CN108246239A - 金属掺杂kp型分子筛吸附剂脱除羰基硫的方法 - Google Patents

金属掺杂kp型分子筛吸附剂脱除羰基硫的方法 Download PDF

Info

Publication number
CN108246239A
CN108246239A CN201810147528.XA CN201810147528A CN108246239A CN 108246239 A CN108246239 A CN 108246239A CN 201810147528 A CN201810147528 A CN 201810147528A CN 108246239 A CN108246239 A CN 108246239A
Authority
CN
China
Prior art keywords
metal
doped
molecular sieve
types
carbonyl sulfur
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.)
Granted
Application number
CN201810147528.XA
Other languages
English (en)
Other versions
CN108246239B (zh
Inventor
陈彦广
宋华
赵亮
高金森
郝天臻
韩洪晶
苑丹丹
张娇静
王海英
李锋
王园园
王雪芹
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.)
China University of Petroleum Beijing
Northeast Petroleum University
Original Assignee
China University of Petroleum Beijing
Northeast Petroleum University
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 China University of Petroleum Beijing, Northeast Petroleum University filed Critical China University of Petroleum Beijing
Priority to CN201810147528.XA priority Critical patent/CN108246239B/zh
Publication of CN108246239A publication Critical patent/CN108246239A/zh
Application granted granted Critical
Publication of CN108246239B publication Critical patent/CN108246239B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203Solid 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
    • B01J20/0233Compounds of Cu, Ag, Au
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203Solid 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
    • B01J20/0222Compounds of Mn, Re
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203Solid 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
    • B01J20/0225Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203Solid 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
    • B01J20/024Compounds of Zn, Cd, Hg
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid 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 surface properties or porosity
    • B01J20/28057Surface area, e.g. B.E.T specific surface area
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid 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 surface properties or porosity
    • B01J20/28069Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L3/00Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/12Liquefied petroleum gas

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

本发明涉及的是金属掺杂KP型分子筛吸附剂脱除羰基硫的方法,这种金属掺杂KP型分子筛吸附剂脱除羰基硫的方法:在吸附温度为20oC‑60 oC,液化气体积空速为0.1 h‑1‑20 h‑1的条件下,金属掺杂KP型分子筛吸附剂脱除羰基硫,羰基硫的脱除率达85%‑99.5%;利用水热合成法制备出粒径均一、形貌规则的金属掺杂KP型分子筛,金属掺杂KP型分子筛为球形的,粒径为0.5μm‑4μm。本发明制备的金属掺杂KP型分子筛吸附剂,较常规的NaP型分子筛具有更强的K+碱性中心,有利于COS的水解,且COS在碱性中心水解后生成H2S被金属氧化物活性中心化学吸附,可进一步提高液化石油气中COS的脱除率。

Description

金属掺杂KP型分子筛吸附剂脱除羰基硫的方法
技术领域
本发明涉及液化石油气净化领域中脱除羰基硫技术,具体涉及金属掺杂KP型分子筛吸附剂脱除羰基硫的方法。
背景技术
液化石油气包括炼油厂液化气、少量裂解液化气和油田气回收液化气等,90 %的液化石油气由炼油厂生产,主要来自催化裂化、加氢裂化、延迟焦化等装置。LPG的主要成分是价值较高的C3、C4烯烃和烷烃,含有微量的硫杂质,主要包括H2S和羰基硫等,LPG可以直接用作燃气,也可以分离后作为化工原料,但硫含量的高低成为制约LPG是否成为高附加值产品的主要瓶颈之一。
随着进口高硫原油加工量的增加和渣油掺炼比的增大,炼油厂催化裂化等装置生产的LPG的总硫含量也随之升高。通常的LPG精制方法对H2S脱除效果较好,但对羰基硫(COS)的脱除效果不理想。目前国内外用于脱除COS的技术主要有两种,即加氢还原法和水解法。其中,加氢还原法反应温度高(一般为350℃-400℃),易引起反应物的裂解,从而使催化剂结碳而失活,同时需要氢气,成本较高。水解法是在水存在的条件下,使含COS与水解催化剂接触,将其转化为硫化氢和二氧化碳,然后再除去硫化氢和二氧化碳。
公告号103506071B的中国专利,该专利公开一种以活性炭为载体、以可溶性锌盐或铜盐为活性组分的同时去除H2S和COS的洁净剂,该洁净剂制备方法简单、成本低廉,但COS脱除效果不够理想。公开号105664659A的中国专利申请公开一种连续吸附脱除醚化后C4中羰基硫和二甲基二硫醚的方法,该法吸附容量较大,但操作繁琐,吸附剂再生过程复杂。公告号105107459的中国专利申请公开发明了一种以处理过的核桃壳制备得到的活性炭为吸附剂,同时脱除H2S、COS和CS2的方法,该法操作简单,成本低廉,但对COS的脱除效果较差。
综上所述,提供一种可以一步脱除液化石油气或其他气体中的羰基硫的方法是本领域亟待解决的问题。
发明内容
本发明的目的是提供金属掺杂KP型分子筛吸附剂脱除羰基硫的方法,这种金属掺杂KP型分子筛吸附剂脱除羰基硫的方法用于解决现有的脱除液化石油气中羰基硫工艺流程复杂或脱除效果不够理想的问题。
本发明解决其技术问题所采用的技术方案是:这种金属掺杂KP型分子筛吸附剂脱除羰基硫的方法:在吸附温度为20oC-60 oC,液化气体积空速为0.1 h-1-20 h-1的条件下,金属掺杂KP型分子筛吸附剂脱除羰基硫,羰基硫的脱除率达85%-99.5%;
金属掺杂KP型分子筛制备方法为:配置一定浓度的金属盐溶液,金属盐溶液中金属为M,金属M的质量分数为0.1wt%-15wt%,依次加入硅酸钾、碱类物质并搅拌均匀,逐滴加入偏铝酸钾搅拌3h-6h,得到合成金属掺杂KP型分子筛溶液,合成金属掺杂KP型分子筛溶液中各物质的摩尔比为K2SiO3/KAlO2 = 0.1-20,KAlO2/M= 0.1-10,K2SiO3/H2O = 0.01-0.5;80 oC-150 oC下晶化1h-24h,过滤后产物用去离子水和乙醇洗涤3-5次,80oC-120oC下干燥12h-24h,得到金属掺杂KP型分子筛,金属掺杂KP型分子筛为球形的,粒径为0.5μm-4μm。
上述方案中金属盐为金属可溶性氯化物或者硝酸盐,金属盐中金属M为Co、Ni、Cu、Zn、Mn中的一种或两种。
上述方案中碱类物质包括KOH,KHCO3,K2CO3,K2C2O4,KOCH3、KOCH2CH3中的一种或两种。
上述方案中合成金属掺杂KP型分子筛合成溶液的pH为10.0-14.0。
上述方案中K2SiO3的摩尔浓度为0.05 mol/L-2.0 mol/L,KAlO2的摩尔浓度为0.05mol/L-2.0 mol/L。
上述方案中金属掺杂KP型分子筛吸附脱除羰基硫的吸附温度为20oC-50oC,液化气体积空速为0.5 h-1-15 h-1,液化气中羰基硫的脱除率达90-99.5%。
本发明具有以下有益效果:
1、本发明利用水热合成法制备出粒径均一、形貌规则的金属掺杂KP型分子筛,具有较大的比表面积和孔容,对COS的吸附性能较强。
2、本发明制备的金属掺杂KP型分子筛吸附剂,较常规的NaP型分子筛具有更强的K+碱性中心,有利于COS的水解,且COS在碱性中心水解后生成H2S被金属氧化物活性中心化学吸附,可进一步提高液化石油气中COS的脱除率。
3、KP型分子筛合成过程中产率较高,且制备过程简单,成本低廉,具有广阔的应用前景。
具体实施方式
下面对本发明作进一步的说明:
实施例1
依次向25mL去离子水中加入4.652g Cu(NO3)2·2.5H2O、1.795g KOH和1.234g K2SiO3并搅拌均匀形成混合溶液;将7.84g KAlO2溶解于50mL去离子水中并搅拌均匀,然后逐滴加入到上述混合溶液中再搅拌3h,得到合成金属掺杂KP型分子筛溶液;此时合成金属掺杂KP型分子筛溶液pH值为12.2,再将合成金属掺杂KP型分子筛溶液移入反应釜中,置于130oC下晶化12 h。晶化结束后将产物过滤,用去离子水和无水乙醇分别洗涤4次,将所得固体置于120oC烘箱中干燥,可得到Cu负载量为4.6%的Cu-KP型分子筛。
反应温度为45oC,LPG空速为6 h-1,经Cu-KP型分子筛吸附剂吸附作用后,LPG中COS含量由108.7μg/g下降至1.6 μg/g,气体中未检测到H2S,COS总脱除率为98.5%。
实施例2
依次向50mL去离子水中加入1.533g ZnCl2、4.146g K2CO3和2.314g K2SiO3并搅拌均匀形成混合溶液;将14.7g KAlO2溶解于40 mL去离子水中并搅拌均匀,然后逐滴加入到上述混合溶液中,将所得溶液搅拌3h,得到合成金属掺杂KP型分子筛溶液,此时合成金属掺杂KP型分子筛溶液pH值为13.0,再将合成金属掺杂KP型分子筛溶液移入反应釜中,置于130oC下晶化10h。晶化结束后将产物过滤,用去离子水和无水乙醇分别洗涤4次,将所得固体置于100oC烘箱中干燥,得到Zn负载量为10.4%的Zn-KP型分子筛。
反应温度为40oC,LPG空速为10h-1,经Zn-KP型分子筛吸附作用后,LPG中COS含量由108.7μg/g下降至0.6 μg/g,未检测到H2S,COS总脱除率达到99.4%。
实施例3
依次向50mL去离子水中加入1.090g Ni(NO3)2·2.5H2O、4.146g K2CO3和2.314g K2SiO3并搅拌均匀形成混合溶液;将14.7g KAlO2溶解于40mL去离子水中并搅拌均匀,然后逐滴加入到上述混合溶液中,将所得溶液搅拌3h,得到合成金属掺杂KP型分子筛溶液,此时溶液pH值为13.1,再将合成金属掺杂KP型分子筛溶液移入反应釜中,置于130oC下晶化10h。晶化结束后将产物过滤,用去离子水和无水乙醇分别洗涤3次,将所得固体置于100oC烘箱中干燥,得到Ni负载为4.4%的Ni-KP型分子筛。
反应温度为40oC,LPG空速为8h-1,经Ni-KP型分子筛吸附作用后,LPG中COS含量由108.7μg/g下降至2.4μg/g,H2S含量低于0.1μg/g,COS总脱除率达到97.8%。
实施例4
依次向25mL去离子水中加入7.03g Mn(NO3)2·4H2O、1.795g KOH和1.234g K2SiO3并搅拌均匀形成混合溶液;将7.84g KAlO2溶解于50mL去离子水中并搅拌均匀,然后逐滴加入到上述混合溶液中再搅拌3h,得到合成金属掺杂KP型分子筛溶液;此时溶液pH值为13.0,再将合成金属掺杂KP型分子筛溶液移入反应釜中,置于130oC下晶化12h。晶化结束后将产物过滤,用去离子水和无水乙醇分别洗涤4次,将所得固体置于110oC烘箱中干燥,可得到Mn负载量为6.8%的Mn-KP型分子筛。
反应温度为40oC,LPG空速为7h-1,经Mn-KP型分子筛吸附剂吸附作用后,LPG中COS含量108.7μg/g下降至1.8 μg/g,未检测到H2S,COS总脱除率达到98.3%。
表1 LPG原料组成
组成 含量
丙烷,%(v/v) 10.3
丙烯,%(v/v) 33.5
正丁烷,%(v/v) 4.9
异丁烷,%(v/v) 32.8
1-丁烯,%(v/v) 5.1
异丁烯,%(v/v) 5.7
顺-2-丁烯,%(v/v) 3.4
反-2-丁烯,%(v/v) 2.9
1,3-丁二烯,%(v/v) 0.8
COS,μg/g 108.7

Claims (6)

1.一种金属掺杂KP型分子筛吸附剂脱除羰基硫的方法,其特征在于:这种金属掺杂KP型分子筛吸附剂脱除羰基硫的方法:在吸附温度为20oC-60 oC,液化气体积空速为0.1 h-1-20 h-1的条件下,金属掺杂KP型分子筛吸附剂脱除羰基硫,羰基硫的脱除率达85%-99.5%;
金属掺杂KP型分子筛制备方法为:配置一定浓度的金属盐溶液,金属盐溶液中金属为M,金属M的质量分数为0.1wt%-15wt%,依次加入硅酸钾、碱类物质并搅拌均匀,逐滴加入偏铝酸钾搅拌3h-6h,得到合成金属掺杂KP型分子筛溶液,合成金属掺杂KP型分子筛溶液中各物质的摩尔比为K2SiO3/KAlO2 = 0.1-20,KAlO2/M= 0.1-10,K2SiO3/H2O = 0.01-0.5;80 oC-150 oC下晶化1h-24h,过滤后产物用去离子水和乙醇洗涤3-5次,80oC-120oC下干燥12h-24h,得到金属掺杂KP型分子筛,金属掺杂KP型分子筛为球形的,粒径为0.5μm-4μm。
2.根据权利要求1所述的金属掺杂KP型分子筛吸附剂脱除羰基硫的方法,其特征在于:所述的金属盐为金属可溶性氯化物或者硝酸盐,金属盐中金属M为Co、Ni、Cu、Zn、Mn中的一种或两种。
3.根据权利要求2所述的金属掺杂KP型分子筛吸附剂脱除羰基硫的方法,其特征在于:所述的碱类物质包括KOH,KHCO3,K2CO3,K2C2O4,KOCH3、KOCH2CH3中的一种或两种。
4.根据权利要求3所述的金属掺杂KP型分子筛吸附剂脱除羰基硫的方法,其特征在于:所述的合成金属掺杂KP型分子筛合成溶液的pH为10.0-14.0。
5.根据权利要求4所述的金属掺杂KP型分子筛吸附剂脱除羰基硫的方法,其特征在于:所述的K2SiO3的摩尔浓度为0.05 mol/L-2.0 mol/L,KAlO2的摩尔浓度为0.05 mol/L-2.0mol/L。
6.根据权利要求5所述的金属掺杂KP型分子筛吸附剂脱除羰基硫的方法,其特征在于:所述的金属掺杂KP型分子筛吸附脱除羰基硫的吸附温度为20oC-50oC,液化气体积空速为0.5h-1-15h-1,液化气中羰基硫的脱除率达90-99.5%。
CN201810147528.XA 2018-02-12 2018-02-12 金属掺杂kp型分子筛吸附剂脱除羰基硫的方法 Expired - Fee Related CN108246239B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810147528.XA CN108246239B (zh) 2018-02-12 2018-02-12 金属掺杂kp型分子筛吸附剂脱除羰基硫的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810147528.XA CN108246239B (zh) 2018-02-12 2018-02-12 金属掺杂kp型分子筛吸附剂脱除羰基硫的方法

Publications (2)

Publication Number Publication Date
CN108246239A true CN108246239A (zh) 2018-07-06
CN108246239B CN108246239B (zh) 2020-11-17

Family

ID=62745372

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810147528.XA Expired - Fee Related CN108246239B (zh) 2018-02-12 2018-02-12 金属掺杂kp型分子筛吸附剂脱除羰基硫的方法

Country Status (1)

Country Link
CN (1) CN108246239B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112691651A (zh) * 2020-12-22 2021-04-23 沈阳三聚凯特催化剂有限公司 一种脱硫剂的制备方法、脱硫剂及应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4424586B2 (ja) * 2003-03-20 2010-03-03 株式会社ジャパンエナジー 有機硫黄化合物を含む液体炭化水素の脱硫方法
JP4907391B2 (ja) * 2007-03-07 2012-03-28 Jx日鉱日石エネルギー株式会社 炭化水素系燃料の脱硫方法
CN103274427A (zh) * 2013-06-18 2013-09-04 北京北大先锋科技有限公司 一种p型分子筛的制备方法
CN105289476A (zh) * 2015-11-19 2016-02-03 上海化工研究院 金属改性13x分子筛脱硫吸附剂及其制备方法和应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4424586B2 (ja) * 2003-03-20 2010-03-03 株式会社ジャパンエナジー 有機硫黄化合物を含む液体炭化水素の脱硫方法
JP4907391B2 (ja) * 2007-03-07 2012-03-28 Jx日鉱日石エネルギー株式会社 炭化水素系燃料の脱硫方法
CN103274427A (zh) * 2013-06-18 2013-09-04 北京北大先锋科技有限公司 一种p型分子筛的制备方法
CN105289476A (zh) * 2015-11-19 2016-02-03 上海化工研究院 金属改性13x分子筛脱硫吸附剂及其制备方法和应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
周慧云等: "以粉煤灰为原料制备高纯度NaP型分子筛", 《环境工程学报》 *
陈彦广等: "有机空间位阻剂对NaP分子筛的调控作用", 《燃料化学学报》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112691651A (zh) * 2020-12-22 2021-04-23 沈阳三聚凯特催化剂有限公司 一种脱硫剂的制备方法、脱硫剂及应用
CN112691651B (zh) * 2020-12-22 2023-05-05 沈阳三聚凯特催化剂有限公司 一种脱硫剂的制备方法、脱硫剂及应用

Also Published As

Publication number Publication date
CN108246239B (zh) 2020-11-17

Similar Documents

Publication Publication Date Title
RU2562459C2 (ru) Способ получения легких олефинов из синтез-газа
CA2718960C (en) Production method of liquid hydrocarbons from natural gas
RU2009107522A (ru) Катализатор и способ получения дистиллята со сверхнизким содержанием серы
CN111701411B (zh) 一种合成气脱硫剂及其制备方法和应用
CN107486226B (zh) 合成气制低碳烯烃的催化剂、制备方法及其用途
CN101250080B (zh) 一种甲醇生产的烯烃的净化工艺
CN108246239A (zh) 金属掺杂kp型分子筛吸附剂脱除羰基硫的方法
CN102698595A (zh) 负载型柱撑粘土催化材料在硫化氢选择氧化过程中的应用
CN109721027B (zh) 甲烷硫化氢重整反应制氢的方法
CN103933927B (zh) 固体脱硫剂及其制备方法
CN109967066B (zh) 纳米片结构的钼酸铋催化剂在催化合成1,3-丁二烯中的应用
CN1948438B (zh) 两段式费托合成方法
CN108315070B (zh) 以金属掺杂kp型分子筛脱除液化石油气中羰基硫的方法
CN106955735A (zh) 一种烃油脱硫催化剂及其制备方法和烃油脱硫的方法
CN106609166B (zh) 脱硫剂及其制备方法
CN106824052A (zh) 脱硫吸附剂及制法和转化为富甲烷气的低碳烃脱硫的应用
CN102847549B (zh) 煤焦油加氢裂化催化剂及其制备方法
CN104496939B (zh) 一种催化加氢制备哌嗪或烷基哌嗪的方法
US9550167B2 (en) Method for preparing hollow carbon structure using cracking reaction of heavy hydrocarbon fraction
CN104226321B (zh) 混合低碳烷烃脱氢催化剂及其制备方法
CN109158107B (zh) 一种由二氧化碳直接加氢制备液体烃的方法
CN109621984B (zh) 耐硫变换甲烷化一体化催化剂及制备方法
CN202988755U (zh) 一种利用粉煤灰合成超细4a型分子筛的装置
CN114100622B (zh) 耐硫预变换催化剂及其制备和硫化方法
CN108479843B (zh) 嵌入式微孔-介孔复合分子筛耐硫甲烷化催化剂的制备

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20201117

CF01 Termination of patent right due to non-payment of annual fee