CN1210201C - Multifunction sulfur recovery catalyst and its preparing method - Google Patents
Multifunction sulfur recovery catalyst and its preparing method Download PDFInfo
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- CN1210201C CN1210201C CN 02151549 CN02151549A CN1210201C CN 1210201 C CN1210201 C CN 1210201C CN 02151549 CN02151549 CN 02151549 CN 02151549 A CN02151549 A CN 02151549A CN 1210201 C CN1210201 C CN 1210201C
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Abstract
The present invention relates to a multifunctional sulfur recovery catalyst and a preparation method thereof, particularly to a multifunctional sulfur recovery catalyst with high O2 disengagement activity, high organic sulfur hydrolysis activity and high H2S and SO2 Claus reactivity and a preparation method of the multifunctional sulfur recovery catalyst. The catalyst of the present invention has the active constituents of 40% to 60% of titanium dioxide, 35% to 50% of active aluminum oxide and 5% to 10% of iron compound by weight. The catalyst overcomes the defects that the generation of the sulphatizing poisoning of a common alumina catalyst is easy because of the existence of trace amount of O2 and SO2, the specific surface area of a titanium dioxide catalyst is small, the mechanical strength is poor, the organic sulfur hydrolysis activity of an O2 disengagement guard catalyst is low, etc. The present invention has the advantages of large specific surface area, high mechanical strength, favorable O2 leakage poisoning resistance, and high O2 leakage disengagement activity, organic sulfur hydrolysis activity and Claus activity; therefore, the catalyst can be used by completely filled in bed and can also be used as the O2 disengagement guard catalyst by matching the common alumina catalyst.
Description
Technical field
The present invention relates to a kind of catalyst for recovering sulfur and preparation method thereof, particularly a kind of have a higher O that takes off
2Active and the higher H of active and higher tempreture organic sulphur hydrolysis
2S and SO
2The active multifunctional sulfur recovery catalyst of claus reaction and preparation method thereof.
Background technology
In the oil and natural gas course of processing, produce a large amount of H
2S gas, in order to protect environment and to reclaim elementary sulfur, industrial common employing claus process is handled and is contained H
2The sour gas of S, its reaction equation is as follows:
Wherein reaction (1) to reaction (4) is carried out in high temperature combustion furnace, except react (2), also carries out the hydrolysis reaction of organic sulfide at catalytic reaction zone (being lower than 538 ℃):
As a kind of well behaved catalyzer, all should have higher activity and stable to reaction (2), (5) and (6).Many researchs and industrial practice show, Al
2O
3Be a kind of well behaved catalyst for recovering sulfur, yet owing to be subjected to the restriction of operational condition, sulphating is poisoned and active decline easily.
Known Al
2O
3The sulphating origin cause of formation of catalyzer comes from three approach: (1) Al
2O
3With SO
3Direct reaction becomes Tai-Ace S 150; (2) SO
2And O
2At Al
2O
3Last catalyzed reaction generates Tai-Ace S 150 subsequently; (3) SO
2At Al
2O
3Surface irreversibleization chemisorption becomes similar vitriol structure.Further the micro-O that exists in the process gas process is also found under Crouse's atmospheric condition in further investigation
2Can destroy Al
2O
3Basic center-the have reduction center of electron donor feature on surface, i.e. the coordinate O fully of certain exposure
2-Ion " defective " position, thus catalyst activity reduction caused, and the hydrolysis reaction of organic sulfide is poisoned more responsive to the catalyst sulfuric acid salinization.In not having the Cross unit of vent gas treatment, the CS that high temperature combustion furnace generates
2Usually will account for about 20% of tail gas desulphurization amount with COS, if set up the low-temperature Claus tail-gas treatment unit, then organic sulfide more will account for more than 50% of tail gas total sulfur loss, therefore removes from " the leakage O in Crouse's high-temp combustion furnace gases
2" and weaken SO
2Irreversible chemical absorption at catalyst surface is the key that alleviates and avoid downstream claus catalyst sulphating to poison.
USP 4,192, and 857 a kind of the taking off that disclose French Societe Nationale Elf Aquitaine exploitation " are leaked O
2" guard catalyst.This catalyzer is carrier with the activated alumina, and the vitriol of dipping iron, nickel, cobalt, molybdenum and zinc is active ingredient, contains the O of 50～5000ppm in the handled gas
2, both can with Al
2O
3The supporting conduct of catalyzer is taken off and " is leaked O
2" the guard catalyst use, also can be used as claus catalyst and use separately.According to the sample data introduction that French Rhone-poulenc company provides, this catalyzer can place Al
2O
3Use on beds top, in order to " the leakage O in the removing process process gas
2", its reactivity mechanism is shown in reaction equation (7) and (8):
In following formula, the H in active constituent metallic salt and the process gas
2The S reaction generates sulfide, exists in process gas and " leaks O
2" time, sulfide is oxidized into vitriol, and vitriol is again by H
2S is reduced to sulfide, and circulation causes micro-O remaining in the claus process gas so repeatedly
2Can reduce to tens ppm, thereby protect following Al
2O
3Catalyzer makes it avoid or alleviate " leaking O
2" to active infringement, but this catalyzer belongs to the solid acid catalyst because of presenting acid essence, and not high for the tempreture organic sulphur hydrolysis reactive activity that on alkaline position, takes place, so under the full scale plant condition, generally only " leak O as taking off
2" guard catalyst used.
Application number is that 00111280.5 Chinese patent discloses a kind of O of taking off that has
2Protection and the active dual-function catalyst of higher claus reaction.This catalyzer is a carrier with the activated alumina, is active constituent with the iron containing compounds, is promotor with the Vanadium Pentoxide in FLAKES, and it takes off O
2Reactivity mechanism except that above-mentioned reaction equation (7) and (8) are described, because of load Vanadium Pentoxide in FLAKES also accelerated H
2S and O
2Between the catalyzed reaction (9) that takes place, take off O thereby make
2Ability is further widened by 5000PPm
To 20000PPm, and have very high claus reaction activity, but itself and USP 4,192,857 disclosed taking off " are leaked O
2" guard catalyst is the same; not high for the tempreture organic sulphur hydrolysis reactive behavior that on alkaline position, takes place; in addition if full bed loads the alumina base catalyst that this type of contains Vanadium Pentoxide in FLAKES; can make the bed hot(test)-spot temperature up to more than 330 ℃ in 100 ℃ of temperature rises that produce because of reaction heat under first reactor operating condition, and because of as reaction (10) the most effective catalytic activity component V
2O
5Existence and accelerated SO
2With O
2Between reaction (10), even produce the SO of ppm level
3The Al that also can cause the downstream
2O
3The catalyst sulfuric acid salinization is poisoned, and therefore takes all factors into consideration its Technological Economy industrial, generally still is seated in the top of the lower reactor bed of temperature in, as taking off O
2Protection and claus catalyst use.
TiO
2Surface chemical property and Al
2O
3Difference is because of its SO to absorption
2Easy desorption, thus be difficult for taking place sulphating, therefore can keep advantages of high catalytic activity, GB 2,122, and 597 disclose a kind of alkaline earth metal sulphate of using, and for example calcium sulfate is as the TiO of binding agent
2Extruded catalyst.According to the sample data introduction that French Rhone-Poulec company provides, this TiO
2Catalyzer is to CS
2Hydrolysis reaction and H with the COS organic sulfide
2S and SO
2Claus reaction than Al
2O
3Catalyzer has higher catalytic activity, and to " the leakage O in the technological process gas
2" poison insensitively, hydrolysis reaction is anti-" to leak O
2" ability is 2000ppm, claus reaction is then up to 10000ppm, but its specific surface area only less＞100m
2/ g, physical strength is only relatively poor＞80N/cm, and physical strength stability, promptly the physical strength under claus process hydro-thermal atmospheric condition is more unsatisfactory.Existing report, the TiO that after turning round on the full scale plant 14 months, has unloaded
2Extruded catalyst declines by a big margin through detect finding its physical strength, only is original about 1/3.
Chinese patent ZL95110393.8 discloses a kind of TiO
2Catalyst based, the chemical constitution that it is characterized in that catalyzer is TiO
2, CaO and CaSO
4, TiO wherein
2Be catalyzer, CaO is a promotor, CaSO
4Be binding agent.
In addition, application number is that 01114905.1 Chinese patent discloses a kind of TiO
2-Al
2O
3Catalyst based, it is characterized in that with TiO
2And Al
2O
3Be catalyzer, with Al
2O
3Precursor pseudo-boehmite aluminium hydroxide be binding agent raw material or CaSO
4Be binding agent, with Na
2O is the alkalimetal oxide of representative or is that the alkaline earth metal oxide of representative is a promotor with MgO, CaO, BaO.
Though above-mentioned two kinds of catalyzer have improved the physical strength of catalyzer or/and specific surface area, also improved the active and claus reaction activity of tempreture organic sulphur hydrolysis of catalyzer simultaneously, anti-" the leakage O of its hydrolysis reaction
2" indifferent, still rest on 2000PPm O
2Contents level, especially TiO
2-Al
2O
3Al in catalyst based
2O
3, because of load not has the O of taking off
2The iron content salt of function and still easily sulphating poison.This TiO in addition
2-Al
2O
3Na in catalyst based
2Alkalimetal oxides such as O as everyone knows under the high hydro-thermal atmospheric condition of claus process, are easy to run off and cause equipment and pipeline corrosions such as condenser, trap.
Summary of the invention
The purpose of this invention is to provide a kind of anti-" leakage O that both had
2" poisoning performance and take off and " leak O
2" protective capability, have active and active multifunctional sulfur recovery catalyst of Crouse of higher tempreture organic sulphur hydrolysis and preparation method thereof again, in order to overcome and to solve common Al
2O
3Catalyst tolerates " is leaked O
2" poisoning performance is poor, sulphating is poisoned and the Al of iron containing compounds easily
2O
3The active low and TiO of catalyst based tempreture organic sulphur hydrolysis
2Defective and problems such as the catalyzer physical strength is relatively poor.
Principal feature of the present invention is as active ingredient with titanium dioxide and activated alumina and iron containing compounds, wherein titanium dioxide and activated alumina can be used as the carrier of catalyzer of the present invention simultaneously again, in catalyst weight, the content of titanium dioxide is 40%～60%, the content of activated alumina is 35%～50%, with FeSO
4The content of the iron containing compounds of meter is 5%～10%.
The profile of catalyzer of the present invention is cylindrical, cloverleaf pattern or Herba Galii Bungei shape.The specific surface area of catalyzer is 150～300m
2/ g, crushing strength is 150～200N/cm.Support of the catalyst TiO
2-Al
2O
3Specific surface area be 150～260m
2/ g, crushing strength is 150～200N/cm.
The precursor of titanium dioxide is a kind of industrial metatitanic acid, and the specific surface area of titanium dioxide is 80～150m
2/ g is preferably 100～150m
2/ g; Precursor as the activated alumina of binding agent and carrier is a kind of industrial pseudo-boehmite aluminium hydroxide in addition, and the specific surface area of the activated alumina after the roasting is 260～350m
2/ g is preferably 300～350m
2/ g, ferruginous compound then are the vitriol of iron and/or the oxide compound of iron, and iron wherein both can be ferrous iron, also can be ferric irons, and for example iron containing compounds can be FeSO
4, Fe
2(SO
4)
3And/or Fe
2O
3
Preparation of catalysts method of the present invention can adopt conventional catalyzer method for making, the shaping carrier of making by metatitanic acid and pseudo-boehmite aluminium hydroxide with the solution impregnation of ferrous sulfate, or behind the direct mixing solutions and metatitanic acid dry powder and pseudo-boehmite aluminium hydroxide dry powder blend and moulding with ferrous sulfate and nitric acid, drying, roasting make catalyzer again.Maturing temperature is 400～600 ℃.
This catalyzer has overcome common aluminium oxide catalyst because of micro-O
2And SO
2Existence produce easily that sulphating is poisoned and the titanium deoxide catalyst specific surface area is less, physical strength is relatively poor, and takes off O
2Shortcomings such as guard catalyst tempreture organic sulphur hydrolysis activity is lower have that specific surface area is big, physical strength is high, anti-ly " leak O
2" poisoning performance is good and take off " leakage O
2" active, tempreture organic sulphur hydrolysis is active and the active equal advantage of higher of Crouse, therefore both full the bed filling use, also can O be taken off in conduct with common aluminium oxide catalyst is supporting
2Guard catalyst uses.
The specific surface area of catalyzer of the present invention low temperature N
2Flow method is measured, and physical strength is measured with ZQJ-II granule strength trier, generally gets the arithmetical av of 50 determination datas; Physical strength stability was boiled in distilled water 2 hours with catalyzer, and through 120 ℃ * 2h oven dry, the ability of catalyst tolerates hydration and hydrothermal treatment consists is investigated and compared to the physical strength of measuring its poach front and back.
Activity rating of catalyst little anti--carry out on the on-line chromatograph on-line unit; Test-reactor is that the stainless steel tube of Φ 14mm is made by internal diameter, and Reaktionsofen adopts Electric heating, approximate isothermal body of heater; Catalyst grain size is 20 orders～40 orders, loading amount 5ml, and the quartz sand of top filling same particle sizes and volume is in order to gas mixing preheating; Unstripped gas is through mixing the laggard reactor reaction of preheating, with the H in day island proper Tianjin GC-14B gas chromatograph on-line analysis entrance and exit gas
2S, SO
2, COS, CS
2And O
2Content adopts the GDX-301 carrier to analyze sulfide, 120 ℃ of column temperatures, and the 5A molecular sieve is analyzed O
2Content, 80 ℃ of column temperatures adopt thermal conductivity detector, use H
2Do carrier gas, flow velocity 28ml/min after the gas column.
With
Be the index reaction, investigate Crouse's activity of catalyst sample; Inlet gas consists of H
2S 2%, SO
21%, O
20.2% or 0.5%, H
2O 30%, and all the other are N
2, gas space velocity is 2500h
-1, temperature of reaction is 230 ℃, transformation efficiency is pressed following formula (9) and is calculated, wherein M
1And M
2Represent the H in reactor inlet and the exit gas respectively
2S and SO
2The volumetric concentration sum.
N
H2S+SO2＝(M
1-M
2)/M
1×100％ (11)
Calculate the O that takes off of catalyzer according to following formula (10)
2Rate, wherein N
1And N
2Represent O in reactor inlet and the exit gas respectively
2Volumetric concentration.
N
O2＝(N
1-N
2)/N
1×100％ (12)
With
Be the index reaction, investigate the tempreture organic sulphur hydrolysis activity of catalyst sample; Inlet gas consists of: CS
21%, SO
21%, O
20.2% or 0.5%, H
2O 30%, and all the other are N
2, gas space velocity is 2500h
-1, temperature of reaction is 330 ℃, percent hydrolysis is pressed following formula (11) and is calculated, wherein h
1And h
2Represent the SO in reactor inlet and the exit gas respectively
2Volumetric concentration.
N
SO2＝(h
1-h
2)/h
1×100％ (13)
Embodiment
Following examples will be carried out concrete description to the present invention, but the present invention is not limited to embodiment itself.
Embodiment 1
With 120 ℃ * 4h oven dry back and be crushed to 180 purpose industrial metatitanic acid dry powder 100g and industrial pseudo-boehmite aluminium hydroxide dry powder 100g and 6g sesbania powder and mix.3% metering elemental iron according to finished catalyst weight takes by weighing 24.3g FeSO
4.7H
2O and 6g HNO
3Be dissolved in the 70ml distilled water, use HNO
3The pH value of regulator solution joins in the above-mentioned powder and stirs after 4-5, after the twin screw banded extruder is mediated 0.5h, orifice plate extruded moulding with Φ 4.5mm, at room temperature place 12h and dry, dry and 400 ℃ * 4h roasting promptly gets catalyst sample A through 120 ℃ * 2h.The chemical constitution of its active ingredient is: TiO
254.2% (m/m), Al
2O
345.8% (m/m).
With FeSO
4The iron containing compounds 7.8% of metering records the specific surface area 218m of this sample
2/ g, crushing strength 152N/cm, physical strength 138N/cm behind the boiling test, activity the results are shown in Table 1.
Embodiment 2
To be crushed to 180 purpose industrial metatitanic acid dry powder 100g and industrial pseudo-boehmite aluminium hydroxide dry powder 100g and 6g sesbania powder mixing mixing after the 120 ℃ * 4h oven dry.Take by weighing the dense HNO of 6g
3Be dissolved in the 85ml distilled water, join in the above-mentioned powder and stir, squeeze the accent machine through twin screw and mediate 0.5h, with the orifice plate extruded moulding of Φ 4.5mm, at room temperature place 12h and dry, dry and 400 ℃ * 4h roasting promptly gets TiO through 120 ℃ * 2h
2-Al
2O
3Carrier, its chemical constitution is: TiO
254.2% (m/m), Al
2O
345.8% (m/m); Again according to 3% metering elemental iron of finished catalyst weight, take by weighing 24.3gFeSO subsequently
4.7H
2O is dissolved in the 25ml distilled water, uses HNO
3The regulator solution pH value is the above-mentioned TiO of 20 orders-40 order size with the granularity of 120 ℃ of oven dry between 4-5
2-Al
2O
3Carrier 158.4g immerses wherein, after stirring, at room temperature places 12h and dries, and dry and 400 ℃ * 4h roasting promptly gets catalyst sample B through 120 ℃ * 2h.Record the specific surface area 236m of this sample
2/ g, crushing strength 169N/cm, physical strength 153N/cm behind the boiling test, activity the results are shown in Table 1.
Embodiment 3
According to embodiment 2 conditions, prepare cloverleaf pattern and Herba Galii Bungei shape catalyst sample B respectively
1And B
2, recording its crushing strength and be respectively 178N/cm and 191N/cm, physical strength is respectively 159N/cm and 174N/cm behind the boiling test.
Comparative Examples 1
The sample TL that according to application number is disclosed Preparation of Catalyst in 01114905.1 the patent application is (in the weight content of catalyzer, TiO
2Be 52.6%, Al
2O
3Be 43.5%, CaO is 0.8%, burn to lose 5.9%), the contrast of its 12 hours activity rating results and catalyzer of the present invention sees Table 1, and the activity of data presentation catalyst A of the present invention and B is better than contrasting sample catalyzer TL significantly.
The specific activity of table 1 catalyst sample
| Catalyst sample | A | B | TL | |
| 0.2％(v/v) O 2Content | Crouse's transformation efficiency % | 80 | 80.5 | 77 |
| Take off O 2Rate % | 99 | 99.5 | 45 | |
| CS 2Percent hydrolysis % | 97 | 98 | 85 | |
Comparative Examples 2
Catalyst B of the present invention and a kind of trade names are the industrial Al of LS-811
2O
3Catalyzer L is (in the weight content of catalyzer, Al
2O
3Be 93.8%, Na
2O is 0.3%, burn to lose 5.9%) and number of patent application be the disclosed O that takes off in 00111280.5
2Guard catalyst F is (in the weight content of catalyzer, Al
2O
3Be 83.5%, iron containing compounds is with Fe
2O
3Count 6.7%, V
2O
5Be 0.8%, burn lose 4.9%) and the patent No. be disclosed TiO among the ZL95110393.8
2Catalyzer T is (in the weight content of catalyzer, TiO
2Be 86.5%, CaO is 0.7%, CaSO
4Be 10.2%, burn lose 2.6%) 12 hours active comparative evaluations the results are shown in Table 2.Data presentation, catalyst B of the present invention and comparative catalyst F take off O
2Active identical, and anti-" leakage O
2" poisoning performance, especially high O
2Crouse's activity and tempreture organic sulphur hydrolysis activity under the content condition then are better than L, F and T comparative catalyst significantly.
The activity contrast of table 2 catalyst sample
| Catalyst sample | B | L | F | T | |
| 0.2％(v/v) O 2Content | Crouse's transformation efficiency % takes off O 2Rate % CS 2Percent hydrolysis % | 80.5 99.5 98 | 75 45 76 | 79.5 99.5 54 | 81 67 98 |
| 0.5％(v/v) O 2Content | Crouse's transformation efficiency % takes off O 2Rate % CS 2Percent hydrolysis % | 79 99.5 98 | 51 32 66 | 76 99.5 45 | 80.5 63 80 |
Comparative Examples 3
Table 3 all loads industrial Al for beds
2O
3Catalyzer L is with the industrial Al of bed bottom filling 2/3rds volumes
2O
3Catalyzer L is under two kinds of situations of the catalyst B of the present invention of top filling 1/3rd volumes, at the high O of 5000ppm
2Active comparative evaluation result under the content condition, data presentation catalyzer of the present invention can be protected Al effectively
2O
3Catalyzer slows down it because of " leaking O
2" loss of activity that causes.
Table 3 catalyst B take off O
2Protection usefulness
| Time (h) | 2 | 4 | 6 | 8 | 10 | 12 | |
| 1/3B+2/3L | Crouse's transformation efficiency % CS 2Percent hydrolysis % | 79 83 | 77 81 | 75 80 | 74 79 | 74 78 | 74 78 |
| L | Crouse's transformation efficiency % CS 2Percent hydrolysis % | 56 76 | 54 72 | 53 69 | 52 66 | 51 66 | 51 66 |
Claims (8)
1, a kind of have an O of taking off
2With tempreture organic sulphur hydrolysis activity and the active multifunctional sulfur recovery catalyst of Crouse, it is characterized in that described catalyzer is an active ingredient with titanium dioxide, activated alumina and ferruginous compound, titanium dioxide and activated alumina while are as the carrier of catalyzer, wherein in catalyst weight, the content of titanium dioxide is 40%～60%, the content of activated alumina is 35%～50%, with FeSO
4The content of the iron containing compounds of meter is 5%～10%.
2,, it is characterized in that ferruginous compound is FeSO according to the catalyzer of claim 1
4, Fe
2(SO
4)
3And/or Fe
2O
3
3, according to the catalyzer of claim 1, the profile that it is characterized in that described catalyzer is cylindrical, cloverleaf pattern or Herba Galii Bungei shape.
4, according to the catalyzer of claim 1, the specific surface area that it is characterized in that catalyzer is 150～300m
2/ g, crushing strength is 150～200N/cm.
5,, it is characterized in that support of the catalyst TiO according to the catalyzer of claim 1
2-Al
2O
3Specific surface area be 150～260m
2/ g, crushing strength is 150～200N/cm.
6, the described Preparation of catalysts method of a kind of claim 1 is characterized in that industrial metatitanic acid dry powder and industrial pseudo-boehmite aluminium hydroxide dry powder are mixed FeSO with field mountain valley with clumps of trees and bamboo powder
47H
2O and HNO
3Being dissolved in the distilled water, is 4～5 with the pH value of nitric acid regulator solution, joins in the above-mentioned powder and stirs, moulding, drying, roasting.
7, the described Preparation of catalysts method of a kind of claim 1, it is characterized in that industrial metatitanic acid dry powder and industrial pseudo-boehmite aluminium hydroxide dry powder are mixed with field mountain valley with clumps of trees and bamboo powder, nitric acid dissolve in distilled water, is joined in the above-mentioned powder and stirs, extruded moulding, dry, roasting gets TiO
2-Al
2O
3Carrier is then with FeSO
47H
2O is dissolved in the distilled water, is 4～5 with nitric acid regulator solution pH value, with TiO2-Al
2O
3Carrier immerses in this solution, and drying, roasting obtain catalyzer.
8,, it is characterized in that described maturing temperature is 400 ℃ according to claim 6 or 7 described preparation methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02151549 CN1210201C (en) | 2002-12-31 | 2002-12-31 | Multifunction sulfur recovery catalyst and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02151549 CN1210201C (en) | 2002-12-31 | 2002-12-31 | Multifunction sulfur recovery catalyst and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1511781A CN1511781A (en) | 2004-07-14 |
| CN1210201C true CN1210201C (en) | 2005-07-13 |
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ID=34234428
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02151549 Expired - Lifetime CN1210201C (en) | 2002-12-31 | 2002-12-31 | Multifunction sulfur recovery catalyst and its preparing method |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102335617B (en) * | 2010-07-14 | 2013-10-16 | 中国石油天然气股份有限公司 | Sulfur recovery organo-sulfur hydrolysis method |
| CN102380311B (en) * | 2010-09-01 | 2013-12-25 | 中国石油化工股份有限公司 | Gasoline adsorption desulfuration regeneration smoke treatment method and tail gas hydrogenation catalyst preparation method thereof |
| CN102951614B (en) * | 2011-08-31 | 2014-12-10 | 中国石油化工股份有限公司 | Filling method of sulfur recovery catalyst |
| CN102463031A (en) * | 2011-10-20 | 2012-05-23 | 常州亚环环保科技有限公司 | Fuel coal waste gas desulphurization method |
| CN104248969B (en) * | 2013-06-25 | 2016-08-31 | 中国石油化工股份有限公司 | The supporting organic sulfur hydrolyst of natural gas large-scale sulfur recovery device and preparation method |
| CN104475104B (en) * | 2014-11-05 | 2018-03-23 | 杨楠 | Selective catalytic oxidation vulcanizes the technique that hydrogen catalyst, tail gas catalyst to burned and treating technology hydrogen sulfide are sulphur |
| TWI688427B (en) * | 2015-06-17 | 2020-03-21 | 大陸商中國石油化工科技開發有限公司 | Alkylated waste acid treatment method and device for implementing the method |
| CN108097257A (en) * | 2017-12-28 | 2018-06-01 | 江汉大学 | A kind of preparation method of low temperature multifunctional sulfur recovery catalyst |
| CN108525672B (en) * | 2018-04-26 | 2020-08-25 | 江苏天东新材料科技有限公司 | Multifunctional composite sulfur recovery catalyst and preparation method thereof |
| CN109126847B (en) * | 2018-08-04 | 2021-10-15 | 山东迅达化工集团有限公司 | Preparation method of iron oxide and titanium dioxide composite sulfur recovery catalyst |
| CN109126831B (en) * | 2018-08-04 | 2021-07-23 | 山东迅达化工集团有限公司 | Iron oxide and titanium dioxide composite sulfur recovery catalyst and preparation method thereof |
| CN111068746B (en) * | 2018-10-22 | 2023-12-05 | 中国石油化工股份有限公司 | Multifunctional sulfur recovery catalyst and preparation method thereof |
| CN113941330A (en) * | 2020-07-15 | 2022-01-18 | 中国石油天然气股份有限公司 | Sulfur recovery catalyst and preparation method thereof |
| CN113731391A (en) * | 2021-08-27 | 2021-12-03 | 江苏朗润环保科技有限公司 | High-antioxidant low-temperature organic sulfur hydrolysis catalyst and preparation method thereof |
| CN113716529B (en) * | 2021-09-15 | 2023-08-18 | 昆明理工大学 | Method for recycling sulfur by low-temperature photocatalytic Claus and photocatalyst |
| CN113731457A (en) * | 2021-09-28 | 2021-12-03 | 四川天人能源科技有限公司 | Organic sulfur hydrolysis catalyst and preparation method thereof |
-
2002
- 2002-12-31 CN CN 02151549 patent/CN1210201C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1511781A (en) | 2004-07-14 |
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