WO2015101275A1 - 高浓度羰基硫转化-吸收型脱硫剂和二硫化碳转化·吸收型脱硫剂及其制备方法 - Google Patents

高浓度羰基硫转化-吸收型脱硫剂和二硫化碳转化·吸收型脱硫剂及其制备方法 Download PDF

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WO2015101275A1
WO2015101275A1 PCT/CN2014/095470 CN2014095470W WO2015101275A1 WO 2015101275 A1 WO2015101275 A1 WO 2015101275A1 CN 2014095470 W CN2014095470 W CN 2014095470W WO 2015101275 A1 WO2015101275 A1 WO 2015101275A1
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weight
parts
desulfurizing agent
absorption type
solid
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PCT/CN2014/095470
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English (en)
French (fr)
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李丽英
宋雯雯
毛文君
张志民
刘博书
刘振义
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北京三聚环保新材料股份有限公司
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Priority claimed from CN201310751598.3A external-priority patent/CN104740981B/zh
Priority claimed from CN201310751120.0A external-priority patent/CN104740994B/zh
Application filed by 北京三聚环保新材料股份有限公司 filed Critical 北京三聚环保新材料股份有限公司
Priority to CA2935501A priority Critical patent/CA2935501C/en
Priority to US15/108,968 priority patent/US10376836B2/en
Publication of WO2015101275A1 publication Critical patent/WO2015101275A1/zh

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    • 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
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
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    • B01J37/06—Washing

Definitions

  • the invention relates to a carbonyl sulfide catalytic conversion-absorption type desulfurizing agent in a gas and a carbon disulfide catalytic conversion-absorption type desulfurizing agent in a gas and a preparation method thereof, and belongs to the technical field of desulfurization.
  • the carbonyl sulfide is neutral or weakly acidic, and its chemical properties are relatively stable. It is difficult to remove it by conventional desulfurization methods.
  • the carbonyl sulfide hydrolysis catalyst can be divided into two types at home or abroad.
  • One is a simple conversion type, and has only a conversion function for carbonyl sulfide. Therefore, it must be used in series with a desulfurizing agent such as zinc oxide or activated carbon; It not only has the ability to convert organic sulfur such as carbonyl sulfide, but also has the ability to absorb hydrogen sulfide formed by conversion. It can be used alone for the removal of trace sulfur. In recent years, the dual-functional desulfurizer capable of converting and absorbing organic sulfur has caused a large attention.
  • Chinese Patent Document ON1069673A discloses a normal temperature organic sulfur hydrolysis catalyst consisting of 2-25% by weight of potassium carbonate and spherical ⁇ -Al 2 O 3 , and the desulfurizing agent can be used for conversion to carbonyl sulfide when used at room temperature. 95%, and the desulfurizing agent can also realize the absorption of hydrogen sulfide while converting carbonyl sulfide.
  • the above-mentioned carbonyl sulfide conversion desulfurizing agent can achieve higher conversion rate when used at normal temperature, it still has the disadvantage that it is suitable for treatment concentration, and is not higher than 30 mg S/m 3 , and is not suitable for high concentration.
  • the treatment of carbonyl sulfide, and how to explore a desulfurizing agent capable of achieving high-efficiency conversion and absorption of carbonyl sulfide under high concentration conditions is an unsolved problem in the prior art.
  • CS 2 content is about 10% of COS content
  • CS 2 is a polar molecule
  • its reaction during hydrolysis is as follows:
  • Chinese patent CN10112123A discloses a medium temperature carbon disulfide hydrolysis catalyst which uses spherical ⁇ -Al 2 O 3 as a carrier and an alkali metal oxide K 2 O as an activity promoter, and a transition metal oxide II. Zirconium oxide and rare earth metal oxide antimony trioxide are used as modifiers, and the catalyst sample is obtained by calcining an activity promoter and a modifier by equal volume, and the catalyst has good anti-carbon deposition and no conversion side reaction. performance.
  • the above catalyst can achieve high-efficiency treatment of CS 2 under certain conditions, the applicable treatment concentration is only 200-500 mgS/m 3 , which is not suitable for the treatment of high-concentration CS 2 , and how to explore one can be high.
  • Desulfurizing agent for achieving high-efficiency conversion and absorption of CS 2 under concentration conditions is an unsolved problem in the prior art.
  • the present invention provides a conversion-absorption type desulfurizing agent having a wide range of carbonyl sulfide removal concentration, and the present invention also provides the A method for preparing a desulfurizing agent.
  • the present invention provides a conversion-absorption type desulfurizing agent having a wide range of CS 2 removal concentration, and the present invention also A method of preparing the desulfurizing agent is provided.
  • a high concentration carbonyl sulfide conversion-absorption type desulfurizer comprising the following components:
  • Binder 5 to 10 parts by weight.
  • the binder is one or more of bentonite, kaolin, attapulgite or artichoke.
  • the preparation method of the high concentration carbonyl sulfide conversion-absorption type desulfurizing agent comprises:
  • the FeSO 4 solid with a base ratio of 1 to 1.1 is mixed with a solid substance solid, and after being kneaded, washed with water, and filtered, calcined at 250 to 400 ° C to obtain magnetic iron oxide red Fe 21.333 O 32 ;
  • the calcination temperature in the step (1) is 350 ° C, and the calcination time is 2 to 5 h.
  • the alkaline substance is one or more of a Group IA hydroxide, Na 2 CO 3 , (NH 4 ) 2 CO 3 , K 2 CO 3 , NaHCO 3 , NH 4 HCO 3 , and KHCO 3 .
  • the anatase type TiO 2 and K 2 O in the step (2) are mixed with 6.142.72.7 parts by weight of metatitanic acid and 7.3-14.7 parts by weight of K 2 CO 3 at 500-700 ° C. Roasting is obtained.
  • the preparation method of the metatitanic acid is:
  • the titanium white by-product ferrous sulfate solid is dissolved in water, heated to 40-100 ° C, acid is added to adjust the pH value of 1-2, and a flocculating agent is added for precipitation, and the metatitanic acid is obtained by filtration.
  • the concentration of FeSO 4 in the solution obtained by dissolving the titanium white by-product ferrous sulfate solid with water is 1 to 2.5 mol/L.
  • the acid used for the acid addition is one or more selected from the group consisting of nitric acid, hydrochloric acid, and sulfuric acid.
  • the method for preparing a high-concentration carbonyl sulfide conversion-absorption type desulfurizing agent according to the present invention, the step (1) mixing a FeSO 4 solution having a base ratio of 1 to 1.1 with a basic substance solution or solid, and after precipitating and filtering, at 250
  • the magnetic iron oxide red Fe 21.333 O 32 is obtained by calcining the filter cake at -400 ° C; wherein the FeSO 4 solution reacts with the alkaline substance solution or solid to react to form a precipitate.
  • the above reaction may be carried out by a solid phase reaction method in which a FeSO 4 solid having a base ratio of 1 to 1.1 is mixed with a solid substance solid, and after being kneaded, washed with water, and filtered, calcination is carried out at 250 to 400 ° C to obtain magnetic iron oxide. Red Fe 21.333 O 32 .
  • Step (2) 50 to 75 parts by weight of the magnetic iron oxide red Fe 21.333 O 32 , 5 to 35 parts by weight of anatase TiO 2 , 5 to 10 parts by weight of K 2 O, and 5 to 10 parts by weight
  • the binder is mixed, and the desulfurizing agent is prepared after the hot rolling ball is formed and dried.
  • the anatase type TiO 2 and K 2 O in the step (2) are from 6.1-42.7 parts by weight of metatitanic acid (TiO(OH) 2 ), 7.3-14.7 parts by weight of K. 2 CO 3 is mixed and calcined at 500-700 ° C.
  • the inventors have found that the mixture of the anatase-type TiO 2 and K 2 O prepared by co-firing the metatitanic acid and K 2 CO 3 is used for preparing the catalytically converted-absorbed carbon disulfide desulfurization.
  • the desulfurizing agent has an exceptionally excellent sulfur capacity.
  • a desulfurizing agent for catalytically transforming-absorbing carbon disulfide comprising the following components:
  • Binder 5 to 10 parts by weight.
  • the binder is one or more of bentonite, kaolin, attapulgite or artichoke.
  • the preparation method of the catalytic conversion-absorption type carbon disulfide desulfurizing agent comprises:
  • the FeSO 4 solid with a base ratio of 1 to 1.1 is mixed with a solid substance solid, and after being kneaded, washed with water, and filtered, calcined at 250 to 400 ° C to obtain magnetic iron oxide red Fe 21.333 O 32 ;
  • the calcination temperature in the step (1) is 350 ° C, and the calcination time is 2 to 5 h.
  • the alkaline substance is one or more of a Group IA hydroxide, Na 2 CO 3 , (NH 4 ) 2 CO 3 , K 2 CO 3 , NaHCO 3 , NH 4 HCO 3 , and KHCO 3 .
  • the anatase type TiO 2 , K 2 O and ⁇ -Al 2 O 3 in the step (2) from 6.1-18.4 parts by weight of metatitanic acid, 2.1-11.7 parts by weight of K 2 CO 3 and 5.9- After mixing 23.5 parts by weight of pseudoboehmite, it is calcined at 500-700 ° C.
  • the preparation method of the metatitanic acid is:
  • the titanium white by-product ferrous sulfate solid is dissolved in water, heated to 40-100 ° C, acid is added to adjust the pH value of 1-2, and a flocculating agent is added for precipitation, and the metatitanic acid is obtained by filtration.
  • the concentration of FeSO 4 in the solution obtained by dissolving the titanium white by-product ferrous sulfate solid with water is 1 to 2.5 mol/L.
  • the acid used for the acid addition is one or more selected from the group consisting of nitric acid, hydrochloric acid, and sulfuric acid.
  • the method for preparing a catalytically converted-absorbed carbon disulfide desulfurizing agent according to the present invention wherein the step (1) is to mix a FeSO 4 solution having a base ratio of 1 to 1.1 with a basic substance solution or solid, and after precipitation and filtration, at 250 to The magnetic iron oxide red Fe 21.333 O 32 is obtained by calcining the filter cake at 400 ° C; wherein the FeSO 4 solution reacts with the alkaline substance solution or solid to react to form a precipitate.
  • after filtration it may be first The filter cake is washed with water and then calcined.
  • the above reaction may be carried out by a solid phase reaction method in which a FeSO 4 solid having a base ratio of 1 to 1.1 is mixed with a solid substance solid, and after being kneaded, washed with water, and filtered, calcination is carried out at 250 to 400 ° C to obtain magnetic iron oxide. Red Fe 21.333 O 32 .
  • Step (2) 50 to 75 parts by weight of the magnetic iron oxide red Fe 21.333 O 32 , 5 to 15 parts by weight of anatase TiO 2 , 2 to 8 parts by weight of K 2 O, 5 to 20 parts by weight ⁇ -Al 2 O 3 and 5 to 10 parts by weight of a binder are mixed, and the desulfurizing agent is prepared by usual hot rolling ball molding and drying.
  • the present invention defines the anatase type TiO 2 , K 2 O and ⁇ -Al 2 O 3 from 6.1-18.4 parts by weight of metatitanic acid (TiO(OH) 2 ), 2.1-11.7.
  • the high-concentration carbonyl sulfide conversion-absorption type desulfurizing agent provided by the present invention comprises magnetic iron oxide red Fe 21.333 O 32 , anatase type TiO 2 , alkali metal oxide K 2 O and a binder, and the invention
  • the desulfurizing agent can convert and absorb carbonyl sulfide in the gas at a moderate temperature, and the concentration is widened, and the carbonyl sulfide can be finely removed under high concentration conditions, and the desulfurizing agent has a high sulfur capacity under medium and low temperature conditions.
  • the suitable content of the anatase TiO 2 , the alkali metal oxide K 2 O and the magnetic iron oxide red Fe 21.333 O 32 in the present invention are matched, so that the desulfurizing agent has a very optimized alkaline active center, even in Very good conversion-absorption effects can also be achieved with high concentrations of carbonyl sulfide.
  • the high-concentration carbonyl sulfide conversion-absorption type desulfurizing agent provided by the present invention further defines that the anatase type TiO 2 is recovered from the titanium white by-product ferrous sulfate, and the sulfuric acid method produces titanium white powder by using ilmenite ( FeTiO 3 ) is used as a raw material, and the ore is decomposed with sulfuric acid. Both titanium and iron are dissolved as sulfate, and then iron is crystallized as ferrous sulfate solid (FeSO 4 ⁇ 7H 2 O), which is separated from the titanium liquid to produce titanium white. The main by-product, this ferrous sulfate solid contains about 5% of Ti.
  • the present invention uses the titanium white By-products, the Ti ions are recovered to prepare metatitanic acid, which effectively reduces the production cost of the desulfurizing agent.
  • the desulfurizing agent for catalytically converting-absorbing carbon disulfide provided by the present invention comprises magnetic iron oxide red Fe 21.333 O 32 , anatase TiO 2 , alkali metal oxide K 2 O, ⁇ -Al 2 O 3 and sticky
  • the composition of the cake, the desulfurizing agent in the invention can convert and absorb CS 2 in the gas at a medium temperature, and the concentration is widened, and the fine removal of CS 2 can be achieved under high concentration conditions, and the desulfurizing agent is used under medium temperature conditions. High sulfur capacity.
  • the suitable content of the anatase TiO 2 , the alkali metal oxide K 2 O, the ⁇ -Al 2 O 3 and the magnetic iron oxide red Fe 21.333 O 32 in the present invention are matched, so that the desulfurizing agent is very optimized.
  • Alkaline active centers achieve very good conversion-absorption effects even at high concentrations of CS 2 .
  • the catalytic conversion-absorption type carbon disulfide desulfurizing agent provided by the present invention further defines that the anatase type TiO 2 is recovered from the titanium white by-product ferrous sulfate, and the sulfuric acid method produces titanium white powder by using ilmenite (FeTiO).
  • the ore is decomposed with sulfuric acid, and both titanium and iron are dissolved as sulfate, and then iron is crystallized as ferrous sulfate solid (FeSO 4 ⁇ 7H 2 O), which is separated from the titanium liquid to become titanium white.
  • the main by-product, this ferrous sulfate solid contains about 5% of Ti.
  • the sulfuric acid process to produce titanium white by-product ferrous sulfate solid has not been effectively recycled, and the present invention uses the titanium white vice
  • the product recovers the Ti ions therein to prepare metatitanic acid, thereby effectively reducing the production cost of the desulfurizing agent.
  • the sulfuric acid method is used to produce 5kg of ferrous sulfate solid as a by-product of titanium dioxide, dissolved in 6L of water, heated at 60 °C for 30min, acid is adjusted to pH 1, and the flocculant polyacrylamide is added and filtered hot.
  • Titanate solid A, the metatitanic acid A was dried at 110 ° C for 1 h.
  • the sulfuric acid method was used to produce 1.67 kg of ferrous sulfate solid as a by-product of titanium dioxide, dissolved in 6 L of water, heated at 100 ° C for 30 min, acid was adjusted to pH 2, and the flocculant polyacrylamide was added and filtered hot.
  • Metatitanic acid solid B, the metatitanic acid B was dried at 110 ° C for 1 h.
  • Example 1 The metatitanic acid A and K 2 CO 3 prepared in Example 1 were calcined at 500 ° C to prepare anatase TiO 2 and K 2 O.
  • the desulfurizing agent in this embodiment contains the following components: magnetic iron oxide red Fe 21.333 O 32 , 50 parts by weight; anatase TiO 2 , 5 parts by weight; K 2 O, 5 parts by weight; bentonite, 5 parts by weight .
  • the desulfurizing agent in this embodiment contains the following components: magnetic iron oxide red Fe 21.333 O 32 , 75 parts by weight; anatase TiO 2 , 35 parts by weight; K 2 O, 10 parts by weight; artichoke, 10 Parts by weight.
  • the desulfurizing agent in this embodiment contains the following components: magnetic iron oxide red Fe 21.333 O 32 , 59 parts by weight; anatase TiO 2 , 15 parts by weight; K 2 O, 8 parts by weight; attapulgite, 5 Parts by weight.
  • the anatase type TiO 2 and K 2 O in the present embodiment were obtained by mixing 18.4 parts by weight of the metatitanic acid B of Example 1, and 11.7 parts by weight of K 2 CO 3 , followed by calcination at 500 °C.
  • the desulfurizing agent in this embodiment contains the following components: magnetic iron oxide red Fe 21.333 O 32 , 59 parts by weight; anatase TiO 2 , 5 parts by weight; K 2 O, 5 parts by weight; bentonite, 10 parts by weight .
  • the anatase type TiO 2 and K 2 O in the present embodiment were obtained by mixing 6.4 parts by weight of the metatitanic acid A of Example 1, and 7.3 parts by weight of K 2 CO 3 , followed by calcination at 700 °C.
  • the metatitanic acid A, K 2 CO 3 and pseudoboehmite prepared in Example 1 were calcined at 500 ° C to prepare anatase TiO 2 , K 2 O and ⁇ -Al 2 O. 3 .
  • the desulfurizing agent in this embodiment contains the following components: magnetic iron oxide red Fe 21.333 O 32 , 50 parts by weight; anatase TiO 2 , 5 parts by weight; K 2 O, 2 parts by weight; ⁇ -Al 2 O 3 , 5 parts by weight; bentonite, 5 parts by weight.
  • Example 7 The anatase type TiO 2 , K 2 O and ⁇ -Al 2 O 3 described in this example were prepared in Example 7.
  • the desulfurizing agent in this embodiment contains the following components: magnetic iron oxide red Fe 21.333 O 32 , 75 parts by weight; anatase TiO 2 , 15 parts by weight; K 2 O, 8 parts by weight; ⁇ -Al 2 O 3 , 20 parts by weight; artichoke, 10 parts by weight.
  • Example 7 The anatase type TiO 2 , K 2 O and ⁇ -Al 2 O 3 described in this example were prepared in Example 7.
  • the desulfurizing agent in this embodiment contains the following components: magnetic iron oxide red Fe 21.333 O 32 , 59 parts by weight; anatase TiO 2 , 15 parts by weight; K 2 O, 8 parts by weight; ⁇ -Al 2 O 3 , 16 parts by weight; attapulgite, 5 parts by weight.
  • the anatase type TiO 2 , K 2 O and ⁇ -Al 2 O 3 in the present embodiment have 6.1 parts by weight of the metatitanic acid B in Example 1, 11.7 parts by weight of K 2 CO 3 and 18.8 parts by weight. After mixing the pseudoboehmite, it is calcined at 500 ° C.
  • the desulfurizing agent in this embodiment contains the following components: magnetic iron oxide red Fe 21.333 O 32 , 59 parts by weight; anatase TiO 2 , 5 parts by weight; K 2 O, 2 parts by weight; ⁇ -Al 2 O 3 , 5 parts by weight; bentonite, 10 parts by weight.
  • the anatase type TiO 2 , K 2 O and ⁇ -Al 2 O 3 in the present embodiment have 6.1 parts by weight of the metatitanic acid A in Example 1, 2.9 parts by weight of K 2 CO 3 and 5.9 parts by weight.
  • the pseudo-boehmite is mixed and calcined at 700 ° C.
  • the alkaline substance used in the preparation of the magnetic iron oxide red Fe 21.333 O 32 in the present invention may be (NH 4 ) 2 CO 3 or K 2 CO 3 in addition to Na 2 CO 3 and NaOH used in the above embodiments.
  • commercially available industrial grade metatitanic acid can also be used.
  • the XRD pattern of the magnetic iron oxide red Fe 21.333 O 32 prepared in the above examples of the present invention is shown in Fig. 1.
  • the present invention sets the experimental example 1, and the experimental conditions of the experimental example are as follows:
  • the space velocity is 500h -1
  • the N 2 is used as the bottom gas
  • the standard gas containing carbonyl sulfide is 3000ppm (8571mgS/m 3 ).
  • the desulfurization tail gas is analyzed by WDL-94 trace sulfur analyzer (chromatography). The test was carried out to calculate the sulfur capacity at the end point of the outlet gas carbonyl sulfide concentration of 20 ppm. The minimum detection amount of the instrument was 0.02 ppm.
  • COS hydrolysis conversion rate (%) (imported COS concentration - export COS concentration) / imported COS concentration ⁇ 100%
  • H 2 S removal rate (%) (imported COS concentration - outlet COS concentration - outlet H 2 S concentration) / (imported COS concentration - outlet COS concentration) ⁇ 100%
  • X represents the sulfur permeable capacity (%)
  • C represents the COS content (%) in the mixed gas
  • V represents the volume (L) of the non-COS gas measured by the wet gas flow meter after the COS is removed by the reactor
  • 22.4 represents the ideal gas molar volume (L/mol) in the standard state
  • G represents the desulfurizer sample (dry sample) mass (g).
  • the present invention provides Experimental Example 2, and the experimental conditions of the experimental example are as follows:
  • the airspeed is 500h -1
  • the N 2 is used as the bottom gas
  • the standard gas containing CS 2 is 3000ppm (8571mgS/m 3 ).
  • the desulfurization tail gas is analyzed by WDL-94 trace sulfur analyzer (chromatography). The test was carried out, and the sulfur capacity was calculated with the outlet gas CS 2 concentration reaching 20 ppm as the end point. The minimum detection amount of the instrument was 0.02 ppm.
  • CS 2 hydrolysis conversion rate (%) (imported CS 2 concentration - outlet CS 2 concentration) / imported CS 2 concentration ⁇ 100%
  • H 2 S removal rate (%) (Import CS 2 concentration - outlet CS 2 concentration - outlet COS concentration - outlet H 2 S concentration) / (Import CS 2 concentration - outlet CS 2 concentration - outlet COS concentration) ⁇ 100%
  • X represents the sulfur permeable capacity (%)
  • C represents the COS content (%) in the mixed gas
  • V represents the volume (L) of the non-COS gas measured by the wet gas flow meter after the COS is removed by the reactor
  • 22.4 represents the ideal gas molar volume (L/mol) in the standard state
  • G represents the desulfurizer sample (dry sample) mass (g).
  • Example 1 >99.9% >99.9% ⁇ 0.02 20%
  • Example 7 >99.9% >99.9% ⁇ 0.02 19%
  • Example 8 >99.9% >99.9% ⁇ 0.02 19%
  • Example 9 >99.9% >99.9% ⁇ 0.02 19%
  • Example 10 >99.9% >99.9% ⁇ 0.02 36%
  • Example 11 >99.9% >99.9% ⁇ 0.02 38%
  • the present invention also provides Comparative Example 1, wherein the preparation process of the desulfurizing agent in the comparative example 1 is:
  • the catalytically-transferred carbonyl sulfide desulfurizer described in the present invention has a higher carbonyl sulfide hydrolysis conversion rate, a H 2 S removal rate, and a higher sulfur capacity at a high concentration of carbonyl sulfide.
  • the present invention also provides Comparative Example 2, wherein the preparation process of the desulfurizing agent in Comparative Example 2 is:
  • ⁇ -Al 2 O 3 powder particles were weighed as a carrier for the desulfurizing agent, and 17.44 g of Zr(NO 3 ) 4 ⁇ 5H 2 O and 5.32 g of La(NO 3 ) 3 ⁇ 6H 2 O were composed by an equal volume impregnation method.
  • the mixed solution was immersed in the ⁇ -Al 2 O 3 , immersed for 2 hours, dried at 100 ° C for 4 hours, calcined at 550 ° C for 4 hours, and then subjected to an equal volume impregnation method to 10.3 g of K 2 CO.
  • the catalytically converted-absorbed carbon disulfide desulfurizing agent described in the present invention has a higher CS 2 hydrolysis conversion rate, a H 2 S removal rate, and a higher sulfur capacity at a high concentration of CS 2 .

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Abstract

一种中低温下高浓度羰基硫转化-吸收型脱硫剂及其制备方法，脱硫剂组成为：磁性氧化铁红Fe 21.333O 3250-75％，碱金属氧化物K 2O5-10%，锐钛矿型TiO 25-35%，成型粘结剂5-10%。还公开了脱硫剂的制备方法：将钛白副产物硫酸亚铁中回收的偏钛酸与K 2CO 3混合均匀，500-700℃焙烧活化，之后与磁性氧化铁红和粘结剂等混合，常温滚球成型，100-150℃干燥。该脱硫剂对羰基硫水解转化率均大于99%，具有较高的硫容，可高达25%以上。

Description

高浓度羰基硫转化-吸收型脱硫剂和二硫化碳转化·吸收型脱硫剂及其制备方法 技术领域
本发明涉及气体中羰基硫催化转化-吸收型脱硫剂和气体中二硫化碳催化转化-吸收型脱硫剂及其制备方法，属于脱硫技术领域。
背景技术
众所周知，有机硫广泛存在于以煤、天然气和石油为原料的化工生产原料气中，它的存在会造成后续生产过程中催化剂中毒失活。随着劣质煤和焦炉气用于合成原料气的制备以及煤制气多联产和低温水蒸气变换等新技术或新工艺的研究、开发与使用，脱除高浓度的有机硫受到高度重视。
羰基硫呈中性或弱酸性，化学性能比较稳定，难以用常规的脱硫方法脱除干净，工业上脱除羰基硫的方法有干法和湿法两种。由于化学平衡等因素的限制，湿法脱除难以达到精脱硫的程度，故目前主要采用干法脱除羰基硫，将羰基硫氢解或水解转化为硫化氢并加以脱除。干法脱硫主要有水解和氢解两种方法。羰基硫水解催化剂在国内或国外又可以分为两种，一种为单纯转化型，对羰基硫只具有转化功能，因此必须与氧化锌、活性炭等脱硫剂串联使用；一种为转化吸收型，它不仅对羰基硫等有机硫有转化能力，且对转化生成的硫化氢有吸收能力，能单独用于微量硫的脱除，近年来，能够转化吸收有机硫的双功能脱硫剂引起了较大关注。如中国专利文献ON1069673A公开了一种常温有机硫水解催化剂，由2-25wt％的碳酸钾和球形γ-Al2O3组成，该脱硫剂在常温下使用时，对于羰基硫的转化率可以高达95％，并且该脱硫剂在对羰基硫进行转化的同时，还可以实现硫化氢的吸收。
上述羰基硫转化脱硫剂在常温下使用虽然能够达到较高的转化率，但其仍旧存在的缺点在于，但其适用的处理浓度较低，不高于30mgS/m3，而不 适用于高浓度羰基硫场合的处理，而如何探索一种能够在高浓度条件下实现羰基硫高效转化、吸收的脱硫剂，是现有技术尚未解决的难题。
在化工原料气中，CS2含量约为COS含量的10％左右，CS2属于极性分子，其水解过程中反应如下所示：
CS2+H2O→COS+H2S      (1)
COS+H2O→CO2+H2S        (2)
CS2+CO2→2COS       (3)
在上述过程中，由于CS2在水解过程中会生成COS，且一氧化碳和硫化氢气氛会影响CS2的水解转化率，因此要实现CS2的彻底去除非常困难。现有技术中，中国专利CN10112123A公开了一种中温二硫化碳水解催化剂，它是以球型γ-Al2O3作为载体，以碱金属氧化物K2O作为活性促进剂，以过渡金属氧化物二氧化锆和稀土金属氧化物三氧化二镧作为改性剂，通过等体积浸渍活性促进剂和改性剂，经焙烧后得到催化剂样品，该催化剂有较好的抗积碳和无变换副反应的性能。
上述催化剂在一定条件下虽然能够实现CS2的高效处理，但其适用的处理浓度只在200～500mgS/m3，而不适用于高浓度CS2场合的处理，而如何探索一种能够在高浓度条件下实现CS2高效转化、吸收的脱硫剂，是现有技术尚未解决的难题。
发明内容
为了解决现有技术中的羰基硫水解催化剂不适用于高浓度羰基硫场合的处理，本发提供一种羰基硫脱除浓度适用范围广的转化-吸收型脱硫剂，本发明还提供了所述脱硫剂的制备方法。
另一方面，为了解决现有技术中的CS2水解催化剂不适用于高浓度CS2场合的处理，本发提供一种CS2脱除浓度适用范围广的转化-吸收型脱硫剂，本发明还提供了所述脱硫剂的制备方法。
本发明所述高浓度羰基硫转化-吸收型脱硫剂及其制备方法的技术方案 为：
一种高浓度羰基硫转化-吸收型脱硫剂，包括以下组分：
磁性氧化铁红Fe21.333O32，50～75重量份；
K2O，5～10重量份；
锐钛矿型TiO2，5～35重量份；
粘结剂，5～10重量份。
所述粘结剂为膨润土、高岭土、凹凸棒土或洋坩土中的一种或多种。
所述高浓度羰基硫转化-吸收型脱硫剂的制备方法，包括：
(1)将碱比为1～1.1的FeSO4溶液与碱性物质溶液或固体混合，经沉淀、过滤后，在250～400℃条件下焙烧得到磁性氧化铁红Fe21.333O32；或者
将碱比为1～1.1的FeSO4固体和碱性物质固体混合，经过混捏、水洗、过滤后，在250～400℃条件下焙烧得到磁性氧化铁红Fe21.333O32；
(2)将50～75重量份的所述磁性氧化铁红Fe21.333O32、5～35重量份锐钛矿型TiO2、5～10重量份的K2O和5～10重量份的粘结剂混合，经常温滚球成型、干燥后即制备得到所述脱硫剂。
步骤(1)中的焙烧温度为350℃，焙烧时间为2～5h。
所述碱性物质为IA族的氢氧化物、Na2CO3，(NH4)2CO3、K2CO3、NaHCO3、NH4HCO3、KHCO3中的一种或者多种。
步骤(2)中的所述锐钛矿型TiO2和K2O，由6.1-42.7重量份的偏钛酸、7.3-14.7重量份的K2CO3混合后，在500-700℃条件下焙烧得到。
所述偏钛酸的制备方法为：
将钛白副产物硫酸亚铁固体加水溶解，加热至40～100℃，加酸调节pH值为1～2，加絮凝剂进行沉淀，经过滤即得到偏钛酸。
所述钛白副产物硫酸亚铁固体加水溶解得到的溶液中，FeSO4的浓度为1～2.5mol/L。
所述加酸调节所用的酸为自硝酸、盐酸、硫酸中的一种或多种。
本发明所述高浓度羰基硫转化-吸收型脱硫剂的制备方法，步骤(1)将碱比为1～1.1的FeSO4溶液与碱性物质溶液或固体混合，经沉淀、过滤后，在250～400℃条件下焙烧滤饼即得到磁性氧化铁红Fe21.333O32；其中FeSO4溶液与碱性物质溶液或固体混合后会发生反应生成沉淀，作为优选的实施方式，在过滤后，可先对滤饼进行水洗，再进行焙烧。
或者上述反应也可采用固相反应的方式：将碱比为1～1.1的FeSO4固体和碱性物质固体混合，经过混捏、水洗、过滤后，在250～400℃条件下焙烧得到磁性氧化铁红Fe21.333O32。
步骤(2)将50～75重量份的所述磁性氧化铁红Fe21.333O32、5～35重量份锐钛矿型TiO2、5～10重量份的K2O和5～10重量份的粘结剂混合，经常温滚球成型、干燥后即制备得到所述脱硫剂。
作为优选的实施方式，步骤(2)中的所述锐钛矿型TiO2和K2O，由6.1-42.7重量份的偏钛酸(TiO(OH)2)、7.3-14.7重量份的K2CO3混合后，在500-700℃条件下焙烧得到。经本发明人研究发现，所述偏钛酸、K2CO3共同焙烧制备得到的所述锐钛矿型TiO2和K2O的混合物，用于制备所述催化转化-吸收型二硫化碳的脱硫剂时，所述脱硫剂具有异常优良的硫容。
另一方面，本发明所述二硫化碳转化-吸收型脱硫剂及其制备方法的技术方案为：
一种催化转化-吸收型二硫化碳的脱硫剂，包括以下组分：
磁性氧化铁红Fe21.333O32，50～75重量份；
锐钛矿型TiO2，5～15重量份；
K2O，2～8重量份；
γ-Al2O3，5～20重量份；
粘结剂，5～10重量份。
所述粘结剂为膨润土、高岭土、凹凸棒土或洋坩土中的一种或多种。
所述催化转化-吸收型二硫化碳的脱硫剂的制备方法，包括：
(1)将碱比为1～1.1的FeSO4溶液与碱性物质溶液或固体混合，经沉淀、过滤后，在250～400℃条件下焙烧得到磁性氧化铁红Fe21.333O32；或者
将碱比为1～1.1的FeSO4固体和碱性物质固体混合，经过混捏、水洗、过滤后，在250～400℃条件下焙烧得到磁性氧化铁红Fe21.333O32；
(2)将50～75重量份的所述磁性氧化铁红Fe21.333O32、5～15重量份锐钛矿型TiO2、2～8重量份的K2O、5～20重量份的γ-Al2O3和5～10重量份的粘结剂混合，经常温滚球成型、干燥后即制备得到所述脱硫剂。
步骤(1)中的焙烧温度为350℃，焙烧时间为2～5h。
所述碱性物质为IA族的氢氧化物、Na2CO3，(NH4)2CO3、K2CO3、NaHCO3、NH4HCO3、KHCO3中的一种或者多种。
步骤(2)中的所述锐钛矿型TiO2、K2O和γ-Al2O3，由6.1-18.4重量份的偏钛酸、2.9-11.7重量份的K2CO3和5.9-23.5重量份的拟薄水铝石混合后，在500-700℃条件下焙烧得到。
所述偏钛酸的制备方法为：
将钛白副产物硫酸亚铁固体加水溶解，加热至40～100℃，加酸调节pH值为1～2，加絮凝剂进行沉淀，经过滤即得到偏钛酸。
所述钛白副产物硫酸亚铁固体加水溶解得到的溶液中，FeSO4的浓度为1～2.5mol/L。
所述加酸调节所用的酸为自硝酸、盐酸、硫酸中的一种或多种。
本发明所述催化转化-吸收型二硫化碳的脱硫剂的制备方法，步骤(1)将碱比为1～1.1的FeSO4溶液与碱性物质溶液或固体混合，经沉淀、过滤后，在250～400℃条件下焙烧滤饼即得到磁性氧化铁红Fe21.333O32；其中FeSO4溶液与碱性物质溶液或固体混合后会发生反应生成沉淀，作为优选的实施方式，在过滤后，可先对滤饼进行水洗，再进行焙烧。
或者上述反应也可采用固相反应的方式：将碱比为1～1.1的FeSO4固体和 碱性物质固体混合，经过混捏、水洗、过滤后，在250～400℃条件下焙烧得到磁性氧化铁红Fe21.333O32。
步骤(2)将50～75重量份的所述磁性氧化铁红Fe21.333O32、5～15重量份锐钛矿型TiO2、2～8重量份的K2O、5～20重量份的γ-Al2O3和5～10重量份的粘结剂混合，经常温滚球成型、干燥后即制备得到所述脱硫剂。作为优选的实施方式，本发明限定所述锐钛矿型TiO2、K2O和γ-Al2O3，由6.1-18.4重量份的偏钛酸(TiO(OH)2)、2.9-11.7重量份的K2CO3和5.9-23.5重量份的拟薄水铝石(一水合氧化铝)混合后，在500-700℃条件下焙烧得到。经本发明人研究发现，所述偏钛酸、K2CO3和拟薄水铝石共同焙烧制备得到的所述锐钛矿型TiO2、K2O和γ-Al2O3的混合物，用于制备所述催化转化-吸收型二硫化碳的脱硫剂时，所述脱硫剂具有异常优良的硫容。
本发明所述的高浓度羰基硫转化-吸收型脱硫剂和催化转化-吸收型二硫化碳的脱硫剂的优点在于：
(1)本发明提供的高浓度羰基硫转化-吸收型脱硫剂，由磁性氧化铁红Fe21.333O32、锐钛矿型TiO2、碱金属氧化物K2O及粘结剂组成，本发明中的脱硫剂可以在中温下将气体中羰基硫转化并吸收，浓度适应范围广，可实现高浓度条件下羰基硫的精脱除，脱硫剂在中低温条件下使用有很高的硫容。本发明中适宜含量的所述锐钛矿型TiO2、碱金属氧化物K2O和磁性氧化铁红Fe21.333O32相配合，使得所述脱硫剂具有非常优化的碱性活性中心，即使在高浓度羰基硫条件下也可以达到非常好的转化-吸收效果。
(2)本发明提供的高浓度羰基硫转化-吸收型脱硫剂，还限定所述锐钛型TiO2为钛白副产物硫酸亚铁中回收得到，硫酸法生产钛白粉是以钛铁矿(FeTiO3)为原料，用硫酸分解矿石，钛和铁均成为硫酸盐而溶解，随后铁以硫酸亚铁固体(FeSO4·7H2O)的形式结晶析出，与钛液分离，成为生产钛白的主要副产品，这种硫酸亚铁固体中大概含有5％的Ti，至今为止，这种硫酸法生产钛白的副产物硫酸亚铁固体尚未得到有效的回收利用，本发明通过使用所述钛白副产物，回收其中的Ti离子制备偏钛酸，有效降低了脱硫剂的生产成本。
(3)本发明提供的催化转化-吸收型二硫化碳的脱硫剂，由磁性氧化铁红Fe21.333O32、锐钛矿型TiO2、碱金属氧化物K2O、γ-Al2O3以及粘结剂组成，本发明中的脱硫剂可以在中温下将气体中CS2转化并吸收，浓度适应范围广，可实现高浓度条件下CS2的精脱除，脱硫剂在中温条件下使用有很高的硫容。本发明中适宜含量的所述锐钛矿型TiO2、碱金属氧化物K2O、γ-Al2O3和磁性氧化铁红Fe21.333O32相配合，使得所述脱硫剂具有非常优化的碱性活性中心，即使在高浓度CS2条件下也可以达到非常好的转化-吸收效果。
(4)本发明提供的催化转化-吸收型二硫化碳的脱硫剂，还限定所述锐钛型TiO2为钛白副产物硫酸亚铁中回收得到，硫酸法生产钛白粉是以钛铁矿(FeTiO3)为原料，用硫酸分解矿石，钛和铁均成为硫酸盐而溶解，随后铁以硫酸亚铁固体(FeSO4·7H2O)的形式结晶析出，与钛液分离，成为生产钛白的主要副产品，这种硫酸亚铁固体中大概含有5％的Ti，至今为止，这种硫酸法生产钛白的副产物硫酸亚铁固体尚未得到有效的回收利用，本发明通过使用所述钛白副产物，回收其中的Ti离子制备偏钛酸，从而有效降低了脱硫剂的生产成本。
附图说明
如图1所示是本发明制备得到的磁性氧化铁红Fe21.333O32的XRD图谱。
具体实施方式
实施例1
偏钛酸的制备：
在反应器中称取硫酸法生产钛白粉的副产物硫酸亚铁固体5kg，加水6L溶解，60℃加热30min，加酸调节pH值为1，加絮凝剂聚丙烯酰胺后趁热过滤，得到偏钛酸固体A，将所述偏钛酸A在110℃干燥1h。
在反应器中称取硫酸法生产钛白粉的副产物硫酸亚铁固体1.67kg，加水6L溶解，100℃加热30min，加酸调节pH值为2，加絮凝剂聚丙烯酰胺后趁热过滤，得到偏钛酸固体B，将所述偏钛酸B在110℃干燥1h。
实施例2
锐钛矿型TiO2和K2O的制备：
将实施例1中制备得到的偏钛酸A、K2CO3分别在500℃条件下进行焙烧，制备得到锐钛矿型TiO2和K2O。
实施例3
本实施例中所述脱硫剂含有如下组分：磁性氧化铁红Fe21.333O32，50重量份；锐钛矿型TiO2，5重量份；K2O，5重量份；膨润土，5重量份。
本实施例中所述催化转化-吸收型羰基硫的脱硫剂的制备方法为：
(1)在烧杯中称取固体FeSO4·7H2O 500g，加入454ml水，放在40℃水浴中溶解，完全溶解后，加入Na2CO3190g，二者的碱比为1；搅拌2h进行沉淀反应，沉淀完成后进行过滤，将滤饼在350℃焙烧3h，得到磁性氧化铁红Fe21.333O32。
(2)将50重量份所述磁性氧化铁红Fe21.333O32、5重量份锐钛矿型TiO2、5重量份K2O和5重量份膨润土混合，经常温滚球成型，制成
Figure PCTCN2014095470-appb-000001
的小球，干燥后即得到所述脱硫剂。
本实施例中所述锐钛矿型TiO2和K2O采用实施例2中制备得到的。
实施例4
本实施例中所述脱硫剂含有如下组分：磁性氧化铁红Fe21.333O32，75重量份；锐钛矿型TiO2，35重量份；K2O，10重量份；洋坩土，10重量份。
本实施例中所述催化转化-吸收型羰基硫的脱硫剂的制备方法为：
(1)称取固体FeSO4·7H2O 500g，称取固体NaHCO3333g，二者的碱比为1.1；将上述FeSO4·7H2O固体和NaHCO3固体在糖衣锅装置中进行混捏2h；将完成混捏的物料用水洗3次，完成水洗后进行过滤，将滤饼在350℃焙烧3h，研磨，得到磁性氧化铁红Fe21.333O32，筛取200目以上细粉备用。
(2)将75重量份所述磁性氧化铁红Fe21.333O32、35重量份的锐钛矿型TiO2、10重量份的K2O和10重量份洋坩土混合，经常温滚球成型，制成
Figure PCTCN2014095470-appb-000002
的小球，在条件下干燥后即得到所述脱硫剂。
本实施例中所述锐钛矿型TiO2和K2O采用实施例2中制备得到的。
实施例5
本实施例中所述脱硫剂含有如下组分：磁性氧化铁红Fe21.333O32，59重量份；锐钛矿型TiO2，15重量份；K2O，8重量份；凹凸棒土，5重量份。
本实施例中所述催化转化-吸收型羰基硫的脱硫剂的制备方法为：
(1)在烧杯中称取固体FeSO4·7H2O 500g，加入454ml水，放在40℃水浴中溶解，完全溶解后，加入Na2CO3190g，二者的碱比为1；搅拌2h，抽滤，水洗3次，将滤饼在350℃焙烧3h，研磨，得到磁性氧化铁红Fe21.333O32，筛取200目以上细粉备用。
(2)将59重量份所述磁性氧化铁红Fe21.333O32、15重量份的锐钛矿型TiO2、8重量份K2O和5重量份凹凸棒土混合，经常温滚球成型，制成
Figure PCTCN2014095470-appb-000003
的小球，干燥后即得到所述脱硫剂。
本实施例中所述锐钛矿型TiO2和K2O由18.4重量份的实施例1中的偏钛酸B、11.7重量份的K2CO3混合后，在500℃条件下焙烧得到。
实施例6
本实施例中所述脱硫剂含有如下组分：磁性氧化铁红Fe21.333O32，59重量份；锐钛矿型TiO2，5重量份；K2O，5重量份；膨润土，10重量份。
本实施例中所述催化转化-吸收型羰基硫的脱硫剂的制备方法为：
(1)在烧杯中称取固体FeSO4·7H2O 500g，加入454ml水，放在40℃水浴中溶解，完全溶解后，加入Na2CO3190g，二者的碱比为1；搅拌2h，抽滤，水洗3次，将滤饼在350℃焙烧3h，研磨，得到磁性氧化铁红Fe21.333O32，筛取200目以上细粉备用。
(2)将59重量份所述磁性氧化铁红Fe21.333O32、5重量份的锐钛矿型TiO2、5重量份的K2O和10重量份膨润土混合，经常温滚球成型，制成
Figure PCTCN2014095470-appb-000004
的小球，干燥后即得到所述脱硫剂。
本实施例中所述锐钛矿型TiO2和K2O由6.4重量份的实施例1中的偏钛酸A、7.3重量份的K2CO3混合后，在700℃条件下焙烧得到。
实施例7
锐钛矿型TiO2、K2O和γ-Al2O3的制备：
将实施例1中制备得到的偏钛酸A、K2CO3和拟薄水铝石分别在500℃条件下进行焙烧，制备得到锐钛矿型TiO2、K2O和γ-Al2O3。
实施例8
本实施例中所述脱硫剂含有如下组分：磁性氧化铁红Fe21.333O32，50重量份；锐钛矿型TiO2，5重量份；K2O，2重量份；γ-Al2O3，5重量份；膨润土，5重量份。
本实施例中所述催化转化-吸收型二硫化碳的脱硫剂的制备方法为：
(1)在烧杯中称取固体FeSO4·7H2O 500g，加入454ml水，放在40℃水浴中溶解，完全溶解后，加入Na2CO3190g，二者的碱比为1；搅拌2h进行沉淀反应，沉淀完成后进行过滤，将滤饼在350℃焙烧3h，得到磁性氧化铁红Fe21.333O32。制备得到的所述磁性氧化铁红Fe21.333O32的XRD图谱如图1所示。
(2)将50重量份所述磁性氧化铁红Fe21.333O32、5重量份锐钛矿型TiO2、2重量份K2O、5重量份的γ-Al2O3和5重量份膨润土混合，经常温滚球成型，制成
Figure PCTCN2014095470-appb-000005
的小球，干燥后即得到所述脱硫剂。
本实施例中所述锐钛矿型TiO2、K2O和γ-Al2O3采用实施例7中制备得到的。
实施例9
本实施例中所述脱硫剂含有如下组分：磁性氧化铁红Fe21.333O32，75重量份；锐钛矿型TiO2，15重量份；K2O，8重量份；γ-Al2O3，20重量份；洋坩土，10重量份。
本实施例中所述催化转化-吸收型二硫化碳的脱硫剂的制备方法为：
(1)称取固体FeSO4·7H2O 500g，称取固体NaHCO3 333g，二者的碱比为1.1；将上述FeSO4·7H2O固体和NaHCO3固体在糖衣锅装置中进行混捏2h；将完成混捏的物料用水洗3次，完成水洗后进行过滤，将滤饼在350℃焙烧3h，研磨，得到磁性氧化铁红Fe21.333O32，筛取200目以上细粉备用。
(2)将75重量份所述磁性氧化铁红Fe21.333O32、15重量份的锐钛矿型TiO2、8重量份的K2O、20重量份的γ-Al2O3和10重量份洋坩土混合，经常温滚球成型，制成
Figure PCTCN2014095470-appb-000006
的小球，在条件下干燥后即得到所述脱硫剂。
本实施例中所述锐钛矿型TiO2、K2O和γ-Al2O3采用实施例7中制备得到的。
实施例10
本实施例中所述脱硫剂含有如下组分：磁性氧化铁红Fe21.333O32，59重量份；锐钛矿型TiO2，15重量份；K2O，8重量份；γ-Al2O3，16重量份；凹凸棒土，5重量份。
本实施例中所述催化转化-吸收型二硫化碳的脱硫剂的制备方法为：
(1)在烧杯中称取固体FeSO4·7H2O 500g，加入454ml水，放在40℃水浴中溶解，完全溶解后，加入Na2CO3190g，二者的碱比为1；搅拌2h，抽滤，水洗3次，将滤饼在350℃焙烧3h，研磨，得到磁性氧化铁红Fe21.333O32，筛取200目以上细粉备用。
(2)将59重量份所述磁性氧化铁红Fe21.333O32、5重量份的锐钛矿型TiO2、8重量份K2O、16重量份的γ-Al2O3和5重量份凹凸棒土混合，经常温滚球成型，制成
Figure PCTCN2014095470-appb-000007
的小球，干燥后即得到所述脱硫剂。
本实施例中所述锐钛矿型TiO2、K2O和γ-Al2O3由6.1重量份的实施例1中的偏钛酸B、11.7重量份的K2CO3和18.8重量份的拟薄水铝石混合后，在500℃条件下焙烧得到。
实施例11
本实施例中所述脱硫剂含有如下组分：磁性氧化铁红Fe21.333O32，59重量份；锐钛矿型TiO2，5重量份；K2O，2重量份；γ-Al2O3，5重量份；膨润 土，10重量份。
本实施例中所述催化转化-吸收型二硫化碳的脱硫剂的制备方法为：
(1)在烧杯中称取固体FeSO4·7H2O 500g，加入454ml水，放在40℃水浴中溶解，完全溶解后，加入Na2CO3190g，二者的碱比为1；搅拌2h，抽滤，水洗3次，将滤饼在350℃焙烧3h，研磨，得到磁性氧化铁红Fe21.333O32，筛取200目以上细粉备用。
(2)将59重量份所述磁性氧化铁红Fe21.333O32、5重量份的锐钛矿型TiO2、2重量份的K2O、5重量份的γ-Al2O3和10重量份膨润土混合，经常温滚球成型，制成
Figure PCTCN2014095470-appb-000008
的小球，干燥后即得到所述脱硫剂。
本实施例中所述锐钛矿型TiO2、K2O和γ-Al2O3由6.1重量份的实施例1中的偏钛酸A、2.9重量份的K2CO3和5.9重量份的拟薄水铝石混合后，在700℃条件下焙烧得到。
本发明中用于制备磁性氧化铁红Fe21.333O32的碱性物质，除了上述实施例中使用的Na2CO3和NaOH外，还可以是(NH4)2CO3、K2CO3、NH4HCO3、KHCO3以及除了Na以外的IA族氢氧化物中的一种或者多种；此外，作为优选的实施方式，本发明中制备所述锐钛型TiO2的偏钛酸可选择使用钛白副产物硫酸亚铁中回收得到，作为可选择的实施方式，也可以使用市售的工业级偏钛酸。
本发明上述实施例制备得到的所述磁性氧化铁红Fe21.333O32的XRD图谱如图1所示。
实验例1
为了证明本发明所述催化转化-吸收型羰基硫脱硫剂的技术效果，本发明设置了实验例1，本实验例的实验条件为：
在常温、常压下，空速500h-1，以N2为底气，含羰基硫为3000ppm(8571mgS/m3)的标准气进行评价测试，脱硫尾气用WDL-94微量硫分析仪(色谱法)进行检测，以出口气体羰基硫浓度达到20ppm为终点计算硫容，该仪器的最低检测量为0.02ppm。
①COS水解转化率
COS水解转化率(％)＝(进口COS浓度-出口COS浓度)/进口COS浓度×100％
②产物H2S脱除率
H2S脱除率(％)＝(进口COS浓度-出口COS浓度-出口H2S浓度)/(进口COS浓度-出口COS浓度)×100％
③硫容
以出口气体COS浓度达到20ppm为终点计算硫容
Figure PCTCN2014095470-appb-000009
式中：X表示穿透硫容量(％)；C表示混合气体中COS的含量(％)；V表示经反应器脱除COS后湿式气体流量计计量的非COS气体的体积(L)；32表示硫的摩尔质量(g/mol)；22.4表示标准状态下理想气体摩尔体积(L/mol)；G表示脱硫剂样品(干样)质量(g)。
测定结果如下表所示：
Figure PCTCN2014095470-appb-000010
实验例2
为了证明本发明所述催化转化-吸收型二硫化碳脱硫剂的技术效果，本发明设置了实验例2，本实验例的实验条件为：
在常温、常压下，空速500h-1，以N2为底气，含CS2为3000ppm(8571mgS/m3)的标准气进行评价测试，脱硫尾气用WDL-94微量硫分析仪(色谱法)进行检 测，以出口气体CS2浓度达到20ppm为终点计算硫容，该仪器的最低检测量为0.02ppm。
①CS2水解转化率
CS2水解转化率(％)＝(进口CS2浓度-出口CS2浓度)/进口CS2浓度×100％
②产物H2S脱除率
H2S脱除率(％)＝(进口CS2浓度-出口CS2浓度-出口COS浓度-出口H2S浓度)/(进口CS2浓度-出口CS2浓度-出口COS浓度)×100％
③硫容
以尾气中CS2浓度达到20ppm为终点计算硫容
Figure PCTCN2014095470-appb-000011
式中：X表示穿透硫容量(％)；C表示混合气体中COS的含量(％)；V表示经反应器脱除COS后湿式气体流量计计量的非COS气体的体积(L)；32表示硫的摩尔质量(g/mol)；22.4表示标准状态下理想气体摩尔体积(L/mol)；G表示脱硫剂样品(干样)质量(g)。
测定结果如下表所示：
  CS2水解转化率 产物H2S脱除率 出口CS2浓度 硫容
实施例1 ＞99.9％ ＞99.9％ ＜0.02 20％
实施例7 ＞99.9％ ＞99.9％ ＜0.02 19％
实施例8 ＞99.9％ ＞99.9％ ＜0.02 19％
实施例9 ＞99.9％ ＞99.9％ ＜0.02 19％
实施例10 ＞99.9％ ＞99.9％ ＜0.02 36％
实施例11 ＞99.9％ ＞99.9％ ＜0.02 38％
对比例1
为了进一步证明本发明所述催化转化-吸收型羰基硫脱硫剂的技术效果，本发明还设置了对比例1，所述对比例1中的脱硫剂制备工艺为：
称取100克γ-Al2O3粉末颗粒作为脱硫剂的载体，利用等体积浸渍法将10gK2CO3浸渍在所述γ-Al2O3上，120℃条件下干燥后即得到脱硫剂。在实验例1所述的条件下对所述脱硫剂的效果进行测试，结果表明，在羰基硫为3000ppm浓度下，羰基硫水解转化率为88％，产物H2S脱除率为92％，硫容为16％。
从测试结果可知，本发明中所述的催化转化-吸收型羰基硫脱硫剂在高浓度羰基硫条件下具有更高的羰基硫水解转化率、H2S脱除率以及更高的硫容。
对比例2
为了进一步证明本发明所述催化转化-吸收型二硫化碳脱硫剂的技术效果，本发明还设置了对比例2，所述对比例2中的脱硫剂制备工艺为：
称取86克γ-Al2O3粉末颗粒作为脱硫剂的载体，利用等体积浸渍法将17.44gZr(NO3)4·5H2O和5.32克La(NO3)3·6H2O组成的混合溶液浸渍在所述γ-Al2O3上，浸渍2小时后，在100℃条件下干燥4个小时，在550℃下焙烧4个小时，再采用等体积浸渍法将10.3克K2CO3浸渍在负载有Zr和La的载体上，浸渍2小时后，在100℃条件下干燥4个小时，在550℃下焙烧4个小时。最终得到7wt％K2O-5wt％ZrO2-25wt％LaO-86wt％γ-Al2O3物料，经常温滚球成型，制成
Figure PCTCN2014095470-appb-000012
的小球，干燥后即得到脱硫剂。在实验例2所述的条件下对所述脱硫剂的效果进行测试，结果表明，在CS2为3000ppm浓度下，CS2水解转化率为89％，产物H2S脱除率为92％，硫容为16％。
从测试结果可知，本发明中所述的催化转化-吸收型二硫化碳脱硫剂在高浓度CS2条件下具有更高的CS2水解转化率、H2S脱除率以及更高的硫容。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围。

Claims (18)

  1. 一种高浓度羰基硫转化-吸收型脱硫剂，其特征在于，包括以下组分：
    磁性氧化铁红Fe21.333O32，50～75重量份；
    K2O，5～10重量份；
    锐钛矿型TiO2，5～35重量份；
    粘结剂，5～10重量份。
  2. 根据权利要求1所述的高浓度羰基硫转化-吸收型脱硫剂，其特征在于，所述粘结剂为膨润土、高岭土、凹凸棒土或洋坩土中的一种或多种。
  3. 根据权利要求1或2所述高浓度羰基硫转化-吸收型脱硫剂的制备方法，包括：
    (1)将碱比为1～1.1的FeSO4溶液与碱性物质溶液或固体混合，经沉淀、过滤后，在250～400℃条件下焙烧得到磁性氧化铁红Fe21.333O32；或者
    将碱比为1～1.1的FeSO4固体和碱性物质固体混合，经过混捏、水洗、过滤后，在250～400℃条件下焙烧得到磁性氧化铁红Fe21.333O32；
    (2)将50～75重量份的所述磁性氧化铁红Fe21.333O32、5～35重量份锐钛矿型TiO2、5～10重量份的K2O和5～10重量份的粘结剂混合，经常温滚球成型、干燥后即制备得到所述脱硫剂。
  4. 根据权利要求3所述高浓度羰基硫转化-吸收型脱硫剂的制备方法，其特征在于，步骤(1)中的焙烧温度为350℃，焙烧时间为2～5h。
  5. 根据权利要求3或4所述高浓度羰基硫转化-吸收型脱硫剂的制备方法，其特征在于，所述碱性物质为IA族的氢氧化物、Na2CO3，(NH4)2CO3、K2CO3、NaHCO3、NH4HCO3、KHCO3中的一种或者多种。
  6. 根据权利要求3-5任一所述高浓度羰基硫转化-吸收型脱硫剂的制备方法，其特征在于，
    步骤(2)中的所述锐钛矿型TiO2和K2O，由6.1-42.7重量份的偏钛酸、 7.3-14.7重量份的K2CO3混合后，在500-700℃条件下焙烧得到。
  7. 根据权利要求6所述高浓度羰基硫转化-吸收型脱硫剂的制备方法，其特征在于，所述偏钛酸的制备方法为：
    将硫酸法生产钛白粉的副产物硫酸亚铁固体加水溶解，加热至40～100℃，加酸调节pH值为1～2，加絮凝剂进行沉淀，经过滤即得到偏钛酸。
  8. 根据权利要求7所述高浓度羰基硫转化-吸收型脱硫剂的制备方法，其特征在于，所述钛白副产物硫酸亚铁固体加水溶解得到的溶液中，FeSO4的浓度为1～2.5mol/L。
  9. 根据权利要求7或8所述高浓度羰基硫转化-吸收型脱硫剂的制备方法，其特征在于，所述加酸调节所用的酸为自硝酸、盐酸、硫酸中的一种或多种。
  10. 一种催化转化-吸收型二硫化碳的脱硫剂，其特征在于，包括以下组分：
    磁性氧化铁红Fe21.333O32，50～75重量份；
    锐钛矿型TiO2，5～15重量份；
    K2O，2～8重量份；
    γ-Al2O3，5～20重量份；
    粘结剂，5～10重量份。
  11. 根据权利要求10所述的脱硫剂，其特征在于，所述粘结剂为膨润土、高岭土、凹凸棒土或洋坩土中的一种或多种。
  12. 根据权利要求10或11所述催化转化-吸收型二硫化碳的脱硫剂的制备方法，包括：
    (1)将碱比为1～1.1的FeSO4溶液与碱性物质溶液或固体混合，经沉淀、过滤后，在250～400℃条件下焙烧得到磁性氧化铁红Fe21.333O32；或者
    将碱比为1～1.1的FeSO4固体和碱性物质固体混合，经过混捏、水洗、过 滤后，在250～400℃条件下焙烧得到磁性氧化铁红Fe21.333O32；
    (2)将50～75重量份的所述磁性氧化铁红Fe21.333O32、5～15重量份锐钛矿型TiO2、2～8重量份的K2O、5～20重量份的γ-Al2O3和5～10重量份的粘结剂混合，经常温滚球成型、干燥后即制备得到所述脱硫剂。
  13. 根据权利要求12所述催化转化-吸收型二硫化碳的脱硫剂的制备方法，其特征在于，步骤(1)中的焙烧温度为350℃，焙烧时间为2～5h。
  14. 根据权利要求12或13所述催化转化-吸收型二硫化碳的脱硫剂的制备方法，其特征在于，所述碱性物质为IA族的氢氧化物、Na2CO3，(NH4)2CO3、K2CO3、NaHCO3、NH4HCO3、KHCO3中的一种或者多种。
  15. 根据权利要求12-14任一所述催化转化-吸收型二硫化碳的脱硫剂的制备方法，其特征在于，
    步骤(2)中的所述锐钛矿型TiO2、K2O和γ-Al2O3，由6.1-18.4重量份的偏钛酸、2.9-11.7重量份的K2CO3和5.9-23.5重量份的拟薄水铝石混合后，在500-700℃条件下焙烧得到。
  16. 根据权利要求15所述催化转化-吸收型二硫化碳的脱硫剂的制备方法，其特征在于，所述偏钛酸的制备方法为：
    将硫酸法生产钛白粉的副产物硫酸亚铁固体加水溶解，加热至40～100℃，加酸调节pH值为1～2，加絮凝剂进行沉淀，经过滤即得到偏钛酸。
  17. 根据权利要求16所述的脱硫剂，其特征在于所述钛白副产物硫酸亚铁固体加水溶解得到的溶液中，FeSO4的浓度为1～2.5mol/L。
  18. 根据权利要求16或17所述催化转化-吸收型二硫化碳的脱硫剂的制备方法，其特征在于，所述加酸调节所用的酸为自硝酸、盐酸、硫酸中的一种或多种。
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