CN109529768A - A kind of absorption desulfurizing agent and its preparation method and application - Google Patents
A kind of absorption desulfurizing agent and its preparation method and application Download PDFInfo
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- CN109529768A CN109529768A CN201811570306.5A CN201811570306A CN109529768A CN 109529768 A CN109529768 A CN 109529768A CN 201811570306 A CN201811570306 A CN 201811570306A CN 109529768 A CN109529768 A CN 109529768A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
The present invention provides a kind of absorption desulfurizing agents and its preparation method and application.The absorption desulfurizing agent includes active carbon and the active material that is supported on the active carbon, and the active material is the mixture of alkaline matter and metal oxide or its esters；The metal oxide is one of oxide of K, Mg, Cu, Ni, Zn, Ag or a variety of, and the alkaline matter is sodium oxide molybdena and/or potassium oxide；The metal oxide accounts for 0.1~20wt% of the active carbon, and the alkaline matter accounts for 0.2~30wt% of the active carbon.Absorption desulfurizing agent of the invention is for removing mercaptan, thioether, thiophene sulfides, it is particularly suitable for fine de-sulfur alcohol, thioether, thiophene etc. in cracking olefin component, remove precision < 5ppm, and the content and property of active olefin substance are basically unchanged in cracking olefin component after desulfurization, while the desulfurizing agent has the characteristics that Sulfur capacity height, Yi Zaisheng.
Description
Technical field
The present invention relates to technical field of desulfurization in industry, more particularly, to a kind of absorption desulfurizing agent and its preparation side
Method and application.
Background technique
With the rapid development of China's oil chemical industry, the production capacity of ethylene improves year by year, so that ethylene unit
By-product cracking c_5 C 9 distillate is also constantly increasing, so that the comprehensive utilization project of China's light dydrocarbon carbon nine be driven vigorously to send out
Exhibition.Foreign countries are highly developed to the utilization technology of light dydrocarbon carbon nine, are mainly used for the production of Petropols, product covered from
Low side colouring resin forms producing in serial form to high-end plus hydrogen colourless resin, such as the Yi Siman in the U.S. and Exxon, Japan
Auspicious father-in-law, Cologne of South Korea etc..The Petropols industrial production in China is started late, by the development of recent two decades, China it is low
Hold Petropols production technology more mature, market tends to be saturated.But high-end Petropols are such as applied to wholesome food, height
The fields such as paint, ink are held, the production of industrial scale has not been completed.China is high-end at present adds hydrogen colourless resin product base
This dependence import, there is an urgent need to the technical bottleneck that domestic enterprise breaks through hydrogenated petroleum resin, and hydrogenated petroleum resin production technologies
Bottleneck be concentrated mainly on hydrogenation catalyst.
Sulfur content due to crude oil peracid, high-sulfur and the inferior heavy processed in recent years, in cracking c_5 C 9 fraction
It gradually increases, wherein sulfide usually has mercaptan, thioether, thiophane and thiophene etc., and thiophene accounts for 80% or more total sulfur.Sulfide
Presence be easy to cause hydrogenation catalyst poisoning and equipment corrosion, seriously restrict the high-end applications of petroleum resin products.Cracking
Sulfur content in light dydrocarbon C 9 fraction is not very high but there is a large amount of active olefin, traditional hydrodesulfurization removing sulphur
While destroy the structure and composition of active olefin component in light dydrocarbon C 9 fraction.Therefore, there is an urgent need to one kind not to influence
The structure and composition of active olefin component in cracking c_5 C 9 fraction, and can be removed in depth in cracking c_5 C 9 fraction
Sulfide method, come meet technique production and high-end product processing requirements at the higher level.
Absorption desulfurization is a kind of method of new effective removing sulfide, can be carried out at ambient temperature and pressure, is had not
Face hydrogen, easy to operate, equipment investment is few, it is pollution-free, be suitable for the advantages that deep desulfuration, especially to condensed ring thiophene class sulfide
Removing will be highly effective, therefore, absorption desulfurization have wide development space and application prospect.
A kind of refined active carbon desulfurizer and preparation removing mercaptan and thioether is provided in patent CN1095393C.The desulfurizing agent
It is made of the oxide or salt and active carbon of Na, Cu, Si.Preparation method is the water soluble compound by above-mentioned element in activity
Addition before charcoal molding, or loaded on active carbon by sub-dip or total immersion, it is then dry and activate in room temperature~300 DEG C.
The desulfurizing agent can remove H simultaneously2S、COS、CS2, mercaptan, thioether, thiophene sulfides, be particularly suitable for fine de-sulfur alcohol, thioether,
It removes precision < 0.05ppm.The Sulfur capacity with higher compared with other similar desulfurizing agents, using 0~100 DEG C of temperature, air speed
100~3000h.It can be widely used for synthesis ammonia, methanol, low-carbon alcohols, synthetic fuel, gas, methanation, food-grade C02, close
At the fine de-sulfur in the production technologies such as polypropylene, while being still used for semiwater gas, water-gas, oven gas, natural gas, liquefied gas
The sulfide essence of equal material gas is de-.The invention is mainly used for the sulfide removing of gas industrial chemicals, it is impossible to be used in liquid
Body hydrocarbon material is less suitable for cracking c5 and C5+ component.
Patent CN1511629A provides a kind of adsorbent of molecular sieve of deep sulfide removing, by Y type molecular sieve gold-supported
Belong to salt composition, the dispersion amount of metallic salt is 0.1~15%, metallic salt be potassium, magnesium, calcium, iron, cobalt, nickel, copper, zinc,
Silver, the sulfate of lanthanum, nitrate, chloride, acetate, carbonate and/or its mixture.By molecular sieve and above-mentioned metallic salt
After mixing at 160~700 DEG C roasting 4~for 24 hours.Adsorbent of molecular sieve after adsorption saturation is passed through N at 200~400 DEG C2
2~6h of purging can be continued to use after being regenerated, and after regeneration twice, the adsorption capacity of sulphur is still initial adsorption capacity in 4h
90%.This adsorbent up to 65mg sulphur/g adsorbent, has preparation method easy the adsorption capacity of sulphur, regenerates convenient special
Point.The adsorbent is particularly suitable for removing thiophene and derivatives.The molecular sieve that the invention uses is carrier, to needing desulfurization
Raw material there are certain requirements, and not be suitable for cracking c5 and C5+ component.
In conclusion the adsorption desulfurizing agent taken off at present specifically for sulfide essence in cracking olefin component is there are also to be developed,
To meet the production needs of high-end hydrogenated petroleum resin.
Summary of the invention
The first object of the present invention is to provide a kind of absorption desulfurizing agent, the absorption desulfurizing agent active carbon and is supported on
Active material on the active carbon, the active material are the mixture of alkaline matter and metal oxide or its esters；Institute
State one of oxide or a variety of that metal oxide is K, Mg, Cu, Ni, Zn, Ag, the alkaline matter be sodium oxide molybdena and/
Or potassium oxide；The metal oxide accounts for 0.1~20wt% of the active carbon, and the alkaline matter accounts for the active carbon
0.2~30wt%.
Absorption desulfurizing agent of the invention is particularly suitable for cracking olefin for removing mercaptan, thioether, thiophene sulfides
Fine de-sulfur alcohol, thioether, thiophene etc. in (C4~C9) component.
Wherein, the salt of metal oxide can be the one of sulfate, nitrate, chloride, acetate and carbonate etc.
Kind is several, preferably chloride, nitrate, acetate and carbonate, preferably nitrate and carbonate.
In a preferred embodiment of the invention, in order to further increase fine de-sulfur effect, the metal oxide is
Zinc oxide and magnesia, the alkaline matter are potassium oxide.
In a preferred embodiment of the invention, in order to further increase fine de-sulfur effect, the metal oxide is
Copper oxide, the alkaline matter are sodium oxide molybdena.
Wherein, in above two preferred embodiment, in order to further increase desulfurization ether, 0.1- can also be added
The silver oxide of 0.1-0.5wt% can also be added in order to further increase fine de-sulfur effect in the nickel oxide of 0.5wt% thereto.
It is particularly preferably that silver oxide can be added in zinc oxide and magnesia and potassium oxide composition.Can in copper oxide and
Silver oxide is added in the composition of sodium oxide molybdena.
In a preferred embodiment of the invention, in order to improve desulfurization effect and reduce olefinic polymerization degree, the gold
Belong to 0.1~11wt%, preferably 2~11wt% that oxide accounts for the active carbon.
In a preferred embodiment of the invention, the alkaline matter accounts for 8~22wt% of the active carbon, preferably
12~18wt%.
When metal oxide is copper oxide, and the alkaline matter is sodium oxide molybdena, i.e., active material is copper oxide and oxidation
Sodium, copper oxide account for 0.1~11wt% of the active carbon, and sodium oxide molybdena accounts for 8~22wt% of the active carbon.
When metal oxide is zinc oxide and magnesia, and the alkaline matter is potassium oxide, i.e., active material is oxidation
Zinc, magnesia and potassium oxide, zinc oxide account for 1~7wt% of the active carbon, magnesia account for the active carbon 1~
4wt%, sodium oxide molybdena account for 8~22wt% of the active carbon.
The active carbon that the present invention uses can be one or more of coal quality, wooden, shell, coconut husk, through crushing, mixing,
It squeezes, molding, dry, charing, activate and be made, shape is bar shaped, spherical shape or amorphous, in order to improve desulfurization and hold sulphur effect
Fruit, active carbon specific surface area of the invention is preferably up to 800~1600m2/ g, micro pore volume 80~90%, micropore size are
10~40A.Active carbon of the invention is preferably the active carbon for being sized to 10~80 mesh, is further preferably sized to 20~60 mesh
Active carbon.
In the present invention, the basic production method for adsorbing desulfurizing agent is by active carbon by the works such as impregnation drying and roasting
Sequence is made.Preferably active carbon is made by processes such as pretreatment, impregnation drying, load and roastings.In order into
One step improves the catalytic effect of absorption desulfurizing agent, and active carbon is more preferably immersed in the corresponding hydroxide of alkaline matter
Aqueous solution water-soluble metal salt corresponding with the metal oxide or its esters in, then thereto be added hydrazine hydrate it is water-soluble
Liquid reaction, roasting.
Wherein, the concentration of the aqueous solution of the hydrazine hydrate is preferably 0.2~0.6mol/L, in the aqueous solution of the hydrazine hydrate
The molar ratio of metal is preferably 0.25~1.5 in the hydrazine hydrate and the metal oxide, and further preferably 0.25~1,
More preferably 0.5~0.85.Reaction time after the aqueous solution of hydrazine hydrate is added is preferably 0.5~2h.
In a preferred embodiment of the invention, absorption desulfurizing agent of the invention includes active carbon and is supported on described
Active material on active carbon, the active material include copper oxide and sodium oxide molybdena；The copper oxide accounts for the 0.1 of the active carbon
~11wt%, the alkaline matter account for 8~22wt% of the active carbon.
In a preferred embodiment of the invention, absorption desulfurizing agent of the invention includes active carbon and is supported on described
Active material on active carbon, the active material include zinc oxide, magnesia and potassium oxide；The zinc oxide accounts for the activity
1~7wt% of charcoal, the magnesia account for 1~4wt% of the active carbon, the sodium oxide molybdena account for the active carbon 8~
22wt%.
Method commonly used in the art can be used to prepare absorption desulfurizing agent of the invention, another object of the present invention
It is to provide the preparation method of above-mentioned absorption desulfurizing agent, which includes the following steps:
The active carbon is immersed in water-soluble metal salt corresponding to metal oxide and alkaline matter pair according to the ratio
The aqueous solution for the hydroxide answered, impregnate after 2~10h dry 6 at room temperature~150 DEG C~for 24 hours, under nitrogen protection, 150~
1~4h of calcination activation at 400 DEG C.
Wherein, water-soluble metal salt is the corresponding water-soluble metal salt of metal oxide, wherein water-soluble metal salt can be with
It is the one or more of sulfate, nitrate, chloride, acetate and carbonate etc., preferably chloride, nitrate, acetate
And carbonate, preferably nitrate and/or carbonate.
Wherein, the time of dipping is preferably 4~10h, further preferably 4~6h.Dry temperature is preferably 80~150
DEG C, further preferably 80~120 DEG C.
Wherein, the concentration of the aqueous solution of the corresponding hydroxide of alkaline matter is preferably 0.2~0.6mol/L.
In a preferred embodiment of the invention, the preparation method of the absorption desulfurizing agent includes the following steps:
After active carbon is impregnated 2~10h in water-soluble metal salt, then dry 6~14h is obtained at room temperature~120 DEG C
To presoma, NaOH or KOH aqueous solution is added into precursor, stirs 10~30min, adds hydrazine hydrate aqueous solution, reacts
After 0.5~2h, filtration washing, dry 12 at 80~150 DEG C~for 24 hours, and under nitrogen protection, calcination activation 1 at 150~400 DEG C
~4h to get to absorption desulfurizing agent.Wherein, water-soluble metal salt is preferably copper nitrate or copper carbonate.
Wherein, preferred parameter no longer repeats one by one herein referring to the related content in product in the program.
Absorption desulfurizing agent provided by the invention and the absorption desulfurizing agent obtained by above-mentioned preparation method are suitable for removing
Mercaptan, thioether, thiophene sulfides are particularly suitable for fine de-sulfur alcohol, thioether, thiophene etc. in cracking olefin (C4~C9) component.
Another object of the present invention is to provide above-mentioned absorption desulfurizing agents or preparation method in removing cracking olefin component
Application in middle trace sulfide.
Wherein, use the temperature of absorption desulfurizing agent of the invention is 40~160 DEG C, and preferably 60~100 DEG C, air speed is
0.5~10h-1, preferably 0.5~5h-1, preferably 1~3h-1, pressure is less than 15MPa, and finish is than control 0.5~2.This hair
The desulfurization degree of bright absorption desulfurizing agent is 85% or more.
Absorption desulfurizing agent of the invention can be especially suitable with desulfurizing agent for removing mercaptan, thioether, thiophene sulfides
For fine de-sulfur alcohol, thioether, thiophene in cracking olefin component etc., precision < 5ppm is removed, and after desulfurization in cracking olefin component
The content and property of active olefin substance are basically unchanged, while (sulfur capacity is than existing raising with Sulfur capacity height for the desulfurizing agent
30%), the characteristics of Yi Zaisheng.
Specific embodiment
With reference to embodiment, the embodiment of the present invention is furthur described in detail.Following embodiment is used for
Illustrate the present invention, but is not intended to limit the scope of the invention.
Unless otherwise specified, the conventional means that technological means used is well known to those skilled in the art in embodiment, institute
It is commercial goods with raw material.
Embodiment 1
A kind of absorption desulfurizing agent is present embodiments provided, is specifically comprised the following steps:
The particle that 30 mesh are obtained after active carbon is sieved, by the Cu (NO of 0.5mol/L3)2Solution incipient impregnation is in activity
On high-area carbon, the amount of CuO is made to account for the 5.5% of activated carbon total weight, place 6h at room temperature, then in 120 DEG C of dry 8h, finally
In 400 DEG C, N2Calcination activation handles 2h under gas shielded, obtains absorption desulfurizing agent A, is denoted as AC-A；
Wherein, the specific surface area of active carbon is 1000m2/ g, micro pore volume 85%, micropore size 25A.
Embodiment 2
A kind of absorption desulfurizing agent is present embodiments provided, is specifically comprised the following steps:
The particle that 30 mesh are obtained after active carbon is sieved, by the Cu (NO of 0.5mol/L3)2Solution incipient impregnation is in activity
On high-area carbon, the amount of CuO is made to account for the 5.3% of activated carbon total weight, places 6h at room temperature, then in 110 DEG C of dry 12h,
The NaOH aqueous solution for rapidly joining 0.6mol/L at room temperature, makes Na2The amount of O accounts for the 15.2% of activated carbon total weight, stirring
30min, then in 120 DEG C of dry 12h, finally in 400 DEG C, N2Calcination activation handles 2h under gas shielded, and it is de- to obtain absorption essence
Sulphur agent B, is denoted as AC-B；
Wherein, the specific surface area of active carbon is 1000m2/ g, micro pore volume 85%, micropore size 25A.
Embodiment 3
A kind of absorption desulfurizing agent is present embodiments provided, is specifically comprised the following steps:
The particle that 30 mesh are obtained after active carbon is sieved, by the Cu (NO of 0.5mol/L3)2Solution incipient impregnation is in activity
On high-area carbon, the amount of CuO is made to account for the 5.2% of activated carbon total weight, places 6h at room temperature, then in 110 DEG C of dry 12h,
The NaOH aqueous solution for rapidly joining 0.6mol/L at room temperature, makes Na2The amount of O accounts for the 14.8% of activated carbon total weight, stirring
The hydrazine hydrate aqueous solution of 0.3mol/L is added in 30min, reacts filtration washing after 1h, the dry 12h at 80 DEG C, finally 400
℃、N2Calcination activation 4h under gas shielded obtains absorption desulfurizing agent C, is denoted as AC-C；
Wherein, the specific surface area of active carbon is 1000m2/ g, micro pore volume 85%, micropore size 25A.
Embodiment 4
A kind of absorption desulfurizing agent is present embodiments provided, specific steps are in the same manner as in Example 3, the difference is that,
It further include a certain amount of nickel nitrate in dipping solution, so that the nickel oxide of finally obtained absorption desulfurizing agent accounts for active carbon gross weight
The 0.5wt% of amount.
Embodiment 5
A kind of absorption desulfurizing agent is present embodiments provided, specific steps are in the same manner as in Example 3, the difference is that,
Dipping solution is zinc nitrate solution and carbonic acid magnesium solution, and alkali is potassium hydroxide solution, so that the amount of zinc oxide accounts for active carbon gross weight
The 6.5% of amount, magnesia accounts for the 3.3% of activated carbon total weight, and potassium oxide accounts for the 12% of activated carbon total weight.
Embodiment 6
A kind of absorption desulfurizing agent is present embodiments provided, specific steps are in the same manner as in Example 5, the difference is that,
It further include a certain amount of silver nitrate in dipping solution, so that the silver oxide of finally obtained absorption desulfurizing agent accounts for active carbon gross weight
The 0.2wt% of amount.
Experimental example
Examples 1 to 6 obtain absorption desulfurizing agent desulfurization degree result as shown in Table-1, wherein operating condition with
Operating condition in table -2 is identical.
The desulfurization degree comparison of -1 Examples 1 to 6 of table absorption desulfurizing agent obtained
To (the air speed 1h under the same operating conditions of the absorption desulfurizing agent obtained in Examples 1 to 3-1, temperature 100
DEG C, pressure 1MPa, for finish than 1) running 6h, the cracking c5 raw material to sulfur-bearing in 47 μ g/g carries out desulfurization effect evaluation, as a result sees
Table -2.
The desulfurization effect of -2 Examples 1 to 3 of table absorption desulfurizing agent obtained
| Runing time | AC-A | AC-B | AC-C |
| 2h | 38.72μg/g | 35.62μg/g | 30.26μg/g |
| 4h | 32.51μg/g | 25.76μg/g | 16.34μg/g |
| 6h | 27.12μg/g | 15.23μg/g | 4.25μg/g |
From in table -2 as can be seen that AC-C adsorption desulfurizing agent the sulphur in cracking c5 alkene can be taken off in a mild condition to
5ppm is hereinafter, and can keep this desulfurization performance 35h or more.
Finally, method of the invention is only preferable embodiment, it is not intended to limit the scope of the present invention.It is all
Within the spirit and principles in the present invention, any modification, equivalent replacement, improvement and so on should be included in protection of the invention
Within the scope of.
Claims (10)
1. a kind of absorption desulfurizing agent, which is characterized in that including active carbon and the active material being supported on the active carbon, institute
State the mixture that active material is alkaline matter and metal oxide or its esters；The metal oxide be K, Mg, Cu, Ni,
One of oxide of Zn, Ag is a variety of, and the alkaline matter is sodium oxide molybdena and/or potassium oxide；The metal oxide accounts for
0.1~20wt% of the active carbon, the alkaline matter account for 0.2~30wt% of the active carbon.
2. absorption desulfurizing agent according to claim 1, which is characterized in that the metal oxide is copper oxide, described
Alkaline matter is sodium oxide molybdena；
Or, the metal oxide is zinc oxide and magnesia, the alkaline matter is potassium oxide.
3. absorption desulfurizing agent according to claim 1 or 2, feature is in the metal oxide accounts for the active carbon
0.1~11wt%, preferably 1~11wt%.
4. absorption desulfurizing agent according to any one of claim 1 to 3, feature is in the alkaline matter accounts for described
8~22wt% of active carbon, preferably 12~18wt%.
5. absorption desulfurizing agent according to any one of claim 1 to 4, feature is in the absorption desulfurizing agent
Preparation method includes the following steps: the aqueous solution that active carbon is immersed in the corresponding hydroxide of alkaline matter and the metal oxygen
In compound or the corresponding water-soluble metal salt of its esters, then the reactant aqueous solution of hydrazine hydrate, roasting are added thereto.
6. absorption desulfurizing agent according to claim 5, feature is in the concentration of the aqueous solution of the hydrazine hydrate is 0.2
The molar ratio of metal is 0.25 in~0.6mol/L, hydrazine hydrate described in the aqueous solution of the hydrazine hydrate and the metal oxide
~1.5.
7. absorption desulfurizing agent according to any one of claim 1 to 6, feature is in the partial size of the active carbon is
10~80 mesh, specific surface area are 800~1600m2/ g, micro pore volume are 80~90%, and micropore size is 10~40A.
8. absorption desulfurizing agent according to any one of claim 1 to 7, feature is in the absorption desulfurizing agent is
Active carbon and the active material being supported on the active carbon, the active material includes copper oxide and sodium oxide molybdena；The oxidation
Copper accounts for 0.1~11wt% of the active carbon, and the alkaline matter accounts for 8~22wt% of the active carbon；
Or, the absorption desulfurizing agent is active carbon and the active material being supported on the active carbon, the active material packet
Include zinc oxide, magnesia and potassium oxide；The zinc oxide accounts for 1~7wt% of the active carbon, and the magnesia accounts for the activity
1~4wt% of charcoal, the sodium oxide molybdena account for 8~22wt% of the active carbon.
9. the preparation method of absorption desulfurizing agent described in any item of the claim 1 to 8, which is characterized in that including walking as follows
It is rapid:
The active carbon is immersed in water-soluble metal salt corresponding to metal oxide according to the ratio and alkaline matter is corresponding
The aqueous solution of hydroxide, impregnate after 2~10h dry 6 at room temperature~150 DEG C~for 24 hours, and under nitrogen protection, 150~400
1~4h of calcination activation at DEG C.
10. absorption desulfurizing agent described in any item of the claim 1 to 8 or preparation method as claimed in claim 9 are removing
Application in cracking olefin component in trace sulfide.
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| CN111974340A (en) * | 2020-08-27 | 2020-11-24 | 中国石油大学(北京) | Desulfurization adsorbent, preparation method thereof and method for deeply desulfurizing hydrocarbon |
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