CN101648107A - Catalytic oxidation adsorption desulfurizer and preparation method thereof - Google Patents
Catalytic oxidation adsorption desulfurizer and preparation method thereof Download PDFInfo
- Publication number
- CN101648107A CN101648107A CN200910018802A CN200910018802A CN101648107A CN 101648107 A CN101648107 A CN 101648107A CN 200910018802 A CN200910018802 A CN 200910018802A CN 200910018802 A CN200910018802 A CN 200910018802A CN 101648107 A CN101648107 A CN 101648107A
- Authority
- CN
- China
- Prior art keywords
- desulfurizer
- catalytic oxidation
- carrier
- adsorption
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a catalytic oxidation adsorption desulfurizer and a preparation method thereof, belonging to the technical field of sulfur recovery. The adsorption desulfurizer is used to remove H2S and SO2 separately or at the same time and is characterized in that the desulfurizer is prepared from active component and carrier through extruding, kneading and soaking methods, wherein theactive component of the desulfurizer is the oxides of Fe, Ti and V or the salts thereof and the carrier is one or more of aluminum oxide, calcium oxide, silicon oxide and activated carbon. The desulfurizer of the invention combines the catalytic oxidation technology and adsorption desulfurization technology, the desulfurization capacity is more than 50%, the outlet of the desulfurizing tower doesnot contain H2O, and the content of SO2 is greatly less than 960mg/m<3> so as to meet the emission standard of national GB16297-1996. the desulfurizer which is after saturation adsorption is rich in more than 50% of sulfur element and is sent to a production facility of sulphuric acid to prepare concentrated sulphuric acid and recycled metals, thus having no environmental pollution problem.
Description
Technical field
The invention belongs to the sulphur recovery technical field, be specifically related to a kind of catalytic oxidation adsorption desulfurizer and method for making thereof.Catalyst of the present invention is mainly used in claus plant.
Background technology
Sulfide in crude oil or the coal is converted into H in process
2S, and H
2S is an extremely toxic substance, and human body and environment are had great toxic action, must carry out harmless treatment, and the only technology of corresponding employing is exactly recovery technology of sulfur.
The sour gas of oil plant is mainly derived from devices such as catalysis drying gas desulfurization, the desulfurization of coking dry gas, sewage gas stripping tower gas, hydro-refining unit desulfurization.The main work flow of the sour gas of oil plant is:
Sulphur → PETROLEUM PROCESSING in the crude oil (normal decompression) → gasoline kerosene diesel oil → hydrofinishing → H2S → sulphur recovery → sulphur
Be in the chemical plant of raw material with the coal, the work flow of sour gas mainly is coal → Coal Chemical Industry → desulfurization → H2S → sulphur recovery → sulphur
Industry generally adopts the improvement claus process to handle the sour gas that contains H2S of generations such as oil plant, chemical plant, and Recovered sulphur is also protected environment.Its basic principle is as follows:
Because the existence of hydro carbons in the sour gas under the hot conditions of combustion furnace, inevitably has a spot of organic sulfur compound CS2 and COS and generates, and therefore must be removed by the tempreture organic sulphur hydrolysis reaction at catalytic reactor:
The basic technology type of claus reaction has three kinds: direct current method, shunting and sulfur cycle method: direct current method be sour gas all by combustion furnace and waste heat boiler, in combustion furnace, generate a large amount of sulphur; Shunting is to have only 1/3rd sour gas to burn into SO by combustion furnace
2, before converter, being mixed into converter with remainder, the sulphur that generates in the stove is seldom; The sulfur cycle method be sour gas by combustion furnace, and the sulphur generation SO that in stove, burn
2And before first converter with contain H
2The sour gas mixing of S is reacted.
The world has proposed more and more higher requirement to the demand of clean fuel and from the pressure of the environmental regulation of increasingly stringent to the total sulfur recovery of sulfur recovery facility, on the one hand, because the H of the increase by-product of oil plant working ability
2S is more and more, and the device discharge capacity that government department requires is more and more lower, improves the total sulfur recovery of device when this just requires to increase the sulfur recovery facility disposal ability to satisfy double requirements.
National environmental protection portion has formulated strict more discharge standard of air pollutants (GB16297-1996) and has stipulated since mandatory enforcement on January 1 in 1997.GB16297 is to SO
2Strict regulations have been made in discharging, new pollution sources SO
2≤ 960mg/m
3(336ppmv), existing pollution sources SO
2≤ 1200mg/m
3(420ppmv), and to the sulfide emission amount also made regulation.By this standard, require oil plant and chemical plant sulphur recovery total sulfur recovery will reach 99.7～99.9%.Claus plant has only the reduction adopted to absorb the requirement that tail gas treatment process just can reach above-mentioned environmental protection standard.
Traditional claus process mainly comprises equipment compositions such as sour gas combustion furnace, waste heat boiler, two or three catalytic reactors and condenser, trap.The total sulfur conversion ratio can reach 94～97% behind general second reactor.The catalyst of corresponding employing mainly contains activated alumina catalyst, auxiliary agent type aluminium oxide catalyst and titanium deoxide catalyst etc.
In order to satisfy higher environmental requirement, must carry out further purified treatment to the tail gas that Cross unit is discharged.The technology that past adopts mainly contains low-temperature Claus technology, super claus process, tail gas hydrogenation reducing process etc.But it is inaccurate to have only the tail gas hydrogenation reducing process can satisfy the strictest environmental protection.Total sulfur recovery can reach more than 99.8%.The cardinal principle of tail gas hydrogenation reducing process is to adopt hydrogen with the non-H in the sulfur recovery facility tail gas
2The sulfur-containing compound of S such as SO
2/ COS/CS
2/ S etc. all are hydrogenated to H
2S passes through methyl diethanolamine (MDEA) then with H
2S absorbs and carries out further sulphur recovery by the sour gas combustion furnace that turns back to sulfur recovery facility after the Steam Heating desorb.The tail gas of discharging from the top, absorption tower only contains the sulfide of trace, by entering atmosphere behind the incinerator high temperature incineration.SO in the flue gas
2Discharge capacity less than 960mg/m
3, satisfy the emission request of GB16297-1996.
That the tail gas hydrogenation reduction reactor adopts is common CoO/MoO/Al
2O
3Hydrogenation catalyst, inlet temperature are 280～300 ℃, and reactor batch temperature is generally 300～330 ℃.
The disadvantage of this technology is that one-time investment is big, and the investment of tail gas hydrogenation treating apparatus is 1.5 times of front sulfur recovery facility investment, and owing to need operations such as hydrogenation, amine absorption, amine lyolysis suction, needs to consume H
2, MDEA amine liquid and regeneration usefulness steam, the operating cost height of device, for 50,000 tons/year sulfur recovery facility of a cover, annual operating cost is about 25,000,000 yuan.And tail gas hydrogenation device itself does not produce any economic benefit.
Summary of the invention
The present invention has introduced a kind of catalytic oxidation newly developed and has absorbed desulfurizing agent, can place behind the sulfur recovery facility remnants with sulfur recovery facility tail gas to vulcanize hydrogen catalysis and be oxidized to elementary sulfur and absorb, with SO remaining in the tail gas
2Mode by chemisorbed is adsorbed on the desulfurizing agent, reaches the purpose that is substantially free of sulfide in the tail gas.Can be used as the tail gas absorption treating device of existing or newly-built sulfur recovery facility, absorb the hydrogenation on tail gas of sulphur treating apparatus with respect to traditional reduction, technical process is simple, easy to operate, can save great amount of investment and reduce floor space, can save simultaneously the steam of a large amount of hydrogen, methyl diethanolamine desulfurizing agent and regeneration usefulness, the save operation expense.
The present invention has introduced a kind of catalytic oxidation desulfurization agent that is applied to the reduction-oxidation absorption techniques, and its major function is the H with trace remaining in the sulfur recovery facility tail gas
2S and SO
2Absorption also is fixed on the desulfurizing agent, reaches the environmental protection purpose of 0 discharging.
Catalyst of the present invention is to be prepared from by traditional dipping or the mixed method of pinching, at first with the predecessor wiring solution-forming of active constituent, then carriers such as aluminium oxide, silica, calcium oxide, active carbon are dipped in wherein to dipping evenly, perhaps adopt and carriers such as predecessor and aluminium oxide, silica, calcium oxide, active carbon are mixed the way of pinching prepare.For guaranteeing dipping evenly, solution is general excessive 20～30% in the preparation process, and the dipping surplus liquid in back fully inclines to, and carries out the drying and roasting catalyst that gets product after then the catalyst sample room temperature being dried.
Wherein the carrier of Cai Yonging mainly contains aluminium oxide, silica, calcium oxide and active carbon and adds suitable binding agent and form.
The specific area of the active oxidation alumina support that adopts is 100～600m
2/ g is preferably 320～400m
2/ g, pore volume is 0.30～1.2ml/g, is preferably 0.4～1.2ml/g.The activated alumina that the crystal formation of activated alumina is preferably γ or p type or meets other suitable crystal formations that These parameters requires also can use.Average crushing strength is in 80～300 newton/best.
Be suitable for the starting material that is used to prepare alumina support of the present invention false boehmite, boehmite, Bayer process gibbsite or a gibbsite or β gibbsite and other forms of aluminium hydroxide are arranged.When to pass through NaAlO
2When fast the false boehmite that obtains of neutralization is as starting material with acid aluminium salt, need remove residual sodium oxide molybdena by washing repeatedly.Need to add the SiO in the sodalite increase aluminium oxide simultaneously
2Content helps to improve catalyst heat endurance at high temperature.Under 400～500 ℃ of conditions, keep at last and aluminium oxide was activated in 2～4 hours.
The specific area of the calcium oxide carrier that adopts is 100～300m
2/ g is preferably in 250～300m
2/ g, pore volume is at 0.2～0.5ml/g, the mechanical strength that is preferably in the calcium oxide carrier that 0.3～0.4ml/g. adopts can be selected cylindrical bar shaped, clover or bunge bedstraw herb or six leaf swath shapes in 100～200 newton/best, also can be spherical or cylindrical.
The active carbon that the present invention adopts can use the wood activated charcoal of feedstock production such as utilizing walnut shell or coconut husk, and also can adopt with pitch is the oily active carbon of feedstock production, and can also adopt with the coal is the coal mass active carbon of feedstock production.Require the technical indicator of the active carbon of employing to reach following requirement: specific area is greater than 800m
2/ g, iodine sorption value be greater than 900mg/g, pH value 8～10, bulk density 0.45～0.55g/L.
The predecessor of the silica support that the present invention adopts can be a sodium metasilicate, also can adopt other alumino-silicates, as long as can be converted into SiO after the roasting
2Material all can use.Also can directly adopt the silica product of spherical or other shapes of typing, the general SiO that requires employing
2Specific area 100～400m
2/ g, average crushing strength be 80～300 newton/.
The present invention has mainly introduced a kind of absorption tail gas of sulphur etc. and has contained micro-H
2S and SO
2The catalytic oxidation of sour gas absorb desulphurization catalyst, method provided by the invention can produce that a kind of what have bigger serface, large pore volume and have good mechanical strength, wear hardness is the composite oxide carrier of raw material with calcium oxide, aluminium oxide, silica or active carbon etc., every physical and chemical performance index of carrier can simply be controlled and change, thus by adding FeO/Fe
2O
3/ Fe
2O
3/ TiO
2/ V
2O
5The catalyst desulfurizing of isoreactivity component preparation is active high, and Sulfur capacity is big, and long service life can satisfy the instructions for use of sulfur recovery facility, reaches environmental emission standard.
The catalytic oxidation that the present invention introduces absorbs the desulphurization catalyst carrier mainly by CaO or Al
2O
3Or SiO
2Perhaps active carbon or wherein said two devices or many persons' mixture form.And add the surface acid alkalescence that one or more alkali metal or alkaline earth oxide are regulated carrier, add in IB, IIB in the periodic table of elements, IIIB, VB, VIB, VIIB, VIII, the VA family element one or more simultaneously and increase the activity stability of carrier.
The catalytic oxidation that the present invention introduces and uses absorbs the desulphurization catalyst carrier can add corresponding assistant formation additive by technology moulding such as traditional extrusion, spin, compressing tablets in the forming process.Carrier that obtains and catalyst can make different shapes such as various bar shapeds, sphere, column, sheet type.The granularity of ball type carrier and catalyst is 2～10mm, and the granularity of bar shaped carrier and catalyst is φ (1-6) * (1-30) mm.
The active constituent that the catalytic oxidation of introduction of the present invention absorbs desulphurization catalyst mainly is FeO/Fe
2O
3/ Fe
2O
3/ TiO
2/ V
2O
5One or more, add decentralization that in IB, IIB in the periodic table of elements, IIIB, VB, VIB, VIIB, VIII, the VA family element one or more increase activity of such catalysts stability and improve active constituent simultaneously.
The catalytic oxidation of introduction of the present invention absorbs desulphurization catalyst can adopt traditional dip loading mode, need to add complexing agents such as ammoniacal liquor, ethylenediamine, ammonium citrate, EDTA in the dipping process, make the preceding active constituent of dipping form complex compound, increase the dispersion of nano-particles degree and the uniformity on the catalyst.
Catalyst of the present invention also can adopt traditional kneading and compacting mode, will contain CaO/SiO
2/ Al
2O
3/ TiO
2Perhaps one or more of the predecessor of active carbon and contain FeO/Fe
2O
3/ Fe
2O
3/ TiO
2/ V
2O
5One or more and the periodic table of elements of predecessor in one or more kneading and compactings simultaneously of predecessor in IB, IIB, IIIB, VB, VIB, VIIB, VIII, the VA family element.
Catalyst after the moulding must at room temperature be placed 0～48 hour, also can place under steam ambient 0～48 hour.Dried 0～24 hour under 100～150 ℃ of conditions then, roasting obtained finished catalyst in 4～8 hours under 100～600 ℃ of conditions.
The specific area of finished product desulphurization catalyst is 100～1000m
2/ g, pore volume are that the average crushing strength of 0.2～0.8ml/g. is 100～300N/.
Adopt catalytic oxidation of the present invention to absorb desulfur technology, can reach higher sulphur recovery efficiency, satisfy stricter environmental requirement.Catalytic oxidation of the present invention absorb desulfurizing agent reach absorption saturated after, can send to sulfuric acid plant as the raw material of making the concentrated sulfuric acid, can satisfy environmental protection and economic ambilateral requirement.
Desulfurizing agent of the present invention adopts fixed bed catalytic oxidation adsorption desulfurize technology, and wherein the ADSORPTION IN A FIXED BED desulfur technology adopts double tower parallel way, blocked operation.The Sulfur capacity of desulfurizing agent of the present invention can reach more than 50%, and the tail gas after the desulfurization can reach GB16297-1996 country emission request fully.And can reach any emission request according to user's requirement, until reaching the zero-emission of outlet sulfide.
The H that only contains trace in the tail gas that sulfur recovery facility is sent
2S and SO
2, entering the catalytic oxidation adsorptive reactor, filling catalytic oxidation adsoption catalyst of the present invention in the reactor can be with the H of remnants
2S and SO
2Adsorbing and removing reaches complete purification effects.Wherein H2S passes through H
2S+O
2=S+H
2The catalytic reaction of O is removed, and the elementary sulfur of generation is deposited on the catalyst, and SO2 is desulfurized agent absorption by metallizing thing generation sulphite to be removed.The mechanism of adsorption desulfurizing agent is as follows:
MO+H
2S＝MS+H
2O??(1)
2MS+O
2＝2S+2MO??(2)
MO+SO
2＝MSO
3(3)
M in above-mentioned reaction (1)～(3) represents one or more different elements, can be major element, also can subgroup element.This sentences+and the divalent element is described the present invention as embodiment, but desulfurizing agent of the present invention can adopt the satisfactory element of any valence state as raw material, only otherwise the desulfurized effect that influences desulfurizing agent can use.Catalytic oxidation absorbs desulfurization reactor and adopts the double tower parallel operation, operation at normal temperatures, and operating temperature is lower than 50 ℃, does not also influence desulfurized effect but be higher than 50 ℃ of uses.Desulfurizing agent of the present invention adopts the catalytic oxidation technology to combine with the adsorption desulfurize technology, and desulfurization capacity is greater than 50%, and the desulfurizing tower outlet does not contain H
2S, SO
2Content is significantly smaller than 960mg/m
3, satisfy the emission request of national GB16297-1996.The desulfurizing agent that adsorbs after saturated is rich in 50% above elementary sulfur, delivers to sulfuric acid production plant and makes the concentrated sulfuric acid and reclaim metal, does not have problem of environmental pollution.
The following examples are done one to the present invention and are briefly described.But the present invention is not limited to embodiment itself.
Embodiment 1
Get industrial ferrous sulfate FeSO
47H
2O 2780g is dissolved in the 5L deionized water, and the ammoniacal liquor that adds 2800ml25% in whipping process reacts, treat that precipitation fully after, the supernatant liquor that inclines, with deionized water repeatedly washing precipitation to using 1%BaCl
2Solution detects less than no SO
4 2-Till.Precipitation is filtered, dry, add alumina cement 200g, carboxymethyl cellulose 20g, NHD 15g mediated 30 minutes in kneader, on banded extruder, be 4mm orifice plate extrusion by diameter, dry, in 120 ℃ of baking ovens dry 12 hours, the specific area that 300 ℃ of roastings obtained desulfurizing agent sample 1. samples 1 in 6 hours in roaster was 145m
2/ g, average crushing strength is that 135 newton/cm. bulk density is 0.83g/ml.
Embodiment 2
Get industrial ferrous sulfate FeSO
47H
2O 2780g is dissolved in the 5L deionized water, and the NaOH solution that adds 8000g 10% in whipping process reacts, treat that precipitation fully after, remove supernatant liquor, with deionized water repeatedly washing precipitation to using 1%BaCl
2Solution detects less than no SO
4 2-Till.Precipitation is filtered, dry, add active oxidation aluminium powder 150g, lime powder 80g, sesbania powder 50g, polyethylene glycol 25g, mediating in kneader 30 minutes, is 4mm orifice plate extrusion by diameter on banded extruder, dries, drying is 12 hours in 120 ℃ of baking ovens, and 300 ℃ of roastings obtained desulfurizing agent sample 2 in 6 hours in roaster.The specification requirement of used active oxidation aluminium powder is as follows in the present embodiment: specific area＞500m
2/ g, bulk density＜0.4g/ml, pore volume＞1.2ml/g.The specification requirement of used lime powder is as follows: specific area＞150m
2/ g, bulk density＜0.5g/ml, pore volume＞0.5ml/g, the granularity sample is less than 320 orders.The specific area of gained catalyst sample 2 is 175m2/g, and average crushing strength is that 128 newton/cm. bulk density is 0.78g/ml.
Embodiment 3
Get 404g ferric nitrate Fe (NO
3)
39H
2O is dissolved in the 1000ml deionized water, add tetrasodium ethylenediamine tetraacetate 15g, being stirred well to fully, dissolving is clear solution, cut-off is directly put into the roller forming machine for the cocoanut active charcoal 1000g of 4mm, in rotary course with above-mentioned spray solution in active carbon till blot fully, spray 10% ammonia spirit 500ml then, room temperature was dried 12 hours, drying is 12 hours in 150 ℃ of baking ovens, at N
2The following 350 ℃ of roastings of protective condition 5 hours obtain desulfurizing agent sample 3.The specification requirement of used cocoanut active charcoal is as follows: outward appearance diameter 4mm bar shaped, and iodine sorption value is greater than 1000mg/g, and intensity is greater than 95%, and specific area is greater than 1050m
2/ g, the specific area of bulk density 0.45～0.55g/ml. gained desulfurizing agent sample 3 is 780m
2/ g.
Embodiment 4
Get industrial ferrous sulfate FeSO
47H
2O 2780g is dissolved in the 5L deionized water, gets the 1000g coal mass active carbon and impregnated in wherein, in continuous whipping process, adds 10%KOH solution 1140g, leaves standstill and places after 1 hour, outwells supernatant liquor, adds the washing of 5L deionized water repeatedly to using 1%BaCl
2Solution detects less than no SO
4 2-Till.Room temperature was dried 24 hours, and the dry technical indicator that obtained desulfurizing agent sample 4. used coal mass active carbons in 12 hours is as follows in 150 ℃ of baking ovens: outward appearance diameter 3mm bar shaped, iodine sorption value is greater than 1100mg/g.The technical indicator of gained desulfurizing agent sample 4 is as follows: specific area 710m2/g, bulk density 0.51g/ml.
Embodiment 5
Get 404g ferric nitrate Fe (NO
3)
39H
2O is dissolved in the 1000ml deionized water, add citric acid 55g, be stirred well to fully dissolving and be clear solution, get granularity and put into above-mentioned solution, add carboxymethyl cellulose 15g less than 350 purposes oil active carbon 1000g, atoleine 5 grams, mediating in kneader 1 hour, is the orifice plate extruded moulding of 3mm by diameter in banded extruder, and room temperature was dried 24 hours, drying is 12 hours in 150 ℃ of baking ovens, at N
2The following 450 ℃ of roastings of protective condition 5 hours, the specification requirement that obtains desulfurizing agent sample 5. used oil activated carbons is as follows: iodine sorption value is greater than 1000mg/g, and intensity is greater than 95%, and specific area is greater than 1050m
2/ g, the specific area of bulk density 0.45～0.55g/ml. gained desulfurizing agent sample 5 is 750m
2/ g, average crushing strength is 155 newton/cm.
Embodiment 6
Get industrial aluminium hydroxide powder 1000g, industrial metatitanic acid powder 1000g, cocoanut active charcoal 1000g, aluminous cement 1000g, sesbania powder 200g, polyethylene glycol 50g, oxalic acid 50g mixes in mixer, adds industrial ferrous sulfate FeSO then
47H
2O 2780g is dissolved in gained solution in the 3L deionized water, in kneader, mediated 2 hours, by 3mm orifice plate extruded moulding on banded extruder, room temperature was dried 24 hours, and the technical indicator that 150 ℃ of dryings obtained desulfurizing agent sample 6. used industrial metatitanic acids in 5 hours is as follows: specific area is greater than 300m
2/ g, granularity is greater than 320 orders, and pore volume is greater than 0.3ml/g.The technical indicator of gained desulfurizing agent sample 6 is as follows: specific area 325m
2/ g, average crushing strength 124 newton/cm, pore volume 0.55ml/g.
Embodiment 7
Get industrial ferrous sulfate FeSO
47H
2O 2780g is dissolved in the 5L deionized water, and the silica bead 10kg of dipping diameter 4mm was dried 24 hours for 120 ℃, continued this carrier impregnation in 117g ammonium metavanadate NH
4VO
3Be dissolved in the ammoniacal liquor gained solution of 5L25%, dipping fully after, room temperature is dried, 150 ℃ of dryings 24 hours, the specific area that 420 ℃ of roastings obtained desulfurizing agent sample 7. samples 7 in 6 hours is 250m
2/ g, average crushing strength 128 newton/cm, pore volume 0.50ml/g.
Embodiment 8
Above-mentioned desulfurizing agent sample is crushed to 20～40 order particles, getting the 20ml internal diameter of packing into is in the stainless steel reactor of 20mm, the desulfurizing agent upper and lower is loaded 5ml20～40 purpose quartz sands respectively and is made diluent and filler, reaches the uniform purpose of air-flow mixed distribution.Adopt following condition to measure the desulphurizing ability of desulfurizing agent (be called for short Sulfur capacity, just measure the weight that the 100g desulfurizing agent can adsorb sulfide) in sulphur.Unstripped gas is composed as follows: H
2S 0.5%, SO
20.3%, O
20.3%, all the other are N
2. assaying reaction device entrance and exit sulfide content equates to be end to exporting sulfide content and inlet sulfide content.Adopt the recruitment of the sulfur content on the microcoulomb sulphur analysis-e/or determining catalyst to be the saturated Sulfur capacity of desulfurizing agent sample then.The Sulfur capacity measurement result of desulfurizing agent sample such as following table 1 in the foregoing description, comparative catalyst wherein derives from a kind of desulfurizing agent of industrial use.
The saturated Sulfur capacity of the different desulfurizing agent samples of table 1.
| The desulfurizing agent sample | Sample 1 | Sample 2 | Sample 3 | Sample 4 | Sample 5 | Sample 6 | Sample 7 | Sample 8 | Comparative Examples |
| Saturated Sulfur capacity (g/100g) | ??49 | ??41 | ??55 | ??53 | ??48 | ??51 | ??55 | ??47 | ??29 |
Claims (3)
1. a catalytic oxidation adsorption desulfurizer is used for the while or removes H separately
2S and SO
2, it is characterized in that, described desulfurizing agent be adopt extrusion, mix pinch, infusion process gets desulfurizer active component preparation and carrier;
Desulfurizer active component is oxide or the salt of Fe, Ti, V;
Carrier is a kind of or any several mixture in aluminium oxide, calcium oxide, silica and the active carbon.
2. catalytic oxidation adsorption desulfurizer according to claim 1 is characterized in that, described catalyst activity component is FeO, Fe
2O
3, Fe
2O
3, TiO
2, V
2O
5In a kind of or two kinds and above mixture.
3. catalytic oxidation adsorption desulfurizer according to claim 1 is characterized in that,
On affiliated carrier, add the surface acid alkalescence that one or more alkali metal or alkaline earth oxide are regulated carrier; Add one or more in IB, IIB, IIIB, VB, VIB, VIIB, VIII, the VA family element in the periodic table of elements, to increase activity of such catalysts stability and to improve the decentralization of active constituent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910018802A CN101648107A (en) | 2009-09-11 | 2009-09-11 | Catalytic oxidation adsorption desulfurizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910018802A CN101648107A (en) | 2009-09-11 | 2009-09-11 | Catalytic oxidation adsorption desulfurizer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101648107A true CN101648107A (en) | 2010-02-17 |
Family
ID=41670500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910018802A Pending CN101648107A (en) | 2009-09-11 | 2009-09-11 | Catalytic oxidation adsorption desulfurizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101648107A (en) |
Cited By (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407102A (en) * | 2011-10-08 | 2012-04-11 | 中国科学院山西煤炭化学研究所 | V205/AC desulfurization catalyst, preparation method and application |
| CN102423711A (en) * | 2011-10-08 | 2012-04-25 | 中国科学院山西煤炭化学研究所 | Catalyst for removing SO2 from flue gas through dry process, its preparation method and application |
| CN104307360A (en) * | 2014-10-28 | 2015-01-28 | 南京大学（苏州）高新技术研究院 | Gas-phase desulfurization oxidant and application thereof as well as method for removing hydrogen sulfide |
| CN104548893A (en) * | 2014-12-26 | 2015-04-29 | 中国科学院广州能源研究所 | Low-temperature composite dry desulfurization material and preparation method thereof |
| CN104785265A (en) * | 2015-04-13 | 2015-07-22 | 长春东狮科贸实业有限公司 | Catalytic oxidation desulfurization catalyst, gas desulfurization treatment system and gas desulfurization treatment method |
| CN105272831A (en) * | 2014-06-06 | 2016-01-27 | 中国石油化工股份有限公司 | Method for deep removal of sulfides from methyl tert-butyl ether |
| CN105293444A (en) * | 2015-11-18 | 2016-02-03 | 山东迅达化工集团有限公司 | Low sulfur emission sulphur recovery process |
| CN105294405A (en) * | 2014-06-06 | 2016-02-03 | 中国石油化工股份有限公司 | Method for removing sulfides in methyl tert-butyl ether by hydrolysis, rectification and adsorption |
| CN105779076A (en) * | 2016-04-19 | 2016-07-20 | 哈尔滨工业大学 | Efficient fire coal desulfurizer and preparing method thereof |
| CN106215847A (en) * | 2016-08-15 | 2016-12-14 | 湖北华邦化学有限公司 | A kind of ferric oxide desulfurizer preparation method |
| CN106391135A (en) * | 2016-09-27 | 2017-02-15 | 长春东狮科贸实业有限公司 | Special catalyst for removing hydrogen sulfide through selective catalytic oxidation and preparation method for special catalyst |
| CN107441931A (en) * | 2017-09-30 | 2017-12-08 | 中晶蓝实业有限公司 | Desulfurizing agent and its preparation method and application |
| CN107469612A (en) * | 2017-09-30 | 2017-12-15 | 中晶蓝实业有限公司 | The method that fume treatment is carried out using fluidized-bed reactor |
| CN107469831A (en) * | 2017-09-30 | 2017-12-15 | 中晶蓝实业有限公司 | Dry-desulphurizer and its production method and application |
| CN107500579A (en) * | 2017-09-30 | 2017-12-22 | 中晶蓝实业有限公司 | The production method of fibre cement product based on red mud desulphurization denitration |
| CN107497285A (en) * | 2017-09-30 | 2017-12-22 | 中晶蓝实业有限公司 | The method that flue gas desulfurization and denitrification is carried out using fluidized-bed reactor |
| CN107497295A (en) * | 2017-09-30 | 2017-12-22 | 中晶蓝实业有限公司 | The method of dry flue gas desulphurization denitration |
| CN107500578A (en) * | 2017-09-30 | 2017-12-22 | 中晶蓝实业有限公司 | The production method of binder materials based on red mud desulphurization denitration |
| CN107596908A (en) * | 2017-09-30 | 2018-01-19 | 中晶蓝实业有限公司 | The method that fume treatment is carried out using fixed bed reactors |
| CN107596885A (en) * | 2017-09-30 | 2018-01-19 | 中晶蓝实业有限公司 | The method of dry flue gas desulphurization |
| CN107640954A (en) * | 2017-09-30 | 2018-01-30 | 中晶蓝实业有限公司 | The production method of foaming thermal-insulating based on red mud desulphurization denitration |
| CN107684915A (en) * | 2017-09-30 | 2018-02-13 | 中晶蓝实业有限公司 | Dry denitration agent and its production method and application |
| CN107721373A (en) * | 2017-09-30 | 2018-02-23 | 中晶蓝实业有限公司 | The production method of light concrete product based on red mud desulphurization denitration |
| CN107812441A (en) * | 2017-12-07 | 2018-03-20 | 中晶环境科技股份有限公司 | Flue gas dry desulfurizing method of denitration based on red mud |
| CN107961660A (en) * | 2017-12-07 | 2018-04-27 | 中晶环境科技股份有限公司 | Flue gas dry desulfurizing method of denitration based on ozone and red mud |
| CN108283883A (en) * | 2017-01-09 | 2018-07-17 | 青州日新特种材料有限公司 | NO in a kind of removing flue gasxMethod |
| WO2018227362A1 (en) * | 2017-06-13 | 2018-12-20 | 中国石油化工股份有限公司 | Vanadium-based catalyst and preparation method therefor |
| CN109107362A (en) * | 2018-08-04 | 2019-01-01 | 山东迅达化工集团有限公司 | A method of preparing large aperture sulphur/aluminium oxide mercury removal agent |
| CN109179339A (en) * | 2018-08-30 | 2019-01-11 | 山东迅达化工集团有限公司 | The recovery technology of sulfur of middle low concentration sour gas |
| CN109414647A (en) * | 2016-10-07 | 2019-03-01 | 托普索公司 | It is a kind of for the clean method of cryogenic gas and for the catalyst of this method |
| CN109603459A (en) * | 2019-01-10 | 2019-04-12 | 西南化工研究设计院有限公司 | A kind of low-temperature dry fume desulfurizing agent and its preparation method and application |
| CN109794145A (en) * | 2017-11-16 | 2019-05-24 | 柳州市皇盛环保科技有限公司 | A kind of fume desulfurizing agent |
| CN113121033A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Oil refining alkaline residue treatment method and device |
| CN113499675A (en) * | 2021-09-10 | 2021-10-15 | 东营联合石化有限责任公司 | Sulfur recovery equipment |
| CN114082277A (en) * | 2021-12-03 | 2022-02-25 | 湖北润驰环保科技有限公司 | Process for fine desulfurization and purification of waste lubricating oil hydrogenation tail gas |
| CN115501741A (en) * | 2022-08-30 | 2022-12-23 | 四川轻化工大学 | High-activity iron oxide desulfurizer based on modified carrier and preparation method and application thereof |
-
2009
- 2009-09-11 CN CN200910018802A patent/CN101648107A/en active Pending
Cited By (49)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102423711A (en) * | 2011-10-08 | 2012-04-25 | 中国科学院山西煤炭化学研究所 | Catalyst for removing SO2 from flue gas through dry process, its preparation method and application |
| CN102407102A (en) * | 2011-10-08 | 2012-04-11 | 中国科学院山西煤炭化学研究所 | V205/AC desulfurization catalyst, preparation method and application |
| CN105294405A (en) * | 2014-06-06 | 2016-02-03 | 中国石油化工股份有限公司 | Method for removing sulfides in methyl tert-butyl ether by hydrolysis, rectification and adsorption |
| CN105272831A (en) * | 2014-06-06 | 2016-01-27 | 中国石油化工股份有限公司 | Method for deep removal of sulfides from methyl tert-butyl ether |
| CN104307360A (en) * | 2014-10-28 | 2015-01-28 | 南京大学（苏州）高新技术研究院 | Gas-phase desulfurization oxidant and application thereof as well as method for removing hydrogen sulfide |
| CN104548893A (en) * | 2014-12-26 | 2015-04-29 | 中国科学院广州能源研究所 | Low-temperature composite dry desulfurization material and preparation method thereof |
| CN104548893B (en) * | 2014-12-26 | 2018-04-10 | 中国科学院广州能源研究所 | A kind of low temperature composite dry sulfur removal material and preparation method thereof |
| CN104785265A (en) * | 2015-04-13 | 2015-07-22 | 长春东狮科贸实业有限公司 | Catalytic oxidation desulfurization catalyst, gas desulfurization treatment system and gas desulfurization treatment method |
| CN104785265B (en) * | 2015-04-13 | 2018-02-27 | 长春东狮科贸实业有限公司 | Catalytic oxidation desulfurization catalyst, gas sweetening processing system and gas sweetening processing method |
| CN105293444A (en) * | 2015-11-18 | 2016-02-03 | 山东迅达化工集团有限公司 | Low sulfur emission sulphur recovery process |
| CN105779076A (en) * | 2016-04-19 | 2016-07-20 | 哈尔滨工业大学 | Efficient fire coal desulfurizer and preparing method thereof |
| CN105779076B (en) * | 2016-04-19 | 2018-09-11 | 哈尔滨工业大学 | A kind of preparation method of efficient fuel coal desulfurizing agent |
| CN106215847A (en) * | 2016-08-15 | 2016-12-14 | 湖北华邦化学有限公司 | A kind of ferric oxide desulfurizer preparation method |
| CN106215847B (en) * | 2016-08-15 | 2018-09-18 | 武汉纺织大学 | A kind of ferric oxide desulfurizer preparation method |
| CN106391135A (en) * | 2016-09-27 | 2017-02-15 | 长春东狮科贸实业有限公司 | Special catalyst for removing hydrogen sulfide through selective catalytic oxidation and preparation method for special catalyst |
| CN109414647A (en) * | 2016-10-07 | 2019-03-01 | 托普索公司 | It is a kind of for the clean method of cryogenic gas and for the catalyst of this method |
| CN108283883A (en) * | 2017-01-09 | 2018-07-17 | 青州日新特种材料有限公司 | NO in a kind of removing flue gasxMethod |
| CN111065458B (en) * | 2017-06-13 | 2021-08-20 | 中国石油化工股份有限公司 | Vanadium-based catalyst and preparation method thereof |
| WO2018227362A1 (en) * | 2017-06-13 | 2018-12-20 | 中国石油化工股份有限公司 | Vanadium-based catalyst and preparation method therefor |
| CN111065458A (en) * | 2017-06-13 | 2020-04-24 | 中国石油化工股份有限公司 | Vanadium-based catalyst and preparation method thereof |
| US10940462B2 (en) | 2017-06-13 | 2021-03-09 | China Petroleum & Chemical Corporation | Vanadium-based catalyst and preparation method therefor |
| CN107684915A (en) * | 2017-09-30 | 2018-02-13 | 中晶蓝实业有限公司 | Dry denitration agent and its production method and application |
| CN107721373A (en) * | 2017-09-30 | 2018-02-23 | 中晶蓝实业有限公司 | The production method of light concrete product based on red mud desulphurization denitration |
| CN107500578A (en) * | 2017-09-30 | 2017-12-22 | 中晶蓝实业有限公司 | The production method of binder materials based on red mud desulphurization denitration |
| WO2019062448A1 (en) * | 2017-09-30 | 2019-04-04 | 中晶环境科技股份有限公司 | Desulfurizer, and preparation method therefor and application thereof |
| CN107497295A (en) * | 2017-09-30 | 2017-12-22 | 中晶蓝实业有限公司 | The method of dry flue gas desulphurization denitration |
| CN107640954A (en) * | 2017-09-30 | 2018-01-30 | 中晶蓝实业有限公司 | The production method of foaming thermal-insulating based on red mud desulphurization denitration |
| CN107497285A (en) * | 2017-09-30 | 2017-12-22 | 中晶蓝实业有限公司 | The method that flue gas desulfurization and denitrification is carried out using fluidized-bed reactor |
| CN107500579A (en) * | 2017-09-30 | 2017-12-22 | 中晶蓝实业有限公司 | The production method of fibre cement product based on red mud desulphurization denitration |
| CN107469831A (en) * | 2017-09-30 | 2017-12-15 | 中晶蓝实业有限公司 | Dry-desulphurizer and its production method and application |
| CN107596908A (en) * | 2017-09-30 | 2018-01-19 | 中晶蓝实业有限公司 | The method that fume treatment is carried out using fixed bed reactors |
| CN107596885A (en) * | 2017-09-30 | 2018-01-19 | 中晶蓝实业有限公司 | The method of dry flue gas desulphurization |
| CN107469612A (en) * | 2017-09-30 | 2017-12-15 | 中晶蓝实业有限公司 | The method that fume treatment is carried out using fluidized-bed reactor |
| CN107441931A (en) * | 2017-09-30 | 2017-12-08 | 中晶蓝实业有限公司 | Desulfurizing agent and its preparation method and application |
| CN109794145A (en) * | 2017-11-16 | 2019-05-24 | 柳州市皇盛环保科技有限公司 | A kind of fume desulfurizing agent |
| CN107961660A (en) * | 2017-12-07 | 2018-04-27 | 中晶环境科技股份有限公司 | Flue gas dry desulfurizing method of denitration based on ozone and red mud |
| CN107812441A (en) * | 2017-12-07 | 2018-03-20 | 中晶环境科技股份有限公司 | Flue gas dry desulfurizing method of denitration based on red mud |
| CN109107362A (en) * | 2018-08-04 | 2019-01-01 | 山东迅达化工集团有限公司 | A method of preparing large aperture sulphur/aluminium oxide mercury removal agent |
| CN109107362B (en) * | 2018-08-04 | 2021-07-23 | 山东迅达化工集团有限公司 | Method for preparing large-aperture sulfur/alumina mercury removal agent |
| CN109179339B (en) * | 2018-08-30 | 2020-10-23 | 山东迅达化工集团有限公司 | Sulfur recovery process for acid gas with medium and low concentration |
| CN109179339A (en) * | 2018-08-30 | 2019-01-11 | 山东迅达化工集团有限公司 | The recovery technology of sulfur of middle low concentration sour gas |
| CN109603459A (en) * | 2019-01-10 | 2019-04-12 | 西南化工研究设计院有限公司 | A kind of low-temperature dry fume desulfurizing agent and its preparation method and application |
| CN113121033A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Oil refining alkaline residue treatment method and device |
| CN113499675A (en) * | 2021-09-10 | 2021-10-15 | 东营联合石化有限责任公司 | Sulfur recovery equipment |
| CN113499675B (en) * | 2021-09-10 | 2021-11-30 | 东营联合石化有限责任公司 | Sulfur recovery equipment |
| CN114082277A (en) * | 2021-12-03 | 2022-02-25 | 湖北润驰环保科技有限公司 | Process for fine desulfurization and purification of waste lubricating oil hydrogenation tail gas |
| CN114082277B (en) * | 2021-12-03 | 2024-02-27 | 湖北润驰环保科技有限公司 | Fine desulfurization purification process for waste lubricating oil hydrogenation tail gas |
| CN115501741A (en) * | 2022-08-30 | 2022-12-23 | 四川轻化工大学 | High-activity iron oxide desulfurizer based on modified carrier and preparation method and application thereof |
| CN115501741B (en) * | 2022-08-30 | 2023-11-03 | 四川轻化工大学 | High-activity ferric oxide desulfurizing agent based on modified carrier, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101648107A (en) | Catalytic oxidation adsorption desulfurizer and preparation method thereof | |
| Song et al. | Research on the low temperature catalytic hydrolysis of COS and CS2 over walnut shell biochar modified by Fe–Cu mixed metal oxides and basic functional groups | |
| CN102049257B (en) | Catalyst for simultaneously reducing SO2 and NO with CO as well as preparation and application of catalyst | |
| CN102357364B (en) | Preparation for the absorbent charcoal based catalyst of flue gas selective reduction desulfurization | |
| CN104069795B (en) | A kind of sulfur method of the gas sweetening adsorbing composition and preparation method thereof with sulfurous gas | |
| CN101564640B (en) | Combined removal method for contaminants from coal-fired flue gas and special purification reactor thereof | |
| CN102847431B (en) | Method for treating claus technical tail gas | |
| CN101745399A (en) | Selective reduction catalyst used for recovering sulfur, preparation method and application thereof | |
| CN102500323B (en) | Modified active carbon desulfurizer and preparation method thereof and treatment method of hydrogen sulfide waste gas | |
| CN104209084A (en) | Claus tail gas SO2 sorbent and preparation and use thereof | |
| CN103028368B (en) | Gas desulfurization sorbent and preparation method thereof and desulfurization method of sulfur-containing gas | |
| CN106362573A (en) | Desulfurizer and desulphurising process for mixed gas containing sulfides in diversified forms | |
| CN107497283A (en) | A kind of big air speed Fe-series desulfurizing agent and preparation method and application | |
| CN103028363B (en) | The sulfur method of gas sweetening adsorbent and preparation method thereof and sulfurous gas | |
| CN103769043B (en) | A kind of gas sweetening adsorbent, its preparation method and application | |
| CN105080487B (en) | Load active carbon desulfurization adsorbent of phthalocyanine cobalt sulfonate and copper and preparation method thereof | |
| CN114502277B (en) | Composite material and its application in desulfurization | |
| CN112642397B (en) | Composite material, preparation method and application thereof | |
| CN103769038B (en) | A kind of gas sweetening adsorbent, its preparation method and application | |
| CN103028367B (en) | Gas desulfurization adsorbent, preparation method thereof and desulfurization method for sulfur-containing gas | |
| CN103028365B (en) | Gas desulfurization sorbent and preparation method thereof and desulfurization method of sulfur-containing gas | |
| CN103769041B (en) | A kind of gas sweetening adsorbent, its preparation method and application | |
| CN111068642B (en) | Catalyst for removing mercaptan in natural gas and preparation method thereof | |
| CN103769044B (en) | A kind of gas sweetening adsorbent and its preparation method and application | |
| CN104560251B (en) | Cleaning agent and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20100217 |