CN103028368B - Gas desulfurization sorbent and preparation method thereof and desulfurization method of sulfur-containing gas - Google Patents
Gas desulfurization sorbent and preparation method thereof and desulfurization method of sulfur-containing gas Download PDFInfo
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Abstract
The present invention relates to a gas desulfurization sorbent, wherein the sorbent includes M41S family mesoporous molecular sieve, a zinc oxide source, an aluminum oxide source, a silicon oxide source and a metal accelerator. The present invention also relates to a preparation method of the gas desulfurization sorbent and the gas desulfurization sorbent prepared by the method. The method comprises: mixing and contacting the silicon oxide source, the aluminum oxide source, the zinc oxide source, the M41S family mesoporous molecular sieve, and an acidic liquid; molding, drying and calcining the resulting mixture; and introducing the metal accelerator to the gas desulfurization sorbent. The present invention also relates to a desulfurization method for sulfur-containing gases by using the gas desulfurization sorbent. The gas desulfurization sorbent of the present invention has improved physical and chemical properties, long service life, high desulfurization activity and adaptability of raw materials.
Description
Technical field
The present invention relates to a kind of gas sweetening adsorbent, the preparation method of this gas sweetening adsorbent, the gas sweetening adsorbent prepared by described method, and the sulfur method of sulfurous gas.
Background technology
Along with people are to the pay attention to day by day of environmental protection, environmental regulation is day by day strict.In recent years, reduce sulphur emissions and be considered to one of most important measure improving air quality.On the one hand, for the tail gas of current a lot of commercial plant, be particularly that these sulfide have to pass through to remove and just can reach emission request containing a large amount of sulfide in the flue gas of the large power plant of fuel with coal.On the other hand, often higher by the sulfur content of the natural gas exploited out in the natural gas well, usually up to 10
4ppm, these natural gases have to pass through deep desulfuration just can reach civilian requirement.
Gas absorption desulfur technology has that treating capacity is large, desulfurization depth is high and to advantages such as various sulfide adaptability are high, has broad application prospects removing in the sulfur-containing compound in natural gas.
CN1559680A discloses a kind of solid desulphurization catalyst removing the poisonous and harmful substance such as sulfide, oxysulfide, thioether in natural gas, in flue gas under certain temperature, pressure condition, with the percentage composition of catalyst weight for benchmark: ZnO content is 6.5% to 65%, NiO content is 0.5% to 2%, CaAlO
3content is 11% to 40%, TiO
2content is 0.5% to 2%, CoO content is 0.9% to 2%, MoO content is 0.7% to 3%, Al
2o
3content is 20% to 70%.The solid desulphurization catalyst of this patent application can be used for the poisonous and harmful substance such as sulfide, oxysulfide, thioether removed in natural gas, in flue gas.But this solid desulphurization catalyst is slightly poor for the desulphurizing ability of the higher sulfurous gas raw material of sulfur content.
CN101970106A discloses a kind of particle sulfur removal material, and it comprises one or more nickel compounds, zinc oxide carrier material and one or more alkali metal compounds, and wherein, the content of nickel is 0.3-10 % by weight, and alkali-metal content is 0.2-10 % by weight.The hydrocarbon hydrogenolysis level that the sulfur removal material of this patent application may be used for reducing makes the desulfurization of appropriate hydrocarbon gas stream.But the abrasion resistance properties of this sulfur removal material and compression strength are all poor, be unfavorable for using in industry.
CN101249440A discloses a kind of hydrogenation adsorption desulfurize catalyst containing aroamtic hydrocarbon raw material, and the weight percentage of this catalyst is: reduced state nickel content is 5 ~ 70%, and zinc oxide content is 30 ~ 95%, and alumina content is 0 ~ 50%.But the described catalyst of this patent application exists the difficulty of shaping aspect, limit its scope of application.
CN1868572A discloses a kind of iron system O composite metallic oxide catalyst, and this catalyst is used for direct oxidation desulfurization.This catalyst forms by weight percentage: iron oxide content is 20 ~ 60%, and alumina content is 15 ~ 45%, and titanium oxide content is 15 ~ 45%, and zinc oxide content is 1 ~ 15%, and vanadium oxide content is 1 ~ 15%.This catalyst has higher activity and selective preferably, to H
2s content range is that the sour gas between 1 ~ 85% can directly process, normal pressure or low pressure (0.4MPa), 180 DEG C, air speed is 1500 ~ 3000h
-1under condition, H
2the conversion ratio of S can reach more than 95.0%.This catalyst efficiently can remove a large amount of hydrogen sulfide contained in gas, but the desulfurization depth of this catalyst is lower slightly, directly the sulfur content in the sulfurous gas of routine cannot be reduced to below 10ppm.
CN1712500A discloses a kind of coal gas of high temperature composite oxide desulfurizing agent, the chief active constituent element of this desulfurizing agent is zinc oxide, secondary active component is industrial oxidation copper, basic copper carbonate and natural manganese ore, wherein the content of zinc oxide be 33 ~ 50%, manganese oxide content be 0 ~ 10% and cupric oxide content be 0 ~ 15%.Although this desulfurizing agent has good mechanical strength close physical and chemical performance, can be applicable to fixed bed, fluid bed, air flow bed desulfurization reactor, this desulfurizing agent is inadequate to the adaptability of sulphur in raw material, and the removal activity for sulfurous organic compound is lower slightly.
Summary of the invention
The object of the invention is the above-mentioned defect in order to overcome existing gas sweetening adsorbent, a kind of new gas sweetening adsorbent and preparation method thereof is provided.
The invention provides a kind of gas sweetening adsorbent, wherein, this adsorbent contains M41S race mesopore molecular sieve, zinc oxide, aluminium oxide, silica source and metallic promoter agent, and described metallic promoter agent is be selected from least one in the oxide of VIIB race metal and the oxide of group VIII metal.
Present invention also offers a kind of preparation method of gas sweetening adsorbent, the method comprises:
(1) silica source, alumina source, zinc oxide source, M41S race mesopore molecular sieve are contacted with acidic liquid mixing, and the mixture obtained is carried out shaping, dry and roasting;
Wherein, the method further comprising the steps of at least one step:
(2a) before described mixing contact, described M41S race mesopore molecular sieve is mixed with metallic promoter agent precursor and contacts;
(2b) product of roasting obtained in step (1) is mixed with metallic promoter agent precursor contact, obtain adsorbent precursors, then described adsorbent precursors is carried out roasting;
Wherein, described metallic promoter agent precursor is at least one in the acetate of the metal be selected from the group that is made up of VIIB race metal and group VIII metal, carbonate, nitrate, sulfate, rhodanate and oxide.
Present invention also offers the gas sweetening adsorbent prepared by said method.
Present invention also offers a kind of sulfur method of sulfurous gas, the method comprises: make sulfurous gas and gas sweetening adsorbent contact, and wherein, described gas sweetening adsorbent is described gas sweetening adsorbent of the present invention.
Gas sweetening adsorbent according to the present invention has higher desulphurizing activated and adaptability to raw material, can be used for carrying out desulfurization to the sulfurous gas raw material of various sulfur content, the sulfurous gas raw material that particularly sulfur content is higher, the sulfur-containing tail gas (as flue gas) etc. of such as natural vapour, casing-head gas and various routine; Further, sulfur content can be obtained after adopting described gas sweetening adsorbent of the present invention to process sulfurous gas to meet the requirements gas.
And described gas sweetening adsorbent of the present invention has the physical and chemical performance (as compression strength) of improvement and longer service life, there is good practical application in industry and be worth.
In addition, described gas sweetening adsorbent of the present invention may be used for desulfurization under low temperature and high temperature, is convenient to commercial Application.
In addition, the preparation method of described gas sweetening adsorbent of the present invention is simple, be easy to realize industrialization, and production cost is lower.
Detailed description of the invention
The invention provides a kind of gas sweetening adsorbent, wherein, this adsorbent contains M41S race mesopore molecular sieve, zinc oxide, aluminium oxide, silica source and metallic promoter agent, and described metallic promoter agent is be selected from least one in the oxide of VIIB race metal and the oxide of group VIII metal.
In the preferred case, with the gross weight of described adsorbent for benchmark, the content of described M41S race mesopore molecular sieve is 5-35 % by weight, the content of zinc oxide is 20-80 % by weight, the content of aluminium oxide is 5-30 % by weight, the content of described silica source is 5-25 % by weight, and the content of described metallic promoter agent is 3-20 % by weight.
In a more preferred case, with the gross weight of described adsorbent for benchmark, the content of described M41S race mesopore molecular sieve is 12-25 % by weight, the content of zinc oxide is 40-65 % by weight, the content of aluminium oxide is 8-20 % by weight, the content of described silica source is 8-18 % by weight, and the content of described metallic promoter agent is 5-12 % by weight.
Gas sweetening adsorbent according to the present invention, described M41S race mesopore molecular sieve is a class crystalline silicate/alumino-silicate mesopore molecular sieve.Described M41S race mesopore molecular sieve can be the M41S race meso-porous molecular sieve material of various routine.Under preferable case, for making described gas sweetening adsorbent have higher desulphurizing activated and service life, described M41S race mesopore molecular sieve is preferably at least one in MCM-41, MCM-48 and MCM-50, is more preferably MCM-41 and/or MCM-48.
Gas sweetening adsorbent according to the present invention, the natural minerals that described silica source can be greater than 50 % by weight for silica and/or silica content.Under preferable case, described silica source is at least one in kaolin, diatomite, expanded perlite, carclazyte, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel, is more preferably kaolin and/or diatomite.When described silica source selects kaolin and/or diatomite, described gas sweetening adsorbent has the physical and chemical performance improved further.
Gas sweetening adsorbent according to the present invention, described metallic promoter agent is preferably selected from the oxide of at least one metal in cobalt, nickel, iron and manganese, most preferably is nickel oxide.When described metallic promoter agent is nickel oxide, described gas sweetening adsorbent has higher desulphurizing activated and regenerability.
Present invention also offers a kind of preparation method of gas sweetening adsorbent, the method comprises:
(1) silica source, alumina source, zinc oxide source, M41S race mesopore molecular sieve are contacted with acidic liquid mixing, and the mixture obtained is carried out shaping, dry and roasting;
Wherein, the method further comprising the steps of at least one step:
(2a) before described mixing contact, described M41S race mesopore molecular sieve is mixed with metallic promoter agent precursor and contacts;
(2b) product of roasting obtained in step (1) is mixed with metallic promoter agent precursor contact, obtain adsorbent precursors, then described adsorbent precursors is carried out roasting;
Wherein, described metallic promoter agent precursor is at least one in the acetate of the metal be selected from the group that is made up of VIIB race metal and group VIII metal, carbonate, nitrate, sulfate, rhodanate and oxide.
For described alumina source, relative to the consumption of the described silica source of 100 weight portions, the consumption of described alumina source can be 50-500 weight portion, is preferably 100-300 weight portion.Described alumina source can be aluminium oxide and/or the alumina precursor that can be converted into aluminium oxide under the condition of the described roasting of step (1).Described alumina precursor can be Alumina gel, the hydrated alumina with structure of similar to thin diaspore, the hydrated alumina with a diaspore structure, the hydrated alumina with gibbsite structure and at least one had in the hydrated alumina of boehmite structure.Described silica source with describe above identical.
For described zinc oxide source, relative to the consumption of the described silica source of 100 weight portions, the consumption of described zinc oxide source can be 100-1000 weight portion, is preferably 300-800 weight portion.Described zinc oxide source can be zinc oxide and/or the zinc oxide precursor that can be converted into zinc oxide under the condition of the described roasting of step (1).Described zinc oxide precursor can be at least one in zinc sulphide, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate and zinc nitrate.
For described M41S race mesopore molecular sieve, relative to the consumption of the described silica source of 100 weight portions, the consumption of described M41S race mesopore molecular sieve can be 30-500 weight portion, is preferably 100-300 weight portion.Described M41S race mesopore molecular sieve with describe above identical.
For described acidic liquid, the consumption of acid preferably makes the pH value of the mixture of described silica source, alumina source, zinc oxide source, M41S race mesopore molecular sieve and acidic liquid be 1-5, is more preferably 1.5-4.Described acidic liquid can be acid or aqueous acid.Described acid can be water-soluble inorganic acid and/or water-soluble organic acid, such as, can be at least one in hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
The preparation method of gas sweetening adsorbent according to the present invention, in step (1), the mixture of described silica source, alumina source, zinc oxide source, M41S race mesopore molecular sieve and acidic liquid can be the forms such as wet mixture, paste mixture, dough or slurries.By described shaping, described mixture is shaped to extrudate, sheet, pill, ball or micro-spherical particle.Such as, when described mixture be dough or paste mixture time, this mixture shaping (preferred extrusion molding) can be made to be particle, and preferred diameter is 1.0-8.0mm, length is the cylindrical extrudates of 2.0-5.0mm, then makes the extrudate of gained carry out drying, roasting; When described mixture is wet mixture, this mixture multiviscosisty can be made, through super-dry aftershaping; When described mixture is slurries, forms the microballoon that granularity is 20-200 micron, reach shaping object by spraying dry, for the ease of spraying dry, before dry, the solid content of slurries is preferably 10-50 % by weight, is more preferably 20-50 % by weight.
The method of described drying and condition have been conventionally known to one of skill in the art, such as, dry method can be dry, dry, forced air drying etc.The temperature of described drying can be room temperature to 400 DEG C, is preferably 100-350 DEG C.
The condition of described roasting is also conventionally known to one of skill in the art, and in general, the temperature of roasting can be 400-700 DEG C, is preferably 450-650 DEG C; The time of roasting can be at least 0.5 hour, is preferably 0.5-100 hour, is more preferably 0.5-10 hour.
The preparation method of gas sweetening adsorbent according to the present invention, in step (1), mixing in the process contacted by described silica source, alumina source, zinc oxide source, M41S race mesopore molecular sieve and acidic liquid, there is no particular limitation for the order fed intake of various material.In one embodiment, first described alumina source can be mixed with described acidic liquid and contact, carry out acidifying to described alumina source, wherein, sour al mole ratio preferably controls as 0.05-0.3; Then, acidified alumina source and described silica source, described zinc oxide source and described M41S race mesopore molecular sieve are mixed contact.In another embodiment, first described silica source, described alumina source and described acidic liquid can be contacted and form slurries, and carry out aging; Then, the slurries obtained after aging and described zinc oxide source and described M41S race mesopore molecular sieve are mixed contact.
The preparation method of gas sweetening adsorbent according to the present invention, the object of step (2a) and step (2b) is to introduce metallic promoter agent in the gas sweetening adsorbent to final preparation.
In step (2a), described M41S race mesopore molecular sieve and metallic promoter agent precursor being mixed the object contacted is to introduce metallic promoter agent precursor on described M41S race mesopore molecular sieve.Concrete method of operating can adopt and well known to a person skilled in the art that dipping method or intermediate processing realize.Described dipping method is with M41S race mesopore molecular sieve described in the solution of metallic promoter agent precursor or suspension impregnation.Described intermediate processing is mixed with described M41S race mesopore molecular sieve the solution of metallic promoter agent precursor or suspension, then adds ammoniacal liquor by metallic promoter agent precursor precipitation on described M41S race mesopore molecular sieve.
In step (2b), the product of roasting obtained in step (1) and metallic promoter agent precursor being mixed the object contacted also is to introduce metallic promoter agent precursor on described product of roasting.Concrete method of operating can be identical with the method for operating of above-described step (2a).
The preparation method of gas sweetening adsorbent according to the present invention, relative to the consumption of the described M41S race mesopore molecular sieve of 100 weight portions, the total amount of the consumption of the described metallic promoter agent precursor in the consumption of the described metallic promoter agent precursor in step (2a) and step (2b) can be 30-300 weight portion, is preferably 50-200 weight portion.
The preparation method of gas sweetening adsorbent according to the present invention, the described metallic promoter agent precursor in step (2a) and step (2b) can be identical or different.Described metallic promoter agent precursor in step (2a) and step (2b) is preferably selected from least one in the acetate of the metal in the group be made up of cobalt, nickel, iron and manganese, carbonate, nitrate, sulfate, rhodanate and oxide separately; Be more preferably at least one in nickel acetate, nickelous carbonate, nickel nitrate, nickelous sulfate, nickel thiocyanide and nickel oxide.Described metallic promoter agent precursor can to contain or not use containing the form of the crystallization water.
The preparation method of gas sweetening adsorbent according to the present invention, in step (2b), the temperature of described roasting can be 300-800 DEG C, and the time of described roasting can be 0.5-100 hour.
Present invention also offers the gas sweetening adsorbent prepared by said method.
Present invention also offers a kind of sulfur method of sulfurous gas, the method comprises: make sulfurous gas and gas sweetening adsorbent contact, and wherein, described gas sweetening adsorbent is described gas sweetening adsorbent provided by the invention.
The sulfur method of sulfurous gas according to the present invention, the condition of described sulfurous gas and gas sweetening adsorbent contact can comprise: temperature is 350-450 DEG C.
After described contact terminates, described method preferably also comprise by through contact after desulfuration adsorbent regenerate.The method of regeneration can comprise: first use inert gas (as nitrogen) to purge, and then passes into oxygen-containing gas (oxygen content can be 30-60 volume %) and carries out high-temperature oxydation.
In the present invention, described sulfurous gas can be the sulfurous gas of various routine, such as, can be the sulfur-containing tail gas (as flue gas) etc. of natural vapour, casing-head gas, various routine.Sulphur in described sulfurous gas can with hydrogen sulfide, sulfur dioxide, carbonyl sulfide (COS), carbon disulfide (CS
2) etc. form exist.
The invention will be further described by the following examples.
In the following Examples and Comparative Examples, the composition of gas sweetening adsorbent adopts the analysis of XRD (X-ray diffraction) method.
Embodiment 1
The present embodiment is for illustration of described gas sweetening adsorbent of the present invention and preparation method thereof.
By 4.21 kilograms of Zinc oxide powders (purchased from Headhorse company, purity is about 99.7 % by weight), the MCM-41 of 2.67 kilograms is (purchased from Nanjing catalyst branch company, containing butt 2.40 kilograms) and 6.30 kilograms of deionized water mixing, stir the mixed serum obtaining zinc oxide and MCM-41 after 30 minutes.
Get 1.92 kilograms, aluminium oxide (purchased from Shandong Aluminum Plant, containing butt 1.40 kilograms), the diatomite of 0.83 kilogram is (purchased from Nanjing catalyst branch company, containing butt 0.8 kilogram) and 4.1 kilograms of deionized waters under agitation mix, then the hydrochloric acid (chemical pure, purchased from Beijing Chemical Plant) adding 300 milliliter 30 % by weight stirs acidifying 1 hour.Then add the mixed serum of zinc oxide and MCM-41, and stir 0.5 hour, obtain the carrier pulp that pH value is 3.
Described carrier pulp adopts Niro Bowen Nozzle Tower
tMthe spray dryer of model carries out spraying dry, and spraying dry pressure is 6.0-6.5MPa, and inlet temperature is less than 340 DEG C, and outlet temperature is about 120 DEG C.The microballoon obtained by spraying dry roasting at 550 DEG C obtains adsorbing agent carrier in 1 hour.
By the aqueous impregnation of the adsorbing agent carrier of 4.4 kilograms containing 2.40 kilograms of Nickelous nitrate hexahydrates (purchased from Beijing chemical reagents corporation, purity is about 98.5%) and 0.7 kilogram of deionized water, the adsorbent precursors obtained.Then, by this adsorbent precursors at 180 DEG C after dry 2 hours, under air atmosphere, the condition of 550 DEG C, roasting 1 hour, obtains gas sweetening adsorbent A 1.
The chemical composition of this gas sweetening adsorbent A 1 is: zinc oxide content is 42 % by weight, and nickel oxide content is 12 % by weight, and alumina content is 14 % by weight, MCM-41 content is 24 % by weight, and diatomite content is 8 % by weight.
Comparative example 1
By 4.21 kilograms of Zinc oxide powders (purchased from Headhorse company, purity is about 99.7 % by weight), the diatomite of 2.48 kilograms is (purchased from Nanjing catalyst branch company, containing butt 2.40 kilograms) and 6.57 kilograms of deionized water mixing, stir and obtain zinc oxide and diatomaceous mixed serum after 30 minutes.
Get 3.01 kilograms, aluminium oxide (purchased from Shandong Aluminum Plant, containing butt 2.20 kilograms) and 6.6 kilograms of deionized waters under agitation mix, then the hydrochloric acid (chemical pure, purchased from Beijing Chemical Plant) adding 500 milliliter 30 % by weight stirs acidifying 1 hour.Then add zinc oxide and diatomaceous mixed serum, and stir 1 hour, obtain the carrier pulp that pH value is 2.
Described carrier pulp is carried out spray drying forming and is introduced metallic promoter agent precursor (Nickelous nitrate hexahydrate) by the method with reference to embodiment 1, obtains gas sweetening adsorbent B 1.
The chemical composition of this gas sweetening adsorbent B 1 is: zinc oxide content is 42 % by weight, and nickel oxide content is 12 % by weight, and alumina content is 22 % by weight, and diatomite content is 24 % by weight.
Embodiment 2
The present embodiment is for illustration of described gas sweetening adsorbent of the present invention and preparation method thereof.
By 5.01 kilograms of Zinc oxide powders (purchased from Headhorse company, purity is about 99.7 % by weight), the MCM-48 of 2.25 kilograms is (purchased from Nanjing catalyst branch company, containing butt 2.00 kilograms) and 6.60 kilograms of deionized water mixing, stir the mixed serum obtaining zinc oxide and MCM-48 after 30 minutes.
Get 1.64 kilograms, aluminium oxide (purchased from Shandong Aluminum Plant, containing butt 1.20 kilograms), the kaolin of 1.13 kilograms is (purchased from Nanjing catalyst branch company, containing butt 0.9 kilogram) and 4.1 kilograms of deionized waters under agitation mix, then the hydrochloric acid (chemical pure, purchased from Beijing Chemical Plant) adding 300 milliliter 30 % by weight stirs acidifying 1 hour.Then add the mixed serum of zinc oxide and MCM-48, and stir 0.5 hour, obtain the carrier pulp that pH value is 3.
Described carrier pulp is carried out spray drying forming and is introduced metallic promoter agent precursor (Nickelous nitrate hexahydrate) by the method with reference to embodiment 1, obtains gas sweetening adsorbent A 2.
The chemical composition of this gas sweetening adsorbent A 2 is: zinc oxide content is 50 % by weight, and nickel oxide content is 9 % by weight, and alumina content is 12 % by weight, MCM-48 content is 20 % by weight, and kaolin content is 9 % by weight.
Comparative example 2
By 5.02 kilograms of Zinc oxide powders (purchased from Headhorse company, purity is about 99.7 % by weight) and 6.20 kilograms of deionized water mixing, stir and obtain zinc oxide slurries after 30 minutes.
Get 2.88 kilograms, aluminium oxide (purchased from Shandong Aluminum Plant, containing butt 2.10 kilograms) and the kaolin of 2.50 kilograms (purchased from Nanjing catalyst branch company, containing butt 2.00 kilograms) under agitation mix, then add after deionized water 6.6 kilograms mixes, the hydrochloric acid (chemical pure, purchased from Beijing Chemical Plant) adding 440 milliliter 30 % by weight stirs acidifying 1 hour.Then add zinc oxide slurries, and stir 1 hour, obtain the carrier pulp that pH value is 3.
Described carrier pulp is carried out spray drying forming and is introduced metallic promoter agent precursor (Nickelous nitrate hexahydrate) by the method with reference to embodiment 1, obtains gas sweetening adsorbent B 2.
The chemical composition of this gas sweetening adsorbent B 2 is: zinc oxide content is 50 % by weight, and nickel oxide content is 9 % by weight, and alumina content is 21 % by weight, and kaolin content is 20 % by weight.
Embodiment 3
The present embodiment is for illustration of described gas sweetening adsorbent of the present invention and preparation method thereof.
By 6.23 kilograms of Zinc oxide powders (purchased from Headhorse company, purity is about 99.7 % by weight), the MCM-41 of 1.78 kilograms is (purchased from Nanjing catalyst branch company, containing butt 1.60 kilograms) and 7.20 kilograms of deionized water mixing, stir the mixed serum obtaining zinc oxide and MCM-41 after 30 minutes.
Get 1.10 kilograms, aluminium oxide (purchased from Shandong Aluminum Plant, containing butt 0.80 kilogram), the carclazyte of 1.0 kilograms is (purchased from Nanjing catalyst branch company, containing butt 0.8 kilogram) and 3.1 kilograms of deionized waters under agitation mix, then the hydrochloric acid (chemical pure, purchased from Beijing Chemical Plant) adding 180 milliliter 30 % by weight stirs acidifying 1 hour.Then add the mixed serum of zinc oxide and MCM-41, and stir 1 hour, obtain the carrier pulp that pH value is 4.
Described carrier pulp is carried out spray drying forming and is introduced metallic promoter agent precursor (Nickelous nitrate hexahydrate) by the method with reference to embodiment 1, obtains gas sweetening adsorbent A 3.
The chemical composition of this gas sweetening adsorbent A 3 is: zinc oxide content is 62 % by weight, and nickel oxide content is 6 % by weight, and alumina content is 8 % by weight, MCM-41 content is 16 % by weight, and carclazyte content is 8 % by weight.
Comparative example 3
By 6.23 kilograms of Zinc oxide powders (purchased from Headhorse company, purity is about 99.7 % by weight) and 8.20 kilograms of deionized water mixing, stir and obtain zinc oxide slurries after 30 minutes.
Get 2.19 kilograms, aluminium oxide (purchased from Shandong Aluminum Plant, containing butt 1.60 kilograms) and the carclazyte of 2.00 kilograms (purchased from Nanjing catalyst branch company, containing butt 1.60 kilograms) under agitation mix, then add after deionized water 4.6 kilograms mixes, the hydrochloric acid (chemical pure, purchased from Beijing Chemical Plant) adding 360 milliliter 30 % by weight stirs acidifying 1 hour.Then add zinc oxide slurries, and stir 1 hour, obtain the carrier pulp that pH value is 3.
Described carrier pulp is carried out spray drying forming and is introduced metallic promoter agent precursor (Nickelous nitrate hexahydrate) by the method with reference to embodiment 1, obtains gas sweetening adsorbent B 3.
The chemical composition of this gas sweetening adsorbent B 3 is: zinc oxide content is 62 % by weight, and nickel oxide content is 6 % by weight, and alumina content is 16 % by weight, and carclazyte content is 16 % by weight.
Embodiment 4
The present embodiment is for illustration of described gas sweetening adsorbent of the present invention and preparation method thereof.
Mixed by the hydrochloric acid (chemical pure, purchased from Beijing Chemical Plant) of hydrated alumina (containing 1.40 kg of alumina) and 30 % by weight, sour al mole ratio is 0.2, and stirs acidifying 1 hour, obtains the Alumina gel of acidifying.
By the MCM-41 of 2.67 kilograms (purchased from Nanjing catalyst branch company, containing butt 2.40 kilograms), the nickelous carbonate of 0.5 kilogram and the mixing of 0.7 kilogram of deionized water, obtain the mixed serum of MCM-41 and nickelous carbonate.
By 4.21 kilograms of Zinc oxide powders (purchased from Headhorse company, purity is about 99.7 % by weight), the diatomite of 0.83 kilogram is (purchased from Nanjing catalyst branch company, containing butt 0.8 kilogram), the mixed serum of 0.5 kilogram of nickelous carbonate, the Alumina gel of described acidifying, described MCM-41 and nickelous carbonate and 10.4 kilograms of deionized waters mixing, and stir 0.5 hour, obtain carrier pulp.
Described carrier pulp adopts Niro Bowen Nozzle Tower
tMthe spray dryer of model carries out spraying dry, and spraying dry pressure is 6.0-6.5MPa, and inlet temperature is less than 340 DEG C, and outlet temperature is about 120 DEG C.The microballoon obtained by spraying dry roasting at 550 DEG C obtains gas sweetening adsorbent A 4 in 1 hour.
The chemical composition of this gas sweetening adsorbent A 4 is: zinc oxide content is 42 % by weight, and nickel oxide content is 12 % by weight, and alumina content is 14 % by weight, MCM-41 content is 24 % by weight, and diatomite content is 8 % by weight.
Embodiment 5
The present embodiment is for illustration of described gas sweetening adsorbent of the present invention and preparation method thereof.
Mixed by the hydrochloric acid (chemical pure, purchased from Beijing Chemical Plant) of hydrated alumina (containing 1.40 kg of alumina) and 30 % by weight, sour al mole ratio is 0.2, and stirs acidifying 1 hour, obtains the Alumina gel of acidifying.
By the MCM-41 of 2.67 kilograms (purchased from Nanjing catalyst branch company, containing butt 2.40 kilograms), the nickel oxide of 0.6 kilogram and the mixing of 0.7 kilogram of deionized water, obtain the mixed serum of MCM-41 and nickel oxide.
By 4.21 kilograms of Zinc oxide powders (purchased from Headhorse company, purity is about 99.7 % by weight), the diatomite of 0.83 kilogram is (purchased from Nanjing catalyst branch company, containing butt 0.8 kilogram), the mixed serum of the Alumina gel of described acidifying, described MCM-41 and nickel oxide and 10.4 kilograms of deionized waters mixing, and stir 0.5 hour, obtain carrier pulp.
Described carrier pulp adopts Niro Bowen Nozzle Tower
tMthe spray dryer of model carries out spraying dry, and spraying dry pressure is 6.0-6.5MPa, and inlet temperature is less than 340 DEG C, and outlet temperature is about 120 DEG C.The microballoon obtained by spraying dry roasting at 550 DEG C obtains gas sweetening adsorbent A 5 in 1 hour.
The chemical composition of this gas sweetening adsorbent A 5 is: zinc oxide content is 42 % by weight, and nickel oxide content is 12 % by weight, and alumina content is 14 % by weight, MCM-41 content is 24 % by weight, and diatomite content is 8 % by weight.
Embodiment 6
The present embodiment is for illustration of described gas sweetening adsorbent of the present invention and preparation method thereof.
Prepare gas sweetening adsorbent according to the method for embodiment 5, difference is, replaces nickel oxide with the manganese oxide of identical weight, thus obtained gas sweetening adsorbent A 6.
The chemical composition of this gas sweetening adsorbent A 6 is: zinc oxide content is 42 % by weight, and manganese oxide content is 12 % by weight, and alumina content is 14 % by weight, MCM-41 content is 24 % by weight, and diatomite content is 8 % by weight.
Test case
(1) specific area of gas sweetening adsorbent A 1-A6 and B1-B3 adopts nitrogen physical adsorption process, and Merck & Co., Inc 2020ASSP adsorption instrument carries out;
(2) intensity of gas sweetening adsorbent A 1-A6 and B1-B3 adopts straight tube wearing and tearing method to evaluate, the standard method of its evaluation method reference RIPP29-90 is (see volumes such as " Petrochemical Engineering Analysis method " (RIPP test method) Yang Cuiding, Science Press, nineteen ninety publishes), wherein, abrasion index is less, shows that abrasion strength resistance is higher;
The test result of gas with various desulfuration adsorbent is as shown in table 1 below.
Table 1
| Adsorbent | A1 | B1 | A2 | B2 | A3 | B3 | A4 | A5 | A6 |
| Specific area (m 2/g) | 86 | 42 | 83 | 36 | 81 | 33 | 79 | 78 | 69 |
| Abrasion index | 5.6 | 6.2 | 5.5 | 6.3 | 5.8 | 6.2 | 5.7 | 5.8 | 6.0 |
As can be seen from the data of table 1, prepared according to the methods of the invention gas sweetening adsorbent has higher specific area and abrasion strength resistance.
Embodiment 7
The present embodiment is for illustration of the sulfur method of described sulfurous gas of the present invention.
Gas sweetening adsorbent A 1 being filled in internal diameter is in 30mm fixed bed reactors, and amount of fill is 30 grams.Then, under an argon atmosphere the gas sweetening adsorbent in reactor is heated to 400 DEG C.Then, in reactor, inject simulation sulfurous gas (2.8 volume % hydrogen sulfide, 0.2 volume %SO
2, 0.2 volume %COS, 47 volume % methane, 5 volume %H
2, 45 volume %N
2), the volume space velocity of injection is 1200h
-1.
Adopt on-line mass spectroscopy instrument to be detector, measure the content of sulphur compound in the gas of discharging from reactor.Think that when the concentration of hydrogen sulfide reaches 20ppm in tail gas described gas sweetening sorbent is saturated, the sulfur content now in described gas sweetening adsorbent is considered to year sulfur content of this gas sweetening adsorbent.Current-carrying capacity is higher, shows the desulphurizing activated higher of gas sweetening adsorbent.
Absorb saturated after, first adopt nitrogen to purge 30 minutes to the gas sweetening adsorbent in reactor, and temperature be raised to 500 DEG C; Then in reactor, pass into the gaseous mixture of 50 volume % air and 50 volume % nitrogen, carry out oxidation regeneration, gaseous mixture flow velocity is 160ml/min, and the recovery time is 2 hours.
Pass into High Purity Nitrogen after having regenerated to purge, and be cooled to reaction temperature, again adopt described simulation sulfurous gas to carry out the evaluation of a new circulation, carry out 6 circulations altogether and evaluate.Year sulfur content of the gas sweetening adsorbent measured by each circulation is as shown in table 2 below.
Embodiment 8-12 and comparative example 4-6
Year sulfur content of gas sweetening adsorbent A 2-A6 and B1-B3 is evaluated according to the method circulation of embodiment 7.Evaluation result is as shown in table 2 below.
Table 2
As can be seen from the data of table 2, prepared according to the methods of the invention gas sweetening adsorbent has higher desulphurizing activated.
Claims (20)
1. the sulfur method of a sulfurous gas, the method comprises: make sulfurous gas and gas sweetening adsorbent contact, it is characterized in that, described gas sweetening adsorbent contains M41S race mesopore molecular sieve, zinc oxide, aluminium oxide, silica source and metallic promoter agent, and described metallic promoter agent is be selected from least one in the oxide of VIIB race metal and the oxide of group VIII metal; Sulphur in described sulfurous gas is the form of hydrogen sulfide, sulfur dioxide, carbonyl sulfide or carbon disulfide; With the gross weight of described adsorbent for benchmark, the content of described M41S race mesopore molecular sieve is 12-25 % by weight.
2. sulfur method according to claim 1, wherein, the content of zinc oxide is 40-65 % by weight, and the content of aluminium oxide is 8-20 % by weight, and the content of described silica source is 8-18 % by weight, and the content of described metallic promoter agent is 5-12 % by weight.
3. sulfur method according to claim 1 and 2, wherein, described M41S race mesopore molecular sieve is at least one in MCM-41, MCM-48 and MCM-50.
4. sulfur method according to claim 1 and 2, wherein, described silica source is the natural minerals that silica and/or silica content are greater than 50 % by weight.
5. sulfur method according to claim 4, wherein, described silica source is at least one in kaolin, diatomite, expanded perlite, carclazyte, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel.
6. sulfur method according to claim 1 and 2, wherein, described metallic promoter agent is the oxide of at least one metal be selected from cobalt, nickel, iron and manganese.
7. sulfur method according to claim 6, wherein, described metallic promoter agent is nickel oxide.
8. sulfur method according to claim 1, wherein, the method preparation of described gas sweetening adsorbent by comprising the following steps:
(1) silica source, alumina source, zinc oxide source, M41S race mesopore molecular sieve are contacted with acidic liquid mixing, and the mixture obtained is carried out shaping, dry and roasting;
Wherein, the method further comprising the steps of at least one step:
(2a) before described mixing contact, described M41S race mesopore molecular sieve is mixed with metallic promoter agent precursor and contacts;
(2b) product of roasting obtained in step (1) is mixed with metallic promoter agent precursor contact, obtain adsorbent precursors, then described adsorbent precursors is carried out roasting;
Wherein, described metallic promoter agent precursor is at least one in the acetate of the metal be selected from the group that is made up of VIIB race metal and group VIII metal, carbonate, nitrate, sulfate, rhodanate and oxide.
9. sulfur method according to claim 8, wherein, in step (1), relative to the consumption of the described silica source of 100 weight portions, the consumption of described alumina source is 50-500 weight portion, the consumption of described zinc oxide source is 100-1000 weight portion, and the consumption of described M41S race mesopore molecular sieve is 30-500 weight portion, and the consumption of acid makes the pH value of described mixture be 1-5.
10. sulfur method according to claim 8 or claim 9, wherein, described acidic liquid is acid or aqueous acid, and described acid is water-soluble inorganic acid and/or water-soluble organic acid.
11. sulfur methods according to claim 10, wherein, described acid is at least one in hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
12. sulfur methods according to claim 8 or claim 9, wherein, described alumina source is aluminium oxide and/or the alumina precursor that can be converted into aluminium oxide under the condition of the described roasting of step (1).
13. sulfur methods according to claim 12, wherein, described alumina precursor is Alumina gel, has the hydrated alumina of structure of similar to thin diaspore, has the hydrated alumina of a diaspore structure, the hydrated alumina with gibbsite structure and at least one had in the hydrated alumina of boehmite structure.
14. sulfur methods according to claim 8 or claim 9, wherein, described zinc oxide source is zinc oxide and/or the zinc oxide precursor that can be converted into zinc oxide under the condition of the described roasting of step (1).
15. sulfur methods according to claim 14, wherein, described zinc oxide precursor is at least one in zinc sulphide, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate and zinc nitrate.
16. sulfur methods according to claim 8, wherein, in step (1), the temperature of described drying is room temperature to 400 DEG C, and the temperature of described roasting is 400-700 DEG C, and the time of described roasting is 0.5-100 hour.
17. sulfur methods according to claim 8, wherein, relative to the consumption of the described M41S race mesopore molecular sieve of 100 weight portions, the total amount of the consumption of the described metallic promoter agent precursor in the consumption of the described metallic promoter agent precursor in step (2a) and step (2b) is 30-300 weight portion.
Sulfur method described in 18. according to Claim 8 or 17, wherein, described metallic promoter agent precursor is at least one in the acetate of the metal be selected from the group that is made up of cobalt, nickel, iron and manganese, carbonate, nitrate, sulfate, rhodanate and oxide.
19. sulfur methods according to claim 18, wherein, described metallic promoter agent precursor is at least one in nickel acetate, nickelous carbonate, nickel nitrate, nickelous sulfate, nickel thiocyanide and nickel oxide.
Sulfur method described in 20. according to Claim 8 or 17, wherein, in step (2b), the temperature of described roasting is 300-800 DEG C, and the time of described roasting is 0.5-100 hour.
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