超重力湿式氧化法脱除焦炉煤气中硫化氢

以H2S、CO2和空气模拟焦炉煤气,以超重机为脱硫设备,采用湿式氧化法脱除焦炉煤气中的H2S,研究了超重力因子、液气比、气液接触时间、原料气中H2S含量等工艺参数对脱硫率的影响规律,结果表明：脱硫效率随着超重力因子、液气比、气液接触时间和原料气中H2S浓度的增大而增大。确定了适宜的工艺参数,在气液接触时间为0.15 s的条件下,获得了98%以上的脱硫效率,CO2的脱除率稳定在1.0%左右,超重力法脱硫技术实现了高效、快速脱硫。在生产现场建成了处理气量为10000 m3/h的工程化超重力湿式氧化法脱硫装置,运行结果显示：超重力湿式氧化法脱除焦炉煤气中H2S技术具有脱硫效率高、气液接触时间短、操作弹性大、设备体积小等优点,H2S脱除率可稳定在90%以上,应用前景广阔。     

室内模拟硫化氢对聚合物粘度影响研究方法的建立

针对配注污水中因硫化氢气体的存在导致所配聚合物溶液粘度损失严重,其含硫化氢污水取样后室内很难存储问题,开展室内合成硫化氢,建立室内研究硫化氢对聚合物粘度影响实验方法。该研究方法为:盐酸与硫化钠反应后生成一定量的硫化氢,以氮气为载气通入聚合物溶液中,考察硫化氢对聚合物溶液粘度的影响。通过控制载气流量、吹脱温度、酸滴加速度确定硫化氢的最佳生成条件,从而确定硫化氢对聚合物粘度影响的最佳室内模拟条件。通过实验研究最终确定反应温度为80℃、氮气流量为0.1L/min、盐酸在5min内滴加完成,在该反应条件下可以准确评价硫化氢对聚合物溶液粘度影响。     

Selective Removal of Hydrogen Sulfide from Gases Containing Hydrogen Sulfide and Carbon Dioxide Using Diethanolamine

Abstract

It is sometimes necessary to selectively remove hydrogen sulfide from gases containing carbon dioxide. This may be the case for example in the production of sulfur using the Claus process. When two gases are simultaneously absorbed into a solution containing a reactant with which each gas can react, the rate of absorption of each component is affected by the presence of the other gas. For the absorption of hydrogen sulfide into primary and secondary amines, the reaction which occurs can usually be considered to be instantaneous. An instantaneous reaction is diffusion-limited since the reaction occurs so rapidly that the liquid phase reactant and the absorbed gas cannot coexist in the same region of the liquid. For primary and secondary amines used for gas treatment, the reaction with carbon dioxide is much slower than for hydrogen sulfide and can often be considered to be second order.

In this work the simultaneous absorption of two gases into a liquid containing a reactant with which both gases can react is modeled using penetration theory. It is assumed that one gas reacts instantaneously and the other gas undergoes a second order reaction. Parameters used in the calculations are those available in the literature corresponding to the absorption of hydrogen sulfide and carbon dioxide in diethanolamine.     

A continuous process for recovery of sulfur from natural gas containing low concentrations of hydrogen sulfide

A continuous catalytic process was developed to remove hydrogen sulfide from a natural gas stream using activated carbon as catalyst. The concentration range of hydrogen sulfide in the gas stream studied was 300–3000 ppmv (0.0126–0.126 moles/m³). Virtually 100 percent conversion of hydrogen sulfide was achieved by the combination of various parameters. The “field gas” employed in this study exhibited cracking of some heavier hydrocarbons and made the product sulfur slightly brown. These hydrocarbons should therefore be separated from the gas stream prior to the oxidation reaction. No carbon monoxide or carbon dioxide was produced during the oxidation of hydrogen sulfide. It is concluded that the process described herein has the potential for the removal of hydrogen sulfide as sulfur from a sour natural gas stream on a continuous basis and could therefore eliminate an environmental problem which now exists.     

Hydrogen sulphide emission control by combined adsorption and catalytic combustion

The removal of low concentrations of hydrogen sulfide by adsorption and catalytic combustion has been studied. Concentration of hydrogen sulfide by adsorption from waste-gas streams is best effected by molecular sieve 13X, if the stream is dry, and by activated carbon, if the gas stream is moist.

Low-temperature catalytic oxidation of hydrogen sulphide in moist gas streams can be effected over activated carbon. The reaction appears to involve ionized hydrogen sulfide, dissolved in water condensed in the pores of the carbon.

At high temperatures, both supported platinum and palladium catalysts are found to be oxidation catalysts. Palladium is the best catalyst for methane oxidation but is partially deactivated in the presence of sulfur-containing gases. In contrast, platinum was more active for the same reaction in the presence of sulfur-containing gases.

Both metals were found to promote the oxidation of hydrogen sulfide above ca. 150°C. The power rate laws describing the kinetics of reaction were determined.     

Shrouded nozzle for selective gas purification

A means is discussed by which a liquid may be atomized and introduced into a continuous medium without that medium being in contact with the liquid during atomization. This offers an advantage if intense mixing in the liquid being atomized is to be avoided, as is the case in the selective gas purification application discussed here. Hydrogen sulfide is to be preferentially removed from a gas with larger quantities of carbon dioxide in a spray reactor; the liquid contains a species that reacts with both absorbed hydrogen sulfide and carbon dioxide, but the reaction rate with hydrogen sulfide is much faster. Thus, by use of a simple shielded nozzle (with or without a shielding gas), selectivity for H₂S transfer is increased.     

文昌13-1/2油田液化石油气铜腐超标治理方法的研究及应用

文昌13-1/2油田液化石油气(LPG)回收项目是中海石油(中国)有限公司湛江分公司首个海上LPG回收项目。近年来文昌油田LPG产品时而会发生铜腐测试不合格情况,本文通过对LPG系统硫化氢检测,LPG气样总硫含量测试以及铜片腐蚀产物的能谱测试,发现文昌油田LPG气样铜腐超标和硫含量超标有关。根据海上油田生产环境特点,拟采取湿法脱硫技术,直接加注脱硫剂的方法治理铜腐不合格问题。现场试验加药点选在进口压缩机进口,这样既可以给脱硫剂与硫化氢反应提供空间和时间,又可以在LPG系统较前端将硫化氢治理到较低水平,防止了硫化氢在LPG系统中的扩散。液化气脱硫剂以加注量50mL/min,在现场实践应用的一个月的时间里,可以有效地将铜腐指标从2a降低到1a,确保LPG产品符合国标标准要求。     

炭基材料脱除H2S研究进展

从反应机理、活性炭表面特性、湿度、活化改性方法及活性组分等因素对反应过程的影响和活性炭失活后的再生方法等方面综述了近年来国内外活性炭脱除H2S的研究进展;进一步阐述了半焦作为一种廉价原料的优势,并提出了用活性半焦脱除原料气和燃料气中H2S的新思路．     

Low Temperature Catalytic Decomposition of Hydrogen Sulfide into Hydrogen and Diatomic Gaseous Sulfur

A new catalytic reaction of hydrogen sulfide decomposition is discovered, the reaction occurs on metal catalysts in gas phase according to equation $$2{\text{H}}_{2} {\text{S}} \leftrightarrow 2{\text{H}}_{2} + {\text{S}}_{2}^{{({\text{gas}})}}$$ 2 H 2 S ? 2 H 2 + S 2 ( gas ) to produce hydrogen and gaseous diatomic sulfur, conversion of hydrogen sulfide at room temperature is close to 15 %. The thermodynamic driving force of the reaction is the formation of the chemical sulfur–sulfur bond between two hydrogen sulfide molecules adsorbed on two adjacent metal atoms in the key surface intermediate and elimination of hydrogen into gas phase. “Fingerprints” of diatomic sulfur adsorbed on the solid surfaces and dissolved in different solvents are studied. In closed vessels in adsorbed or dissolved states, this molecule is stable for a long period of time (weeks). A possible electronic structure of diatomic gaseous sulfur in the singlet state is considered. According to DFT/CASSCF calculations, energy of the singlet state of S₂ molecule is over the triplet ground state energy for 10.4/14.4 kcal/mol. Some properties of gaseous diatomic sulfur are also investigated. Catalytic solid systems, both bulk and supported on porous carriers, are developed. When hydrogen sulfide is passing through the solid catalyst immersed in liquid solvent which is capable of dissolving sulfur generated, conversion of hydrogen sulfide at room temperature achieves 100 %, producing hydrogen in gas phase. This gives grounds to consider hydrogen sulfide as inexhaustible potential source of hydrogen—a very valuable chemical reagent and environmentally friendly energy product.     

H_2S在Fe_3O_4表面的吸附反应研究

根据含硫原油加工过程中常温活性硫的腐蚀状况,研究了低体积分数H2S气体在Fe3O4表面的吸附反应过程,考察了温度、反应气体相对湿度、Fe3O4中w(H2O)对吸附反应的影响。研究结果表明,温度升高,反应气体相对湿度及Fe3O4w(H2O)的增加均促进吸附反应。     

活性炭担载金属氧化物用于热煤气脱硫

以热煤气脱硫并回收单质硫为目的,考察了活性炭担载金属氧化物(M/AC)在中温范围150—250℃内,催化氧化硫化氢生成单质硫的研究。担载量1%(质量分数)的M/AC通过等体积浸渍法制得,在固定床上评价了其脱硫活性,并考察了温度、反应气氛等工艺条件对脱硫效果的影响。M/AC脱硫的活性顺序为:Mn/ACCu/ACCe/ACFe/ACCo/ACV/AC。通过DTG分析,硫化氢选择性氧化的主要产物是单质硫。M/AC上金属氧化物起主要的催化作用,催化硫化氢和氧气反应生成单质硫,生成的单质硫被吸附在活性炭的孔道中。     

生物膜法净化低浓度硫化氢气体的试验研究

论述了采用生物膜填料塔净化低浓度Ｈ２Ｓ气体的可行性。研究表明：构成生物膜的脱硫杆菌对废气中低浓度Ｈ２Ｓ气体有很强的生化去除能力,生物膜填料对废气中的Ｈ２Ｓ的生化去除量可达９５．１ｇ／（ｍ３填料·ｈ）,而且当入口的Ｈ２Ｓ气体的浓度在２．３ｇ／ｍ３以下时,生物膜填料塔的净化效率在８８％以上。     

四丙氟橡胶在硫化氢与二氧化碳混合气相环境中的耐老化性能

研究了3 种四丙氟橡胶( 100 S、VTR － 8802 和TP － 2) 在不同温度、二氧化碳含量和硫化氢含量条件下的耐高温高压硫化氢老化的性能。结果表明,100 S 在硫化氢环境中具有较好的耐高温性能,100 S 和VTR 8802 在二氧化碳含量较高的硫化氢环境中具有较好的耐老化性能,VTR 8802 的耐高含量 硫化氢的性能较好,而TP － 2 在本研究测试条件下的耐硫化氢老化性能较差。     

Oxidative absorption of hydrogen sulfide using an iron‐chelate based process: chelate degradation

BACKGROUND: Oxidative absorption of hydrogen sulfide into a solution of ferric chelates is studied in a stirred cell glass reactor. The experiments were performed to investigate the degradation of chelates sodium salt of nitrilotriacetic acid (NTA) (Merck), ethylenediaminetetraacetic acid diadisodium salt (EDTA) and diethylenetriaminepentaacetic acid (DTPA) at 313 K, pH 6, iron concentration 10 000 g L^?1 and Fe:chelate molar ratio 1:2. RESULTS: Oxidative absorption of hydrogen sulfide into a solution of Fe‐NTA was found to be more successful, therefore, further experiments with 10%, 50% and 100% concentrations of hydrogen sulfide were performed. It was shown that this process is applicable for removal of low and high concentrations of hydrogen sulfide. The effect of antioxidants using sodium thiosulfate was also studied in order to minimize degradation of NTA. The kinetics were studied and it was observed that the reaction appeared to be first order in ferric chelate with rate constants for 100, 50 and 10% hydrogen sulfide concentration: 0.035, 0.013 and 0.019 h^?1, respectively. CONCLUSIONS: Gas sweetening processes have commercial importance in natural gases, refinery of gases and biogas processing. Desulphurization and cleaning (i.e. removal of H₂S and CO₂) of petroleum gas and biogas is important to make the gas methane rich and to increase the calorific value of fuel. The same techniques of desulphurization and cleaning can be used for treating natural gas or petroleum gas. The desulphurization and cleaning processes can minimize the atmospheric emission of gases like SOx, NOx and CO. As the iron chelate based process is based on the principle of redox reaction of metal chelate with hydrogen sulfide, this method is very useful for desulphurization of petroleum gas and biogas. This work studied the effective use of Fe‐NTA solution for removal of high to low concentrations of H₂S as found in biogas and industrial waste gases. © 2012 Society of Chemical Industry     

混合轻烃碱洗脱硫在塔河油田的成功应用

塔河油田四号联合站负压气提脱硫(稳定)装置所产混合轻烃中硫化氢含量达0.06%,经与NaOH溶液反应脱出硫化氢,从而保证后续加工生产的液化气、稳定轻烃的含硫指标满足规范要求。     

Nucleophilic addition of hydrogen sulfide to methyl oleate,methyl linoleate,and soybean oil

Hydrogen sulfide was added to methyl oleate, methyl linoleate, and soybean oil at −70 and 25 C in the presence of boron trifluoride. Major reaction compounds were identified by gas liquid chromatography and mass spectrometry. At −70 C with a 200 molar ratio of hydrogen sulfide to ester, the reactions were complete in 4 hr. Primary reaction product from methyl oleate was methyl 9(10)-mercaptostearate. Methyl linoleate gave ca. equal amounts of methyl 9-(2-pentyl-1-thiolan-5-yl) nonanoate and methyl 8-(2-hexyl-1-thiolan-5-yl) octanoate. At 25 C, the reaction of methyl oleate and linoleate with hydrogen sulfide was less complete, and more side reactions were noted. When equimolar amounts of methyl oleate and methyl 9(10)-mercaptostearate were reacted in the presence of boron trifluoride at 25 C, a new compound was formed, bis(methyl n-octadecanoate 9[10]-yl) sulfide. The addition of liquid hydrogen sulfide to soybean oil at −70 C in the presence of boron trifluoride yields a product which, upon saponification, acidification, and methylation analyzes by gas liquid chromatography as ca. 52% thiolan, 27% mercaptostearate, 10% palmitate, 6% stearate, and 5% unidentified compounds.     

二巯基丙磺酸钠的合成和表征

以丙烯磺酸钠为原料,经溴化、巯基化、成汞盐络合物、用硫化氢对络合物脱汞四个步骤合成二巯基丙磺酸钠,并对结构进行表征。     

A Process of Washing and Ozonation to Deodorize an Atmosphere Contaminated by Sulfides

A treatment process of gas polluted by hydrogen sulfide or alkyl sulfide is described in this paper. It includes pollutant absorption by an aqueous solution and a continuous regeneration by an ozone oxidation of absorbed compounds. The effects of the main parameters of the process are discussed (pH, concentrations, flow rate,… ). Results are linked to the theory of mass transfer with chemical reaction.     

SULFUR RECOVERY WITH REDUCED EMISSIONS, LOW CAPITAL INVESTMENT AND HYDROGEN CO-PRODUCTION

The main disadvantage of the Claus process is that by introducing air as oxidant a large volume of tail gas is produced. This must be treated to reduce atmospheric emissions of sulfur-containing gases. The costs of the tail-gas unit are a significant fraction of the total capital and operating costs for sulfur recovery. A new process uses thermal decomposition of hydrogen sulfide in the presence of carbon dioxide instead of air oxidation. The products of this reaction are hydrogen, carbon monoxide, elemental sulfur, water vapor and carbonyl sulfide. Carbonyl sulfide is easily converted to H₂S and C0₂ by liquid- or vapor-phase hydrolysis. Unreacted H₂S and C0₂ are recovered by absorption and recycled to the reactor. Since no air is introduced, there is no tail gas and the tail-gas unit is eliminated, giving a substantial reduction in capital investment. The concentrations of sulfur-containing gases in the product streams depend only on the operation of the absorber and stripper units and can be controlled to very low levels by increasing stripper boil-up. Process operating costs depend on the level of sulfur recovery required and can also be much lower than those of the modified Claus Process.

The process chemistry depends on a shift in the equilibrium of H₂S decomposition caused by reaction of hydrogen with C0₂ by the reverse of the water-gas-shift reaction. Catalysts for this chemistry have been identified. Reactor conversion is further improved by rapid cooling of the reactor effluent gas. Other aspects of process design and operation confer further advantages with respect to the Claus process; however, the process equipment used is similar to that used in a Claus plant. Retrofit of existing plant to the new technology can therefore be considered.     

介质阻挡放电等离子体脱除沼气中硫化氢的实验研究

介质阻挡放电（DBD）等离子体技术是一种有效的气体污染物控制技术。开展了利用DBD等离子体技术脱除模拟沼气中硫化氢的实验研究,考察了放电能量密度、硫化氢初始体积浓度、停留时间以及含氧量对硫化氢脱除效果的影响,并分析了DBD等离子体反应器中脱除硫化氢的产物。结果表明,DBD等离子体能有效脱除模拟沼气中的硫化氢气体,脱除效率随放电能量密度、停留时间和含氧量的增大而提高,并且随硫化氢初始体积浓度的增加而下降;当模拟沼气处理气量为382mL／min、硫化氢初始体积浓度为4000×10^-6、氧气体积浓度为2％、能量密度为24．1kJ／L时,硫化氢气体被完全脱除,同时氧气的体积含量也低于0．5％,达到了国家规定的车用天然气标准内的硫化氢和氧气含量标准。根据产物分析,硫化氢的脱除产物主要为二氧化硫,少量的单质硫粉。