BLUER-PRO工艺

技术来源

　　BLUER-PRO硫磺回收技术属于螯合铁湿式氧化法脱硫工艺，国外同类技术为美国Merichem公司的LO-CAT技术。LO-CAT技术是于上世纪70年代开发出的专利硫化氢回收技术，经过四十多年的发展，已经成为应用最多的螯合铁湿式氧化法脱硫工艺，目前全球已经建设有200多套LO-CAT装置，应用领域涵盖天然气开采、石油提炼、生物气处理、垃圾填埋沼气处理、炼焦、地热气体发电、饮料业CO2气体生产、润滑油生产等，是一种非常可靠的硫磺回收技术。

　　烟台新瑞环保科技有限公司早期采用了由外国公司提供工艺设计包，自已承担基础工程设计和详细工程设计的合作方式，并结合工程建设和生产实际，不断总结经验，通过数套装置的设计，已经掌握了LO-CAT硫磺回收全套装置的设计技术，开发研究出了XR-SR系列螯合铁脱硫溶剂，其主要由铁离子浓缩剂、螯合剂、表面活性剂、杀菌剂、消泡剂、初始剂等组成。形成了有自己特色的BLUER-PRO硫磺回收技术，打破了LO-CAT工艺和催化剂依靠国外引进的格局。

BLUER-PRO process

Technical source

BLUER-PRO sulfur recovery technology belongs to the wet oxidation desulfurization process of chelated iron, and the foreign similar technology is LO-CAT technology of Merichem company in the United States. LO-CAT technology is a patented hydrogen sulfide recovery technology developed in the 1970s. After more than 40 years of development, it has become the most widely used wet oxidation desulfurization process of chelated iron. At present, more than 200 sets of LO-CAT devices have been built around the world. Application fields cover natural gas extraction, petroleum refining, biogas treatment, landfill biogas treatment, coking, geothermal gas power generation, beverage industry CO2 gas production, lubricant production, etc., is a very reliable sulfur recovery technologies.

 

Early on, Yantai Sunrise Environmental Protection Technology Co., Ltd. adopted the cooperation mode of providing process design packages by foreign companies and undertaking basic engineering design and detailed engineering design by itself. Combined with the actual construction and production of engineering, it constantly summarized experience. XR-SR series of chelated iron desulphurization solvent was developed, which mainly consists of an iron ion concentration agent, chelating agent, surfactant, bactericide, defoamer, initial agent, etc. BLUER-PRO sulfur recovery technology with its characteristics has been formed, breaking the pattern of the LO-CAT process and catalyst relying on foreign introduction.

工艺原理

BLUER-PRO的基本反应过程可以分为吸收与再生两个阶段

Principle of technology

The basic reaction process of BLUER-PRO can be divided into two stages: Absorption and regeneration

吸收反应：Absorption reaction:

H2S(气体)+2Fe3+→2H++S°+2Fe2+

再生反应：Regeneration reaction:

1/2 O2(气体)+H2O+2Fe2+→2OH-+2Fe3+

总反应：Total Response:

H2S+1/2O2→H2O+S°

　　这一反应发生于水基溶液中，所用水基溶液中的金属离子能够清除硫化物离子（S2-）的电子（负电荷），使之转变成元素硫。此外，在再生过程中，该金属能够将俘获的电子转移给氧（O2），使自己重新恢复到原来的金属离子状态。虽然具备这种功能的金属有许多种，但是BLUER-PRO处理工艺技术选择了铁（Fe），因为铁无毒而且活性好，转化效率高。

This reaction occurs in a water-based solution where metal ions are able to remove the electrons (negative charge) of the sulfide ion (S2-) and convert it into elemental sulfur. In addition, during the regeneration process, the metal is able to transfer the captured electrons to oxygen (O2), returning itself to its original metal ion state. Although there are many kinds of metals with this function, the BLUER-PRO process technology chose iron (Fe) because iron is non-toxic and has good activity and high conversion efficiency.

工艺

工艺过程

BLUER-PRO工艺分为常规工艺和自循环工艺两种

（1）常规BLUER-PRO

　　在处理易燃气体或其它有用的气体产物时，BLUER-PRO系统设有单独的吸收器和氧化器，BLUER-PRO的螯合铁催化剂泵入两容器间。吸收器把H2S从含硫气体中分离出来并转化成单质硫。氧化器则可恢复铁催化剂。将脱硫和再生分别各在二个塔中进行，故称双塔流程。

BLUER-PRO常规流程

常规流程H2S的吸收和氧化再生分别在吸收塔和氧化塔两个塔中进行。

吸收塔：

H2S(气体)+2Fe3+→2H++S°+2Fe2+

氧化塔：

1/2 O2(气体)+H2O+2Fe2+→2OH-+2Fe3+

Technology

Technological process

The BLUER-PRO process is divided into two types: conventional process and self-recycling process

(1) Regular BLUER-PRO

When dealing with flammable gases or other useful gas products, the BLUER-PRO system has a separate absorber and oxidizer, and BLUER-PRO's chelated iron catalyst is pumped between the two containers. The absorber separates H2S from the sulfur-containing gas and converts it into elemental sulfur. The oxidizer recovers the iron catalyst. The desulfurization and regeneration are carried out in two towers respectively, so it is called the two-tower process.

BLUER-PRO routine process

The conventional process of H2S absorption and oxidation regeneration is carried out in the absorption tower and the oxidation tower respectively.

Absorption tower:

H2S (gas) +2Fe3+→2H++S°+2Fe2+

Oxidation tower：

H2S (gas) +2Fe3+→2H++S°+2Fe2+

（2）自循环BLUER-PRO

　　在处理胺酸气体及其它非易燃低压气体时可以使用专利系统自循环。在该系统中，吸收器和氧化器被整合为一个装置，从而减少一个容器，省去了溶液循环泵以及相关的管道等装置。

BLUER-PRO自循环工艺

吸收区反应：

H2S(气体)+2Fe3+→2H++S°+2Fe2+

氧化区反应：

1/2 O2(气体)+H2O+2Fe2+→2OH-+2Fe3+

BLUER-PRO硫磺回收工艺其反应器结构包含常规的四种或由这四种结合的结构，为鼓泡、移动床、静态混合、文丘里四种，目前国内也有使用填料的结构方式。

(2) Self-circulating BLUER-PRO

The patented system can be used for self-circulation when dealing with amine gases and other non-flammable low pressure gases. In this system, the absorber and oxidizer are integrated into one unit, thereby eliminating one container and eliminating the need for solution circulation pumps and associated piping.

BLUER-PRO self-recycling process

Absorption zone reaction:

H2S(gas)+2Fe3+→2H++S°+2Fe2+

Oxidation zone reaction:

1/2 O2(gas)+H2O+2Fe2+→2OH-+2Fe3+

The reactor structure of BLUER-PRO sulfur recovery process contains four conventional or a combination of these four structures, which are bubbling, moving bed, static mixing and venturi. At present, there are also structural ways of using fillers in China.

 

工艺特点

BLUER-PRO工艺适用于0.2-20t/d的硫磺回收装置，是中小规模硫磺回收工艺技术的世界领先者。主要工艺特点如下：

（1）硫化氢脱除率高，一步反应的脱除率达到99.99%以上，处理过的尾气H2S浓度在1ppm以下。

（2）应用范围广，可以处理各种含H2S气体，选择性高。

（3）操作弹性大，能够适应原料气中H2S浓度、原料气流量从0-100%的大幅度波动变化。

（4）环境友好，没有三废产生。

（5）反应条件温和，为液相、常温常压反应过程。

（6）工艺简单，开、停工及日常操作均简单。

（7）经济性能高，占地面积小，投资费用少，日常运行成本低。

（8）安全性能高，系统不使用任何有毒的化学物质，硫磺产品中没有H2S气体。

（9）运行可靠，独特的设计能够保证无堵塞现象发生，保证长周期稳定运行。

与克劳斯工艺比较

与当前国内成熟应用的克劳斯干法脱硫回收技术比较:

Process characteristics

The BLUER-PRO process is suitable for 0.2-20 t/d sulfur recovery plants and is the world leader in small and medium-scale sulfur recovery process technology. The main process features are as follows:

(1) The removal rate of hydrogen sulfide is high, the removal rate of one-step reaction is more than 99.99%, and the H2S concentration of the treated tail gas is below 1ppm.

(2) Wide range of applications, can deal with a variety of H2S gases, high selectivity.

(3) Operation flexibility, can adapt to the H2S concentration in raw gas, raw gas flow from 0-100% fluctuations.

(4) Environmentally friendly, no three wastes produced.

(5) The reaction conditions are mild, and the reaction process is a liquid phase, normal temperature, and atmospheric pressure.

(6) The process is simple, the opening, shutdown, and daily operation are simple.

(7) High economic performance, small footprint, less investment costs, and low daily operating costs.

(8) High safety performance, the system does not use any toxic chemicals, and there is no H2S gas in sulfur products.

(9) Reliable operation, unique design can ensure that no blockage occurs, to ensure long-term stable operation.

Comparison with Krauss process

Compared with the current domestic mature application of Klaus dry desulfurization recovery technology:

比较项目	XR-999	克劳斯/CLAUS
适用的处理负荷	70-7500吨/年	7000吨/年以上
适用进料气体	各种气体，包括克劳斯尾气	酸性气，但处理酸性水汽提出来的酸性气很困难
最小处理负荷 吨/天	0	20
进料中H2S含量	0-100%	40%以上
硫磺脱出率	99.99%以上，尾气H2S含量低于1PPM	95-96%
工艺过程和处理效果	工艺简单，一步转化过程达到要求处理结果	包括酸性气灼烧、两段固定床反应器，尾气需要在焚烧后排放，为保证脱硫效果，还要增设 尾气处理装置
开工率	100%	小硫磺开工率非常低
操作条件	常温	在高温下操作
操作性能	没有任何操作问题，可以保持长周期稳定运行	对于7000吨/年以下的装置极易造成频繁阻塞和停工
产品硫磺	固体	气体/液体，含有h2S气体

Comparison item	XR-999	CLAUS
Applicable processing load	70-7500 tons per year	7000 tons/year or more
Applicable feed gas	All kinds of gases	Acid gas, but it is difficult to deal with acid gas from acidic water vapor
Minimum handling load tons/day	0	20
H2S content in fee	0-100%	More than 40%
Sulfur extraction rate	Above 99.99%, H2S content of exhaust gas is less than 1PPM	95-96%
Process and treatment effect	The process is simple, one step conversion process to achieve the required processing results	Including acid gas burning, two-stage fixed bed reactor, the tail gas needs to be discharged after incineration, in order to ensure the desulfurization effect, but also add the tail gas treatment device
Rate of operation	100%	Small sulfur operation rate is very low
Operating condition	Normal temperature	Operate at high temperatures
Operating performance	Without any operational problems, it can maintain a long period of stable operation	For units under 7,000 tons/year, it is very easy to cause frequent blocking and downtime
Product sulfur	solidity	Gas/liquid, combined with H2S gas

适用范围

Scope of application

　　BLUER-PRO硫化氢气体处理工艺广泛应用于石油提炼、天然气开采、地热气体发电、生物气处理、垃圾填埋沼气处理、饮料业二氧化碳气体生产、润滑油生产等行业。对生产过程中产生的含硫化氢气体几乎可以完全回收，达到真正意义上的节能减排效果。

BLUER-PRO hydrogen sulfide gas treatment process is widely used in oil refining, natural gas exploitation, geothermal gas power generation, biogas treatment, landfill biogas treatment, beverage industry carbon dioxide gas production, lubricant production, and other industries. The hydrogen sulfide gas produced in the production process can be almost completely recovered, to achieve the real sense of energy saving and emission reduction effect.

　　在这些工业生产中，需处理的气体流量从几个立方米每小时到上万个立方米每小时，气体H2S浓度从100ppm到100%，气压从50KPa到4.5MPa，每天产生的硫从0.2吨到20多吨。

In this industrial production, the gas flow to be treated ranges from a few cubic meters per hour to tens of thousands of cubic meters per hour, the gas H2S concentration ranges from 100ppm to 100%, the air pressure ranges from 50KPa to 4.5MPa, and the sulfur produced per day ranges from 0.2 tons to more than 20 tons.