WO2008125016A1 - Procédé de purification du hbr présent dans des hydrocarbures - Google Patents

Procédé de purification du hbr présent dans des hydrocarbures Download PDF

Info

Publication number
WO2008125016A1
WO2008125016A1 PCT/CN2008/000770 CN2008000770W WO2008125016A1 WO 2008125016 A1 WO2008125016 A1 WO 2008125016A1 CN 2008000770 W CN2008000770 W CN 2008000770W WO 2008125016 A1 WO2008125016 A1 WO 2008125016A1
Authority
WO
WIPO (PCT)
Prior art keywords
hbr
metal oxide
purification
hydrocarbons
hydrocarbon
Prior art date
Application number
PCT/CN2008/000770
Other languages
English (en)
French (fr)
Inventor
Xiaoping Zhou
Zhen Liu
Wensheng Li
Yanqun Ren
Original Assignee
Microvast Technologies, Ltd.
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 Microvast Technologies, Ltd. filed Critical Microvast Technologies, Ltd.
Priority to EP08733968A priority Critical patent/EP2147908A1/en
Priority to US12/595,781 priority patent/US20100135895A1/en
Publication of WO2008125016A1 publication Critical patent/WO2008125016A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/14833—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds
    • C07C7/1485—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds oxides; hydroxides; salts
    • 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
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • 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
    • B01J20/0237—Compounds of Cu
    • 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
    • B01J20/04—Solid 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
    • B01J20/041—Oxides or hydroxides
    • 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
    • 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
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/09—Bromine; Hydrogen bromide
    • C01B7/093—Hydrogen bromide
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/16—Metal oxides

Definitions

  • the present invention relates to a process for separating HBr from a hydrocarbon, and more particularly to a process for separating and recovering HBr from an olefin.
  • the present invention is in the technical field of chemical absorption separation of HBr in hydrocarbons. Background technique
  • a lower hydrocarbon such as decane is first reacted with HBr/H 2 O and oxygen on Catalyst A to form a brominated hydrocarbon:
  • the brominated hydrocarbon can be efficiently converted to high carbon hydrocarbons such as olefins, aromatic hydrocarbons, alkanes (small amounts) and HBr on the catalyst B.
  • high carbon hydrocarbons such as olefins, aromatic hydrocarbons, alkanes (small amounts) and HBr on the catalyst B.
  • the present invention discloses a purification process for separating HBr from a hydrocarbon, characterized in that the hydrocarbon is an olefin, an aromatic hydrocarbon and an alkane.
  • the HBr-containing hydrocarbon is contacted with a silica-supported metal oxide-containing solid material (MO x /Si0 2 ), and the metal oxide reacts with HBr to absorb HBr in the hydrocarbon and A corresponding metal bromide is formed, and then the bromide in the solid material is reacted with oxygen in oxygen or air to regenerate the metal oxide on the support and recover Br 2 .
  • a silica-supported metal oxide-containing solid material MO x /Si0 2
  • the HBr-containing hydrocarbon is first flow-through contacted at a certain temperature (100 to 600 ° C) through a vessel packed with MO x /SiO 2 , metal oxide MO x selectivity. Reacts with HBr to form non-volatile metal bromide and water for the purpose of purifying hydrocarbons; switching HBr-containing hydrocarbon materials to another MO x when MO x /Si0 2 absorbs HBr to saturation
  • the container of /Si0 2 continues the same operation; the container filled with HBr and filled with MO x /Si0 2 is purged with water or oxygen and is supplied with air or oxygen at a certain temperature (250 - 600 °C).
  • the metal oxide MO x is regenerated therein and bromine is recovered, so that two or more parallel containers packed with MO x /SiO 2 can achieve the purpose of continuously purifying hydrocarbons and recovering bromine by a purification-regeneration cycle operation.
  • the MO x /SiO 2 loaded in the purification container of the present invention is a mixture of one or more of MgO, CoO, Co 2 O 3 and CuO supported on silica gel.
  • silica gel is commercially available as silica gel and is prepared by hydrolysis from silicon-containing precursors such as silicate, SiCl 4 and silicate, and then soluble in acetate, nitrate, bromide, etc. of metal Mg, Co and Cu. The aqueous solution of the salt is soaked in the carrier silica gel, and then baked and calcined to form the desired MO x /SiO 2 solid. Material.
  • HBr absorption during operation when the hydrocarbon is contacted with HBr MO x / Si0 2 and the metal oxide MO x / Si0 2 MOx (MgO , CoO, Co 2 0 3 and CuO in a
  • the reaction of one or several mixtures) is carried out at 100 to 60 CTC, preferably at a reaction temperature in the range of 150 to 400 ° C, and the most preferred reaction temperature is in the range of 170 to 300 ° C.
  • the regeneration of MO x /Si0 2 after absorption of HBr is generally carried out at 250 to 600 ° C, the preferred regeneration temperature range is 300 to 500 ° C, and the best regeneration temperature is 320 to 45 (TC between.
  • the entire purification system is generally connected by two to eight containers filled with MO x /Si0 2 through a switching valve.
  • Each of the containers filled with MO x /Si0 2 may be a fixed bed purification tower in which both ends of the column shape are connected to the switching valve.
  • each operation cycle is completed by switching the switching valves at both ends to the four steps of purging, purging, regenerating and purging.
  • the switching valve at the inlet of the purification tower is switched to the hydrocarbon material containing HBr, and the switching valve at the outlet of the purification tower is switched to the hydrocarbon storage tank.
  • the switching valve at the inlet of the purification tower is switched to water vapor, the outlet is switched to a gas-liquid separator, and the outlet of the gas-liquid separator is connected to the hydrocarbon material tube containing HBr. After purging out the residual hydrocarbons, it is possible to enter the regeneration operation stage.
  • the switching valve at the inlet of the purification tower is switched to the air or oxygen supply system, and the outlet of the purification tower is switched to the Br 2 collection storage tank.
  • the purge must be performed first, and the oxygen in the blower can be used for a purification operation.
  • the inlet of the purifier is switched.
  • the valve is switched to water vapor and the outlet is switched to the venting state. From this operation, it can be seen that for each purifier, its operation is not continuous.
  • two are usually used. Or two or more identical purification towers. When one of them is in the absorption operation, the other purification towers are the same At the same time, the other three operations are performed, so that the separation operation is continuously performed.
  • Si0 2 can be prepared using commercially available silica gel or hydrolyzed from SiCl 4 and a silicate.
  • 120.0 mL of SiCl 4 or Si(OC 2 H 5 ) 4 was added to 800 mL of water and stirred at room temperature for 12 hr to obtain a sample of aqueous silica gel.
  • the aqueous silica gel was dried at 120 ° C for 6 hr, then at 450 °. C was burned for 4 hr to obtain silica gel Si0 2 , and pellets of 40 to 60 mesh were prepared.
  • the metal oxide MO x in the prepared MO x /SiO 2 solid material includes a mixture of one or more of MgO, CoO, Co 2 O 3 and CuO.
  • composition of the gas that needs to be purified is
  • B gas methane (>75%), isobutylene (10.0%), propylene (1.0%), cyclopentene (6.0%), cyclohexane (3.0%), benzene (2.0%), toluene (1.0%) and A mixture of diphenylbenzene (2.0%).
  • the 40 wt% HBr/H 2 0 solution was pumped into a quartz tube filled with quartz sand and heated to 200 ° C at a rate of 3.0 mL/hr, and the propylene was simultaneously flowed at a flow rate of 5.0 mL/min.
  • the heated quartz tube is connected to a gas-liquid separator at the outlet of the tube, and the gas obtained at the gas outlet is a mixture containing HBr.
  • the effluent gas was bubbled through a solution of AgN0 3 (4.0 M, 5.0 mL), and the concentration of HBr in propylene was determined from the weight gain of the solution.
  • the concentration of HBr in propylene was 5.3% (mol).
  • This mixed gas inlet Equipped with heating 10.0 g MgO / Si0 2 to a purge tube to 200 ° C, the sulfur effluent HBr gas detection with AgN0 3 solution (5.0 mL, 4.0 M), typically found 10 to generate AgBr 12.5 hr, this
  • the material in the purification tube absorbs HBr to reach saturation
  • the volume of propylene flowing through is recorded to be purified.
  • the material After three times of preparation, the material reaches a steady state. At this time, 0.375 L of propylene can be purified per g of MgO/SiO 2 , and about 0.1 g of HBr is absorbed.
  • the concentration of Br- in the solution is 1. 4 x 10' 13 M 5 5.0 mL of AgN0 3 solution (4,0 M) has 7,0 X l (T 16 mol ⁇ . And these Br- are derived from 3.75 L of propylene, so residual in propylene
  • the concentration of HBr in the solution should be less than 1.87 xl (T 16 mol/L.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Description

碳氢化合物中 HBr的净化方法 技术领域
本发明涉及一种从碳氢化合物中分离 HBr的方法， 尤其是从烯 烃中分离回收 HBr的方法。 本发明属于碳氢化合物中 HBr的化学吸 收分离的技术领域。 背景技术
在本领域的研究中， 由于一般没有从碳氢化合物中分离 HBr的 需求， 所以没有见到类似的报道和相关专利。 在我们近年来的研究 中， 我们设计了把曱烷等低碳烃转化成碳氢化合物， 尤其是烯烃等 产品的新流程， 如申请号为 200610031377.9的中国专利所公开， 两 步流程如反应 （A ) 和 （B ) 所示：
第一步， 低碳烃如曱烷， 在催化剂 A上首先与 HBr/H20和氧气 反应生成溴代烃：
mm A
C¾ + ί¾ + HEr · J*- CH^r CH ¾ + ¾0 (A)
第二步， 溴代烃再在催化剂 B上可以被有效地转化成烯烃、 芳 烃、 烷烃 （少量） 等高碳烃和 HBr。 前期的研究工作表明， 溴代烃 的转化率可达 99%以上。 反应式如下：
^ 催化剂 B
<M^Br+ CB^ 2 ^ (^ρ,, + ΧΒΒΓ ί6)
UL„m,x =¾ 3:, 4I 5, 6> 7, 8, 9, 10, 11, 1¾ 13 在制烯烃、 芳烃和烷烃的反应（B ) 中都有 HBr的生成。 这些产 物中大量的 HBr 先用常规方法进行粗洗5 比如用第一步反应 （A ) 以后的稀 HBr溶液进行粗洗， HBr循环使用。 但是粗洗后产物中仍 残余有 HBr, 因烯烃等化合物都有 Lewis碱性， 采用常规的分离方 法， 是不能把 HBr从烯烃和芳烃类化合物中很好分离出来的， 同时 也难于纯化烯烃和芳烃类化合物。 发明内容
本发明公开了从一种碳氢化合物中分离 HBr 的净化方法， 其特 征在于所述的碳氢化合物为烯烃、 芳烃和烷烃。
在本发明的净化方法中， 含 HBr的碳氢化合物与一种硅胶负载 金属氧化物的固体材料（MOx/Si02 )接触， 金属氧化物与 HBr反应， 吸收了碳氢化合物中的 HBr并且生成相应的金属溴化物， 然后固体 材料中的溴化物经过与氧气或空气中的氧气反应， 再生载体上的金 属氧化物并且回收 Br2。
在这一分离过程中， 含 HBr的碳氢化合物首先通过一个装填有 MOx/Si02的容器， 在一定温度 （ 100至 600°C ) 下进行流过式接触， 金属氧化物 MOx选择性地与 HBr反应生成不挥发的金属溴化物和 水， 以达到净化碳氢化合物的目的； 在 MOx/Si02吸收 HBr达到饱和 时把含 HBr 的碳氢化合物物料切换到另一个装填有 MOx/Si02的容 器， 继续进行同样的操作； 而已经吸收有 HBr 的装填有 MOx/Si02 的容器经过水蒸汽吹扫后通入空气或氧气，在一定温度 (250 - 600 °C ) 下再生其中的金属氧化物 MOx并且回收溴， 这样两个或两个以上的 装填有 MOx/Si02的并列容器通过净化-再生循环操作就可以达到连 续净化碳氢化合物和回收溴的目的。
在本发明的净化容器中装填的 MOx/Si02是釆用硅胶为载体负载 MgO、 CoO、 Co203和 CuO 中的一种或几种的混合物。 其中硅胶是 市售商品硅胶以及从含硅前体如硅酸盐、 SiCl4和硅元酸酯水解制备 , 然后再把金属 Mg、 Co和 Cu的的醋酸盐、 硝酸盐、 溴化物等可溶性 盐的水溶液浸泡载体硅胶， 然后烘干焙烧制成需要的 MOx/Si02固体 材料。
在进行 HBr的吸收操作时，碳氢化合物中的 HBr在与 MOx/Si02 进行接触时与 MOx/Si02中的金属氧化物 MOx ( MgO、 CoO、 Co203 和 CuO中的一种或几种的混合物）的反应一^:在 100至 60CTC进行， 较好的反应温度范围是 150至 400°C， 最好的反应温度范围是在 170 至 300Ό之间。在吸收了 HBr后 MOx/Si02的再生一般是在 250至 600 °C之间进行， 较好的再生温度范围是 300至 500 °C , 最好的再生温度 是在 320至 45(TC之间。
采用本发明的方法净化含 HBr的碳氢化合物时， 整个净化系统 一般由两个至八个装填有 MOx/Si02的容器通过切换阀连接。 每个装 填有 MOx/Si02的容器可以是一个柱体形状的两端与切换阀相连接的 固定床净化塔。 在净化过程中每个都是通过两端的切换阀切换到净 化、 吹扫、 再生和吹扫四个步骤完成每一个操作循环的。 在固定床 净化塔处于吸收操作阶段时， 净化塔进口处切换阀切换到含 HBr的 碳氢化合物物料, 净化塔出口处切换阀切换到碳氢化合物储罐。 在 吸收 HBr接近饱和时， 床层中的碳氢化合物需要以水蒸汽吹扫后才 能通氧气或空气再生， 所以接下去进入吹扫操作阶段。 在固定床净 化塔处于吹扫操作阶段时， 净化塔进口处切换阀切换到水蒸汽， 出 口切换到一个气液分离器， 气液分离器出口与含 HBr的碳氢化合物 物料管连接。 在吹扫出残留的碳氢化合物后 , 可以进入再生操作阶 段。 在再生操作阶段净化塔进口处切换阀切换到空气或氧气供给系 统，净化塔出口处切换阔切换到 Br2收集储罐。在再生操作完成以后， 由于系统中有氧气， 所以不能立即进入下一个净化操作， 必须先进 行吹扫， 吹出器中的氧气以后才能进行一个净化操作， 在此吹扫操 作中净化器进口处切换阀切换到水蒸汽， 出口切换到放空状态， 从 这个操作过程可以看出， 对于每一个净化器， 它的搮作都不是连续 的， 为了保证连续净化含 HBr的碳氢化合物， 通常采用两个或两个 以上同样的净化塔。 当其中的一个处于吸收操作时， 其它净化塔同 时在进行其它三个操作， 从而使分离操作连续进行。 具体实施方式
金属氧化物 /硅胶 (MOx/Si02)的制备
硅胶载体制备
Si02可以使用市场上购买的硅胶， 或从 SiCl4和硅元酸酯水解制 备。 在制备 Si02时， 把 120.0 mL的 SiCl4或 Si(OC2H5)4加入 800 mL 水中在室温下搅拌 12 hr得到含水硅胶样品， 含水硅胶在 120°C干燥 6 hr，然后在 450°C烧 4 hr得硅胶 Si02，制成 40至 60目的颗粒备用。
MOx/S 32的制备
称取 20,00 g上面制备的 40至 60 目的硅胶和 99,25 mmol的 M 的醋酸盐、 硝酸盐、 溴化物等可溶性盐在搅拌下加入 100 mL 去离 子水中， 在室温下放置 2 hr, 然后在 120°C干燥 6 hr, 最后在 450°C 空气中烧 4 hr, 降温至室温后得 MOx/Si02, 制成 40至 60 目的颗粒 备用。
制成的 MOx/Si02固体材料中金属氧化物 MOx,包括 MgO、CoO、 Co203和 CuO中的一种或几种的混合物。
碳氢化合物的净化
需要净化的气体组成为
A气体： 丙烯
B气体：甲烷 (>75%)、异丁烯（10.0%)、丙烯（1.0%)、环戊烯 (6.0%)、 环己烷 (3.0%)、 苯 (2.0%)、 甲苯 (1.0%)和二曱苯 (2.0%)的混和气。
在净化 A气体时， 以 3.0 mL/hr的速度把 40 wt%HBr/H20溶液 泵入一个填有石英沙并且加热到 200 °C的石英管中， 丙烯以 5.0 mL/min的流量同时通入这个加热的石英管， 在管的流出口连接一个 气液分离器， 气体出口得到的气体就是含有 HBr的混合气。 流出气 鼓泡经过 AgN03 (4.0 M, 5.0 mL)溶液， 从溶液增重量测定 HBr在丙 烯中的浓度。 HBr在丙烯中的浓度为 5.3% (mol)。 这个混合气体通入 一个装有 10.0 g MgO/Si02的加热到 200°C的净化管， 硫出的气体用 AgN03 溶液 （5.0 mL, 4.0 M)检测 HBr的流出， 通常在 10至 12.5 hr 发现 AgBr生成， 此时净化管中的材料吸收 HBr达到饱和， 记录流 过的丙烯体积得净化量。 在把净化管中的气体从 HBr/C3H6切换到水 蒸汽吹扫 5分钟，用空气或氧气在 320至 450 °C再生净化管中的材料， 到没有溴流出时， 切换到水蒸汽吹扫 5分钟， 进行下一循环操作。
在搡作三次以后， 材料达到稳定状态， 此时每 g MgO/Si02可以 净化 0.375 L丙烯， 约吸收 0.1 g HBr, 在 AgN03 溶液中出现 AgBr 时，溶液中 Br-的浓度为 l。4 x 10'13 M5 5.0 mL 的 AgN03溶液 （4,0 M) 有 7,0 X l(T16 mol的 ΒΓ·。 而这些 Br-是由 3.75 L丙烯带来的， 所以残 留在丙烯中的 HBr浓度应该小于 1.87 x l (T16 mol/ L。
采用 B气体重复以上实验得到同样的结杲。

Claims

权 利 要 求
1 ,一种含 HBr的碳氢化合物的净化方法， 包括以下步骤：
1)含 HBr的碳氢化合物通过一个装填有包含一种金属氧化物有 效成分和一种载体的固体材料的容器， 在一定温度下进行流过式接 触， 固体材料中的金属氧化物选择性地与 HBr反应生成金属溴化物和 水， 流出的碳氢化合物收集在储罐中实现净化操作；
2)在固体材料吸收 HBr达到饱和时， 把含 HBr的碳氢化合物物料 切换到另一个装填有相同固体材料的容器继续进行与 1 )中同样的净 化操作，而已经吸收有 HBr的装填有固体材料的容器经过水蒸汽吹扫 后， 通入氧气在一定温度下再生其中的金属氧化物并且回收溴， 以 备下一循环净化使用；
3)两个或两个以上的装填有固体材料的容器通过切换阀连接成 一个净化系统， 经过净化再生循环操作达到连续净化碳氢化合物和 回收溴的目的。
2„根据权利要求 1所述方法，其特征在于所述碳氢化合物是烷烃、 烯烃和芳烃。
3,根据权利要求 1所述方法， 其特征在于所述金属氧化物有效成 分是 MgO、 CoO、 Co203和 CuO中的一种或几种的混合物。
4.根据权利要求 3所述方法， 其特征在于所述金属氧化物有效成 分是由 Mg、 Co和 Cu的一种或几种醋酸盐、 硝酸盐或溴化物的水溶液 浸泡载体， 然后烘干焙烧制成的并且负载于硅胶载体上的金属氧化 物。
5,根据权利要求 1所述方法， 其特征在于载体是硅胶载体。
6.根据权利要求 5所述方法， 其特征在于硅胶载体是市售商品硅 胶或从含硅前体如硅酸盐、 SiCl4和硅元酸酯制备的硅胶。
7。根据权利要求 1所述方法， 其特征在于步驟 1 )中碳氢化合物中 HBr与固体材料中金属氧化物的反应的温度范围为 100至 600 °C。 8。根据权利要求 7所述方法， 所述反应温度范围为 150至 400 Ό。
9。根据权利要求 8所述方法， 所述反应范围温度为 170至 300 °C。
10。 根据权利要求 1所述方法， 其特征在于步骤 2 ) 中金属氧化 物的再生的反应的温度范围为 250至 600 °C。
1 1。 根据权利要求 10所述方法， 所述反应温度范围为 300至 500
°C。
12。 根据权利要求 11所述方法， 所述反应温度范围为 320至 450
°C。
13。 根据权利要求 1所述方法， 其特征在于步驟 3 ) 中的净化系 统是由 2 ~ 8个装填有固体材料的容器通过切换阀连接而成的。
14。 根据权利要求 13所述方法， 其特征在于所述容器是一个柱 体形状的两端与切换阀相连接的固定床净化塔。
PCT/CN2008/000770 2007-04-13 2008-04-14 Procédé de purification du hbr présent dans des hydrocarbures WO2008125016A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP08733968A EP2147908A1 (en) 2007-04-13 2008-04-14 A PROCESS FOR PURIFYING HBr IN HYDROCARBONS
US12/595,781 US20100135895A1 (en) 2007-04-13 2008-04-14 Process for Purifying HBr in Hydrocarbons

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNA2007100347271A CN101284756A (zh) 2007-04-13 2007-04-13 碳氢化合物中HBr的净化方法
CN200710034727.1 2007-04-13

Publications (1)

Publication Number Publication Date
WO2008125016A1 true WO2008125016A1 (fr) 2008-10-23

Family

ID=39863251

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2008/000770 WO2008125016A1 (fr) 2007-04-13 2008-04-14 Procédé de purification du hbr présent dans des hydrocarbures

Country Status (4)

Country Link
US (1) US20100135895A1 (zh)
EP (1) EP2147908A1 (zh)
CN (1) CN101284756A (zh)
WO (1) WO2008125016A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104829411B (zh) * 2015-05-15 2017-09-29 南京工业大学 一种微通道反应器中连续制备对二甲苯的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6465696B1 (en) * 2001-06-20 2002-10-15 Grt, Inc. Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
WO2003062172A2 (en) * 2002-01-24 2003-07-31 Grt, Inc. Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
CN1754622A (zh) * 2004-09-06 2006-04-05 石油工业研究院 直接转换甲烷成乙烷及乙烯的高效能催化剂及该转换方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5914455A (en) * 1997-09-30 1999-06-22 The Boc Group, Inc. Air purification process
US6486368B1 (en) * 2001-06-20 2002-11-26 Grt, Inc. Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
US7064238B2 (en) * 2004-01-02 2006-06-20 Marathon Oil Company Conversion of alkanes to oxygenates
US20060100469A1 (en) * 2004-04-16 2006-05-11 Waycuilis John J Process for converting gaseous alkanes to olefins and liquid hydrocarbons

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6465696B1 (en) * 2001-06-20 2002-10-15 Grt, Inc. Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
WO2003062172A2 (en) * 2002-01-24 2003-07-31 Grt, Inc. Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
CN1754622A (zh) * 2004-09-06 2006-04-05 石油工业研究院 直接转换甲烷成乙烷及乙烯的高效能催化剂及该转换方法

Also Published As

Publication number Publication date
CN101284756A (zh) 2008-10-15
EP2147908A1 (en) 2010-01-27
US20100135895A1 (en) 2010-06-03

Similar Documents

Publication Publication Date Title
JP5545114B2 (ja) 触媒の再生方法
KR101740419B1 (ko) 천연 가스를 액체 탄화수소로 변환시키는 연속 공정
JP4927331B2 (ja) 物質流から一酸化炭素を除去する吸着組成物、及びその除去方法
EA022995B1 (ru) Непрерывный способ превращения природного газа в жидкие углеводороды
CN1420078A (zh) 合成气的纯化方法
KR20060043542A (ko) 탄화수소 분리 방법
KR101017697B1 (ko) Ｃ2-ｃ3 올레핀의 정제를 위한 흡착제
JP2764178B2 (ja) メタノールの接触リフォーミングによる高純度水素の製造方法
CN105324354B (zh) 催化脱氢方法中痕量氯化物污染物的高温脱除方法
WO2018022199A1 (en) Process for purifying ethylene produced from a methanol-to-olefins facility
JP5685870B2 (ja) プロピレンの製造方法
JP2000317246A (ja) アンモニアの回収方法及び回収装置
JP2004202393A (ja) 二酸化炭素の脱着方法
WO2008125016A1 (fr) Procédé de purification du hbr présent dans des hydrocarbures
JP2002037624A (ja) アンモニアの精製方法
JP2732262B2 (ja) アルシンの精製方法
KR20150035796A (ko) 탄화수소 흐름으로부터 산소를 제거하기 위한 촉매 및 방법
MXPA02007459A (es) Proceso para la preparacion de oxidos de alqueno a partir de alquenos.
CZ284087B6 (cs) Způsob přípravy parciálních oxidačních produktů, odvozených od propylenu
JPH07179377A (ja) エタノールおよびイソプロパノールの製造方法
ZHANG et al. Effect of Ce Promoter on Catalytic Performance of V/SiO2 in Oxidative Dehydrogenation of Ethylbenzene with Carbon Dioxide
CN109718740B (zh) 负载型氯化氢吸附剂及其制备方法、再生方法和应用
JP5903878B2 (ja) １，３−ブタジエン及びメタクロレインの製造方法
CN112675809A (zh) 具有吸附功能的含硅材料及其制备方法以及脱除物料中极性化合物的方法
WO2021198175A1 (en) Gas to olefins process with coproduction of hydrogen together with electrified reactional section

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: 08733968

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2008733968

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 12595781

Country of ref document: US