CN101791532A - Normal-temperature natural-gas sulphur adsorbent and preparation method thereof - Google Patents
Normal-temperature natural-gas sulphur adsorbent and preparation method thereof Download PDFInfo
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- CN101791532A CN101791532A CN 201010104061 CN201010104061A CN101791532A CN 101791532 A CN101791532 A CN 101791532A CN 201010104061 CN201010104061 CN 201010104061 CN 201010104061 A CN201010104061 A CN 201010104061A CN 101791532 A CN101791532 A CN 101791532A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 92
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000003345 natural gas Substances 0.000 title claims abstract description 40
- 239000003463 adsorbent Substances 0.000 title claims abstract description 29
- 239000005864 Sulphur Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 21
- 238000001556 precipitation Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 229910006299 γ-FeOOH Inorganic materials 0.000 claims abstract description 7
- 238000000975 co-precipitation Methods 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 239000011593 sulfur Substances 0.000 claims description 74
- 229910052717 sulfur Inorganic materials 0.000 claims description 73
- 239000002250 absorbent Substances 0.000 claims description 46
- 230000002745 absorbent Effects 0.000 claims description 46
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- 239000004202 carbamide Substances 0.000 claims description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- 125000001741 organic sulfur group Chemical group 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 150000003463 sulfur Chemical class 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 230000003009 desulfurizing effect Effects 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 2
- 230000001376 precipitating effect Effects 0.000 claims 2
- 229910052788 barium Inorganic materials 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 15
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 9
- 239000011575 calcium Substances 0.000 description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 8
- 230000000149 penetrating effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000000496 anti-anoxic effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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Abstract
The invention discloses a method for preparing a normal-temperature natural-gas sulphur adsorbent by a fractional precipitation method. The method comprises the following steps: firstly, preparing active gamma-FeOOH by adopting a coprecipitation method; then, preparing oxide of one or more of other metal elements, namely Ti, Cu, Co, Ni, Zn, Ca, Mg, Ba, Mo and Mn by adopting a homogeneous precipitation method to form a precursor of the sulphur adsorbent; and finally baking the precursor at the temperature of between 400 and 700 DEG C to obtain the sulphur adsorbent with a perovskite structure. The sulphur adsorbent can endure high carbon dioxide concentration (0 to 5.0 percent (v/v)), can be used at the normal temperature, and can simultaneously remove inorganic sulphur and organic sulphur in the natural gas.
Description
Technical field:
The invention belongs to the purified treatment field of natural gas, relate to a kind of preparation method of natural-gas sulphur adsorbent, the sulfur absorbent of this method preparation can effectively remove hydrogen sulfide and the organic sulfur compound in the natural gas.
Technical background:
Key component in the natural gas is a hydro carbons, also contains impurity such as hydrogen sulfide, mercaptan, thioether, carbon dioxide, oxygen-free.Sulfide is poisonous, can severe contamination atmosphere, animal and plant are all had very big harm, and can make corrosion of metal generation hydrogen embrittlement and electrochemistry weight-loss corrosion, can make the catalyst poisoning in the Chemical Manufacture of downstream and lost efficacy.Hydrogen sulfide corrosion pipeline in the long distance pipeline, the iron sulfide powder meeting occluding device and the throttling arrangement of generation, influence metering and adjusting, the also spontaneous combustion of iron sulfide powder has the potential danger that causes combustion of natural gas and blast.Contain H
2Generate SO behind the combustion of natural gas of S
2, it is the main gas that forms acid rain.Therefore, the natural gas of sulfur compound must be handled and could use for the user through desulfurization.
Usually the CO that contains 2-5% in the natural gas
2Gas belongs to typical C O
2Desulfurization system.The sulfur absorbent that adopts traditional handicraft production is owing to acid ingredient CO in the system
2Existence, can be very fast with adsorbent in CaO, Ca (OH)
2Deng basic component in conjunction with generating CaCO
3Etc. foulant, thereby stop up the adsorbent duct, cause the adsorbent rapid deactivation, the H of refining back gas
2The S equal size exceeds standard, and the comprehensive Sulfur capacity of adsorbent descends, and bed quickens to harden gas permeability variation, air-flow skewness.In addition, the existing inorganic sulfur of the sulfide in the natural gas is as hydrogen sulfide, organic sulfur is arranged again, as mercaptan, thioether etc., sulfur absorbent is wanted and can simultaneously organic sulfur and inorganic sulfur all be worked, and the natural gas after making with extra care could satisfy the requirement of GB17820-1999 " natural gas ".
GB17820-1999 " natural gas "
The research of sulfur absorbent and production patent are many, see Table one.Conclude and get up to mainly contain two classes: a class is primarily aimed at inorganic sulfur, and second class all works to inorganic sulfur and organic sulfur.In view of the compositing characteristic of natural gas, can only remove the sulfur absorbent of inorganic sulfur, can not make the natural gas after making with extra care qualified.In the patent of enumerating, inorganic sulfur and organic sulfur are all worked, perhaps sweetening process needs oxygen to participate in, perhaps carbon dioxide is not had tolerance.All be not suitable for doing the sulfur absorbent of natural gas.
The table 1 sulfur absorbent patent of being correlated with
Among the preparation method of the second class sulfur absorbent, the reactive metal element that can the catalysis organic sulfur be converted into inorganic sulfur has plenty of by the method for co-precipitation to be introduced, and has plenty of by infusion process and introduces, and does not see the report of method of fractional steps precipitation preparation.
In view of above situation, the object of the present invention is to provide under a kind of normal temperature and to use, can remove inorganic sulfur again can organic sulfide removal, anti-anoxic simultaneously, sulfur absorbent of anti-carbon dioxide and preparation method thereof.
With the iron oxide is the sulfur absorbent of main component, and the content of iron oxide and activity have a direct impact the size of Sulfur capacity, improve iron oxide content, can increase Sulfur capacity; In addition, sulfide at first will be adsorbed on the inner surface of sulfur absorbent, could react with metal oxide wherein, and organic sulfur is converted into inorganic sulfur, inorganic sulfur and iron oxide reaction then, thus reach the purpose that removes.Therefore, sulfur absorbent will have big specific area, suitable pore passage structure, so that sulfide is diffused rapidly to sulfur absorbent inside, reacts.In order to reach these purposes, we adopt step-by-step precipitation method to prepare sulfur absorbent, and the first step obtains active gamma-iron oxide earlier, and washing removes the impurity that generates in the dereaction, improves the content of iron oxide.In second step, in the suspension of gamma-iron oxide, use one or more metal oxides among urea Preparation by Uniform Precipitation Ti, Cu, Co, Ni, Zn, Ca, Mg, Ba, Mo, the Mn.In the 3rd step, mixed-metal oxides is squeezed into required form, and then, drying and moulding remains in the urea in the precipitation, decomposes gradually when dry, emits carbon dioxide and ammonia, produces suitable pore passage structure in sulfur absorbent inside.In the 4th step, the sulfur absorbent of drying and moulding cures at 400-700 ℃, obtains having the product of perovskite structure feature.
Perovskite composite oxide is structure and perovskite Ca TiO
3An identical big compounds is often with general formula ABO
3Expression, the component of perovskite structure compound substitutes and can change in very wide scope by part, forms as A
1-xA
x' BO
3, AB
1-xB
x' O
3And A
1-xA
x' B
1-yB
y' O
3The type compound.Do not change though partly replaced its structure of noval chemical compound of generation by element, the doping of different elements can cause appraising at the current rate of new lattice vacancy and other ion of coordination, finally causes the very big change of physics, chemical property.
Summary of the invention:
It is a kind of under the no oxygen condition that main purpose of the present invention is to provide, the natural-gas sulphur adsorbent and the production technology thereof of big, the anti-high carbon dioxide content of Sulfur capacity, long service life, non-secondary pollution.This technology adopts fractional precipitation and baking process, finally makes high accuracy, high CO
2The natural-gas sulphur adsorbent of tolerance.
The present invention is achieved through the following technical solutions:
The invention provides a kind of natural-gas sulphur adsorbent, this adsorbent is a kind of composite metal oxide that presents the perovskite structure feature, it is characterized in that comprising iron oxide, and the composite metal oxide that one or more oxide is formed in other metal element Ti, Cu, Co, Ni, Zn, Ca, Mg, Ba, Mo, Mn.
The present invention also provides a kind of preparation method of above-mentioned natural-gas sulphur adsorbent, adopt the preparation of the distribution precipitation method, the first step, soluble ferric iron salt and carbonate generation coprecipitation reaction, generate active γ-FeOOH, second step, in the suspension of γ-FeOOH, add one or more soluble-salt solution homogeneous precipitations in urea liquid among Ti, Cu, Co, Ni, Zn, Ca, Mg, Ba, Mo, the Mn, obtain their oxide, in the 3rd step, mixed precipitation is squeezed into required shape, drying and moulding then, in the 4th step, cure the formation perovskite structure.
More particularly, technical scheme of the present invention is
1 with iron oxide and other metal element Ti, Cu, Co, Ni, Zn, Ca, Mg, Ba, Mo, and one or more oxide is a precursor among the Mn, and through baking and banking up with earth, preparation has the active component of perovskite structure.The composite metal oxide of perovskite structure promotes the absorption of sulfide in iron oxide surface, and the catalysis organic sulfur is converted into hydrogen sulfide simultaneously, thereby reaches the purpose of organic sulfide removal.
The composite metal oxide of perovskite structure mainly plays following effect:
1) alkalescence on increase sulfur absorbent surface promotes the absorption of hydrogen sulfide and organic sulfur compound.
2) promote that organic sulfur is converted into hydrogen sulfide
COS+H
2O＝H
2S+CO
2
RSH+H
2O＝ROH+H
2S
2 adopt fractional precipitation technology to prepare catalyst
The first step: coprecipitation prepares active gamma-iron oxide
Soluble ferric iron salt is as FeSO
4, FeCl
2, Fe (NO
3)
2, Fe
2(SO
4)
3, FeCl
3, Fe (NO
3)
3Deng, be mixed with the aqueous solution of 5-40%, under the condition of aerobic, add carbonate in batches, as sodium carbonate, potash, ammonium carbonate, carbonic hydroammonium.The control pH value is 8-9, obtains γ-FeOOH precipitation, and abandoning supernatant adds washing 2-3 time.
Second step: the oxide of other metal of Preparation by Uniform Precipitation
Adopt other metal oxide of urea Preparation by Uniform Precipitation.Decomposition reaction can take place and generate NH in aqueous solution of urea about 70 ℃
4OH, NH
4OH guarantees that the precipitation in the solution is in a kind of poised state, thereby separates out precipitation uniformly by slowly discharging equably in the solution.
CO(NH
2)
2+3H
2O＝2NH
3·H
2O+CO
2
NH
3·H
2O＝NH
4 ++OH
-
Ti, Cu, Co, Ni, Zn, Ca, Mg, Ba, Mo, one or more soluble-salt wiring solution-formings of Mn add in the suspension of iron hydroxide, stir.Add excessive urea, be heated to boiling, reacted 8 hours, through the solid that Separation of Solid and Liquid obtains, extrusion modling.
The 3rd step: improve the pore passage structure of sulfur absorbent, increase specific area
Dry under the condition of 10-120 ℃ of aerobic.Remain in the precipitation urea, when drying, decompose gradually, emit carbon dioxide and ammonia, sulfur absorbent obtains porosity and pore passage structure preferably.
The 4th step: cure
Dry good sulfur absorbent after the cooling, obtained product at 400-1000 ℃ of roasting 0.5-4 hour.Most preferred stoving temperature is 400-700 ℃.Obtain having the product of perovskite structure.See accompanying drawing one.
The present invention to organic sulfur change into inorganic sulfur have catalytic activity for the Ca-Ti ore type composite metal oxide, the general formula of perovskite composite oxide is: ABO
3, A represents terres rares or alkaline-earth metal element in the formula, and B represents transition metal, and A represents a kind of element among Ca, Mg, the Ba among the present invention, and B represents one or more the element among Ti, Cr, Mn, Fe, Co, Ni, the Cu.
The chemical formula of preferred perovskite composite oxide is CaFe
0.8Ti
0.2O
3,, BaFe
0.8Ti
0.2O
3, CaFe
0.8Cu
0.2O
3,, CaFe
0.7Mn
0.3O
3, BaFe
0.6Cr
0.4O
3, MgFe
0.5Ni
0.5O
3, MgFe
0.8Cu
0.2O
3
Adopt step-by-step precipitation method, bag is mixed, is carried secretly phenomenon and obviously reduces in the precipitation process, and deposit seed is even and particle diameter is little, in addition, goes up attached to precipitation and to have made a lot of ducts again when unreacted urea oven dry is decomposed, and has obviously improved the specific area of sulfur absorbent.In addition, it is also influential to the specific area of sulfur absorbent to bake and bank up with earth temperature, measures the specific area of product under the different sintering temperatures, and 400-700 ℃, specific area is at 40-50m
2/ g, temperature surpasses 800 degree, sulfur absorbent generation agglomeration phenomenon, specific area obviously descends, and has only 20-30m
2/ g.
The specific area 40-50m of sulfur absorbent
2/ g, its compression strength 40-100N.cm
-1, bulk density 0.8-0.9Kg/L.
Desulfurizing agent of the present invention, bubbling air can be regenerated, and reaches reusable purpose.
Natural-gas sulphur adsorbent of the present invention can remove organic sulfur and inorganic sulfur in the natural gas simultaneously.This sulfur absorbent can tolerate concentration of carbon dioxide scope 0-5.0% (volume ratio).
Use this sulfur absorbent under the room temperature, air speed is 1000hr
-1, CO in the natural gas
2Content 2.55% (volume ratio), H
2S content 65mg/m
3, total sulfur 370mg/m
3Situation under.After the desulfurization, with H in the natural gas
2S content 〉=0.5mg/m
3As breakthrough point, one action Sulfur capacity 〉=20%.
The present invention has following advantage:
The catalyst that 1 the present invention synthesizes can remove cos, mercaptan and inorganic sulfur simultaneously, reaches GB one class gas or two class gas standards after making natural gas fine purification, need not organic sulfur and inorganic sulfur are handled respectively, has simplified technological process, saves the equipment investment expense.
2 sulfur absorbents of the present invention have perovskite structure, and all there is oxygen vacancy more or less in the oxide of perovskite structure in its structure; From the viewpoint of crystal structure, in the compound of ABO3 type perovskite structure, the cation of the brilliant position of A also occurs vacant easily, causes the surplus of oxygen simultaneously.The vacant lattice vacancy that produces causes that the ion that is attached thereto appraises at the current rate, and the metal ion that appraises at the current rate has very high reactivity, can react with inorganic sulfur, can react with organic sulfur again.
In 3 sweetening processes, need not feed water, air or oxygen, satisfy the safety requirements of handling combustible gas.
4 sulfur absorbents are strong to the adaptability of source of the gas, can remove the unstripped gas that contains higher concentration cos, mercaptan and hydrogen sulfide, simultaneously, the carbon dioxide in the unstripped gas had very strong tolerance.
Description of drawings
Accompanying drawing is the X-ray diffraction contrast spectrogram that the present invention adopts the baking process front and back.
The specific embodiment
The present invention is further elaborated with embodiment below, but these embodiment have any restriction to the present invention absolutely not, and any change that those skilled in the art of the present technique are done in to the invention process under the enlightenment of this specification all will drop in the scope of claims.
Given below is the prepared in laboratory method, when the needs suitability for industrialized production, can amplify production in proportion.
Embodiment one
Get FeCl
230g places the reactor of 500ml, adds water 350ml, stirring and dissolving was divided in 6 hours under intense stirring condition and is added 25g sodium carbonate three times, added the back and continued to stir 2 hours, natural subsidence is removed supernatant, adds water, the solid that washing is avaled and, it is inferior to give a baby a bath on the third day after its birth repeatedly, then, adds titanyl sulfate 10g, calcium chloride 35.6g, stirring and dissolving adds urea 40g, is heated to boiling, vigorous stirring reaction 8 hours, centrifugal filtration, extruded moulding, 80 ℃ of dryings, activation 12 hours, 600 degree cured 3 hours, obtained 63g bar shaped sulfur absorbent.Chemical formula through the elementary analysis sulfur absorbent is CaFe
0.8Ti
0.2O
3, form the perovskite composite oxide thing phase of knowing clearly through X-ray diffraction analysis.
Table 2 associated gas is formed table
| Form | ??CH 4 | ??C 2H 6 | ??C 3H 8 | ??iC 4H 10 | ??nC 4H 10 | ??iC 5H 12 | ??nC 5H 12 | ??C 6 + | ??CO 2 | ??N 2 |
| ??V％ | ??82.11 | ??5.70 | ??5.34 | ??0.59 | ??1.67 | ??0.15 | ??0.21 | ??0.07 | ??3.04 | ??1.12 |
H
2S content: 150mg/m
3Total sulfur content :≤200mg/m
3
This sulfur absorbent is contained in the glass tube reactor of internal diameter 30mm, interior dress sulfur absorbent 200 grams, and Reactor inlet gas composition sees Table 2, and at normal temperature, air speed is 800hr
-1Under the condition, once penetrating Sulfur capacity is 21.2%, (contains H in the reactor outlet gas
2S 〉=0.5ppm is considered as penetrating)
Embodiment two
FeSO
47H
2O 30g adds the 500ml reactor, adds water 200ml, starts stirring and dissolving, adds (NH after the dissolving in batches
4)
2CO
315g, after adding, vigorous stirring 5 hours, natural subsidence, abandoning supernatant then, adds MgCl
212.8g, CuSO
44.5g urea 15g is heated to boiling, stirring reaction 10 hours filters, and filter cake is squeezed into particle, 70 ℃ of dry 20h in drying room.700 degree roastings are 2 hours then, get sulfur absorbent 15.6g.Chemical formula through the elementary analysis sulfur absorbent is MgFe
0.8Cu
0.2O
3, form the perovskite composite oxide thing phase of knowing clearly through X-ray diffraction analysis.
Table 3 reservoir gas is formed table
| Form | ??CH 4 | ??C 2H 6 | ??C 3H 8 | ??iC 4H 10 | ??nC 4H 10 | ??iC 5H 12 | ??nC 5H 12 | ??CO 2 | ??N 2 |
| ??V％ | ??92.9 | ??1.81 | ??0.21 | ??0.01 | ??0.02 | ??0.01 | ??0.01 | ??2.05 | ??3.00 |
H
2S content: 65mg/m
3Total sulfur content :≤300mg/m
3
This sulfur absorbent is contained in the glass tube reactor of internal diameter 30mm, interior dress sulfur absorbent 200 grams, and Reactor inlet gas composition sees Table 3, and at normal temperature, normal pressure, air speed is 300hr
-1Under the condition, once penetrating Sulfur capacity is 20.9% (weight), (contains H in the reactor outlet gas
2S 〉=0.5ppm is considered as penetrating).
Embodiment three
Fe
2(SO
4)
330g adds the 1000ml reactor, adds 350ml water, and dissolving after the dissolving, slowly adds (NH in batches
4)
2HCO
333g, the limit edged stirs, and after adding, stirs 3 hours, and natural subsidence is removed supernatant, washs 2 times, adds NiCl then
210g, MgCl
214.3g urea 25g is heated to boiling, stirs centrifugal filtration 12 hours.Filter cake is pressed into particle, dries 5 hours for 100 ℃ in drying room.600 degree cured 2 hours, obtained sulfur absorbent 16.5g.Chemical formula through the elementary analysis sulfur absorbent is MgFe
0.5Ni
0.5O
3, form the perovskite composite oxide thing phase of knowing clearly through X-ray diffraction analysis.
This sulfur absorbent is contained in the glass tube reactor of internal diameter 30mm, interior dress sulfur absorbent 200 grams, and Reactor inlet gas composition sees Table 3, and at normal temperature, normal pressure, air speed is 600hr
-1Under the condition, once penetrating Sulfur capacity is 28.9% (weight), (contains H in the reactor outlet gas
2S 〉=0.5ppm is considered as penetrating).
Embodiment four
FeSO
47H
2O 30g adds the 500ml reactor, adds water 350ml, starts stirring and dissolving, adds (NH after the dissolving in batches
4)
2HCO
310g, after adding, vigorous stirring 2 hours stops stirring, and natural subsidence is removed supernatant, and washed twice then, adds CaCl
217.0g, Mn (NO
3)
28.2g urea 25g is heated to boiling, reacts 5 hours, filters, filter cake is squeezed into particle, and 100 degree are dry 5 hours in drying room.700 degree cured 1 hour, got sulfur absorbent 19.1g.Chemical formula through the elementary analysis sulfur absorbent is CaFe
0.7Mn
0.3O
3, form the perovskite composite oxide thing phase of knowing clearly through X-ray diffraction analysis.
This sulfur absorbent is contained in the glass tube reactor of internal diameter 30mm, interior dress sulfur absorbent 200 grams, and Reactor inlet gas composition sees Table 2, and at normal temperature, normal pressure, air speed is 800hr
-1Under the condition, once penetrating Sulfur capacity is 29.2%, (contains H in the reactor outlet gas
2S 〉=0.5ppm is considered as penetrating).
Claims (11)
1. natural-gas sulphur adsorbent, this adsorbent is a kind of composite metal oxide that presents the perovskite structure feature, it is characterized in that comprising iron oxide, and the composite metal oxide that one or more oxide is formed in other metal element Ti, Cu, Co, Ni, Zn, Ca, Mg, Ba, Mo, Mn.
2. natural-gas sulphur adsorbent as claimed in claim 1, its active component are the Ca-Ti ore type composite metal oxide, and the general formula of Ca-Ti ore type composite metal oxide is ABO
3, A represents terres rares or alkaline-earth metal element in the formula, and B represents one or more transition metal.
3. natural-gas sulphur adsorbent as claimed in claim 2, wherein alkali earth metal is Ca, Mg, Ba, transition metal is Ti, Zn, Mn, Fe, Co, Ni, Cu, Mo.
4. natural-gas sulphur adsorbent as claimed in claim 2, the chemical formula of Ca-Ti ore type composite metal oxide are CaFe
0.8Ti
0.2O
3, BaFe
0.8Ti
0.2O
3, CaFe
0.8Cu
0.2O
3, CaFe
0.7Mn
0.3O
3, BaFe
0.6Cr
0.4O
3, MgFe
0.5Ni
0.5O
3, MgFe
0.8Cu
0.2O
3
5. natural-gas sulphur adsorbent as claimed in claim 1, its feature also are to remove simultaneously organic sulfur and the inorganic sulfur in the natural gas.
6. natural-gas sulphur adsorbent as claimed in claim 1, its feature are that also this sulfur absorbent can tolerate concentration of carbon dioxide scope 0-5.0% (volume ratio).
7. the preparation method of natural-gas sulphur adsorbent as claimed in claim 1, adopt the preparation of the distribution precipitation method, the first step, soluble ferric iron salt and carbonate generation coprecipitation reaction, generate active γ-FeOOH, second step, in the suspension of γ-FeOOH, add Ti, Cu, Co, Ni, Zn, Ca, Mg, Ba, Mo, one or more soluble-salt solution homogeneous precipitations in urea liquid among the Mn, obtain their oxide, in the 3rd step, mixed precipitation is squeezed into required shape, then 10-120 ℃ of drying and moulding, in the 4th step, 400-700 ℃ is cured the formation perovskite structure.
8. as the preparation method of natural-gas sulphur adsorbent as described in the claim 7, in its preparation process, two-step precipitation is finished in same reactor, and the active γ-FeOOH of generation will be through washing.
9. the preparation method of natural-gas sulphur adsorbent as claimed in claim 7, its feature is that also baking temperature at 10-120 ℃, remains in the urea in the desulfurizing agent, decomposes during dry activation, emits gas, plays the effect of sulfur absorbent pore-creating.
10. the preparation method of natural-gas sulphur adsorbent as claimed in claim 7, it is 400-700 ℃ that its feature also is to bake and bank up with earth temperature, bakes and banks up with earth time 0.5-8 hour, baking and banking up with earth the back specific area is 40-50m
2/ g, compression strength 40-80N.cm
-1, bulk density 0.8-0.9Kg/L.
11. the preparation method of natural-gas sulphur adsorbent as claimed in claim 7, in its preparation process, the precipitating reagent of the first step adopts carbonate, comprises sodium carbonate, potash, ammonium carbonate, carbonic hydroammonium; The precipitating reagent in second step adopts excessive urea.
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| CN104667926A (en) * | 2013-11-29 | 2015-06-03 | 福建三聚福大化肥催化剂国家工程研究中心有限公司 | Low-temperature carbonyl sulfide hydrolysis catalyst and preparation method thereof |
| CN106673068A (en) * | 2016-11-22 | 2017-05-17 | 中国科学院生态环境研究中心 | Application of perovskite type composite oxide catalytic material to process of selective oxidation of H2S |
| CN108187611A (en) * | 2018-01-26 | 2018-06-22 | 山东星火科学技术研究院 | A kind of adsorbent for gasoline naphtha desulfurization |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1194077C (en) * | 2000-10-10 | 2005-03-23 | 北京三聚环保新材料有限公司 | Alkali-free refining process of liquefied petroleum gas or natural gas |
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| CN104667926A (en) * | 2013-11-29 | 2015-06-03 | 福建三聚福大化肥催化剂国家工程研究中心有限公司 | Low-temperature carbonyl sulfide hydrolysis catalyst and preparation method thereof |
| CN104667926B (en) * | 2013-11-29 | 2017-01-25 | 福建三聚福大化肥催化剂国家工程研究中心有限公司 | Low-temperature carbonyl sulfide hydrolysis catalyst and preparation method thereof |
| CN106673068A (en) * | 2016-11-22 | 2017-05-17 | 中国科学院生态环境研究中心 | Application of perovskite type composite oxide catalytic material to process of selective oxidation of H2S |
| CN108187611A (en) * | 2018-01-26 | 2018-06-22 | 山东星火科学技术研究院 | A kind of adsorbent for gasoline naphtha desulfurization |
| CN108889057A (en) * | 2018-08-10 | 2018-11-27 | 中国恩菲工程技术有限公司 | Flue gas purification device and method, gas cleaning adsorbent and its application |
| CN113351008A (en) * | 2020-03-04 | 2021-09-07 | 中国科学院生态环境研究中心 | Application of perovskite composite oxide material in low-temperature carbonyl sulfide hydrolysis reaction |
| CN113663665A (en) * | 2021-08-09 | 2021-11-19 | 中国科学院大学 | Organic sulfur hydrolysis catalyst suitable for Claus process and preparation method and application thereof |
| CN113663665B (en) * | 2021-08-09 | 2023-09-22 | 中国科学院大学 | Organic sulfur hydrolysis catalyst suitable for Claus process, preparation method and application thereof |
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