合成氨氣體脫硫技術(shù)進展中英

1、合成氨氣體脫硫技術(shù)的進展Advances in Desulfurization Technology for Ammonia Production摘要 全面回顧了國內(nèi)、外濕式氧化法和干法脫硫技術(shù)的發(fā)展及技術(shù)進展，分析了各種技術(shù)的優(yōu)勢及存在的問題。關(guān)鍵詞氣體凈化脫硫進展Abstract An overall review is given of the development of the technology for we-t process oxidation and dry-process desulfurization and technological advances both at

2、 home and abroad, and an ana-lysis is made of the advantages of various technologies and their problems.Keywords gas purification desulfurization progress在合成氨生產(chǎn)過程中，無論采用何種原料路線(煤、油、天然氣)、 何種工藝技術(shù)，In the process of ammonia production,no matter adopt what kind of raw material route (coal, oil, natural gas

3、), what kind of technology其粗合成氣中都含有大量的CO2,以煤為原料的合成氣中還含有多種 硫化物。Its crude syngas, contain large amounts of CO2 from coal as the rawmaterial also contains a variety of sulfide in the syngasCO2和硫化物對氨合成催化劑有很強的毒性，因此在合成氣進入氨合成塔之前，需將CO2和硫化物脫除，稱為脫硫、脫碳工藝。CO2 and sulfides of ammonia synthesis catalyst has very

4、strong toxicity, so before the syngas into ammonia synthesis tower, CO2 and sulfide removal, must be referred to as desulfurization and decarburization process幾十年來，脫硫、脫碳工藝不斷發(fā)展、進步，新工藝的開發(fā)和老工藝 的改進大量涌現(xiàn)，本文不可能一一論述，只將典型的、常用的工藝及其 進展加以匯總，供選擇工藝時參考。For decades, the Desulfurization and decarbonization technolog

5、y continuous development and progress, the development of new process and old process improvement, this paper could not have one, will only typical, common process and progress of the summary, reference for choosing process.1脫硫技術(shù)的發(fā)展現(xiàn)狀Desulfurization technology development present situation 原料氣脫除硫化物技

6、術(shù)分為干法和濕法兩大類,濕法脫硫又分為濕式 氧化法和胺法。Feed gas removing sulfide technology falls into two types: dry and wet, wet desulfurization is divided into wet oxidation method and the amine method濕式氧化法是溶液吸收H2S后直接轉(zhuǎn)化為單質(zhì)硫，單質(zhì)硫分離后溶 液循環(huán)使用;胺法是將吸收的H2S在再生系統(tǒng)釋放,然后將H2S送至克勞斯裝置再轉(zhuǎn)化為單質(zhì)硫，溶液則循環(huán)使用。Wet oxidation method is directly conve

7、rted to elemental sulfur after solution absorbs H2S, elemental sulfur separation solution circulation after use; Amine method is to release absorption of H2S in the regenerative system, and then H2S Klaus device to the converted to elemental sulfur, the solution is to recycle濕法脫硫多用于合成氨原料氣中大量硫化物的脫除汗法

8、脫硫則多用 作精脫且對無機硫和有機硫都有較高的凈化度。Wet desulfurization is more used in the ammonia feed gas of plenty of sulfide removal, the dry process desulfurization is used for finishing off more of the inorganic sulfur and organic sulfur has a high degree of purification11濕式氧化法脫硫技術(shù)的進展Wet oxidation desulfurization tec

9、hnology progress濕式氧化法脫硫是將硫化氫在液相中氧化成元素硫并予以分離，其特 點為：Wet oxidation desulfurization is the separation of sulfur and hydrogen sulfide in the liquid phase oxidation to elements, its characteristic is: 可將H2S直接轉(zhuǎn)化為單質(zhì)硫;脫硫效率高，凈化后的氣體殘硫量低;既 可在常壓下操作,又可在加壓下操作;脫硫劑可以再生循環(huán)使用，運行成本低。H2S can be directly converted to elem

10、ental sulfur; Desulfurization efficiency is high, after purification of gas residual sulfur content is low;As well as operating under atmospheric pressure, can operate under pressure; Desulfurization agent can be recycling use, operation cost is low.蒽釀二磺酸鈉法(ADA法)the method of anthraquinone di-sulfon

11、ic acid sodium (ADA)蒽釀二磺酸鈉法稱為Streford法或ADA法，近年來的技術(shù)進步 主要體現(xiàn)在脫硫氣體的預(yù)處理、硫回收、廢液處理等方面。Anthraquinone di-sulfonic acid sodium method called Stretford method or ADA method,Technological advances in recent years is mainly manifested in the desulfurization of gas pretreatment, sulfur recovery, waste liquid proc

12、essing, etc.該法以釩作為脫硫的基本催化劑，并采用恵釀2 7 -二磺酸鈉(ADA)作 為還原態(tài)釩的再生載氧體，吸收液由碳酸鹽作介質(zhì)。The vanadium as desulfurization catalyst, and using anthraquinone 2, 7 - di-sulfonic acid sodium (ADA) body of carrying oxygen of square one as vanadium regeneration, absorbing liquid medium by carbonate.ADA法的不足之處主要有:懸浮的硫顆粒回收困難，易

13、造成過濾器堵塞;副產(chǎn)物使化學(xué)藥品耗量增大;脫有機硫和HCN的效率 較低;有害廢液處理困難，可能造成二次污染;細菌易積累;腐蝕 嚴重。ADA method mainly has the disadvantages of:(1) suspended sulfur particles collection difficulties, easy to cause filter clogging; (2) byproducts make chemicals consumption increases; (3) to take off the organic sulfur and HCN low effi

14、ciency; (4) harmful waste liquid processing difficulty, may cause secondary pollution; (5) bacteria easy accumulation; (6) Corrosion is serious.為克服該工藝存在的問題,又相繼開發(fā)了 Sufolyn法和Unisuf法。Sulfolyn法在吸收溶液中加入一種有機氮化物,以克服Stretford 法溶液中鹽類的生成;Unisulf法在吸收液中加入硫氰酸鹽、羧酸（通常 是檸檬酸和芳香族磺酸鹽螯合劑目的是消除副產(chǎn)物鹽類的生成抑 制微生物的生長。To overco

15、me the problems existing in the process, and subsequently developed Sulfolyn and Unisulf method. Sulfolyn method adding a kind of organic nitrogen compounds in the absorption solution to overcome Stretford law of salts in the solution generated; Unisulf method into absorbing liquid thiocyanate, carb

16、oxylic acid (usually citric acid) and aromatic sulfonic acid salt, chelating agent, the purpose is to eliminate the formation of by-product salt, inhibit the growth of microorganisms.國內(nèi)南化研究院、四川化工廠及上海吳淞煤氣廠于20世紀(jì)60 年代初聯(lián)合開發(fā)了以Streford工藝為基礎(chǔ)的改良ADA法:溶液中添 加酒石酸鉀鈉，以阻止釩酸鹽的生成；添加少量三氯化鐵及乙二胺四 乙酸,使螯合劑起穩(wěn)定溶液作用。Domesti

17、c NaHua research institute, sichuan chemical plant andShanghai wusong gasworks in joint development in the early I960 s the Stretford process based improved ADA method:栲膠法（TV法）（2）extract method （TV）TV法是我國特有的脫硫技術(shù)，是目前國內(nèi)使用廠家最多的脫硫 方法之一,主要分堿性栲膠脫硫（以橡椀栲膠和偏釩酸鈉作催化劑）和 氨法栲膠（以氨代替堿）2種。TV method is characteristic

18、 of the desulfurization technology in China, one of the most popular desulfurization method is the present domestic use,Main points and the alkaline extract desulfurization (with rubber 椀 extract and sodium meta vanadate as catalyst) and ammonia method extract (with ammonia alkali) instead of 2 kind

19、s.栲膠是由植物的果皮、葉和莖干經(jīng)水萃液熬制而成，主要成份是丹寧。由于來源不同丹寧組成也不同但都是由化學(xué)結(jié)構(gòu)十分復(fù)雜的多羥基 芳烴化合物組成，具有酚式或醌式結(jié)構(gòu)。 Extract is made from plants peel, leaf and stem the water extraction solution boil into the system, the main ingredient is tannin. Due to different sources, tannin composition is also different, but are made by chemica

20、l structure is very complicated hydroxy aromatic compounds, phenol type or quinoid structure.TV法的特點:栲膠資源豐富，價廉易得，運行費用比改良ADA 法低;無硫堵塔問題;栲膠既是氧化劑又是釩的配合劑，溶液組成 比改良ADA法簡單;栲膠脫硫液對設(shè)備腐蝕性小;栲膠需要熟化 預(yù)處理。TV method features:(1) extract resources are abundant, cheap, operation cost is lower than improved ADA method; (

21、2) no sulfur plugging problems; (3) extract as oxidant and vanadium compound, solution composition than improved ADA method is simple; (4) on the corrosion of equipment in tannic extract desulfurizing solution;(5) Need curing pretreatment extract.栲膠質(zhì)量及其配制方法是決定TV法使用效果的主要因素。廣 西化工研究院研制的改良栲膠脫硫劑KCA除了釆用制備

22、栲膠的原料 外，還添加其它少量助劑進行降解、復(fù)配、改性。與栲膠相比,KCA使 用更簡單，活性更好,性能更穩(wěn)定。Quality of extract and its preparation method is the main factor of decide TV method using effect Guangxi chemical industry research institute developed improved extract desulfurizer KCAbesides using extract preparation of raw materials, also ad

23、d a small amount of other additives on the degradation, distribution and modification. Compared with extract, KCA is more easy to use and activity better, more stable performance.PDS法PDS methodPDS脫硫催化劑是酞菁鉆磺酸鹽金屬有機化合物的混和物，主 要成份是雙核酞菁鉆磺酸鹽。在堿性溶液條件下，由PDS、堿性物質(zhì) 和助催化劑3種成份組成。PDS desulfurization catalyst is or

24、ganic compounds of phthalocyanine cobalt sulphonate metal mixture that ingredient is di-nuclear cobalt phthalocyanine sulfonate.Under the condition of alkaline solution, by PDS, alkaline substances and cocatalyst of three components.PDS法工藝特點:PDS目前在工業(yè)上一般還是與ADA、栲膠 法配合使用,只需在原脫硫液中加入微量PDS即可，因此消耗費用很 低;PDS

25、活性好，用量少;生成的單質(zhì)硫易分離,一般不會發(fā)生硫堵; 在脫除H2S的同時能脫除部分有機硫;PDS無毒,脫硫液對設(shè)備 不腐蝕;PDS亦可單獨使用，可以不加釩，副反應(yīng)少,無廢液排放。PDS method process characteristics:(l)PDS in industry at present is usually used with ADA, extract method, only need to add trace PDS in the desulfurization liquid, so the consumption cost is low; (2) theactivi

26、ty of PDS is good, less dosage; (3) generated by the elemental sulfur easy separation, general wont happen sulfur plugging; (4) in the removal of H2S and organic sulfur removal part;PDS non-toxic, desulfurization liquid no corrosion to equipment;PDS can also be used alone, can not add vanadium, less

27、 side effects, no liquid waste emissions.近年來,PDS法經(jīng)過不斷改進和完善,脫硫催化劑已由最初的原型 開發(fā)至目前的P-400和888型。其中P-400脫硫催化劑由東北師范大 學(xué)精細化工開發(fā)公司開發(fā)，適用于各種低硫、高硫(H2S含量在0 35000 gm3)氣體和低粘度液體的脫硫、脫氰。溶液組成簡單，不需 加任何助劑，運行成本比ADA法低70%左右。888脫硫催化劑由東北 師范大學(xué)實驗化工廠開發(fā)，適用范圍廣，除具備PDS的特性外,還具有 如下特點:不加其它助催化劑;脫硫貧液懸浮硫含量低，不堵塔; 再生時，浮選出的硫磺顆粒大,溶液粘度低,硫磺易分離;脫除有

28、機硫 效率為50% 80%;在同等負荷和工況條件下，催化劑消耗費用比同 類產(chǎn)品低20%以上。PDS method in recent years, through continuous improvement and improvement of the desulfurization catalyst has been developed from the initial prototyping to P - 400 and 888.The P - 400 desulfurization catalyst developed by northeast normal university fi

29、ne chemicals development co., suitable for all kinds of low sulfur, high sulfur (H2S content in the 0. 3 500. 0 g/m3) gas and lowviscosity liquid desulfurization and cyanide. Solution composition is simple, do not need to add any additives, running cost about 70% less than ADA method. 888 desulfuriz

30、ation catalyst developed by northeast normal university experimental chemical plant, the applicable scope is wide, in addition to having the features of PDS, also has the following features:(1) do not add other cocatalyst; (2) desulfurization barren solution suspended sulfur content is low, no block

31、ing by the tower; (3) regeneration, flotation of sulfur particles is large, low solution viscosity, sulfur easy separation; (4) removal efficiency of organic sulfur is 50% 50%; (5) under the condition of same load and condition, catalyst consumption cost is lower than similar products more than 20%.

32、MSQ法MSQ methodMSQ法脫硫催化劑是由對苯二酚、硫酸錳和水楊酸按一定比例 配制而成。MSQ-2型脫硫催化劑是在MSQ基礎(chǔ)上增加了螯合劑L 及Lc,螯合劑L與 Mn2+有良好的配位作用，使 Mn2+不易生成MnCO3沉淀,在脫硫液中能夠保持較高的溶解錳含量,從而有利于提高脫硫過程中溶液的再生性能;螯合劑Lc與VO2+起配位作用，減少VOS沉淀生成,不但降低釩的消耗量，而且有利于發(fā)揮V2O5在脫硫過 程中吸收H2S的作用，提高脫硫效率。MSQ-3型脫硫催化劑則是在MSQ-2型的基礎(chǔ)上增加了 1種防腐劑。MSQ desulfurization catalyst consists of h

33、ydroquinone, made from manganese sulfate and salicylic acid in a certain proportion.MSQ - 2 type desulfurization catalyst is based on the MSQ added chelating agent L and L c, chelating agent and Mn2 + L have good coordination effect, make the Mn2 + is not easy to generate MnC03 precipitation, the de

34、sulfurization can maintain higher dissolved manganese content in the liquid, and thus to improve the desulfurization solution regeneration in the process of performance c with VO2 + chelating agent plays a role of coordination, reduce VOS precipitation generated, not only reduce the amount of vanadi

35、um, but also play a role of V2O5 in the process of desulfurization absorption of H2S, and improve the efficiency of desulfurization. MSQ - 3 type desulfurization catalyst is on the basis of MSQ - type 2 increased 1 kind of preservatives.(5)氨水液相催化法(Perox法)ammonia liquid phase catalysis (Perox method)

36、Perox法在國外主要用于焦?fàn)t氣的脫硫凈化,20世紀(jì)70年代起我 國將該法用于小型合成氨廠半水煤氣的脫硫。氨水液相催化法的過程 比較簡單，一般是在氨水溶液中加入0. 3 gL的對苯二酚催化劑。 Perox method is mainly used for purification of coke oven gas desulfurization in a foreign country, the law used in the 1970 s, China will small ammonia plant of semi-water gasdesulfurization.Ammonia liq

37、uid phase catalysis process is simple, general is in ammonia solution adding 0. 3 g/L of hydroquinone catalyst.(6)配合鐵法Cooperate with tie fa coal industry group配合鐵法亦稱絡(luò)合鐵法,其脫硫原理是H2S在堿性溶液中被配 合鐵鹽催化氧化成元素硫，被H2S還原了的催化劑用空氣再生，將 Fe2+氧化為Fe3+。Cooperate with tie fa coal industry group which is also called comple

38、xation tie fa coal industry group, its desulfurization principle of H2S with iron in alkaline solution catalytic oxidation to elements sulfur, with air by H2S reduction of the catalyst regeneration, the Fe2 + oxidation of Fe3 +.美國空氣資源公司開發(fā)了 LO -CAT工藝,采用鐵螯合物，克服了 以往只加鐵而生成副產(chǎn)物的缺陷，脫硫效率大大提高，目前已開發(fā)出常 規(guī)LO-CAT

39、、自循環(huán)LO-CAT系統(tǒng)及Aqua-CAT系統(tǒng)3種工藝模式。 LO-CAT法主要優(yōu)點是溶液無毒性,在常溫下操作，脫硫效率最高可達 9999%,且固體鹽生成少控氣量不大及壓力不高，洗液用量少，因此該 法目前在國外應(yīng)用較多。Air resources companies in the United States developed LO - CAT technology, using iron chelation, overcoming the past only plus iron and generate by-products defects, and the desulfurization

40、efficiency is greatly improved, has now developed the conventional LO - CAT, since the cycle LO - and Aqua - CAT CAT system three kinds of process model.LO - main advantage is the CAT method solution non-toxic, operating at room temperature, the desulfurization efficiency of up to 99. 99%, and less

41、solid salt formation, and the pressure is not high, the air is lotion dosage is less, so the method is widely applied in foreign countries.維也納技術(shù)大學(xué)與奧地利聯(lián)合工程公司開發(fā)的Sulfint工藝是對 LO-CAT工藝的改進，可減少試劑損失，降低成本。而Sulferox工藝則 是對LO-CAT工藝的另一種改進，適用于高CO2含量氣體的選擇性脫 硫，如用于回收CO2氣體的脫硫。Sulferox工藝還可脫除氣體中有機 硫，硫醇脫除率50% 90%, COS、C

42、S2則水解為H2S與CO2后再脫 除。國內(nèi)對LO-CAT工藝也作了一些改進，包括FD法、HEDP-NTA 法等，但工業(yè)應(yīng)用較少。Vienna university of technology engineering firms to develop alliance with Austria Sulfint technology is the improvement of LO - CAT technology, can reduce the reagent cost, reduce the cost.Sulferox process is to LO - another CAT techno

43、logy improvement, applied to selective desulfurization of high CO2 content gas, such as used for recycling CO2 gasdesulfurization.Sulferox process can also be removal of organic sulfur in gas, mercaptan removal rate is 50% 90%, COS, CS2, hydrolysis after the removal of H2S and CO2.Domestic of LO - C

44、AT technology also made some improvements, including FD method, HEDP - NTA method, but less in industrial application.(7)雜多酸法Heteropoly acid method雜多酸法由石油大學(xué)(北京)開發(fā)，利用鎢鉬雜多化合物為催化劑, 其原理是將H2S氧化為硫磺，雜多酸被還原為單電子雜多藍,雜多藍 被空氣氧化再生后循環(huán)使用。該技術(shù)于1997年通過鑒定。Heteropoly acid method developed by university of petroleum (Be

45、ijing), using tungsten molybdenum heteropoly compound as catalyst, the principle is the oxidation of H2S to sulfur, heteropoly acid was reduced to single electron heteropoly blue, heteropoly blue is used after air oxidation regeneration cycle. In 1997 through the identification of the technolog yDDS

46、 法(8)DDS methodDDS法是/鐵-堿溶液催化法氣體脫碳脫硫脫氰技術(shù)的簡稱，由北京大學(xué)開發(fā)，據(jù)稱是一種生化脫硫技術(shù)，脫硫液是堿（氨、有機胺、有機 堿或其它無機堿)的水溶液中配入DDS催化劑、DDS催化劑輔料和 活性碳酸亞鐵組成。DDS法具有脫硫效率高、溶液循環(huán)量小等優(yōu)點, 目前已成功應(yīng)用于合成氨廠半水煤氣和變換氣脫硫，但實際使用中還 存在一些問題。DDS method is/iron - alkali catalysis gas decarbonization desulfurization short for cyanide technology, developed by Bei

47、jing university,ls said to be a biological desulfurization technology, the desulfurization liquid is alkali (ammonia, organic amine and organic alkali or other inorganic base) in aqueous solution with the DDS catalyst, DDS catalyst materials and activity of ferrous carbonate.DDS method, with the hig

48、h desulfurization efficiency, solution cycle, the advantages of small volume, has been successfully applied in ammonia plant of semi-water gas and shift gas desulfurization, but also there are some problems in practical use.(9)TEA絡(luò)合鐵法TEA complexing tie fa coal industry groupTEA絡(luò)合鐵法是華東理工大學(xué)開發(fā)的以TEA為Fe3

49、+的絡(luò)合劑和脫硫吸收劑,以檸檬酸作為Fe2+的絡(luò)合劑的二元絡(luò)合體系。模擬 試驗表明，該法具有硫容大、脫硫效率高、副反應(yīng)少、溶液穩(wěn)定、腐 蝕性小、成本低等特點。TEA complexing tie fa coal industry group is the east China university of science and technology development of TEA as the complexing agent of Fe3 + and desulfurization absorbent, with citric acid as complexing agent of F

50、e2 + of binary complex system.Simulation test shows that this method has a large sulfur capacity, high desulfurization efficiency, less side effects, solution stability, corrosive small, low cost, etc.(10)改良絡(luò)合鐵法Improved complexation tie fa coal industry group改良絡(luò)合鐵法由南化集團研究院開發(fā),主要在穩(wěn)定劑、緩蝕劑以 及硫結(jié)晶改性劑等方面進行了大量篩選試驗工作，在解決絡(luò)合劑的降 解、防止鐵沉淀以及溶液腐蝕等方面取得了進展。改良絡(luò)合鐵法采用 堿的水溶液吸收硫化物,H2S氣體與堿發(fā)生反應(yīng)生成HS-,通過高價態(tài) 絡(luò)合鐵還原成低價態(tài)絡(luò)合鐵，將HS-轉(zhuǎn)化成硫磺。在再生過程中，低價 態(tài)的絡(luò)合鐵溶液與空氣接觸氧化成高價態(tài)絡(luò)合鐵溶液，恢復(fù)氧化性能, 溶液循環(huán)吸收硫化氫氣體。Improved complexation tie fa coal industry group by