SU1655545A1 - Method for purifying gas from sulfurous compounds and method for obtaining catalyst for gas purification - Google Patents
Method for purifying gas from sulfurous compounds and method for obtaining catalyst for gas purification Download PDFInfo
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- SU1655545A1 SU1655545A1 SU894730140A SU4730140A SU1655545A1 SU 1655545 A1 SU1655545 A1 SU 1655545A1 SU 894730140 A SU894730140 A SU 894730140A SU 4730140 A SU4730140 A SU 4730140A SU 1655545 A1 SU1655545 A1 SU 1655545A1
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- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000000746 purification Methods 0.000 title claims abstract description 9
- 150000001875 compounds Chemical class 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 4
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000000694 effects Effects 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 239000011572 manganese Substances 0.000 claims abstract description 4
- 230000018044 dehydration Effects 0.000 claims abstract description 3
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 3
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 3
- 238000000465 moulding Methods 0.000 claims abstract 4
- 230000003647 oxidation Effects 0.000 claims abstract 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract 4
- 239000000654 additive Substances 0.000 claims abstract 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract 2
- 235000021355 Stearic acid Nutrition 0.000 claims abstract 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000002156 mixing Methods 0.000 claims abstract 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000004014 plasticizer Substances 0.000 claims abstract 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract 2
- 239000008117 stearic acid Substances 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims abstract 2
- 239000010936 titanium Substances 0.000 claims abstract 2
- 229910052719 titanium Inorganic materials 0.000 claims abstract 2
- 239000007789 gas Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 1
- 239000000292 calcium oxide Substances 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 abstract 1
- 239000011230 binding agent Substances 0.000 abstract 1
- 239000001768 carboxy methyl cellulose Substances 0.000 abstract 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 abstract 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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Abstract
Изобретение относитс к способам каталитической очистки газа от сернистых со- единений путем их превращени в элементарную серу и может найти применение в газовой, нефт ной и нефтехимической промышленности. Целью насто щего изобретени вл етс повышение эффективности процессов очистки за счет увеличени активности катализатора и удешевление процесса. Цель достигаетс способом очистки газа от сернистых соединений путем их окислени до элементарной серы в присутствии оксидного титансодержащего катализатора при 220-240°С, в котором окисление ведут в присутствии катализатора состава, мае % Мп02 0,24-2,2; МоОз 0,4-5,0; SI02 0,6-4,5, А120з1,6-8, СаО 3,2-15,1; S04 2 1-6, ТЮ2 остальное,при времени контакта 1-3,4 с, а также способом получени катализатора дл очистки газа от сернистых соединений, включающим смешение исходной метатита- новой кислоты с добавками, формовку, сушку и прокалку, в котором исходную метатитановую кислоту дел т на две части в соотношении 30:70 - 55 45, первую из которых подвергают обезвоживанию при 60- 110°С затем ее смешивают со второй частью и добавками марганцевой руды, вз той в количестве (%) 1-6, оксида молибдена 0,4-5, св зующего (алюмината кальци ) 5- 20; пластификатора, выбранного из группы полиэтиленоксид, поливиниловый спирт, карбоксиметилцеллюлоза, полиакриламид, стеаринова кислота 1-10% от массы катализатора с последующим перемешиванием полученной смеси в течение 0,5-4 ч при 40-80°С и подают на формовку. Причем сушку катализатора осуществл ют в две ступени при 90- 120°С и 220-250°С соответственно в течение 1,5-6 ч и 1-4 ч. 2 с и 2 з.п ф-лы, 2 табл (Л С о ел ел ел 4 СЛThe invention relates to methods for the catalytic purification of gas from sulfur compounds by converting them to elemental sulfur and can be used in the gas, oil and petrochemical industries. The aim of the present invention is to increase the efficiency of the purification processes by increasing the activity of the catalyst and cheapening the process. The goal is achieved by the method of gas purification from sulfur compounds by their oxidation to elemental sulfur in the presence of an oxide titanium-containing catalyst at 220-240 ° C, in which the oxidation is carried out in the presence of a catalyst of composition,% Mn0.24-2.2; MOZ 0.4-5.0; SI02 0.6-4.5, A120z1.6-8, CaO 3.2-15.1; S04 2 1-6, TiO2 else, with a contact time of 1-3.4 s, as well as a method for preparing a catalyst for gas purification from sulfur compounds, including mixing the initial metatitic acid with additives, molding, drying and calcining, in which the initial metatitanic acid is divided into two parts in a ratio of 30:70 - 55 45, the first of which is subjected to dehydration at 60-110 ° C and then it is mixed with the second part and with the addition of manganese ore, taken in an amount (%) 1-6 , molybdenum oxide 0.4-5, binder (calcium aluminate) 5-20; plasticizer selected from the group polyethylene oxide, polyvinyl alcohol, carboxymethylcellulose, polyacrylamide, stearic acid 1-10% by weight of the catalyst, followed by stirring the mixture for 0.5-4 hours at 40-80 ° C and served on the molding. Moreover, the catalyst was dried in two steps at 90-120 ° C and 220-250 ° C, respectively, for 1.5-6 hours and 1-4 hours, 2 seconds and 2 ° C f-crystals. 2 tabl (L o eat ate 4 SL
Description
Изобретение относитс к способам каталитической очистки газа от сернистых соединений путем их превращени в элементарную серу и может найти применение в газовой, нефт ной и нефтехимической промышленности.The invention relates to methods for the catalytic purification of gas from sulfur compounds by converting them to elemental sulfur and can be used in the gas, oil and petrochemical industries.
Целью изобретени вл етс повышение эффективности процесса очистки, увеличение активности катализатора и удешевление процесса.The aim of the invention is to increase the efficiency of the purification process, increase the activity of the catalyst and reduce the cost of the process.
П р и м е р 1. Катализатор очистки газа от сернистых соединений получают следующим образом.PRI me R 1. Catalyst gas purification from sulfur compounds obtained as follows.
Берут следующие исходные компоненты: метатитановую кислоту, отобранную после узла фильтрации (до прокалки) вTake the following starting components: metatitanic acid, selected after the filtration unit (before calcination) in
производстве пигментного диоксида титана Крымского ПО Титан, состава, мас.%:ТЮ2 50; H2S04 3; НаО 47 в количестве 100 г; марганцевую руду состава, мас,%: Мп0240; СаО 8; А1аОз 9; РеаОз 3; Si02 остальное в количестве 1,86 г; парамолибдата аммони - (NH4)6Mo7024 4H20 (ГОСТ 3765-78) в количестве 2,2 г; алюминат кальци - талюм (ТУ 6-03-339-78) в количестве 6,23 г.the production of titanium dioxide pigment Crimean software Titan, composition, wt.%: TiO2 50; H2S04 3; NAO 47 in the amount of 100 g; manganese ore composition, wt.%: Mn0240; CaO 8; A1aOz 9; ReaOz 3; Si02 the rest in the amount of 1.86 g; ammonium paramolybdate - (NH4) 6Mo7024 4H20 (GOST 3765-78) in the amount of 2.2 g; Calcium aluminate - talum (TU 6-03-339-78) in the amount of 6.23 g.
Метатитановую кислоту дел т на две части в соотношении 40:60. Первую часть подвергают обезвоживанию путем сушки при температуре 90°С, получают 20,5 г обезвоженной метатитановой кислоты.Metatitanic acid is divided into two parts in a 40:60 ratio. The first part is subjected to dehydration by drying at a temperature of 90 ° C, receive 20.5 g of dehydrated metatitanic acid.
В емкость, снабженную паровой рубашкой и перемешивающим устройством, загружают смесь (г): обезвоженную метатитановую кислоту 20,5, вторую часть исходной метатитановой кислоты 60, тонкоизмельченную марганцевую руду 1,86, водный раствор парамолибдата аммони (Т:Ж 1:1) 4,4, алюминат кальци 6,23, полиакри- ламид2,3, которую перемешивают при температуре 60°С в течение 2 ч. Полученную массу довод т до влажности 32,5% и формуют в цилиндрические гранулы, имеющие диаметр 4 мм, длину 6 мм. Сформованные гранулы подвергают двухступенчатой сушке: при температуре 105°С в течение 4 ч и затем при температуре 230°С в течение 2 ч. Просушенный таким образом катализатор подвергают прокалке при 360°С в течение 10 ч в атмосфере газа состава, об;%: H2S 7; S02 3,5; С02 20; НаО 15; Na остальное, соответствующего атмосфере газов процесса Клауса. При этом объемна скорость составл ет 600 .In a tank equipped with a steam jacket and a stirrer, mix (g): dehydrated metatitanic acid 20.5, the second part of the starting metatitanic acid 60, finely divided manganese ore 1.86, aqueous solution of ammonium paramolybdate (T: W 1: 1) 4 , 4, calcium aluminate 6.23, polyacrylamide, 2.3, which is stirred at 60 ° C for 2 hours. The resulting mass is brought to a moisture content of 32.5% and formed into cylindrical granules having a diameter of 4 mm, length 6 mm The formed granules are subjected to two-stage drying: at a temperature of 105 ° C for 4 hours and then at a temperature of 230 ° C for 2 hours. The catalyst, dried in such a manner, is subjected to calcination at 360 ° C for 10 hours in an atmosphere of composition gas,%; H2S 7; S02 3.5; C02 20; NAO 15; Na rest, corresponding to the atmosphere of Claus process gases. The volumetric rate is 600.
В результате было получено 62,26 г катализатора состава, мас.%: МпОа 1,2; МоОз 3; 5Ю2 1,4; ,8; СаО 7,1; 3,2; ТЮ2 остальное, имеющего удельную поверхность 123 м2/г, пористость 52,4%, насыпной вес 0,81 кг/м3.As a result, 62.26 g of catalyst composition was obtained, wt.%: MpOa 1,2; MoO3; SiO2 1.4; ,eight; CaO 7.1; 3.2; TiO2 the rest, having a specific surface of 123 m2 / g, a porosity of 52.4%, a bulk weight of 0.81 kg / m3.
Полученный предлагаемым способом катализатор испытывалс в проточном реакторе с неподвижным слоем. Объем загрузки катализатора 3 мл. В реактор подавалась смесь состава, об. %: HaS 1; SOa 0,5; НаО 30; N2 остальное, температура поддерживалась равной 220°С, врем контакта 3 с. Извлечение серы составило 70,6%.The catalyst prepared by the inventive method was tested in a fixed bed flow reactor. Catalyst loading volume 3 ml. A mixture of the composition, vol. %: HaS 1; SOa 0.5; NaO 30; N2 the rest, the temperature was maintained at 220 ° C, the contact time was 3 s. Sulfur recovery was 70.6%.
П р и м е р 2. Катализатор, полученный таким же способом, что и в примере 1, был загружен в проточный реактор с неподвижным слоем в количестве 3 мл. В реактор в течение 48 ч подавалась смесь состава, об.%: HaS 1; SOa Q,5:0HaO 30; Ma остальное, при температуре 220 С и времени контакта 3 с. Затем в течение 26 ч подавалась смесь,PRI mme R 2. The catalyst obtained in the same manner as in Example 1 was loaded into a fixed-bed flow reactor in an amount of 3 ml. A mixture of the composition, vol.%: HaS 1; SOa Q, 5: 0HaO 30; Ma the rest, at a temperature of 220 ° C and a contact time of 3 s. Then for 26 h the mixture was fed
об.%: H2S 1; S02 0,5; 02 2; НаО 30; N2 остальное . После этого в течение 2 ч через катализатор пропускали смесь состава, об.%: HaS 1; SOa 0,5; НаО 30; N2 остальное, По истече- нии 2 ч было измерено извлечение серы, которое составило 70,4%.vol.%: H2S 1; S02 0.5; 02 2; NaO 30; N2 else. After that, for 2 h, the mixture of the composition, vol.%, Was passed through the catalyst: HaS 1; SOa 0.5; NaO 30; N2 else, After 2 hours, sulfur recovery was measured, which was 70.4%.
Другие примеры осуществлени предлагаемого способа сведены в табл.1 и 2.Other embodiments of the proposed method are summarized in Tables 1 and 2.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU894730140A SU1655545A1 (en) | 1989-06-27 | 1989-06-27 | Method for purifying gas from sulfurous compounds and method for obtaining catalyst for gas purification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU894730140A SU1655545A1 (en) | 1989-06-27 | 1989-06-27 | Method for purifying gas from sulfurous compounds and method for obtaining catalyst for gas purification |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SU1655545A1 true SU1655545A1 (en) | 1991-06-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SU894730140A SU1655545A1 (en) | 1989-06-27 | 1989-06-27 | Method for purifying gas from sulfurous compounds and method for obtaining catalyst for gas purification |
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| SU (1) | SU1655545A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2149137C1 (en) * | 1996-04-03 | 2000-05-20 | Рон-Пуленк Шими | Method for direct oxidation of sulfur compounds into sulfur using copper-based catalyst |
| RU2225247C1 (en) * | 2002-07-22 | 2004-03-10 | Кочетков Алексей Юрьевич | Method of oxidation of sulfides in gas emissions (variants) |
| RU2372140C2 (en) * | 2008-01-09 | 2009-11-10 | Открытое акционерное общество "Ангарский завод катализаторов и органического синтеза" (ОАО "АЗКиОС") | Catalyst for binding sulphur oxides in recycle gases from catalytic cracking process |
-
1989
- 1989-06-27 SU SU894730140A patent/SU1655545A1/en active
Non-Patent Citations (1)
| Title |
|---|
| Патент FR № 2501532, кл. B01J 27/02, 1981. * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2149137C1 (en) * | 1996-04-03 | 2000-05-20 | Рон-Пуленк Шими | Method for direct oxidation of sulfur compounds into sulfur using copper-based catalyst |
| RU2225247C1 (en) * | 2002-07-22 | 2004-03-10 | Кочетков Алексей Юрьевич | Method of oxidation of sulfides in gas emissions (variants) |
| RU2372140C2 (en) * | 2008-01-09 | 2009-11-10 | Открытое акционерное общество "Ангарский завод катализаторов и органического синтеза" (ОАО "АЗКиОС") | Catalyst for binding sulphur oxides in recycle gases from catalytic cracking process |
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