CN102078749B - Fine desulfurizing agent and preparation method thereof - Google Patents
Fine desulfurizing agent and preparation method thereof Download PDFInfo
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- CN102078749B CN102078749B CN201010620065.8A CN201010620065A CN102078749B CN 102078749 B CN102078749 B CN 102078749B CN 201010620065 A CN201010620065 A CN 201010620065A CN 102078749 B CN102078749 B CN 102078749B
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- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 78
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 43
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims abstract description 37
- 229940116318 copper carbonate Drugs 0.000 claims abstract description 35
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 35
- 239000004568 cement Substances 0.000 claims abstract description 33
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 229910002588 FeOOH Inorganic materials 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 13
- 230000036541 health Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000001143 conditioned effect Effects 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 abstract description 22
- 239000011593 sulfur Substances 0.000 abstract description 22
- 239000011148 porous material Substances 0.000 abstract description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 5
- 238000009825 accumulation Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 34
- 238000006477 desulfuration reaction Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- 239000011787 zinc oxide Substances 0.000 description 17
- 230000023556 desulfurization Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000012752 auxiliary agent Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 235000004416 zinc carbonate Nutrition 0.000 description 3
- 239000011667 zinc carbonate Substances 0.000 description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- PCHQDTOLHOFHHK-UHFFFAOYSA-L zinc;hydrogen carbonate Chemical compound [Zn+2].OC([O-])=O.OC([O-])=O PCHQDTOLHOFHHK-UHFFFAOYSA-L 0.000 description 1
Abstract
A raw material for fine desulfurizing agent comprises the following raw materials: 55 to 70 part of basic zinc carbonate, 15 to 30 part of copper carbonate, 8 to 13 part of alumina cement and 1 to 4 part of binder. The raw materials of the fine desulfurizing agent contain basic zinc carbonate and copper carbonate, larger pore paths can be generated in the accumulation process as the copper carbonate molecules have larger volume; and unreacted sulfide can be diffused into crystal lattices of active components more easily, therefore, the fine desulfurizing agent has higher desulfurizing precision and higher sulfur capacity.
Description
Technical field
The present invention relates to a kind of fine desulfurizing agent and preparation method thereof, be specially a kind of that under normal temperature, low temperature, use, can remove gaseous feed in H
2fine desulfurizing agent of S and cos and preparation method thereof.
Background technology
Zinc oxide desulfurizer is to take ZnO as main component, adds binding agent alumina cement or cellulose, sometimes also adds certain pore creating material to change the pore structure of Zinc oxide desulfurizer, to improve activity and the crushing strength of desulfurizing agent.Zinc oxide desulfurizer is easy to use with it, the advantage of stable performance is widely used in the industries such as synthetic ammonia, synthesizing methanol, Coal Chemical Industry, petroleum refining.But traditional Zinc oxide desulfurizer generally all need to be used under high temperature (220～420 ℃) condition, therefore need to there is thermal source, consume certain energy, and in desulphurization reaction process, organic matter is easy to occur methanation side reaction and makes desulfurizing agent bed temperature runaway in the process of above-mentioned pyroreaction, or occur that coking side reaction causes carbon distribution to be coated on desulfurizing agent surface, thereby affect the desulphurizing activated of desulfurizing agent.
For overcoming above shortcoming, those skilled in the art have launched research to normal temperature and low temperature series desulfurizing agent in recent years, and as disclosed a kind of normal temp zinc oxide desulfuriging agent in Chinese patent literature CN1046213C, described Zinc oxide desulfurizer is by ZnO, CaO, Fe
2o
3, Al
2o
3deng composition, wherein the content of active component ZnO is more than 80～95% (m/m).Active component ZnO in described Zinc oxide desulfurizer can zinc oxide, the form of zinc hydroxide, zinc carbonate or basic zinc carbonate adds, wherein with zinc oxide and the mixing of basic zinc carbonate form, add fashionable desulfurized effect best, in described mixture, preferential oxidation zinc accounts for 10～50% (m/m), and basic zinc carbonate accounts for 90～50% (m/m); Described Zinc oxide desulfurizer has also added calcium aluminoferrite cement as structural promoter, in described structural promoter calcium aluminoferrite cement, mainly comprises CaO, Fe
2o
3, Al
2o
3deng composition; In the final Zinc oxide desulfurizer forming, the content of CaO is 0.5～5.0% (m/m), Fe
2o
3be 0.5～5.0% (m/m), Al
2o
3be 0.5～5.0% (m/m).Described Zinc oxide desulfurizer can be used under cryogenic conditions, has higher low temperature active and intensity.But the shortcoming that above-mentioned desulfurizing agent exists is that desulfurization precision is lower, H in the tail gas after above-mentioned desulfurizing agent is processed
2the content of S can only reach below 0.05ppm.
In above-mentioned technology, to adopt zinc oxide as desulphurizing activated material, its all to further decompose basic zinc carbonate as raw material after as desulphurizing activated material, yet basic zinc carbonate itself just can be used as desulphurizing activated material and uses, visible above-mentioned technology re-uses after the active component that itself can be used as desulphurizing activated material is further decomposed, and has strengthened on the contrary the manufacturing cost of desulfurizing agent.
In prior art, < < chemical industry and engineering > > volume the 5th October the 28th in 2007 is interim, name is called to disclose in the article of research > > of < < carbonate constant temperature fine desulfurizing catalyst uses one or both in copper carbonate, zinc carbonate, basic zinc carbonate as raw material, to carry out the preparation of desulfurizing agent, the proportioning of How to choose above-mentioned raw materials openly not in this technology; In Fig. 1 of the document, the quality Sulfur capacity that discloses a kind of active component and be the desulfurizing agent of zinc carbonate and copper carbonate can reach 29.81%.But, in the document, mention, when the performance of desulfurizing agent sample is evaluated, " when there being continuously 2 data to surpass 1mg/m
3time, think that desulfurizing agent is penetrated by sulphur ", this desulfurization precision that proves described desulfurizing agent is poor, only can reach 1mg/m
3(0.7ppm).
Summary of the invention
Problem to be solved by this invention is the low problem of desulfurization precision that the fine desulfurizing agent that uses under normal temperature, low temperature in prior art exists, and then a kind of that use under normal temperature, low temperature, fine desulfurizing agent that to take containing zinc raw material be active component with high desulfurization precision and preparation method thereof is provided.
For solving the problems of the technologies described above, the invention provides a kind of fine desulfurizing agent, at least by the raw material of following weight portion, made:
Basic zinc carbonate, 55～70 parts;
Copper carbonate, 15～30 parts;
Alumina cement, 8～13 parts;
Binding agent, 1～4 part.
Wherein, described fine desulfurizing agent also comprises the FeOOH of 3～10 parts.
Described FeOOH is r-FeOOH.
Described basic zinc carbonate is 60 parts;
Described copper carbonate is 25 weight portions.
Described alumina cement at least comprises the component of following mass percent: aluminium oxide, 50～65%; Calcium oxide, 29～40%.
The present invention also, disclosing on the basis of above-mentioned fine desulfurizing agent, further discloses the preparation method of described fine desulfurizing agent, comprises the steps:
(1) basic zinc carbonate of specified weight part, copper carbonate and three kinds of components of alumina cement or basic zinc carbonate, copper carbonate, FeOOH and four kinds of components of alumina cement are mixed, and stir;
(2) binding agent of specified weight part is soluble in water, form viscous solution, and stir;
(3) mixture obtaining in described step (1) is evenly mixed with the viscous solution of the binding agent obtaining in step (2), through extruded moulding, health, after dry, obtain described fine desulfurizing agent.
Described FeOOH is r-FeOOH.
In step (2), the mass ratio of described binding agent and water is 1～4.
The temperature of described health is 20～40 ℃, and conditioned time is at least 48 hours.
Described dry temperature is 110～130 ℃, and be 2 hours drying time.
The advantage of fine desulfurizing agent of the present invention is:
(1) fine desulfurizing agent of the present invention, contains basic zinc carbonate and copper carbonate in raw material, because the volume of carbonate molecule is larger, in banking process, can produce larger duct; Unreacted sulfide is more easily diffused in active component lattice, thereby obtains larger desulfuration efficiency.
But, inventor finds in research process, although the volume of carbonate molecule is larger, in banking process, can produce larger duct, be conducive to absorb sulfide and sulfide is discharged in the lattice that active component is piled into, but expand simply the use amount of carbonate and reduce the use amount of alumina cement and binding agent, can cause the excessively loose of pore passage structure, the intensity of the desulfurizing agent that impact prepares, be easy in use cause the breakage of pore passage structure, desulfuration efficiency is reduced, even make technological operation carry out.That is to say only have raw material of the present invention to form to meet basic zinc carbonate 55～70 weight portions, copper carbonate 15～30 weight portions, alumina cement 8～13 weight portions, binding agent 1～4 weight portion just can obtain suitable intensity, the highest desulfuration efficiency and maximum Sulfur capacity.
In addition, inventor also finds, the weight portion proportioning of desulphurizing activated component basic zinc carbonate and copper carbonate also need to have suitable ratio relation, consider that copper carbonate has higher desulfurization precision on the one hand, but expensive, and basic zinc carbonate price is relatively cheap, the content of the present invention by described basic zinc carbonate and copper carbonate are set is in suitable scope, realized when guaranteeing the desulfurization precision of described desulfurizing agent, also reduce as far as possible the cost of material of described desulfurizing agent, obtained the balance of a performance and cost.
(2) fine desulfurizing agent of the present invention, in raw material, also added a small amount of FeOOH, described FeOOH assists in removing cos, in addition, adding of active component FeOOH, also make in its pore passage structure that can be distributed to active component basic zinc carbonate and copper carbonate, thereby can carry out haptoreaction fully with the sulfide that is fully discharged into pore passage structure inside, further promoted the raising of desulfuration efficiency.But, under study for action, inventor also finds, adding equally of described FeOOH will have suitable weight portion, that is to say and will there is suitable and weight portion ratio desulphurizing activated component basic zinc carbonate and copper carbonate, FeOOH addition very little, cannot be distributed in the pore passage structure of desulphurizing activated component basic zinc carbonate and copper carbonate equably, and the raising of function that desulfuration efficiency is especially removed to cos is little; Similarly, if addition is too large, copper and zinc component reduce, and certainly will cause the decline of desulfurization precision and penetrate the reduction of Sulfur capacity.
(3) fine desulfurizing agent of the present invention, also selecting the described FeOOH arrange in raw material is r-FeOOH, uses the advantage of described r-FeOOH to be, for normal temperature condition lower time, there is higher Sulfur capacity, contribute to removing of cos simultaneously.
(4) fine desulfurizing agent of the present invention, selecting the content of the described basic zinc carbonate in raw material is 60 weight portions, the content of described copper carbonate is 25 weight portions, reason is, under this content condition, controlled the cost of described fine desulfurizing agent, also guaranteed that described fine desulfurizing agent has higher Sulfur capacity and higher desulfuration efficiency simultaneously.
(5) fine desulfurizing agent of the present invention, adds alumina cement in described fine desulfurizing agent to as structural auxiliary agent, and the component that described alumina cement at least comprises following mass percent is set: aluminium oxide, 50～65%; Calcium oxide, 29～40%, above-mentioned content condition has guaranteed that described alumina cement has suitable shaping strength, make to add the desulfurizing agent of this component can obtain suitable intensity of desulfurizer, thereby also with regard to having guaranteed that it can be not damaged because of use, also just guaranteed the desulfurization specific area of desulfurizing agent on the basis that guarantees its intensity.
(6) in the preparation method of fine desulfurizing agent of the present invention, select first active component to be mixed together with structural auxiliary agent, then the viscous solution of water-soluble binding agent is added to above-mentioned in mixed mixture, carry out again afterwards health and oven dry; In above-mentioned preparation method, first, active component is mixed together with structural auxiliary agent, thereby structural auxiliary agent can be scattered in desulphurizing activated material fully, be convenient to like this support that desulphurizing activated material in kneading process and drying course can fully obtain structural auxiliary agent; Secondly, separately binding agent is carried out to aqueous solution preparation, can be so that after binding agent disperses in the aqueous solution, after mixing with active component, can realize the abundant dispersion of binding agent in desulphurizing activated material and structural auxiliary agent by the mobilization of the aqueous solution, be conducive to like this dispersed of the framework of desulfurizing agent and desulphurizing activated material.
The specific embodiment
For content of the present invention is more likely to be clearly understood, be described in further detail according to a particular embodiment of the invention below.
embodiment 1
The preparation method of the fine desulfurizing agent described in the present embodiment is:
(1) basic zinc carbonate of following weight portion, copper carbonate and three kinds of components of alumina cement are mixed, and stir:
Basic zinc carbonate, 65 parts;
Copper carbonate, 15 parts;
Alumina cement, 10 parts;
(2) waterglass of 2 weight portions is soluble in water, form viscous solution, and stir;
(3) mixture obtaining in described step (1) is evenly mixed with the viscous solution of the binding agent obtaining in step (2), in banded extruder, be extruded into
strip, health is 60 hours at 30 ℃, sends into drying box, at 110 ℃, dries 1h, makes fine desulfurizing agent A.The Sulfur capacity of this desulfurizing agent at 100 ℃ is that the Sulfur capacity at 11.3%, 170 ℃ is 12.4%.
embodiment 2
(1) basic zinc carbonate of following weight portion, copper carbonate, FeOOH and four kinds of components of alumina cement are mixed, and stir:
Basic zinc carbonate, 60 parts;
Copper carbonate, 15 parts;
R-FeOOH, 3.5 parts;
Alumina cement, 10 parts;
(2) waterglass of 1.5 weight portions is soluble in water, form viscous solution, and stir;
(3) mixture obtaining in described step (1) is evenly mixed with the viscous solution of the binding agent obtaining in step (2), in banded extruder, be extruded into
strip, health is 36 hours at 20 ℃, sends into drying box, at 130 ℃, dries 3h, makes fine desulfurizing agent B.The Sulfur capacity of this desulfurizing agent at 100 ℃ is that the Sulfur capacity at 12.8%, 170 ℃ is 13.3%.
embodiment 3
The preparation method of the fine desulfurizing agent described in the present embodiment is:
(1) basic zinc carbonate of following weight portion, copper carbonate, FeOOH and four kinds of components of alumina cement are mixed, and stir:
Basic zinc carbonate, 55 parts;
Copper carbonate, 20 parts;
R-FeOOH, 5 parts;
Alumina cement, 9.5 parts;
(2) the carboxymethyl cellulose powder of 4 weight portions is soluble in water, form viscous solution, and stir;
(3) mixture obtaining in described step (1) is evenly mixed with the viscous solution of the binding agent obtaining in step (2), in banded extruder, be extruded into
strip, health is 48 hours at 40 ℃, sends into drying box, at 120 ℃, dries 2h, makes fine desulfurizing agent C.The Sulfur capacity of this desulfurizing agent at 20 ℃ is that the Sulfur capacity at 11.5%, 170 ℃ is 15.0%.
embodiment 4
(1) basic zinc carbonate of following weight portion, copper carbonate, FeOOH and four kinds of components of alumina cement are mixed, and stir:
Basic zinc carbonate, 60 parts;
Copper carbonate, 25 parts;
R-FeOOH, 6 parts;
Alumina cement, 11 parts;
(2) sesbania gum powder of 2 weight portions is soluble in water, form viscous solution, and stir;
(3) mixture obtaining in described step (1) is evenly mixed with the viscous solution of the binding agent obtaining in step (2), in banded extruder, be extruded into
strip, health is 48 hours at 20 ℃, sends into drying box, at 130 ℃, dries 1.5h, makes fine desulfurizing agent D.The Sulfur capacity of this desulfurizing agent at 20 ℃ is that the Sulfur capacity at 13.8%, 170 ℃ is 15.9%.
embodiment 5
(1) basic zinc carbonate of following weight portion, copper carbonate, FeOOH and four kinds of components of alumina cement are mixed, and stir:
Basic zinc carbonate, 70 parts;
Copper carbonate, 25 parts;
R-FeOOH, 10 parts;
Alumina cement, 13 parts;
(2) waterglass of 2 weight portions is soluble in water, form viscous solution, and stir;
(3) mixture obtaining in described step (1) is evenly mixed with the viscous solution of the binding agent obtaining in step (2), in banded extruder, be extruded into
strip, health is 48 hours at 20 ℃, sends into drying box, at 130 ℃, dries 2h, makes fine desulfurizing agent E.The Sulfur capacity of this desulfurizing agent at 20 ℃ is that the Sulfur capacity at 11.8%, 170 ℃ is 15.9%.
embodiment 6
(1) basic zinc carbonate of following weight portion, copper carbonate, FeOOH and four kinds of components of alumina cement are mixed, and stir:
Basic zinc carbonate, 66.5 parts;
Copper carbonate, 15 parts;
Amorphous FeOOH, 7.5 parts;
Alumina cement, 8 parts;
(2) sodium carboxymethylcellulose of 1 weight portion is soluble in water, form viscous solution, and stir;
(3) mixture obtaining in described step (1) is evenly mixed with the viscous solution of the binding agent obtaining in step (2), in banded extruder, be extruded into
strip, health is 48 hours at 20 ℃, sends into drying box, at 130 ℃, dries 2h, makes fine desulfurizing agent F.The Sulfur capacity of this desulfurizing agent at 100 ℃ is that the Sulfur capacity at 11.5%, 170 ℃ is 13.0%
embodiment 7
(1) basic zinc carbonate of following weight portion, copper carbonate, FeOOH and four kinds of components of alumina cement are mixed, and stir:
Basic zinc carbonate, 67.5 parts;
Copper carbonate, 16 parts;
R-FeOOH, 3 parts;
Alumina cement, 8 parts;
(2) sodium carboxymethylcellulose of 1.5 weight portions is soluble in water, form viscous solution, and stir;
(3) mixture obtaining in described step (1) is evenly mixed with the viscous solution of the binding agent obtaining in step (2), in banded extruder, be extruded into
strip, health is 48 hours at 40 ℃, sends into drying box, at 130 ℃, dries 2h, makes fine desulfurizing agent G.The Sulfur capacity of this desulfurizing agent at 100 ℃ is that the Sulfur capacity at 13.0%, 170 ℃ is 14.1%.
In above-described embodiment 1-6, each unit " part " represents 1 gram or 1 kilogram.
Alumina cement described in above-described embodiment can be selected commercially available alumina cement arbitrarily; As preferred embodiment, described alumina cement at least comprises the component of following mass percent: aluminium oxide, 50～65%; Calcium oxide, 29～40%.
experimental example
experimental example 1
Fine desulfurizing agent A to preparation in above-described embodiment 1 tests, and method is:
Unstripped gas is set for containing 5000PPmH
2s and N
2gaseous mixture;
Get 3ml desulfurizing agent A, under normal pressure, temperature is between 20～170 ℃, to carry out respectively repeatedly desulfurization, and gas air speed is 2000h
-1;
Finally record, under each temperature conditions, described unstrpped gas is after desulfurizing agent A processes, and outlet total sulfur is lower than 0.02PPm.
experimental example 2
Fine desulfurizing agent B-G to preparation in above-described embodiment 2-embodiment 7 tests, and method is:
Unstripped gas is set for containing 5000PPmH
2s and 500PPm COS and N
2gaseous mixture;
Get every kind of desulfurizing agent 3ml, under normal pressure, temperature is between 20～170 ℃, to carry out respectively repeatedly desulfurization, and gas air speed is 2000h
-1;
Finally record, under each temperature conditions, described unstrpped gas is after above-mentioned 6 kinds of fine desulfurizing agents are processed, and outlet total sulfur is all lower than 0.02PPm.
Visible according to the result of above-mentioned two experimental examples, the desulfurization precision of fine desulfurizing agent of the present invention can reach 0.02ppm, be well below the desulfurization precision (0.07ppm) of fine desulfurizing agent of the prior art.
Crushing strength>=the 50N/cm of fine desulfurizing agent A-G finished product of the present invention, specific surface is 50～75m
2/ g, pore volume>=0.5ml/g.
Desulfurizing agent of the present invention can be applied to the meticulous desulfurization of the various sulfide hydrogens such as hydrogen, coal gas, synthesis gas, gaseous hydrocarbons, cos gas under normal temperature～170 ℃, 0.1～6.0MPa.
Obviously, above-described embodiment is only for example is clearly described, and the not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without also giving all embodiments, and the apparent variation of being extended out thus or change are still among the protection domain in the invention.
Claims (8)
1. a fine desulfurizing agent, is characterized in that, at least by the raw material of following weight portion, is made:
Basic zinc carbonate, 55～70 parts;
Copper carbonate, 15～30 parts;
Alumina cement, 8～13 parts;
Binding agent, 1～4 part;
R-FeOOH, 3～10 parts.
2. fine desulfurizing agent according to claim 1, is characterized in that, described basic zinc carbonate is 60 parts.
3. fine desulfurizing agent according to claim 1 and 2, is characterized in that, described copper carbonate is 25 parts.
4. fine desulfurizing agent according to claim 3, is characterized in that, described alumina cement at least comprises the component of following mass percent: aluminium oxide, 50～65%; Calcium oxide, 29～40%.
5. the preparation method of the arbitrary described fine desulfurizing agent of claim 1-4, comprises the steps:
(1) basic zinc carbonate of specified weight part, copper carbonate, r-FeOOH and four kinds of components of alumina cement are mixed, and stir;
(2) binding agent of specified weight part is soluble in water, form viscous solution, and stir;
(3) mixture obtaining in described step (1) is evenly mixed with the viscous solution of the binding agent obtaining in step (2), through extruded moulding, health, after dry, obtain described fine desulfurizing agent.
6. the preparation method of fine desulfurizing agent according to claim 5, is characterized in that, in step (2), the mass ratio of described binding agent and water is 1～4.
7. according to the preparation method of the fine desulfurizing agent described in claim 5 or 6, it is characterized in that, the temperature of described health is 20～40 ℃, and conditioned time is at least 48 hours.
8. according to the preparation method of the fine desulfurizing agent described in claim 5 or 6, it is characterized in that, described dry temperature is 110～130 ℃, and be 2 hours drying time.
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| CN102512942B (en) * | 2011-12-20 | 2015-07-01 | 北京三聚环保新材料股份有限公司 | Low-temperature fine desulfurizer and its preparation method |
| CN104117374B (en) * | 2014-07-30 | 2016-04-20 | 沈阳三聚凯特催化剂有限公司 | A kind of copper zinc-aluminium base hydrolytic catalyst of carbonyl sulfur and preparation method thereof |
| CN105967301A (en) * | 2016-08-02 | 2016-09-28 | 含山县科宇环境工程有限公司 | Industrial wastewater desulfurizing agent and preparation method thereof |
| CN110115921A (en) * | 2019-05-27 | 2019-08-13 | 沈阳三聚凯特催化剂有限公司 | A kind of Fe-series desulfurizing agent and preparation method thereof |
| CN111330424B (en) * | 2020-01-20 | 2020-11-27 | 北京宝聚能源科技有限公司 | Flue gas desulfurizing agent and preparation method and application thereof |
| CN113617217B (en) * | 2021-08-25 | 2023-09-15 | 济源市鲁泰纳米材料有限公司 | Desulfurizing agent containing nano zinc oxide and production process thereof |
| CN114471133B (en) * | 2022-02-25 | 2023-08-01 | 射洪科瑞沃环保技术有限公司 | Desulfurizing agent for preventing desulfurizing rich agent from forming hardening at low temperature and preparation method thereof |
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| EP0243052A2 (en) * | 1986-04-25 | 1987-10-28 | Imperial Chemical Industries Plc | Sulphur compounds removal |
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