WO2014134917A1 - 工业含硫废气脱硫处理的催化体系及其工艺 - Google Patents

工业含硫废气脱硫处理的催化体系及其工艺 Download PDF

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WO2014134917A1
WO2014134917A1 PCT/CN2013/084793 CN2013084793W WO2014134917A1 WO 2014134917 A1 WO2014134917 A1 WO 2014134917A1 CN 2013084793 W CN2013084793 W CN 2013084793W WO 2014134917 A1 WO2014134917 A1 WO 2014134917A1
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sulfur
waste gas
industrial
catalytic system
containing waste
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English (en)
French (fr)
Inventor
肖天存
黄瑜
陈浩逸
卢永春
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GUANGZHOU BOXENERGY TECHNOLOGY Co Ltd
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GUANGZHOU BOXENERGY TECHNOLOGY Co Ltd
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8612—Hydrogen sulfide
    • B01D53/8615—Mixtures of hydrogen sulfide and sulfur oxides
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0202—Alcohols or phenols
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0204—Ethers
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/068—Polyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/05—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by wet processes

Definitions

  • the invention relates to the field of exhaust gas treatment, in particular to a catalytic system for desulfurization of industrial sulfur-containing waste gas and a process thereof. Background technique
  • Hydrogen sulfide is one of the important sulfur resources, mainly produced in natural gas desulfurization, petroleum refining processes, coking and coal gasification production. Hydrogen sulfide gas is highly toxic, flammable, and explosive, and cannot be directly discharged. Therefore, it is necessary to recycle hydrogen sulfide gas, which is both a resource utilization requirement and an environmental protection requirement.
  • Sulfide in crude oil is mainly converted into hydrogen sulfide in the refining process.
  • the domestic smelter generally uses the Claus method to treat sulfuric acid gas to recover sulfur.
  • the current Claus method needs to be carried out above the boiling point of sulfur because
  • the Claus process employs a fixed bed catalytic reactor which, if present in solid form, necessarily blocks the catalyst bed.
  • the Claus reaction is a strong exothermic reaction, and the thermodynamic law of the sulfur product produced indicates that the high temperature reaction inevitably leads to a lower conversion rate, and the sulfur recovery rate can only reach 94 to 97%. Therefore, the exhaust gas must be equipped with an exhaust gas treatment device to meet environmental protection requirements.
  • the exhaust gas treatment process is more complicated and there are many types.
  • SCOT process ammonia process
  • lime milk wash process The SCOT process is the most widely used in domestic refineries, and the total sulfur recovery rate can reach 99.8%, which can meet the environmental emission requirements, but the hydro-reduction section needs to be added.
  • the heat source consumes more hydrogen, the whole process is longer, and the running cost and equipment cost are higher.
  • Phillips Petroleum Company patented S-Zorb catalyzed gasoline desulfurization technology.
  • Yanshan Petrochemical built the first domestic gasoline desulfurization device with this technology, and the S- Zorb desulfurization technology was quickly promoted.
  • S-Zorb desulfurization technology will produce a large amount of sulfur dioxide waste gas during the regeneration process.
  • the mature treatment method in China is to absorb with alkali liquid, but the waste alkali liquor produced is difficult to handle, the cost is high, and sulfur resources are caused. waste. Summary of the invention
  • a catalytic system for desulfurization of industrial sulfur-containing waste gas comprising the following components by mass: 2-50% of a polyol, 1-40% of an acidic catalyst, the balance being water; the acidic catalyst It is one or more of a mineral acid, a mineral acid salt, an organic carboxylic acid or a soluble salt thereof.
  • the catalytic system comprises the following mass percent components: 10-40% polyol, 2-8% acidic catalyst, balance to water.
  • the polyol is selected from one or more of the group consisting of ethylene glycol, glycerin, diethylene glycol, and polyethylene glycol.
  • the polyol acts to increase the solubility of sulfur dioxide and hydrogen sulfide.
  • the inorganic acid is selected from the group consisting of: phosphoric acid, sulfuric acid, hydrochloric acid or nitric acid;
  • the inorganic acid salt is selected from the group consisting of: sodium hydrogen sulfate, potassium hydrogen sulfate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate Or dipotassium hydrogen phosphate.
  • the role of the inorganic or inorganic acid salt is to control the pH of the catalytic system and to act as an active ingredient to catalyze the Claus reaction of sulfur dioxide and hydrogen sulfide in the liquid phase.
  • the organic carboxylic acid or soluble salt thereof is selected from the group consisting of: citric acid, sodium citrate, potassium citrate, sodium benzoate, potassium benzoate, sodium phthalate or sodium salicylate.
  • Organic carboxylic acid or Its soluble salt acts to control the pH of the catalytic system and as an active ingredient to catalyze the Claus reaction of sulfur dioxide and hydrogen sulfide in the liquid phase.
  • Another object of the present invention is to provide a process for the industrial sulfur-containing exhaust gas desulfurization treatment using the above catalytic system.
  • Exhaust gas pretreatment Pretreatment of two industrial waste gases containing hydrogen sulfide and sulfur dioxide, respectively, to ensure that the non-sulfur gas in the two industrial waste gases does not react with the reaction medium and the reactants under the reaction conditions;
  • step (2) Absorption reaction: The industrial waste gas containing hydrogen sulfide pretreated in step (1) is mixed with industrial waste gas containing sulfur dioxide and then introduced into the catalytic system for absorption reaction. The reactor is stirred with a stirring paddle to ensure the mixed gas. Fully contact with the catalytic system, the flow rate of the mixed gas treated per liter of the catalytic system is 100-2000 ml / min, wherein the mixing ratio of hydrogen sulfide and sulfur dioxide is 1.8-2.2:1;
  • the absorption reaction of the step (2) is one or more stages of series absorption.
  • the mixing ratio of hydrogen sulfide to sulfur dioxide is 2:1.
  • the temperature of the absorption reaction is controlled at 0-130 ° C, the pressure is controlled at 0. l-3MPa.
  • the temperature of the absorption reaction of the step (2) is room temperature, and the pressure is controlled to be 0.1-0.2 MPa.
  • the invention relates to a desulfurization process and principle: hydrogen sulfide and sulfur dioxide are dissolved and absorbed into a liquid phase, and a catalytic reaction occurs under acidic conditions, and the main reaction occurring is expressed as:
  • the reaction is rapid, and in theory the two can react 100% completely.
  • the present invention can also employ a secondary or even multi-stage series absorption process to further increase the total sulfur removal rate.
  • the invention can be applied to the treatment of Claus tail gas in the refinery, the sulfur-containing tail gas in the smelting plant, the regeneration tail gas of the FCC, the treatment of the tail gas and the deep desulfurization waste gas of the oil product, the acid water treatment of the refinery and the sewage treatment plant, and the regeneration treatment of the desulfurizer. Wait.
  • the main feature of the desulfurization process of the present invention is that two exhaust gases containing hydrogen sulfide and sulfur dioxide can be simultaneously treated, and the two gases do not need to be separated and enriched, so there is no need to use an organic amine adsorbent, and there is no problem of defoaming; Heating does not require the addition of an iron catalyst.
  • the desulfurization process of the present invention overcomes the insufficiency of the existing high-temperature Claus sulfur recovery technology (total sulfur removal rate of 99.8%), and uses a hydrogen sulfide-containing gas and a sulfur dioxide-containing exhaust gas to recover a sulfur catalytic reaction system.
  • the process uses a low-temperature aqueous phase reaction, and the low temperature can ensure the deep conversion of hydrogen sulfide and sulfur dioxide (the total sulfur removal rate is increased to 99.95%), and the catalytic system of the invention is simple in formulation and low in cost.
  • the desulfurization process of the invention has mild operating conditions and a simple process, and can simultaneously treat hydrogen sulfide and sulfur dioxide waste gas, and recover elemental sulfur, thereby effectively reducing environmental pollution and saving sulfur resources.
  • Figure 1 is a flow chart of the desulfurization process of the present invention.
  • 201 catalytic system storage tank
  • 202 filter
  • 203 metering pump
  • 204 primary absorption reactor
  • 205 secondary absorption reactor
  • 206 pressure reducing valve
  • 207 check valve
  • 208 flow meter
  • a flow chart of an industrial sulfur-containing waste gas desulfurization process includes a catalytic system storage tank 201, a filter 202, a metering pump 203, a primary absorption reactor 204, a secondary absorption reactor 205, and a pressure reducing valve 206. , check valve 207 and flow meter 208.
  • Two exhaust gases containing hydrogen sulfide and sulfur dioxide respectively are mixed in a pipeline by a gas flow meter and then enter the kettle from the gas distributor at the bottom of the primary absorption reactor. Most of the exhaust gas is in the first-stage absorption reactor. Catalytic system contact reaction produces elemental sulfur. The catalytic system containing elemental sulfur can be discharged from the bottom of the reactor. The sulfur can be recovered by filtration. The remaining exhaust gas enters the secondary absorption reactor through the gas distributor. The sulfur-containing gas is almost completely absorbed. , the exhaust gas is directly emptied; the required catalytic system is added by a metering pump.
  • the mass percentage composition of the catalytic system of the present embodiment is: ethylene glycol 40%, sodium dihydrogen phosphate 5%, and the balance is water. Ethylene glycol and sodium dihydrogen phosphate were dissolved in water to prepare a 1.5 L catalytic system. The solution was pumped into the reaction vessel using a metering pump.
  • a process for desulfurization of an industrial sulfur-containing waste gas wherein the industrial sulfur-containing waste gas is an industrial waste gas containing hydrogen sulfide and sulfur dioxide, respectively, comprising the following steps:
  • Exhaust gas pretreatment Pretreatment of two industrial waste gases containing hydrogen sulfide and sulfur dioxide, respectively, to ensure that the non-sulfur gas in the two industrial waste gases does not react with the reaction medium and the reactants under the reaction conditions;
  • step (1) The industrial waste gas containing hydrogen sulfide (10% by volume) pretreated in step (1) is mixed with industrial waste gas containing sulfur dioxide (5% by volume) and then introduced into the first-stage absorption reaction.
  • the absorption system is carried out in the catalyst system in the kettle 204, wherein the mixing ratio of hydrogen sulfide to sulfur dioxide is 2:1; at room temperature and 0. IMPa pressure, the total gas flow rate is kept at 0.6 L/min, and the catalyst system can be continuously operated 100.
  • the absorption reaction in this example is a two-stage series reaction
  • the mixed gas in the first-stage absorption reactor absorbs the reaction
  • the tail gas enters the secondary absorption reactor and continues to absorb the reaction, multi-stage series suction
  • the harvesting process can achieve the purpose of deep desulfurization, and the series number is determined according to the desulfurization depth requirement.
  • the concentration of sulfur-containing gas in the exhaust gas was measured by gas chromatography, and the total sulfur removal rate was 99.97% or more.
  • composition of the mass percentage of the catalytic system of this example is: 20% polyethylene glycol, 0.1% sulfuric acid, 1% citric acid, 1% disodium hydrogen phosphate, and the balance being water.
  • the above raw materials were dissolved in water to obtain a 1.5 L catalytic system, which was pumped into the reaction vessel by a metering pump.
  • An industrial sulfur-containing waste gas desulfurization treatment process wherein the industrial sulfur-containing waste gas is an industrial waste gas containing hydrogen sulfide and sulfur dioxide, respectively, comprising the following steps:
  • Exhaust gas pretreatment Pretreatment of two industrial waste gases containing hydrogen sulfide and sulfur dioxide, respectively, to ensure that the non-sulfur gas in the two industrial waste gases does not react with the reaction medium and the reactants under the reaction conditions;
  • the concentration of sulfur-containing gas in the exhaust gas was measured by gas chromatography, and the total sulfur removal rate was 99.95% or more.
  • composition of the mass percentage of the catalytic system of this example is: 30% glycerol, 5% phosphoric acid, 0.5% sodium benzoate, and the balance being water.
  • the above raw materials were dissolved in water to obtain a 1.5 L catalytic system, and the solution was pumped into the reaction vessel by a metering pump.
  • An industrial sulfur-containing waste gas desulfurization treatment process wherein the industrial sulfur-containing waste gas is an industrial waste gas containing hydrogen sulfide and sulfur dioxide, respectively, comprising the following steps: (1) Exhaust gas pretreatment: Pretreatment of two industrial waste gases containing hydrogen sulfide and sulfur dioxide, respectively, to ensure that the non-sulfur gas in the two industrial waste gases does not react with the reaction medium and the reactants under the reaction conditions;
  • the industrial waste gas containing hydrogen sulfide (10% by volume) pretreated by the step (1) is mixed with industrial waste gas containing sulfur dioxide (5% by volume) and then introduced into the reaction vessel.
  • the catalyst system can be continuously operated at a temperature of 80 ° C and 0. IMPa, maintaining a total gas flow rate of 1. 6 L / min, the catalyst system can be continuously operated 100 More than an hour;
  • the concentration of sulfur in the exhaust gas was determined by gas chromatography, and the total sulfur removal rate was 99.95% or more.
  • composition of the mass percentage of the catalytic system of this example is: 10% polyethylene glycol, 2% sodium salicylate, 4% disodium hydrogen phosphate, and the balance being water.
  • the above raw materials were dissolved in water to obtain a 1.5 L catalytic system, and the solution was pumped into the reaction vessel using a metering pump.
  • An industrial sulfur-containing waste gas desulfurization treatment process wherein the industrial sulfur-containing waste gas is an industrial waste gas containing hydrogen sulfide and sulfur dioxide, respectively, comprising the following steps:
  • Exhaust gas pretreatment Pretreatment of two industrial waste gases containing hydrogen sulfide and sulfur dioxide, respectively, to ensure that the non-sulfur gas in the two industrial waste gases does not react with the reaction medium and the reactants under the reaction conditions;
  • the industrial waste gas containing hydrogen sulfide (10% by volume) pretreated by the step (1) is mixed with industrial waste gas containing sulfur dioxide (5% by volume) and then introduced into the reaction vessel.
  • the catalytic system can be continuously operated for more than 100 hours; at room temperature and 0. 2MPa pressure, maintaining a total gas flow rate of 3.0 L / min, the catalyst system can be continuously operated for more than 100 hours;
  • the gas removal rate of the exhaust gas was determined by gas chromatography, and the total sulfur removal rate was 99.95% or more.
  • composition of the mass percentage of the catalytic system of the present embodiment is: 15% diethylene glycol, 2% sodium phthalate, 0.5% sodium hydrogen sulfate, and the balance being water.
  • the above raw materials were dissolved in water to obtain a 1.5 L catalytic system, which was pumped into the reaction vessel by a metering pump.
  • An industrial sulfur-containing waste gas desulfurization treatment process wherein the industrial sulfur-containing waste gas is an industrial waste gas containing hydrogen sulfide and sulfur dioxide, respectively, comprising the following steps:
  • Exhaust gas pretreatment Pretreatment of two industrial waste gases containing hydrogen sulfide and sulfur dioxide, respectively, to ensure that the non-sulfur gas in the two industrial waste gases does not react with the reaction medium and the reactants under the reaction conditions;
  • the concentration of sulfur in the exhaust gas was determined by gas chromatography, and the total sulfur removal rate was 99.95% or more.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

本发明公开了一种工业含硫废气脱硫处理的催化体系及其工艺，该催化体系包含如下质量百分含量的组分：2-50%的多元醇、1-40%的酸性催化剂、余量为水；所述酸性催化剂为无机酸、无机酸盐、有机羧酸或其可溶性盐中的一种或几种。工艺包括：废气预处理、吸收反应和产物硫磺的回收。本发明脱硫工艺的主要特点在于可以同时对两股分别含硫化氢和二氧化硫的废气进行处理，反应过程采用低温水相反应，低温能够确保了硫化氢和二氧化硫的深度转化（总硫脱除率提高至99.95%），且本发明的催化体系配制简单，成本较低。

Description

工业含硫废气脱硫处理的催化体系及其工艺
技术领域
本发明涉及废气处理领域， 特别是涉及一种工业含硫废气脱硫处理的催化 体系及其工艺。 背景技术
硫化氢是重要的硫资源之一， 主要产生于天然气脱硫、 石油炼制过程、 炼 焦和煤气化生产等过程中产生。 硫化氢气体有剧毒、 易燃、 易爆等特性， 不能 直接排放。 因此， 必须对硫化氢气体进行回收， 既是资源利用的需要， 也是环 境保护的要求。
原油中的硫化物在炼制过程中主要转化为硫化氢， 目前国内冶炼厂普遍采用 克劳斯法对硫化氢气体进行处理回收硫磺， 目前的克劳斯法需要在硫磺沸点以 上进行， 因为一般的克劳斯法采用固定床催化反应器， 如果以固体形式存在， 必然堵住催化剂床层。 但是克劳斯反应是强放热反应， 产生的硫磺产物热力学 规律表明， 高温反应必然导致较低的转化率， 硫的回收率只能达到 94〜97%。 因 此， 其尾气必须设置尾气处理装置才能满足环保要求， 尾气处理工艺比较复杂， 种类也比较多， 主要有两大类， 一类是直接氧化工艺或低温转化工艺， 一类是 溶剂洗涤或溶剂氧化。 直接氧化或者低温转化法具有代表性的工艺有： 超级或 者超优克劳斯工艺、 低温转化系列 （MCRC 亚露点， sulfreen) 、 CLINSULF-D0 工艺。 超级或者超优克劳斯工艺、 低温转化系列 （MCRC亚露点， sulfreen) 总 硫回收率 99%〜99. 5%， 尾气不能保证达到排放标准， CLINSULF-D0工艺国内应 用较少，实际的总硫回收率也只有 99. 6%。溶剂洗涤法分为物理法和化学法两种， 这种硫回收工艺只能与克劳斯硫回收工序串联使用。 代表性的工艺有： SCOT 工 艺 、 氨法洗涤工艺、 石灰乳洗涤工艺。 SCOT工艺在国内炼厂中应用最广， 总硫 回收率可以达到 99. 8%, 能够满足环保排放要求， 但是其加氢还原工段需要外加 热源， 消耗较多氢气， 整个工艺流程较长， 运行成本及设备成本都较高。
另外， so2是导致酸雨的罪魁祸首， 是对自然环境最具危害性的气体之一。 若直接排放对生产操作、 周边环境及厂区工人造成恶劣影响， 属于必须消除或 控制的环境污染物之一。 煤电厂二氧化硫的排放已经造成了巨大的环境污染和 酸雨。 目前已经有要求富集烟气中的二氧化硫， 再回收利用。 从中石化引进了
Phillips石油公司专利 S-Zorb催化汽油脱硫技术， 在 2007年 5月在燕山石化 建成了国内第一套应用该技术的汽油脱硫装置， 并取得成功， S- Zorb脱硫技术 迅速得到了推广。 但是， S- Zorb脱硫技术吸附剂再生过程中会产生大量的二氧 化硫废气， 目前国内成熟的处理方法是用碱液吸收， 但产生的废碱液处理困难， 成本较高， 并且造成了硫资源的浪费。 发明内容
基于此， 本发明的目的是提供一种工业含硫废气脱硫处理的催化体系。 具体的技术方案如下：
一种工业含硫废气脱硫处理的催化体系， 该催化体系包含如下质量百分含 量的组分： 2-50%的多元醇、 1-40%的酸性催化剂、 余量为水； 所述酸性催化剂 为无机酸、 无机酸盐、 有机羧酸或其可溶性盐中的一种或几种。
在其中一些实施例中，所述催化体系包含如下质量百分含量的组分： 10-40% 的多元醇、 2-8%的酸性催化剂、 余量为水。
在其中一些实施例中， 所述多元醇选自： 乙二醇、 甘油、 二乙二醇、 聚乙 二醇中的一种或几种。 多元醇作用在于增加二氧化硫和硫化氢的溶解度。
在其中一些实施例中， 所述无机酸选自： 磷酸、 硫酸、 盐酸或硝酸； 无机 酸盐选自： 硫酸氢钠、 硫酸氢钾、 磷酸二氢钠、 磷酸氢二钠、 磷酸二氢钾或磷 酸氢二钾。 无机酸或无机酸盐的作用在于控制催化体系的酸碱度以及作为活性 成分催化二氧化硫和硫化氢在液相中进行克劳斯反应。
在其中一些实施例中， 所述有机羧酸或其可溶性盐选自： 柠檬酸、 柠檬酸 钠、 柠檬酸钾、 苯甲酸钠、 苯甲酸钾、 邻苯二甲酸钠或水杨酸钠。 有机羧酸或 其可溶性盐的作用在于控制催化体系的酸碱度以及作为活性成分催化二氧化硫 和硫化氢在液相中进行克劳斯反应。
本发明的另一目的是提供一种利用上述催化体系进行工业含硫废气脱硫处 理的工艺。
具体的技术方案如下：
一种利用上述催化体系进行工业含硫废气脱硫处理的工艺， 所述工业含硫 废气为分别含有硫化氢和二氧化硫的工业废气， 包含如下歩骤：
(1)废气预处理： 对分别含有硫化氢和二氧化硫的两股工业废气进行预处 理， 确保 2 股工业废气中非硫气体在反应条件下不会和反应介质以及反应物发 生反应；
(2) 吸收反应： 将歩骤 （1) 预处理后的含硫化氢的工业废气与含二氧化 硫的工业废气混合后通入催化体系中进行吸收反应， 反应釜内采用搅拌桨搅拌， 确保混合气体与催化体系充分接触， 每升所述催化体系处理的混合气的流量为 100-2000ml/min, 其中硫化氢与二氧化硫的混合比为 1.8-2.2:1;
(3) 回收歩骤 （2) 吸收反应的产物单质硫，单质硫采用真空过滤或增压过 滤进行回收， 过滤后的液体循环利用。
在其中一些实施例中， 所述歩骤 （2) 的吸收反应为一级或多级串联吸收。 在其中一些实施例中， 所述硫化氢与二氧化硫的混合比为 2:1。
在其中一些实施例中， 所述歩骤 （2) 吸收反应的温度控制在 0-130°C， 压 力控制在 0. l-3MPa。
在其中一些实施例中， 所述歩骤 （2) 吸收反应的温度为室温， 压力控制在 0.1-0.2MPa。 本发明的原理：
目前， 现有的克劳斯硫磺回收技术及其尾气处理技术中总硫脱除率最高的 为 SCOT工艺， 达到 99.8%, 但其加氢还原过程在实际应用中不可能完全转化为 硫化氢， 此外， 溶剂吸收过程已经很难再去提高其吸收效率。 本发明涉及的脱硫过程及原理： 硫化氢和二氧化硫被溶解吸收到液相中， 在 酸性条件下发生催化反应， 发生的主要反应表示为：
2H2S+S03 2— +2H+==3S+3 0 或 4H2S+S205 2— +2H+==6S+5 0
反应迅速， 理论上来说两者能 100%完全反应。 此外， 本发明还可采用二级甚至 多级串联吸收的工艺， 进一歩提高总硫脱除率。 本发明的有益效果：
本发明可应用于炼厂中克劳斯尾气处理， 冶炼厂含硫尾气， FCC再生尾气， 电厂尾气和油品深度脱硫废气的处理， 炼油厂和污水处理厂酸水处理以及脱硫 剂的再生处理等。
本发明脱硫工艺的主要特点在于可以同时对两股分别含硫化氢和二氧化硫 的废气进行处理， 两股气体不需要分离富集， 因此不需要使用有机胺吸附剂， 没有消泡的问题； 不需要加热， 也不需要添加铁催化剂。
本发明的脱硫工艺克服了现有的高温克劳斯硫磺回收技术不足 （总硫脱除 率为 99. 8%)， 利用含硫化氢的气体和含二氧化硫的废气反应回收硫磺的催化体 系， 反应过程采用低温水相反应， 低温能够确保了硫化氢和二氧化硫的深度转 化 （总硫脱除率提高至 99. 95%) , 且本发明的催化体系配制简单， 成本较低。
本发明的脱硫工艺操作条件温和， 工艺过程较为简单， 可以同时对硫化氢 和二氧化硫废气进行处理， 并回收单质硫， 有效的减少了环境的污染以及节约 了硫资源。 附图说明
图 1本发明脱硫工艺流程图。
附图标记说明：
201、 催化体系储料罐； 202、 过滤器； 203、 计量泵； 204、 一级吸收反应 釜； 205、 二级吸收反应釜； 206、 减压阀； 207、 单向阀； 208、 流量计。 具体实施方式
参考图 1， 本发明工业含硫废气脱硫工艺的流程图， 包括催化体系储料罐 201、 过滤器 202、 计量泵 203、 一级吸收反应釜 204、 二级吸收反应釜 205、 减 压阀 206、 单向阀 207和流量计 208。
两股分别含硫化氢和二氧化硫的废气经气体流量计按一定比例在管线中混 合后从一级吸收反应釜底部的气体分布器进入釜内， 绝大部分的废气在一级吸 收反应釜内与催化体系接触反应生成单质硫， 含单质硫的催化体系可从反应釜 底部排出， 经过滤可回收硫磺， 剩余的废气再经气体分布器进入二级吸收反应 釜， 含硫气体几乎完全被吸收反应， 尾气直接排空； 所需催化体系通过计量泵 添加。
以下通过实施例对本发明做进一歩阐述。
实施例 1
本实施例催化体系的质量百分含量组成为： 乙二醇 40%、 磷酸二氢钠 5%、 余量为水。 将乙二醇和磷酸二氢钠溶解到水中， 配制得到 1. 5L催化体系。 利用 计量泵将该溶液打到反应釜内。
参考图 1， 一种工业含硫废气脱硫处理的工艺， 所述工业含硫废气为分别含 有硫化氢和二氧化硫的工业废气， 包含如下歩骤：
( 1 )废气预处理： 对分别含有硫化氢和二氧化硫的两股工业废气进行预处 理， 确保 2 股工业废气中非硫气体在反应条件下不会和反应介质以及反应物发 生反应；
( 2 ) 吸收反应： 将歩骤（1 ) 预处理后的含硫化氢（体积含量为 10%) 的工 业废气与含二氧化硫 （体积含量为 5%) 的工业废气混合后通入一级吸收反应釜 204内的催化体系中进行吸收反应， 其中硫化氢与二氧化硫的混合比为 2 : 1 ; 在 室温和 0. IMPa压力下， 保持气体总流量 0. 6L/min， 该催化体系可连续运行 100 小时以上； 如图 1 所示， 本实施例吸收反应为二级串联反应， 混合气体在一级 吸收反应釜中吸收反应后尾气进入二级吸收反应釜继续吸收反应， 多级串联吸 收的工艺可以达到深度脱硫的目的， 串联级数根据脱硫深度要求来决定。
(3) 过滤回收歩骤 （2) 吸收反应的产物单质硫， 滤液循环利用。
用气相色谱检测尾气含硫气体浓度，结果显示总硫脱除率达到 99.97%以上。 实施例 2
本实施例催化体系的质量百分含量的组成为： 20%聚乙二醇、 0.1%的硫酸， 1%柠檬酸、 1%磷酸氢二钠、 其余为水。 将上述原料溶解到水中， 得到 1.5L催化 体系， 利用计量泵将该溶液打到反应釜内。
一种工业含硫废气脱硫处理的工艺， 所述工业含硫废气为分别含有硫化氢 和二氧化硫的工业废气， 包含如下歩骤：
(1)废气预处理： 对分别含有硫化氢和二氧化硫的两股工业废气进行预处 理， 确保 2 股工业废气中非硫气体在反应条件下不会和反应介质以及反应物发 生反应；
(2) 吸收反应： 将歩骤（1) 预处理后的含硫化氢（体积含量为 10%) 的工 业废气与含二氧化硫 （体积含量为 5%) 的工业废气混合后通入反应釜内的催化 体系中进行吸收反应， 其中硫化氢与二氧化硫的混合比为 1.8:1; 在 50°C和 0. IMPa压力下， 保持气体总流量 2.4L/min， 该催化体系可连续运行 100小时以 上；
(3) 过滤回收歩骤 （2) 吸收反应的产物单质硫， 滤液循环利用。
用气相色谱检测尾气含硫气体浓度，结果显示总硫脱除率达到 99.95%以上。 实施例 3
本实施例催化体系的质量百分含量的组成为： 30%甘油、 5%磷酸， 0.5%苯甲 酸钠、 其余为水。 将上述原料溶解到水中， 得到 1.5L催化体系， 利用计量泵将 该溶液打到反应釜内。
一种工业含硫废气脱硫处理的工艺， 所述工业含硫废气为分别含有硫化氢 和二氧化硫的工业废气， 包含如下歩骤： ( 1 )废气预处理： 对分别含有硫化氢和二氧化硫的两股工业废气进行预处 理， 确保 2 股工业废气中非硫气体在反应条件下不会和反应介质以及反应物发 生反应；
(2) 吸收反应： 将歩骤（1 ) 预处理后的含硫化氢（体积含量为 10%) 的工 业废气与含二氧化硫 （体积含量为 5%) 的工业废气混合后通入反应釜内的催化 体系中进行吸收反应， 其中硫化氢与二氧化硫的混合比为 2. 2 : 1 ; 在 80°C和 0. IMPa压力下， 保持气体总流量 1. 6L/min， 该催化体系可连续运行 100小时以 上；
(3) 过滤回收歩骤 （2 ) 吸收反应的产物单质硫， 滤液循环利用。
用气相色谱检测尾气含硫气体浓度，结果显示总硫脱除率达到 99. 95%以上。 实施例 4
本实施例催化体系的质量百分含量的组成为： 10%聚乙二醇、 2%水杨酸钠、 4%磷酸氢二钠、 其余为水。 将上述原料溶解到水中， 得到 1. 5L催化体系， 禾 1J用 计量泵将该溶液打到反应釜内。
一种工业含硫废气脱硫处理的工艺， 所述工业含硫废气为分别含有硫化氢 和二氧化硫的工业废气， 包含如下歩骤：
( 1 )废气预处理： 对分别含有硫化氢和二氧化硫的两股工业废气进行预处 理， 确保 2 股工业废气中非硫气体在反应条件下不会和反应介质以及反应物发 生反应；
(2) 吸收反应： 将歩骤（1 ) 预处理后的含硫化氢（体积含量为 10%) 的工 业废气与含二氧化硫 （体积含量为 5%) 的工业废气混合后通入反应釜内的催化 体系中进行吸收反应，其中硫化氢与二氧化硫的混合比为 2 : 1;在室温和 0. 2MPa 压力下， 保持气体总流量 3. 0L/min， 该催化体系可连续运行 100小时以上；
(3) 过滤回收歩骤 （2 ) 吸收反应的产物单质硫， 滤液循环利用。
用气相色谱检测尾气含硫气体浓度，结果显示总硫脱除率达到 99. 95%以上。 实施例 5
本实施例催化体系的质量百分含量的组成为： 15%二乙二醇、 2%邻苯二甲酸 钠、 0. 5%硫酸氢钠、 其余为水。 将上述原料溶解到水中， 得到 1. 5L催化体系， 利用计量泵将该溶液打到反应釜内。
一种工业含硫废气脱硫处理的工艺， 所述工业含硫废气为分别含有硫化氢 和二氧化硫的工业废气， 包含如下歩骤：
( 1 )废气预处理： 对分别含有硫化氢和二氧化硫的两股工业废气进行预处 理， 确保 2 股工业废气中非硫气体在反应条件下不会和反应介质以及反应物发 生反应；
( 2 ) 吸收反应： 将歩骤（1 ) 预处理后的含硫化氢（体积含量为 10%) 的工 业废气与含二氧化硫 （体积含量为 5%) 的工业废气混合后通入反应釜内的催化 体系中进行吸收反应，其中硫化氢与二氧化硫的混合比为 2 : 1 ;在室温和 0. 2MPa 压力下， 保持气体总流量 2. 0L/min， 该催化体系可连续运行 100小时以上；
( 3 ) 过滤回收歩骤 （2 ) 吸收反应的产物单质硫， 滤液循环利用。
用气相色谱检测尾气含硫气体浓度，结果显示总硫脱除率达到 99. 95%以上。 以上所述实施例仅表达了本发明的几种实施方式， 其描述较为具体和详细， 但并不能因此而理解为对本发明专利范围的限制。 应当指出的是， 对于本领域 的普通技术人员来说， 在不脱离本发明构思的前提下， 还可以做出若干变形和 改进， 这些都属于本发明的保护范围。 因此， 本发明专利的保护范围应以所附 权利要求为准。

Claims

权 利 要 求
1、 一种工业含硫废气脱硫处理的催化体系， 其特征在于， 该催化体系包含如下 质量百分含量的组分： 2-50%的多元醇、 1-40%的酸性催化剂、 余量为水； 所述 酸性催化剂为无机酸、 无机酸盐、 有机羧酸或其可溶性盐中的一种或几种。
2、 根据权利要求 1所述的工业含硫废气脱硫处理的催化体系， 其特征在于， 所 述催化体系包含如下质量百分含量的组分： 10-40%的多元醇、 2-8%的酸性催化 剂、 余量为水。
3、 根据权利要求 1或 2所述的工业含硫废气脱硫处理的催化体系，其特征在于， 所述多元醇选自： 乙二醇、 甘油、 二乙二醇、 聚乙二醇中的一种或几种。
4、 根据权利要求 1或 2所述的工业含硫废气脱硫处理的催化体系， 其特征在于 所述无机酸选自： 磷酸、 硫酸、 盐酸或硝酸； 无机酸盐选自： 硫酸氢钠、 硫酸 氢钾、 磷酸二氢钠、 磷酸氢二钠、 磷酸二氢钾或磷酸氢二钾。
5、 根据权利要求 1或 2所述的工业含硫废气脱硫处理的催化体系，其特征在于， 所述有机羧酸或其可溶性盐选自： 柠檬酸、 柠檬酸钠、 柠檬酸钾、 苯甲酸钠、 苯甲酸钾、 邻苯二甲酸钠或水杨酸钠。
6、 一种利用权利要求 1-5任一项所述催化体系进行工业含硫废气脱硫处理的工 艺， 所述工业含硫废气为分别含有硫化氢和二氧化硫的工业废气， 其特征在于， 包含如下歩骤：
( 1 )废气预处理： 对分别含有硫化氢和二氧化硫的两股工业废气进行预处 理， 确保 2 股工业废气中非硫气体在反应条件下不会和反应介质以及反应物发 生反应；
( 2 ) 吸收反应： 将歩骤 （1 ) 预处理后的含硫化氢的工业废气与含二氧化 硫的工业废气混合后通入催化体系中进行吸收反应， 每升所述催化体系处理的 混合气的流量为 100-2000ml/min， 其中硫化氢与二氧化硫的混合比为 1. 8-2. 2 : 1； (3) 回收歩骤 （2) 吸收反应的产物单质硫。
7、 根据权利要求 6所述的工业含硫废气脱硫处理的工艺， 其特征在于， 所述歩 骤 （2) 的吸收反应为一级或多级串联吸收。
8、 根据权利要求 6或 7所述的工业含硫废气脱硫处理的工艺， 其特征在于， 所 述硫化氢与二氧化硫的混合比为 2:1。
9、 根据权利要求 6或 7所述的工业含硫废气脱硫处理的工艺， 其特征在于， 所 述歩骤 （2) 吸收反应的温度控制在 0-130°C， 压力控制在 0. l-3MPa。
10、 根据权利要求 9所述的工业含硫废气脱硫处理的工艺， 其特征在于， 所述 歩骤 （2) 吸收反应的温度为室温， 压力控制在 0. l-0.2MPa。
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CN110106004A (zh) * 2018-12-29 2019-08-09 河南农业大学 沼气脱硫器、脱硫方法及提纯工艺

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CN104801153A (zh) * 2015-04-16 2015-07-29 广东省宜华木业股份有限公司 一种用于车间尾气处理的喷淋液及其制备方法
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CN115340887B (zh) * 2022-10-18 2023-01-31 山东鹏达生态科技股份有限公司 高炉煤气精脱硫及硫资源化工艺

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103203242A (zh) * 2013-03-06 2013-07-17 广州博能能源科技有限公司 工业含硫废气脱硫处理的催化体系及其工艺

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2635987B1 (fr) * 1988-09-02 1993-10-15 Rhone Poulenc Chimie Catalyseurs pour le traitement des effluents gazeux et procede de traitement de ces effluents
CN101322915A (zh) * 2007-06-14 2008-12-17 兰州理工大学 一种复合吸附脱硫剂及其制备方法
CN101417230B (zh) * 2007-10-26 2010-06-09 中国石油化工股份有限公司 一种加氢催化剂应用前的处理方法
CN102527202B (zh) * 2012-01-06 2014-05-14 肖天存 一种含硫废气脱硫并回收单质硫的工艺及其设备

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103203242A (zh) * 2013-03-06 2013-07-17 广州博能能源科技有限公司 工业含硫废气脱硫处理的催化体系及其工艺

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LI, ZHENGXI: "The Method of Refining the Tail Gas of Liquid Catalytic Method", CHEMICAL ENGINEERING DESIGN, April 1990 (1990-04-01), pages 34 - 37 *
SHI, YAJUN ET AL.: "The Liquid Catalytic Reaction which Remove the Sulfide in the Claus Tail Gas(Polyglycol 400 Method", CHEMICAL WORLD, February 1980 (1980-02-01), pages 35 AND 36 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110106004A (zh) * 2018-12-29 2019-08-09 河南农业大学 沼气脱硫器、脱硫方法及提纯工艺

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