CN102703148A - Organic sulfur hydro-conversion and methane pre-synthesis combined treatment method - Google Patents
Organic sulfur hydro-conversion and methane pre-synthesis combined treatment method Download PDFInfo
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- CN102703148A CN102703148A CN2012101748190A CN201210174819A CN102703148A CN 102703148 A CN102703148 A CN 102703148A CN 2012101748190 A CN2012101748190 A CN 2012101748190A CN 201210174819 A CN201210174819 A CN 201210174819A CN 102703148 A CN102703148 A CN 102703148A
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Abstract
The invention relates to an organic sulfur hydro-conversion and methane pre-synthesis combined treatment method. According to the treatment method, an organic sulfur hydro-conversion catalyst and an inorganic sulfur removal catalyst are used. The treatment method comprises the following steps of: (a) performing hydro-conversion of organic sulfur and pre-synthesizing methane, namely allowing raw gas to pass through the organic sulfur hydro-conversion catalyst under the condition of first space velocity, first temperature and first pressure; (b) removing inorganic sulfur, namely allowing the raw gas treated in the step of the hydro-conversion of the organic sulfur and the pre-synthesis of the methane to pass through the inorganic sulfur removal catalyst under the condition of second space velocity, second temperature and second pressure; and (c) synthesizing the methane, namely allowing the raw gas treated in the step of the removal of the inorganic sulfur to pass through a methane synthesis catalyst under the condition of third space velocity, third temperature and third pressure. The organic sulfur hydro-conversion catalyst used in the method is not required to be pre-vulcanized; and the methane pre-synthesis reaction is also performed in the method.
Description
Technical field
The present invention relates to organosulfur hydrocracking and the synthetic treatment process that combines of preparatory methane; Said treatment process is particularly suitable in coke(oven)gas or producing synthesis gas from coal synthesizing methane, using, and the invention still further relates at said organosulfur hydrocracking to synthesize organic sulfur hydroconversion catalyst that uses in the treatment process that combines and preparation method thereof with preparatory methane.
Background technology
Utilize coke(oven)gas or producing synthesis gas from coal production synthetic natural gas to become focus in recent years.The methane building-up reactions that this process relates generally to is a strong exothermal reaction, and 1% CO reacts in the virgin gas, and the gas temperature rise can reach 72 ℃; 1% CO
2React, the gas temperature rise can reach 60 ℃.So must be with CO in the virgin gas and CO
2Content is strict controlled in the technic index scope of regulation, in order to avoid the sintering of catalyst inactivation.In addition, methane synthetic catalyst activity is good, selectivity is high, to poisonous substance and sensitivity thereof, and easy poisoning and deactivation, wherein the murder by poisoning of sulfide is the most serious.
Most H in common coke(oven)gas or the producing synthesis gas from coal
2S is removed in process of wet desulphurization, removes afterwards and need be converted into inorganic sulfur with the organosulfur that forms such as carbonylsulfide, mercaptan, thioether and thiophene exist again.
The method of organic sulfide removal is generally: utilize hydrocracking that the organosulfur hydrogenolysis is inorganic sulfur H
2S uses desulfurization such as sorbent material such as zinc oxide, gac, red stone, molecular sieve again.The hydrogenolysis of organosulfur is exemplified below:
COS+H
2→CO+H
2S
C
2H
5SH+H
2→C
2H
6+H
2S
CH
3SC
2H
5+2H
2→CH
4+C
2H
6+H
2S
C
4H
4S+4H
2→C
4H
10+H
2S
Patent CN101224871A discloses a kind of deep-purifying method of producing synthesis gas from coal, and it utilizes depth hydrolysis, the smart desulfurization of the degree of depth etc. will contain (H
2S+COS) total sulfur in the producing synthesis gas from coal of 10ppbv～10ppmv is reduced to below the 10ppbv; Patent CN101560414A discloses a kind of producing synthesis gas from coal combination purification technique, purifies the back total sulfur content and is lower than 10ppbv, has prolonged the life-span of methane synthetic catalyst greatly, and can this technology be used for coal system oil and coal system methyl alcohol; Patent CN101797508A discloses a kind of coking oven gas hydrodesulfurizationcatalyst catalyst and preparation method thereof.
More than these patent disclosed methods can sulphur content be removed to lower degree, but there is the common shortcoming in they: do not relate to preparatory methanation; Organic sulfur hydroconversion catalyst needs prevulcanized before use, and is desulphurizing activated to obtain better conversion; In addition, when very low, need replenish the reversal of cure that vulcanizing agent carries out catalyzer again, to keep the stabilizing active of catalyzer as if the virgin gas sulphur content.Therefore, above method complex process, facility investment are high, the time that has high input of driving is long, the feature of environmental protection is poor.
Patent CN1272398A discloses a kind of hydrodesulphurizatiomethod method of gas containing hydrocarbon and catalyzer and application.Associated catalysts is with TiO
2Be carrier, comprise the catalyst A of nickeliferous, active component of cobalt and contain the catalyst B of cobalt, active component of cobalt.This method is to be that the hydrogen manufacturing of raw material, the production technique of system synthetic ammonia have been opened up a new way with the refinery gas.Do not produce methane but this patent relates to the combination process of preparatory methanation and deep desulfuration, and this method catalyst system therefor specific surface area is lower than 200m
2/ g can't bring into play the advantage of the catalyzer of titania-alumina mixed oxide load cobalt, molybdenum, is not suitable for doing the catalyzer of coke(oven)gas or the desulfurization of producing synthesis gas from coal hydrocracking.
Patent CN101199935A discloses a kind of titania-alumina mixed oxide Hydrobon catalyst and preparation method.The gained catalyzer is mainly used in the sulphur that removes in the diesel oil, do not relate to being used to make the coke(oven)gas of methane or the preparatory methanation and the deep desulfuration of producing synthesis gas from coal, and catalyzer adopts Prepared by Sol Gel Method, complex process, cost height.
Summary of the invention
Deficiency to prior art; The present invention combines with the hydroconversion process that need not prevulcanized preparatory methane is synthetic, has developed a kind of composite catalyst and related process, and a small amount of methanation reaction takes place when coke(oven)gas or producing synthesis gas from coal are carried out the desulfurization of degree of depth essence; Simplified sulfur removal technology; Reduced investment, saved on-stream time, prolonged the follow-up methanation catalyst life-span, reduced and produced load.
" methane is synthetic in advance " among the present invention is meant in the sweetening process of virgin gas before synthesizing methane main reaction device, and a small amount of methanation reaction takes place, and generally transforms CO and/or CO
2About 0.1～3%, thus follow-up methanation reaction load reduced.
In first aspect of the present invention; Relate to a kind of organosulfur hydrocracking and the synthetic combination treatment method of preparatory methane; Said treatment process uses organic sulfur hydroconversion catalyst, inorganic sulfur to remove catalyzer; The treating method comprises following steps: (a) organosulfur hydrocracking and preparatory methane synthesis step wherein make said unstripped gas under the condition of first air speed, first temperature and first pressure, pass through said organic sulfur hydroconversion catalyst; (b) inorganic sulfur removes step, wherein makes through said organosulfur hydrocracking and preparatory methane synthesis step unstripped gas afterwards and under the condition of second air speed, second temperature and second pressure, removes catalyzer through said inorganic sulfur.
In an embodiment of first aspect of the present invention, first air speed is 500 to 4000h in organosulfur hydrocracking and preparatory methane synthesis step
-1, preferred 1000～3000h
-1, more preferably 1500～2500h
-1, 2000～2800h most preferably
-1When first air speed is lower than 500h
-1The time, the virgin gas residence time is longer, and hydrogenation conversion catalyst utilising efficiency step-down is when first air speed is higher than 4000h
-1The time, the virgin gas residence time is shorter, and the organosulfur hydroconversion reactions is insufficient.
In an embodiment of first aspect of the present invention, first temperature is 350 to 620 ℃ in organosulfur hydrocracking and preparatory methane synthesis step, preferred 400 to 600 ℃, and more preferably 420 to 600 ℃, most preferably 420 to 580 ℃.When first temperature was lower than 350 ℃, the transformation efficiency of organosulfur hydrocracking was very low, the organic sulfur removal poor effect, and when first temperature was higher than 620 ℃, side reaction increased, and influenced product purity, increased post-processing difficulty.
In an embodiment of first aspect of the present invention, in organosulfur hydrocracking and preparatory methane synthesis step first pressure be normal pressure to 8MPa, preferred 1 to 6Mp, more preferably 1 to 4MPa, most preferably 2 to 4MPa.When first pressure was lower than normal pressure, speed of reaction was lower, was unfavorable for that desulphurization reaction takes place, and is harsh to the requirement of reactor drum when first pressure is higher than 8MPa, increased investment and production cost.
In an embodiment of first aspect of the present invention, removing in the step second air speed at inorganic sulfur is 500 to 4000h
-1, preferred 1000 to 3000h
-1, more preferably 2000 to 3000h
-1, most preferably 2500 to 3000h
-1When second air speed is lower than 500h
-1The time, the virgin gas residence time is longer, and desulfurization catalyst utilising efficiency step-down is when second air speed is higher than 4000h
-1The time, the virgin gas residence time is shorter, and it is insufficient that inorganic sulfur removes reaction.
In an embodiment of first aspect of the present invention, remove at inorganic sulfur that second temperature is 200 to 450 ℃ in the step, preferred 300 to 400 ℃, more preferably 320 to 390 ℃, most preferably 350 to 380 ℃.When second temperature was lower than 200 ℃, the transformation efficiency that inorganic sulfur removes was very low, and sweetening effectiveness is not good, and when second temperature was higher than 450 ℃, side reaction increased, and influenced product purity, increased post-processing difficulty.
In an embodiment of first aspect of the present invention, inorganic sulfur remove in the step second pressure be normal pressure to 8MPa, preferred 1 to 7MPa, more preferably 2 to 5MPa, most preferably 2 to 4MPa.When second pressure was lower than normal pressure, speed of reaction was lower, was unfavorable for that desulphurization reaction takes place, and when second pressure was higher than 8MPa, the virgin gas residence time was shorter, and it is insufficient that inorganic sulfur removes reaction.
In an embodiment of first aspect of the present invention, organosulfur is less than 10ppbv, H after inorganic sulfur removes step after organosulfur hydrocracking and preparatory methane synthesis step
2S is less than 10ppbv.
In an embodiment of first aspect of the present invention; Organosulfur hydrocracking of the present invention is the preposition step of methane synthetic with the synthetic combination treatment method of preparatory methane; Use therein unstripped gas comprises producing synthesis gas from coal, coke(oven)gas, converter gas, blast furnace gas, semicoke gas or two or more gas mixtures wherein, preferred coke(oven)gas or producing synthesis gas from coal.
In an embodiment of first aspect of the present invention, the total sulfur content in the said virgin gas is less than or equal to 3ppmv, preferably is less than or equal to 2.5ppmv, is more preferably less than or equals 2ppmv, most preferably less than 1ppmv.When total sulfur content during greater than 3ppmv, final sweetening effectiveness is not good, and the life of catalyst of using among the present invention reduces.
In an embodiment of first aspect of the present invention; Synthesizing the organic sulfur hydroconversion catalyst that uses in the combination treatment method at organosulfur hydrocracking and preparatory methane prepares according to the following method for preparing organic sulfur hydroconversion catalyst: (a) preparation process of titanium aluminium dry glue powder; Wherein at first in reactor drum, adding entry, is under 8 to 10 the condition in the pH value, will contain the salts solution and the ammoniacal liquor uniform mixing of aluminum ion and titanium ion; Aging; This weathering process was preferably carried out 1 to 3 hour, filtered afterwards, washed, dry and pulverize, thereby obtain titanium aluminium dry glue powder; (b) titanium alumina supporter forming step mixes titanium aluminium dry glue powder with extrusion aid, add sticker and mediate, and moulding afterwards, drying, calcining obtain titanium aluminium complex carrier; (c) activity component impregnation step is immersed in titanium aluminium complex carrier in the solution of first active ingredient, afterwards oven dry, roasting; Again titanium aluminium complex carrier is immersed in the solution of second active ingredient, afterwards oven dry, roasting.
Above-mentioned pH value is preferably 9, when this pH value is lower than 8, in be difficult to filter and washing with slurry, influence is produced and quality product, when this pH value was higher than 10, the specific pore volume of titanium aluminium dry glue powder was less, the activity of such catalysts reduction.
Preferred 1 to 2 hour of above-mentioned digestion time, when digestion time was shorter than 1 hour, the degree of disorder of titanium aluminium dry glue powder granularity and pore size distribution increased, and when digestion time is longer than 3 hours, loses time, and influences productivity.
In an embodiment of first aspect of the present invention; In the preparation process of the titanium aluminium dry glue powder in preparing the method for organic sulfur hydroconversion catalyst, salts solution makes in the following manner: with aluminum chloride salts solution and titanium tetrachloride solution by making TiO in the titanium aluminium complex carrier described in the said step (b)
2Content be 10% to 60% mixed.In an embodiment of first aspect of the present invention, mixing time was preferably more than 1 hour.In an embodiment of first aspect of the present invention, the aluminum chloride salts solution preferably contains aluminium 1 weight % to 5 weight %.In an embodiment of first aspect of the present invention, the preferred titaniferous 1% to 3% of titanium tetrachloride solution.
In an embodiment of first aspect of the present invention, preferred 2 weight % to the 4 weight % of the aluminum content of aluminum chloride salts solution, more preferably 3 weight %, when aluminum content was lower than 1 weight %, production efficiency was low, and when aluminum content was higher than 5 weight %, the reaction uniformity coefficient was low.
In an embodiment of first aspect of the present invention, preferred 1.5 weight % to 2.5 weight %, the more preferably 2 weight % of the titaniferous amount of titanium tetrachloride salts solution; When the titaniferous amount is lower than 1 weight %; Production efficiency is low, and when the titaniferous amount was higher than 3 weight %, the reaction uniformity coefficient was low.
In an embodiment of first aspect of the present invention, TiO in the titanium aluminium complex carrier
2Content be preferably 20% to 50%, more preferably 20% to 40%, most preferably 20% to 30%; When it was lower than 10%, the organosulfur hydrocracking activity of catalyzer was low, when it is higher than 60%; The specific surface of carrier is low, and the katalysis of active ingredient is not given full play to.
In an embodiment of first aspect of the present invention, in the preparation process of the titanium aluminium dry glue powder in preparing the method for organic sulfur hydroconversion catalyst, reuse deionized water and carry out said washing, Na in stem-based catalyst
+Be less than 0.05 weight %.Make Na
+Be less than 0.05 weight %, can improve dispersion degree of active components, thereby improve the activity of organic sulfur hydroconversion catalyst.More preferably, make Na
+Be less than 0.04 weight %.
In an embodiment of first aspect of the present invention, in the preparation process of the titanium aluminium dry glue powder in preparing the method for organic sulfur hydroconversion catalyst, reuse deionized water and carry out said washing, Cl in stem-based catalyst
-Be less than 0.05 weight %, more preferably, make Cl
-Be less than 0.04 weight %.
In an embodiment of first aspect of the present invention; In the titanium alumina supporter forming step in preparing the method for organic sulfur hydroconversion catalyst; Extrusion aid is methylcellulose gum, sesbania powder or their mixture; Preferred sesbania powder, sticker is rare nitric acid or the acetic acid,diluted of 1 weight % to 6 weight %, preferred acetic acid,diluted.Extruded velocity when the use of said extrusion aid can improve the carrier moulding, the use of said sticker can increase the bond strength of titanium aluminium dry glue powder particle.
In an embodiment of first aspect of the present invention, in the titanium alumina supporter forming step in preparing the method for organic sulfur hydroconversion catalyst, calcination time is 1 to 10 hour, is preferably 2 to 6 hours, more preferably 2.5 to 4 hours.
In an embodiment of first aspect of the present invention, calcining temperature is 450 ℃ to 600 ℃, is preferably 450 ℃ to 550 ℃, more preferably 500 ℃ to 550 ℃.Calcining temperature is lower than 450 ℃, and then the raw material decomposition is insufficient, and carrier can not form required crystal phase structure, and calcining temperature is higher than 600 ℃, and then the specific surface of carrier and specific pore volume are affected.
In an embodiment of first aspect of the present invention; In the titanium alumina supporter forming step in preparing the method for organic sulfur hydroconversion catalyst; Temperature rise rate is per hour 20 ℃ to 50 ℃, is preferably per hour 30 ℃ to 50 ℃, more preferably per hour 40 ℃ to 50 ℃.Temperature rise rate is lower than per hour 20 ℃, then influences production capacity, and temperature rise rate is higher than per hour 50 ℃, and then the catalyzer inequality of being heated influences its intensity.
In an embodiment of first aspect of the present invention; In said activity component impregnation step; Wherein dipping in said first active ingredient and the dipping in said second active ingredient all carried out 2 to 5 hours, were preferably 2 to 4 hours, more preferably 2 to 3 hours.
In an embodiment of first aspect of the present invention; Roasting after said first active ingredient of dipping and the roasting after said second active ingredient of dipping were all carried out 3 to 5 hours at 400 ℃ to 600 ℃; Preferably carried out 3 to 4 hours, more preferably carried out 3 to 3.5 hours at 500 ℃ to 550 ℃ at 450 ℃ to 550 ℃.The time of immersion and the maturing temperature of two kinds of components can be the same or different.When time of immersion is lower than 2 hours, flood insufficiently, when time of immersion was higher than 5 hours, production efficiency reduced.When maturing temperature was lower than 400 ℃, the salt of active ingredient decomposed insufficient, when maturing temperature is higher than 600 ℃; The specific surface and the specific pore volume of carrier are affected; When roasting time was lower than 3 hours, the salt of active ingredient decomposed insufficient, when roasting time is higher than 5 hours; Waste energy, and increase cost.
In an embodiment of first aspect of the present invention; In the activity component impregnation step in preparing the method for organic sulfur hydroconversion catalyst; The solution of first active ingredient is the molybdenum salts solution, preferred ammonium molybdate solution, and the solution of second active ingredient is cobalt salt solution; Preferred cobalt nitrate solution or nickel salt solution, preferred nickel nitrate solution.Use Mo and Co or Ni, can make the organosulfur in the virgin gas be converted into inorganic sulfur, be convenient to removing of sulphur.Use nitrate soln, be convenient to solubilization of active ingredient.
In an embodiment of first aspect of the present invention, the specific surface area of the titanium aluminium complex carrier that obtains in the titanium alumina supporter forming step in preparing the method for organic sulfur hydroconversion catalyst is 200 to 350m
2/ g, preferred 230 to 320m
2/ g, more preferably 260 to 320m
2/ g, most preferably 280 to 300m
2/ g.In an embodiment of first aspect of the present invention, specific pore volume is 0.4 to 1.1mL/g, and preferred 0.6 to 1.1mL/g, and more preferably 0.8 to 1.1mL/g, and most preferably 0.8 to 1.0mL/g.When specific surface area is lower than 200m
2When/g or specific pore volume were lower than 0.4mL/g, the activity of such catalysts component was not fully utilized, when specific surface area is higher than 350m
2When/g or specific pore volume were higher than 1.1mL/g, the intensity step-down of catalyzer caused the working conditions of catalyzer to be restricted, and the life-span is affected.
In an embodiment of first aspect of the present invention, in the said organic sulfur hydroconversion catalyst that the method according to said organic sulfur hydroconversion catalyst prepares, with respect to the quality of said titanium aluminium complex carrier, with oximeter; Mo is 3% to 15%, and is preferred 5% to 13%, more preferably 7% to 12%; Most preferably 8% to 11%, and Co is 1% to 5%, preferred 2% to 4%; More preferably 2.5% to 4%, most preferably 2.5% to 3.5%, perhaps Ni is 1% to 10%; Preferred 2% to 8%, more preferably 3% to 7%, most preferably 4% to 7%.As active substance, can effectively organosulfur be converted into inorganic sulfur with the Mo in this scope, Co and Ni.
In second aspect of the present invention; The present invention relates to prepare the method for organic sulfur hydroconversion catalyst; Said method is the method for mentioning in the first aspect in the present invention for preparing organic sulfur hydroconversion catalyst, and the said method for preparing organic sulfur hydroconversion catalyst can be included in the arbitrary combination of any a plurality of technical characterictics of mentioning in the first aspect of the present invention aptly.
In the third aspect of the invention; The present invention relates to organic sulfur hydroconversion catalyst; Said organic sulfur hydroconversion catalyst is the organic sulfur hydroconversion catalyst of mentioning in the first aspect in the present invention, and said organic sulfur hydroconversion catalyst can be included in the arbitrary combination of any a plurality of technical characterictics of mentioning in the first aspect of the present invention aptly.
In an embodiment of the third aspect of the invention, organic sulfur hydroconversion catalyst of the present invention is the catalyzer with organosulfur hydrocracking and the synthetic dual-use function of preparatory methane.
With the prior art ratio, the invention has the beneficial effects as follows: need not pre-vulcanization process when being used for the coke(oven)gas organic sulfide removal of synthesizing methane, technology is simple, facility investment is low, drive to save time, environmental protection; Desulfurization precision is high; Sweetening process is attended by preparatory methane building-up reactions, produces a small amount of methane, reduces the load of follow-up methane building-up reactions.
Description of drawings
Fig. 1: Fig. 1 is the process flow diagram of the preparatory methanation of organosulfur hydrocracking.R1 filling EJZ type hydrogenation conversion catalyst (hydrocracking of the present invention is named as EJZ with the synthetic united catalyst of preparatory methane), R2 filling EJT type inorganic sulfur removes catalyzer (commercially available inorganic sulfur removes catalyzer).Reactor feed gas entering R1 carries out the hydrocracking removal of organic sulfur from and methane is synthetic in advance, after heat exchange, gets into R2 then and removes inorganic sulfur, gets into the methane synthesis unit at last.
Fig. 2: reactor drum top filling EJZ type hydrogenation conversion catalyst, reactor lower part filling EJT type inorganic sulfur removes catalyzer.Virgin gas process organosulfur hydrocracking, preparatory methane synthesize, inorganic sulfur removes the back and gets into the methane synthesis unit.
Fig. 3: exemplary process general flow chart of the present invention.
Embodiment
In one embodiment of the invention, exemplary process general flow chart of the present invention is as shown in Figure 3.
In Fig. 3, the coke(oven)gas sulphur content of thick desulfurization is 0.5～2.0ppmv, adopts EJZ type organic sulfur hydroconversion catalyst, at air speed 1000～3000h
-1, 420～580 ℃ of temperature and pressure be under normal pressure～5MPa condition with organic sulfur removal to＜10ppbv; EJT moldeed depth degree desulfurizing agent is at air speed 1000～3000h
-1, under 200～400 ℃ of temperature and the pressure normal pressure～4MPa condition with H
2S is removed to＜10ppbv; Coke(oven)gas total sulfur content (H after the smart desulfurization
2The S+ organosulfur)＜and 20ppbv, get into the methane synthesizing section, at 320～650 ℃ of following synthesizing methanes of temperature of reaction.
In one embodiment of the invention, methane is synthetic in advance adopts γ-Al with the hydrocracking organic sulfide removal
2O
3-TiO
2Composite oxides are carrier; Active ingredient is Mo, Co and Ni.This catalyst hydrodesulfurization active is high, and desulfurization is deep, does not need prevulcanized to handle, and its active phase structure and catalyst performance stabilised, is suitable for the lower material depth desulfurization of sulphur content, for example is used to make the coke(oven)gas of the thick desulfurization of process of methane.
In one embodiment of the invention, the preparation of organic sulfur hydroconversion catalyst EJZ realizes through following method:
(1) preparation of titanium aluminium dry glue powder
A. preparation contains the aluminum chloride salts solution of aluminium 1～5 weight % and the titanium tetrachloride solution of titaniferous 1～3%, slowly mixes in proportion, processes solution A; 5～12 weight % ammonia solns are solution B.Wherein raw materials mix is carried out in stainless steel or enamel reaction mixing equipment, and mixing time generally was not less than 1 hour, and it is mixed;
B. in reactor drum, add water of certain end, stir, preferred stirring velocity 80～300r/ minute, temperature preferably was controlled in 40～80 ℃ of scopes;
C. under the condition of pH value 8～10, solution A and solution B carry out and flow being neutralized into glue, and the time was generally 30～60 minutes, and temperature is 40～80 ℃ and neutralizes, aging 1～3 hour;
D. again through filtration, deionized water wash is some all over Na to stem-based catalyst
+Less than 0.05 weight %;
E. filter cake makes titanium aluminium dry glue powder 120 ℃ of dry down, pulverizing.
(2) titanium alumina supporter moulding:
Take by weighing above-mentioned preparation method and obtain a certain amount of titanium aluminium dry glue powder, take by weighing the extrusion aid of 0.5～2.0 weight % again, preferred: methylcellulose gum, sesbania powder etc., the two mixes.Mixed siccative adds sticker again, rare nitric acid, the acetic acid,diluted of preferred 1～6 weight %, and the kneading time was not less than 0.5 hour, moulding then.Put into baking oven after the moulding dry 12～24 hours, calcined 1～10 hour down for preferred 450～600 ℃ at 300～800 ℃ dry back, and preferred 3～8 hours, the calcining temperature rise rate was generally 20～50 ℃/h, obtains titanium aluminium complex carrier.
γ-the Al that makes
2O
3-TiO
2Double oxide carrier, wherein TiO
2Content is 10～60%.Carrier specific surface area 200～350m
2/ g; Specific pore volume is 0.4～1.1mL/g.
(3) step impregnation active ingredient:
The carrier that step (2) is made under 30～70 ℃ in molybdenum salts solution (preferred ammonium molybdate solution) dipping 2～5 hours, dry then, in 400～600 ℃ of following roastings 3～5 hours.The carrier that will be impregnated with molybdenum then is in flooding 2～5 hours in cobalt salt solution (preferred cobalt nitrate solution) under 30～70 ℃, and oven dry in 400～600 ℃ of following roastings 3～5 hours, makes organic sulfur hydroconversion catalyst EJZ then.MoO wherein
3Be respectively with respect to the quality (in oxide compound) of carrier with Co: 3～15% and 1～5%.
Organic sulfur hydroconversion catalyst of the present invention can carry out the organosulfur hydrocracking simultaneously and methane is synthetic in advance; Its principle is that Mo, Co etc. are the active ingredients of organosulfur hydrocracking and methanation; And Ti can play the effect of stably dispersing to active ingredient, thereby makes virgin gas more effectively participate in organosulfur hydrocracking and methane building-up reactions.
Organic sulfur hydroconversion catalyst of the present invention need not prevulcanized, because Ti participates in MoO
3It is active that the reduction process of isoreactivity component, the active ingredient of the lower valency after the reduction have the organosulfur hydrocracking, and need not to change into sulphided state.
In one embodiment of the invention, remove inorganic sulfur and select commercially available Zinc oxide desulfurizer for use: zinc oxide content 70～95%, all the other are auxiliary agent and sticker.
In one embodiment of the invention; Coke(oven)gas or producing synthesis gas from coal are methanation catalyst prepared can to select commercially available methanation catalyst, preferably adopts the methane synthetic catalyst of patent CN 102125849A (a kind of preparation method of synthetic methane catalyst and catalyst precursor) preparation.As not having specified otherwise, used EHM is meant the catalyzer by the embodiment 1 method preparation of patent 102125849A among the embodiment; Adsorption desulfurizing agent EJT is the JX-4B type sweetening agent available from the Beijing Sanju New Environmental Protection Materials Co., Ltd.
Below in conjunction with embodiment the present invention is done to further describe, but can not limit scope of the present invention with this.Every variation or modification of doing according to the claim of application of the present invention all should belong in the scope that patent of the present invention contains.
Embodiment
In an embodiment of the present invention, measure each parameter index according to following method:
The specific surface of catalyzer and specific pore volume adopt the BET method to measure with the ASAP2020M of U.S. Merck & Co., Inc type physical adsorption appearance.Wherein, specific surface is meant the total area that the unit mass material is had, the m of unit
2/ g; Add the volume of the real sky of 1 all granule interior of gram catalyzer is exactly specific pore volume together, Unit/g.
Each component concentration is measured with the U.S. Optima2100DV of PE company type inductively coupled plasma transmitter in stem-based catalyst sodium ions content and the catalyzer finished product.
In an embodiment of the present invention, the source of each chemical reagent and specification such as following table:
| Reagent | Specification | The source |
| Aluminum chloride | Analytical pure | Chemical Reagent Co., Ltd., Sinopharm Group |
| Titanium tetrachloride | Analytical pure | Tianjin sky over the river chemical industry technology ltd |
[0076]
| Ammoniacal liquor | Analytical pure | Tianjin Fengchuan Chemical Reagent Science & Technology Co., Ltd. |
| The sesbania powder | Technical grade | Zhengzhou sincere prosperous chemical industry ltd |
| Methylcellulose gum | Technical grade | Beijing Henderson Investment Science and Technology Ltd. |
| Acetate | Analytical pure | Chemical Reagent Co., Ltd., Sinopharm Group |
| Ammonium molybdate | Technical grade | Yantai permanent brightness chemical industry ltd |
| Nickelous nitrate | Analytical pure | Chemical Reagent Co., Ltd., Sinopharm Group |
| Xiao Suangu | Technical grade | Xia County transport power chemical industry ltd |
Catalyst preparation example 1
Get the aluminum trichloride solution 1100g that contains aluminium 4 weight %, the titanium tetrachloride solution 1800g of titaniferous 4% slowly mixes; Be mixed with mixed solution A, prepare the ammonia soln B of 8 weight %, in the WHFS-2 type reaction kettle that Weihai automatic control reaction kettle ltd produces, add 200 ml deionized water earlier and do end water; Temperature is controlled at 65～70 ℃; Low whipping speed is that PM 150 changes down and stream adds solution A and B carries out neutralization reaction, and the pH value is controlled at 8.2～8.5, and the reinforced time is about 30 minutes.Aging 1 hour.With deionized water wash to stem-based catalyst sodium ions content and chloride ion content all less than 0.05%, filter cake is dried down at 120 ℃, with HK-820 type Stainless Steel Powder grinding machine with dried filter cake mechanical disintegration to 200 order.Take by weighing the auxiliary agent sesbania powder of the dry glue powder weight 1.0 weight % that process, the two mixes.Mixed siccative usefulness contains 4% acetic acid soln as sticker, mediated 30 minutes, and extruded moulding, drying is 15 hours under 120 ℃, and 550 ℃ of roastings obtained titanium aluminium complex carrier in 3 hours in retort furnace then.In in the ammonium molybdate solution of 25 weight %, flooding 3 hours under 40 ℃, 120 ℃ of oven dry then were in 550 ℃ of following roastings 3 hours with 100g titanium aluminium complex carrier.The carrier that will be impregnated with molybdenum then is in flooding 3 hours in 7 weight % cobalt nitrate solutions under 45 ℃, and 120 ℃ of oven dry in 550 ℃ of following roastings 3 hours, make organic sulfur hydroconversion catalyst EJZ-1.
Contain TiO in the titanium aluminium complex carrier
260 weight % contain γ-Al
2O
340 weight %; Active ingredient MoO
3Be respectively with respect to the quality (in oxide compound) of carrier with Co: 11 weight % and 3 weight %.
The specific surface of catalyzer is 230m
2/ g, specific pore volume are 0.64mL/g.
Catalyst preparation example 2
Get the aluminum trichloride solution 1200g that contains aluminium 4 weight %, the titanium tetrachloride solution 1600g of titaniferous 4% slowly mixes; Be mixed with mixed solution A, prepare the ammonia soln B of 8 weight %, in reactor drum, add 200 ml deionized water earlier and do end water; Temperature is controlled at 65～70 ℃; Low whipping speed is that PM 150 changes down and stream adds solution A and B carries out neutralization reaction, and the pH value is controlled at 8.0～8.3, and the reinforced time is about 30 minutes.Aging 1 hour.With deionized water wash to stem-based catalyst sodium ions content and chloride ion content all less than 0.05%, filter cake is dried down at 120 ℃, with HK-820 type Stainless Steel Powder grinding machine with dried filter cake mechanical disintegration to 200 order.Take by weighing the auxiliary agent sesbania powder of the dry glue powder weight 1.0 weight % that process, the two mixes.Mixed siccative usefulness contains 4% acetic acid soln as sticker, mediated 30 minutes, and extruded moulding, drying is 15 hours under 120 ℃, and 550 ℃ of roastings obtained titanium aluminium complex carrier in 3 hours in retort furnace then.In in the ammonium molybdate solution of 25 weight %, flooding 3 hours under 40 ℃, 120 ℃ of oven dry then were in 550 ℃ of following roastings 3 hours with 100g titanium aluminium complex carrier.The carrier that will be impregnated with molybdenum then is in flooding 3 hours in 7 weight % cobalt nitrate solutions under 45 ℃, and 120 ℃ of oven dry in 550 ℃ of following roastings 3 hours, make organic sulfur hydroconversion catalyst EJZ-2.
Contain TiO in the titanium aluminium complex carrier
240 weight % contain γ-Al
2O
360 weight %; Active ingredient MoO
3Be respectively with respect to the quality (in oxide compound) of carrier with Co: 13 weight % and 4 weight %.
The specific surface of catalyzer is 280m
2/ g, specific pore volume are 0.71mL/g.
Catalyst preparation example 3
Get the aluminum trichloride solution 600g that contains aluminium 4 weight %, the titanium tetrachloride solution 2100g of titaniferous 4% slowly mixes; Be mixed with mixed solution A, prepare the ammonia soln B of 8 weight %, in reactor drum, add 200 ml deionized water earlier and do end water; Temperature is controlled at 65～70 ℃; Low whipping speed is under 150r/ minute and stream adds solution A and B carries out neutralization reaction, and the pH value is controlled at 7.5～7.8, and the reinforced time is about 30 minutes.Aging 1 hour.With deionized water wash to stem-based catalyst sodium ions content and chloride ion content all less than 0.05%, filter cake is dried down at 120 ℃, with HK-820 type Stainless Steel Powder grinding machine with dried filter cake mechanical disintegration to 200 order.Take by weighing the auxiliary agent sesbania powder of the dry glue powder weight 1.0 weight % that process, the two mixes.Mixed siccative usefulness contains 1% salpeter solution as sticker, mediated 30 minutes, and extruded moulding, drying is 15 hours under 120 ℃, and 550 ℃ of roastings obtained titanium aluminium complex carrier in 3 hours in retort furnace then.In in the ammonium molybdate solution of 30 weight %, flooding 3 hours under 40 ℃, 120 ℃ of oven dry then were in 550 ℃ of following roastings 3 hours with 100g titanium aluminium complex carrier.The carrier that will be impregnated with molybdenum then is in flooding 3 hours in 9 weight % cobalt nitrate solutions under 45 ℃, and 120 ℃ of oven dry in 550 ℃ of following roastings 3 hours, make organic sulfur hydroconversion catalyst EJZ-3.
Contain TiO in the titanium aluminium complex carrier
220 weight % contain γ-Al
2O
380 weight %; Active ingredient MoO
3Be respectively with respect to the quality (in oxide compound) of carrier with Co: 13 weight % and 3.3 weight %.
The specific surface of catalyzer is 310m
2/ g, specific pore volume are 0.59mL/g.
Catalyst preparation example 4
Method with catalyst preparation example 1 prepares catalyzer EJZ-4, and used ammonium molybdate solution concentration was 13 weight % when difference was to flood, and contains TiO in the gained catalyst Ti aluminium complex carrier
260 weight % contain Al
2O
340 weight %; Active ingredient MoO
3Be respectively with respect to the quality (in oxide compound) of carrier with Co: 5 weight % and 3.1 weight %.
The specific surface of catalyzer is 240m
2/ g, specific pore volume are 0.65mL/g.
Catalyst preparation example 5
Method with catalyst preparation example 2 prepares catalyzer EJZ-5, and difference is to flood Ni after having flooded Mo, and flooding used nickel nitrate solution concentration is 18 weight %, contains TiO in the gained catalyst Ti aluminium complex carrier
240 weight % contain Al
2O
360 weight %; Active ingredient MoO
3Be respectively with respect to the quality (in oxide compound) of carrier with Ni: 13 weight % and 7 weight %.
The specific surface of catalyzer is 280m
2/ g, specific pore volume are 0.70mL/g.
Catalyst preparation example 6
Method with catalyst preparation example 2 prepares catalyzer EJZ-6, and time of immersion was 5 hours when difference was to flood Mo and Co.
Contain TiO in the titanium aluminium complex carrier
240 weight % contain γ-Al
2O
360 weight %; Active ingredient MoO
3Be respectively with respect to the quality (in oxide compound) of carrier with Co: 13.2 weight % and 4.1 weight %.
The specific surface of catalyzer is 278m
2/ g, specific pore volume are 0.70mL/g.
Catalyst preparation example 7
Method with catalyst preparation example 2 prepares catalyzer EJZ-7, and difference is that the dipping back was 570 ℃ of following roastings 4 hours.
Contain TiO in the titanium aluminium complex carrier
240 weight % contain γ-Al
2O
360 weight %; Active ingredient MoO
3Be respectively with respect to the quality (in oxide compound) of carrier with Co: 13.1 weight % and 4 weight %.The specific surface of catalyzer is 274m
2/ g, specific pore volume are 0.69mL/g.
Catalyst preparation example 8
Method with catalyst preparation example 1 prepares catalyzer EJZ-8, and used extrusion aid was a methylcellulose gum when difference was moulding, contains TiO in the gained catalyst Ti aluminium complex carrier
260 weight % contain γ-Al
2O
340 weight %; Active ingredient MoO
3Be respectively with respect to the quality (in oxide compound) of carrier with Co: 11 weight % and 3 weight %.
The specific surface of catalyzer is 236m
2/ g, specific pore volume are 0.63mL/g.
Catalyst preparation example 9
Method with catalyst preparation example 1 prepares catalyzer EJZ-9, and maturing temperature was 600 ℃ when difference was the carrier moulding, contains TiO in the gained catalyst Ti aluminium complex carrier
260 weight % contain γ-Al
2O
340 weight %; Active ingredient MoO
3Be respectively with respect to the quality (in oxide compound) of carrier with Co: 11 weight % and 3 weight %.
The specific surface of catalyzer is 223m
2/ g, specific pore volume are 0.65mL/g.
Catalyst preparation example 10
Method with catalyst preparation example 1 prepares catalyzer EJZ-10, and roasting time was 6 hours when difference was the carrier moulding, contains TiO in the gained catalyst Ti aluminium complex carrier
260 weight % contain γ-Al
2O
340 weight %; Active ingredient MoO
3Be respectively with respect to the quality (in oxide compound) of carrier with Co: 11 weight % and 3 weight %.
The specific surface of catalyzer is 225m
2/ g, specific pore volume are 0.64mL/g.
Embodiment 1
General flow chart is referring to Fig. 1.Desulphurization reactor R1 dress hydrocracking sweetening agent EJZ, reactor drum R2 dress adsorption desulfurizing agent EJT, the methane synthetic catalyst is EHM.Use H before the reaction earlier
2At 300 ℃ of following reducing catalyst EJZ, air speed is 1300h
-1, the recovery time is 2h.Coke(oven)gas sulphur content after the thick desulfurization is 2ppmv, through carrying out methanation reaction behind the desulphurization reactor.Air speed through catalyzer EJZ is 2900h
-1, temperature of reaction is 500 ℃; Air speed through EJT is 2900h
-1, temperature of reaction is 360 ℃; The methanation reaction temperature is 620 ℃, and air speed is 8000h
-1
When using the organic sulfur hydroconversion catalyst of different methods preparation, each component percentages of gas sees the following form before and after the desulfurization:
| Catalyzer | Component | CO 2 | H 2 | CO | CH 4 | CH 3OH | Total sulfur | Carbonylsulfide |
| ? | Reactor inlet | 2.34 | 66.10 | 7.16 | 24.39 | ----- | 2ppmv | 153ppbv |
| EJZ-1 | Reactor outlet | 3.59 | 61.97 | 3.70 | 30.69 | 0.037 | ＜20ppbv | ＜10ppbv |
| EJZ-2 | Reactor outlet | 3.29 | 60.83 | 3.28 | 32.53 | 0.050 | ＜20ppbv | ＜10ppbv |
| EJZ-3 | Reactor outlet | 3.41 | 59.97 | 3.70 | 31.89 | 0.046 | ＜20ppbv | ＜10ppbv |
| EJZ-4 | Reactor outlet | 3.01 | 62.10 | 6.77 | 27.38 | 0.013 | ＜20ppbv | ＜10ppbv |
| EJZ-5 | Reactor outlet | 0.98 | 50.41 | ----- | 48.19 | 0.038 | ＜20ppbv | ＜10ppbv |
| EJZ-6 | Reactor outlet | 3.28 | 60.80 | 3.26 | 32.58 | 0.051 | ＜20ppbv | ＜10ppbv |
| EJZ-7 | Reactor outlet | 3.30 | 60.86 | 3.31 | 32.48 | 0.047 | ＜20ppbv | ＜10ppbv |
| EJZ-8 | Reactor outlet | 3.60 | 61.96 | 3.71 | 30.68 | 0.036 | ＜20ppbv | ＜10ppbv |
| EJZ-9 | Reactor outlet | 3.60 | 61.98 | 3.71 | 30.67 | 0.038 | ＜20ppbv | ＜10ppbv |
| EJZ-10 | Reactor outlet | 3.59 | 61.98 | 3.71 | 30.65 | 0.041 | ＜20ppbv | ＜10ppbv |
The methane building-up reactions is through 300h, and methane synthetic catalyst activity is not fallen as follows.The methanation catalyst under the post analysis dismounting is accomplished in reaction, uses infrared carbon sulfur analyzer to measure, and learns that the catalyst body sulphur content is 0.0006%.
Comparative Examples 1
Technical process is not except that installing additional the desulphurization reactor, and other is identical with embodiment 1.Reaction is through 30h, CO and CO
2Transformation efficiency drops to 70% and 65% respectively by initial 100%.The methanation catalyst under the post analysis dismounting is accomplished in reaction, uses infrared carbon sulfur analyzer to measure, and learns that the catalyst body sulphur content is 0.1912%.
Can find out that from Comparative Examples 1 and the comparison of embodiment 1 desulphurization reactor can significantly reduce the catalyst body sulphur content, thereby prevent the methanation catalyst poisoning effectively, avoid transformation efficiency to decline to a great extent
Comparative Examples 2
General flow chart is referring to Fig. 1, and desulphurization reactor R1 adorns hydrocracking sweetening agent EJZ, reactor drum R2 dress adsorption desulfurizing agent EJT.Earlier with organic sulfur hydroconversion catalyst EJZ prevulcanized, other operation is identical with embodiment 1 with condition before the reaction.Can adopt the prevulcanized of liquid and gas method, the present embodiment vulcanizing agent is H
2S, the prevulcanized condition is: temperature 280, pressure 2MPa, air speed 12000h
-1, H in the charging
2S volume content 15%, curing time 20h.
When using the organic sulfur hydroconversion catalyst of different methods preparation, each component percentages of gas sees the following form before and after the desulfurization:
| Catalyzer | Component | CO 2 | H 2 | CO | CH 4 | CH 3OH | Total sulfur | Carbonylsulfide |
| ? | Reactor inlet | 2.34 | 66.10 | 7.16 | 24.39 | ----- | 2ppmv | 153ppbv |
| EJZ-1 | Reactor outlet | 3.58 | 61.96 | 3.71 | 30.70 | 0.037 | ＜20ppbv | ＜10ppbv |
| EJZ-2 | Reactor outlet | 3.26 | 60.75 | 3.30 | 32.61 | 0.051 | ＜20ppbv | ＜10ppbv |
| EJZ-3 | Reactor outlet | 3.40 | 59.96 | 3.71 | 31.89 | 0.047 | ＜20ppbv | ＜10ppbv |
| EJZ-4 | Reactor outlet | 3.02 | 62.11 | 6.76 | 27.39 | 0.014 | ＜20ppbv | ＜10ppbv |
| EJZ-5 | Reactor outlet | 0.97 | 50.42 | ----- | 48.16 | 0.038 | ＜20ppbv | ＜10ppbv |
| EJZ-6 | Reactor outlet | 3.27 | 60.81 | 3.26 | 32.57 | 0.053 | ＜20ppbv | ＜10ppbv |
| EJZ-7 | Reactor outlet | 3.31 | 60.87 | 3.31 | 32.46 | 0.048 | ＜20ppbv | ＜10ppbv |
| EJZ-8 | Reactor outlet | 3.61 | 61.94 | 3.73 | 30.67 | 0.035 | ＜20ppbv | ＜10ppbv |
| EJZ-9 | Reactor outlet | 3.61 | 61.97 | 3.71 | 30.66 | 0.037 | ＜20ppbv | ＜10ppbv |
| EJZ-10 | Reactor outlet | 3.57 | 61.97 | 3.72 | 30.67 | 0.042 | ＜20ppbv | ＜10ppbv |
Reaction is through 300h, and the methanation catalyst activity is not fallen as follows.The methanation catalyst under the post analysis dismounting is accomplished in reaction, uses infrared carbon sulfur analyzer to measure, and learns that the catalyst body sulphur content is 0.0007%.
According to Comparative Examples 2 and embodiment 1 learn that relatively pre-vulcanization process does not significantly improve the activity of organic sulfur hydroconversion catalyst of the present invention, so need not to carry out pre-vulcanization process for organic sulfur hydroconversion catalyst of the present invention.
General flow chart is referring to Fig. 1.Desulphurization reactor R1 dress hydrocracking sweetening agent EJZ, reactor drum R2 dress adsorption desulfurizing agent EJT.The methane synthetic catalyst is EHM.Use H before the reaction earlier
2At 300 ℃ of following reducing catalyst EJZ, air speed is 1300h
-1, the recovery time is 2h.Producing synthesis gas from coal sulphur content after the thick desulfurization is 2ppmv, through carrying out methanation reaction behind the desulphurization reactor.Air speed through catalyzer EJZ is 2900h
-1, temperature of reaction is 500 ℃; Air speed through catalyzer EJZ is 2900h
-1, temperature of reaction is 360 ℃.The methanation reaction temperature is 635 ℃, and air speed is 8000h
-1
Before and after the desulfurization, the gas volume composition sees the following form:
| Catalyzer | Component | CO 2 | H 2 | CO | CH 4 | CH 3OH | Total sulfur | Carbonylsulfide |
| ? | Reactor inlet | 1.45 | 61.21 | 17.17 | 19.33 | ----- | 2ppmv | 162ppbv |
| EJZ-1 | Reactor outlet | 2.49 | 53.69 | 12.73 | 30.34 | 0.052 | ＜20ppbv | ＜10ppbv |
| EJZ-2 | Reactor outlet | 2.40 | 51.90 | 12.52 | 32.96 | 0.051 | ＜20ppbv | ＜10ppbv |
| EJZ-3 | Reactor outlet | 2.18 | 52.69 | 14.28 | 30.87 | 0.045 | ＜20ppbv | ＜10ppbv |
| EJZ-4 | Reactor outlet | 1.98 | 55.29 | 15.61 | 26.95 | 0.044 | ＜20ppbv | ＜10ppbv |
| EJZ-5 | Reactor outlet | 1.16 | 29.31 | 6.29 | 63.12 | 0.038 | ＜20ppbv | ＜10ppbv |
| EJZ-6 | Reactor outlet | 2.46 | 53.56 | 12.46 | 30.84 | 0.051 | ＜20ppbv | ＜10ppbv |
| EJZ-7 | Reactor outlet | 2.41 | 51.53 | 12.35 | 32.64 | 0.044 | ＜20ppbv | ＜10ppbv |
| EJZ-8 | Reactor outlet | 2.32 | 52.66 | 14.67 | 30.25 | 0.051 | ＜20ppbv | ＜10ppbv |
| EJZ-9 | Reactor outlet | 1.69 | 55.21 | 15.63 | 26.55 | 0.053 | ＜20ppbv | ＜10ppbv |
| EJZ-10 | Reactor outlet | 1.24 | 29.14 | 6.35 | 63.22 | 0.039 | ＜20ppbv | ＜10ppbv |
The methane building-up reactions is through 300h, and methane synthetic catalyst activity is not fallen as follows.The methanation catalyst under the post analysis dismounting is accomplished in reaction, uses infrared carbon sulfur analyzer to measure, and learns that the catalyst body sulphur content is 0.0007%.
Can find out that from use the embodiment 2 of synthesizer this method also is applicable to synthetic gas desulfurization and carries out methane and synthesize as virgin gas.
Embodiment 3
General flow chart is referring to Fig. 1.Desulphurization reactor R1 dress hydrocracking sweetening agent EJZ-1, reactor drum R2 dress adsorption desulfurizing agent EJT, the methane synthetic catalyst is EHM.Use H before the reaction earlier
2At 300 ℃ of following reducing catalyst EJZ, air speed is 1300h
-1, the recovery time is 2h.Coke(oven)gas sulphur content after the thick desulfurization is 2ppmv, through carrying out methanation reaction behind the desulphurization reactor.The air speed of coke(oven)gas during through catalyzer EJZ is 1500h
-1, temperature is 500 ℃; Air speed through catalyzer EJT is 2900h
-1Temperature of reaction is 360 ℃; The methanation reaction temperature is 620 ℃, and air speed is 8000h
-1
Each component percentages of gas sees the following form before and after the desulfurization:
| Catalyzer | Component | CO 2 | H 2 | CO | CH 4 | CH 3OH | Total sulfur | Carbonylsulfide |
| ? | Reactor inlet | 2.34 | 66.10 | 7.16 | 24.39 | ----- | 2ppmv | 153ppbv |
| EJZ-1 | Reactor outlet | 4.19 | 59.38 | 3.50 | 32.88 | 0.023 | ＜20ppbv | ＜10ppbv |
[0135]Embodiment 4
General flow chart is referring to Fig. 1.Desulphurization reactor R1 dress hydrocracking sweetening agent EJZ-2, reactor drum R2 dress adsorption desulfurizing agent EJT., the methane synthetic catalyst is EHM (according to the methanation catalyst of patent CN 102125849A embodiment 1 preparation).Use H before the reaction earlier
2At 300 ℃ of following reducing catalyst EJZ, air speed is 1300h
-1, the recovery time is 2h.Coke(oven)gas sulphur content after the thick desulfurization is 2ppmv, through carrying out methanation reaction behind the desulphurization reactor.The air speed of coke(oven)gas during through catalyzer EJZ is 2900h
-1, temperature is 450 ℃; Air speed through catalyzer EJT is 2900h
-1Temperature of reaction is 360 ℃; The methanation reaction temperature is 620 ℃, and air speed is 8000h
-1
Each component percentages of gas sees the following form before and after the desulfurization:
| Catalyzer | Component | CO 2 | H 2 | CO | CH 4 | CH 3OH | Total sulfur | Carbonylsulfide |
| ? | Reactor inlet | 2.34 | 66.10 | 7.16 | 24.39 | ----- | 2ppmv | 153ppbv |
| EJZ-1 | Reactor outlet | 3.91 | 61.99 | 3.88 | 30.04 | 0.106 | ＜20ppbv | ＜10ppbv |
Embodiment 5
General flow chart is referring to Fig. 1.Desulphurization reactor top filling organic sulfur hydroconversion catalyst EJZ-3; The bottom dress removes inorganic sulfur catalyzer EJT (the commercially available inorganic sulfur catalyzer that removes), and the methane synthetic catalyst is EHM (according to the methanation catalyst of patent CN 102125849A embodiment 1 preparation).Use H before the reaction earlier
2At 300 ℃ of following reducing catalyst EJZ, air speed is 1300h
-1, the recovery time is 2h.Coke(oven)gas sulphur content after the thick desulfurization is 2ppmv, through carrying out methanation reaction behind the desulphurization reactor.The air speed of coke(oven)gas during through catalyzer EJZ is 2900h
-1, temperature is 580 ℃; Air speed through catalyzer EJT is 3500h
-1, temperature of reaction is 360 ℃; The methanation reaction temperature is 620 ℃, and air speed is 8000h
-1
Each component percentages of gas sees the following form before and after the desulfurization:
| Catalyzer | Component | CO 2 | H 2 | CO | CH 4 | CH 3OH | Total sulfur | Carbonylsulfide |
| ? | Reactor inlet | 2.34 | 66.10 | 7.16 | 24.39 | ----- | 2ppmv | 153ppbv |
| EJZ-3 | Reactor outlet | 2.89 | 61.79 | 4.30 | 30.86 | 0.032 | ＜20ppbv | ＜10ppbv |
Embodiment 6
General flow chart is referring to Fig. 1.Desulphurization reactor R1 dress hydrocracking sweetening agent EJZ-4, reactor drum R2 dress adsorption desulfurizing agent EJT, the methane synthetic catalyst is EHM.Use H before the reaction earlier
2At 300 ℃ of following reducing catalyst EJZ, air speed is 1300h
-1, the recovery time is 2h.Coke(oven)gas sulphur content after the thick desulfurization is 2ppmv, through carrying out methanation reaction behind the desulphurization reactor.The air speed of coke(oven)gas during through catalyzer EJZ is 2900h
-1, temperature is 500 ℃; Air speed through catalyzer EJT is 2900h
-1, temperature of reaction is 300 ℃; The methanation reaction temperature is 620 ℃, and air speed is 8000h
-1
Each component percentages of gas sees the following form before and after the desulfurization:
| Catalyzer | Component | CO 2 | H 2 | CO | CH 4 | CH 3OH | Total sulfur | Carbonylsulfide |
| ? | Reactor inlet | 2.34 | 66.10 | 7.16 | 24.39 | ----- | 2ppmv | 153ppbv |
| EJZ-3 | Reactor outlet | 2.94 | 61.72 | 4.16 | 30.72 | 0.030 | ＜20ppbv | ＜10ppbv |
Embodiment 7
General flow chart is referring to Fig. 2.Desulphurization reactor top filling organic sulfur hydroconversion catalyst EJZ-3, the bottom dress removes inorganic sulfur catalyzer EJT, and the methane synthetic catalyst is EHM.Use H before the reaction earlier
2At 300 ℃ of following reducing catalyst EJZ, air speed is 1300h
-1, the recovery time is 2h.Coke(oven)gas sulphur content after the thick desulfurization is 2ppmv, through carrying out methanation reaction behind the desulphurization reactor.The air speed of coke(oven)gas during through catalyzer EJZ is 2900h
-1, temperature is 360 ℃; Air speed through catalyzer EJT is 3500h
-1, temperature of reaction is 360 ℃; The methanation reaction temperature is 620 ℃, and air speed is 8000h
-1
Each component percentages of gas sees the following form before and after the desulfurization:
| Catalyzer | Component | CO 2 | H 2 | CO | CH 4 | CH 3OH | Total sulfur | Carbonylsulfide |
| ? | Reactor inlet | 2.34 | 66.10 | 7.16 | 24.39 | ----- | 2ppmv | 153ppbv |
| EJZ-3 | Reactor outlet | 2.86 | 62.38 | 5.79 | 28.94 | 0.026 | ＜20ppbv | ＜10ppbv |
Can find out from embodiment 1 to 7; Air speed when within the specific limits different are passed through catalyzer EJZ and temperature and through under the air speed and temperature of catalyzer EJT; The conversion that can realize sulphur is carried out with methanation in advance the time, realizes having prolonged the follow-up methanation catalyst life-span, has reduced the purpose of producing load.
Claims (13)
1. an organosulfur hydrocracking synthesizes combination treatment method with preparatory methane, and said treatment process uses organic sulfur hydroconversion catalyst, inorganic sulfur to remove catalyzer, the treating method comprises following steps:
(a) organosulfur hydrocracking and preparatory methane synthesis step wherein make said unstripped gas under the condition of first air speed, first temperature and first pressure, pass through said organic sulfur hydroconversion catalyst;
(b) inorganic sulfur removes step, wherein makes through said organosulfur hydrocracking and preparatory methane synthesis step unstripped gas afterwards and under the condition of second air speed, second temperature and second pressure, removes catalyzer through said inorganic sulfur.
2. gas processing method according to claim 1, wherein said first air speed are 500 to 4000h
-1, said first temperature is that 350 to 620 ℃ and said first pressure are that normal pressure is to 8MPa; Said second air speed is 500 to 4000h
-1, said second temperature is that 200 to 450 ℃ and said second pressure are that normal pressure is to 8MPa.
3. treatment process according to claim 1; Wherein said treatment process is the preposition step of methane synthetic; Said unstripped gas comprises producing synthesis gas from coal, coke(oven)gas, converter gas, blast furnace gas, semicoke gas or two or more gas mixtures wherein, and the total sulfur content in the said virgin gas is less than or equal to 3ppmv.
4. treatment process according to claim 1, the said organic sulfur hydroconversion catalyst that wherein in said treatment process, uses prepares according to the following method for preparing organic sulfur hydroconversion catalyst:
(a) preparation process of titanium aluminium dry glue powder wherein at first adds entry in reactor drum, be under 8 to 10 the condition in the pH value; The salts solution and the ammoniacal liquor uniform mixing that will contain aluminum ion and titanium ion; Aging, filter afterwards, wash, dry and pulverize, thereby obtain titanium aluminium dry glue powder;
(b) titanium alumina supporter forming step mixes titanium aluminium dry glue powder with extrusion aid, add sticker and mediate, and moulding afterwards, drying, calcining obtain titanium aluminium complex carrier;
(c) activity component impregnation step is immersed in titanium aluminium complex carrier in the solution of first active ingredient, afterwards oven dry, roasting; Again titanium aluminium complex carrier is immersed in the solution of second active ingredient, afterwards oven dry, roasting.
5. treatment process according to claim 4; Wherein in the preparation process of the said titanium aluminium dry glue powder in the said method for preparing organic sulfur hydroconversion catalyst, said salts solution makes in the following manner: with aluminum chloride salts solution and titanium tetrachloride solution by making TiO in the titanium aluminium complex carrier described in the said step (b)
2Content be 10% to 60% mixed.
6. treatment process according to claim 4 wherein in the preparation process of the titanium aluminium dry glue powder in the said method for preparing organic sulfur hydroconversion catalyst, is reused deionized water and is carried out said washing, Na in stem-based catalyst
+Be less than 0.05 weight %, Cl
-Content is less than 0.05 weight %.
7. treatment process according to claim 4; Wherein in the titanium alumina supporter forming step in the said method for preparing organic sulfur hydroconversion catalyst; Said extrusion aid is methylcellulose gum, sesbania powder or their mixture, and said sticker is rare nitric acid or the acetic acid,diluted of 1 weight % to 6 weight %.
8. treatment process according to claim 4; Wherein in the titanium alumina supporter forming step in the said method for preparing organic sulfur hydroconversion catalyst; Said calcination time is 1 to 10 hour, and calcining temperature is 450 ℃ to 600 ℃, and temperature rise rate is per hour 20 ℃ to 50 ℃; In said activity component impregnation step; Wherein dipping in said first active ingredient and the dipping in said second active ingredient all carried out 2 to 5 hours, and roasting after said first active ingredient of dipping and the roasting after said second active ingredient of dipping were all carried out 3 to 5 hours at 400 ℃ to 600 ℃.
9. treatment process according to claim 4; Wherein in the activity component impregnation step in the said method for preparing organic sulfur hydroconversion catalyst; The solution of said first active ingredient is the molybdenum salts solution, and the solution of said second active ingredient is cobalt salt solution or nickel salt solution.
10. treatment process according to claim 4, the specific surface area of the titanium aluminium complex carrier that wherein obtains in the titanium alumina supporter forming step in the said method for preparing organic sulfur hydroconversion catalyst are 200 to 350m
2/ g, specific pore volume are 0.4 to 1.1mL/g.
11. treatment process according to claim 9; Wherein in the said organic sulfur hydroconversion catalyst that the method according to said organic sulfur hydroconversion catalyst prepares; With respect to the quality of said titanium aluminium complex carrier, in oxide compound, Mo is 3% to 15%; And Co is 1% to 5% under the situation of Co existing, and Ni is 1% to 10% under the situation of Ni existing.
12. a method for preparing organic sulfur hydroconversion catalyst, the said method for preparing organic sulfur hydroconversion catalyst is the employed method for preparing organic sulfur hydroconversion catalyst in claim 4 to 11.
13. an organic sulfur hydroconversion catalyst, said organic sulfur hydroconversion catalyst are employed organic sulfur hydroconversion catalyst in claim 4 to 11.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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