,而后加入氧化铝10克,石墨1克混合碾压,以沉淀物和石墨的总重量百分比计,再加入30重量%的水,造粒,干燥,压片成型,得到样品组成见表1。
【实施例11】
将硝酸锌55克,硝酸铜45克,硝酸铝12克和水450克混合搅拌均匀得到金属盐溶液,将碳酸钠49克和水550克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液充分混合,用1重量%碳酸钠调节溶液的pH值为5.5,在70℃反应1小时,将沉淀物洗涤干燥,而后加入氧化铝10克,石墨1克混合碾压,以沉淀物和石墨的总重量百分比计,再加入30重量%的水,造粒,干燥,压片成型,得到样品组成见表1。
【实施例12】
将硝酸锌55克,硝酸铜45克,硝酸铝12克和水450克混合搅拌均匀得到金属盐溶液,将碳酸钠49克和水550克混合均匀得到碳酸钠溶液,将碳酸钠溶液与金属盐溶液充分混合,用1重量%碳酸钠调节溶液的pH值为9.0,在70℃反应1小时,将沉淀物洗涤干燥,而后加入氧化铝10克,石墨1克混合碾压,以沉淀物和石墨的总重量百分比计,再加入30重量%的水,造粒,干燥,压片成型,得到样品组成见表1。
表1
【实施例13】
将上述实施例制备的硫砷净化剂粉碎成20~40目的颗粒,将其填充到内径为1cm的反应器中,在常温、常压、体积空速为1500h-1的条件下,以含不同浓度硫、砷化合物杂质的氮气通过该反应器,对该硫砷净化剂进行评价,结果如表2所示。
表2
【实施例14】
将上述实施例制备的硫砷净化剂粉碎成20~40目的颗粒,将其填充到内径为1cm的反应器中,在常温、常压、体积空速为1500h-1的条件下,以含不同浓度硫、砷化合物杂质的合成气通过该反应器,对该硫砷净化剂进行评价,结果如表3所示。
表3
【实施例15】
将上述实施例制备的硫砷净化剂粉碎成20~40目的颗粒,将其填充到内径为1cm的反应器中,在常温、压力3.0MPa、质量空速为3.5h-1的条件下,以含不同浓度硫、砷化合物杂质的液态丙烯通过该反应器,对该硫砷净化剂进行评价,结果如表4所示。
表4
Claims (9)
1.一种硫砷净化剂,以重量百分比计,包括以下组分:
a)20~75%的类水滑石;
b)20~75%的绿铜锌矿;
c)1~10%的碱式碳酸铜;
其中,所述类水滑石为[CuyZn(1-x-y)Alx(OH)2](CO3)x/2.mH2O),x为Al/(Zn+Cu+Al)的摩尔比,x为0.2~0.33,m为结晶水数目。
2.根据权利要求1所述硫砷净化剂,其特征在于以硫砷净化剂重量百分比计,类水滑石的含量为30~65%。
3.根据权利要求1所述硫砷净化剂,其特征在于以硫砷净化剂重量百分比计,绿铜锌矿的含量为30~65%。
4.根据权利要求1所述硫砷净化剂,其特征在于以硫砷净化剂重量百分比计,碱式碳酸铜的含量为2~8%。
5.根据权利要求1所述硫砷净化剂,其特征在于硫砷净化剂的堆密度小于0.9kg/m3。
6.根据权利要求1所述硫砷净化剂,其特征在于硫砷净化剂的侧压强度大于70N/粒。
7.权利要求1~6任一项所述的硫砷净化剂的制备方法,依次包括以下步骤:
(1)将硝酸铜、硝酸锌、硝酸铝的水溶性无机盐和水按摩尔比计:Cu/Zn为0.3~2;Al/Zn为0.1~0.7;(Cu+Zn+Al)/H2O为0.01~0.04的比例混合,搅拌均匀得到溶液Ⅰ;
(2)将碳酸钠、碳酸氢钠、碳酸铵中的至少一种和水按摩尔比为0.01~0.04的比例混合,搅拌均匀得到溶液Ⅱ;
(3)将溶液Ⅰ和Ⅱ混合均匀,用碳酸钠溶液调节溶液的pH值为6.0~9.0,在40~90℃,反应0.5~3小时得沉淀物,将沉淀物洗涤干燥;
(4)将沉淀物、粘结剂、石墨混合碾压均匀,以沉淀物和石墨的重量百分比计,加入10~50重量%的水,造粒、压片成型为硫砷净化剂。
8.根据权利要求7所述的硫砷净化剂的制备方法,其特征在于所述粘结剂 为氧化铝、矾土水泥及纤维素中的至少一种。
9.将权利要求1~6任一项所述的硫砷净化剂用于天然气、合成气、轻质气液态烃类的净化中。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310512282.9A CN104549128B (zh) | 2013-10-28 | 2013-10-28 | 硫砷净化剂及其用途 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310512282.9A CN104549128B (zh) | 2013-10-28 | 2013-10-28 | 硫砷净化剂及其用途 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104549128A CN104549128A (zh) | 2015-04-29 |
CN104549128B true CN104549128B (zh) | 2017-02-15 |
Family
ID=53066837
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310512282.9A Active CN104549128B (zh) | 2013-10-28 | 2013-10-28 | 硫砷净化剂及其用途 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104549128B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111068611B (zh) * | 2018-10-18 | 2022-07-12 | 中国石油化工股份有限公司 | 低碳烯烃脱硫剂及其制备方法和应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0243052A3 (en) * | 1986-04-25 | 1988-12-14 | Imperial Chemical Industries Plc | Sulphur compounds removal |
CN101327419A (zh) * | 2008-08-01 | 2008-12-24 | 中国海洋石油总公司 | 一种催化裂化汽油吸附脱硫剂的制备方法 |
CN101591554A (zh) * | 2008-05-30 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | 一种常温复合脱硫脱砷剂及其制备方法 |
-
2013
- 2013-10-28 CN CN201310512282.9A patent/CN104549128B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0243052A3 (en) * | 1986-04-25 | 1988-12-14 | Imperial Chemical Industries Plc | Sulphur compounds removal |
CN101591554A (zh) * | 2008-05-30 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | 一种常温复合脱硫脱砷剂及其制备方法 |
CN101327419A (zh) * | 2008-08-01 | 2008-12-24 | 中国海洋石油总公司 | 一种催化裂化汽油吸附脱硫剂的制备方法 |
Non-Patent Citations (1)
Title |
---|
Cu-Zn-Al mixed metal oxides derived from hydroxycarbonate precursors for H2S removal at low temperature;Dahao Jiang et al.;《Applied Surface Science》;20091205;第256卷;第3216-3223页 * |
Also Published As
Publication number | Publication date |
---|---|
CN104549128A (zh) | 2015-04-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105582877B (zh) | 常温脱硫脱砷剂及其制备方法 | |
CN105214599B (zh) | 硫砷吸附剂及其制备方法 | |
EP2384814B1 (en) | Method for preparing materials containing amorphous iron oxyhydroxide | |
EP2383227B1 (en) | Preparation of material containing amorphous iron oxyhydroxide | |
CN104560250B (zh) | 净化剂及其制备方法 | |
CN107952412B (zh) | 硫、砷、磷净化剂及其制备方法 | |
CN107952409B (zh) | 硫、砷、磷吸附剂及其制备方法 | |
CN102961959B (zh) | 一种氧化锌精脱硫剂及其制备和应用方法 | |
CN102489150B (zh) | 一种常温负载型铁基硫化氢脱除剂的制备方法 | |
CN104549128B (zh) | 硫砷净化剂及其用途 | |
CN104548867B (zh) | 硫和砷的吸附方法 | |
CN104549122B (zh) | 常温脱硫脱砷剂及其制备方法 | |
CN104549123B (zh) | 脱硫脱砷剂 | |
CN104560251B (zh) | 净化剂及其用途 | |
CN106609166B (zh) | 脱硫剂及其制备方法 | |
CN104549129B (zh) | 硫砷净化剂及其制备方法 | |
CN105582879B (zh) | 硫砷净化剂及其制备方法 | |
CN107952408B (zh) | 硫、砷、磷净化剂及其制备方法 | |
CN105524670B (zh) | 硫砷净化剂及其用途 | |
CA3000078A1 (en) | Highly active nano iron catalyst for the absorption of hydrogen sulfide | |
CN105268276A (zh) | 硫或砷的吸附方法 | |
CN107952410B (zh) | 硫、砷、磷吸附剂及其制备方法 | |
CN106606926A (zh) | 常温精脱硫方法 | |
CN107952411B (zh) | 硫、砷、磷净化剂及其制备方法 | |
CN111097361B (zh) | 吸附剂及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |