CN106622096A - Nickel-based adsorbent for deep desulfurization and deodorization of isopropanol and preparation method and application thereof - Google Patents
Nickel-based adsorbent for deep desulfurization and deodorization of isopropanol and preparation method and application thereof Download PDFInfo
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- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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Abstract
The invention provides a nickel-based adsorbent for deep desulfurization and deodorization of isopropanol and a preparation method and application thereof. The nickel-based adsorbent for deep desulfurization and deodorization of isopropanol contains nickel, aluminum and an assistant, wherein the nickel content is 40-80% by weight, the aluminum content is 20-60% by weight, the assistant content is 0-10% by weight, and the assistant is selected from one or more of Pd, Ru, Ag, Cu, Zn, Fe, Mn and Co. The isopropanol treated by the nickel-based adsorbent can meet the quality requirements of cosmetic-class and medical-class isopropanol. Compared with the prior art, the nickel-based adsorbent is high in desulfurization precision, high in sulfur capacity, remarkable in deodorization effect, low in energy consumption, low in price, simple in production process and easy to industrialize and has good application prospect and huge economic benefits.
Description
Technical field
The present invention relates to a kind of isopropanol deep desulfuration and deodorant nickel-based sorbent and its preparation method and application, specifically
It is related to technical grade, cosmetics-stage and pharmaceutical grade isopropanol deep desulfuration and deodorant nickel-based sorbent and preparation method thereof and should
With.
Technical background
Isopropanol is important chemical products and raw material.It is mainly used in pharmacy, cosmetics, plastics, spices, coating etc..Example
Such as in medicine, it is mainly used for manufacturing baste and bactericidal liquid；In terms of cosmetics, isopropanol and its derivative are used as solvent
And solubilizer；In shampoo and similar products, isopropanol is used for solubilized synthetic detergent.At present, industrial isopropanol is basic
It is from propylene synthesis.Because propylene can bring different sulphur-containing substances and Ammonia material into due to technological reason, therefore can cause different
The sulfur content of propyl alcohol is exceeded and smell exception, has a strong impact on the product quality of isopropanol and the application in high-grade purposes.
General sulfur method has sulfuric acid treatment, extracting rectifying, freezing and crystallizing, catalytic hydrogenation, choosing in existing organic compound
Select oxidation, select absorption, precipitation desulfurization, and ionic liquid and biological desulphurization etc..And adsorb desulfurization have equipment investment it is little,
Process is simple, condition are easy to control, effect is significant the advantages of, be currently the common method of domestic and international desulfurization.
The principle of absorption desulfurization is, using the adsorbent based on transition metal, to be supported on porous solid carrier, certain
Selectively make the sulphur atom in the sulfur-containing compounds such as thiophene, mercaptan, thioether that phase occur with metallic atom under temperature and pressure
Interaction, so as to sulfur-containing compound absorption be removed on the surface of adsorbent.In general, the metallic element with unoccupied orbital
All there is sulfur-containing compound of the absorption containing lone pair electrons.The transition metal be generally Pd, Ag, Au, Cu, Sn, Zn, Fe, Ru,
Ni, Mn, Mo, Co etc..
In the prior art, the smell of isopropanol is relevant with mercaptan, thioether sulfides, but between peculiar smell and sulfur content
There is no direct relation.Therefore, in order that isopropanol is applicable in the product of cosmetics-stage and pharmaceutical grade, not only to take off
Except sulfur-containing compounds such as mercaptan, thioethers, stink is also removed.The pungent odour of isopropanol is also possible to by aldehyde except vulcanizing beyond the region of objective existence
Class, amine etc. cause.Therefore it is required that adsorbent not only has deep desulfuration function, deodorization functions have also been needed.
United States Patent (USP) US4219685A discloses a kind of low-carbon alcohols deodour method：Low-carbon alcohols are made to aoxidize with metal or metal
Thing or the deodorization contact that the two is constituted together contact, and metal oxide party is reduced into metal.It is representative
Be stannous chloride, preferable granularity is of about 0.79mm, and it is less than 1000m that preferable deodorization contact has effective surface area2/
g。
Zheng Kuishan (Liaoning chemical industry, 1984,03,27-31) describes deodorant for isopropanol from skeleton nickel and carrier nickel
Method：Deodorization condition is 60 DEG C and 80 DEG C, using fixed bed or fluid bed, and can think that hydrogenation catalyst can be used for
Isopropanol deodorization.And the document only focuses on deodorization, there is no related data to deep desulfuration.Meanwhile, the document is thought at skeleton nickel
Product is muddy after reason, and isopropanol has dehydrogenation phenomenon after process.
Yang Zhisheng (Liaoning chemical industry, 1985,12,14-16) is reported and is fixed an isopropyl from seven kinds of industrial catalysts
Alcohol deodorization：Catalyst preferably 804, process conditions are 50 DEG C, normal pressure, and air speed is 10 hours-1.However, sulfur content after its process
In 0.2ppm or so.
In sum, current isopropanol is deodorant general using industrial hydrogenation catalyst, not dedicated for isopropanol depth
Degree desulfurization and deodorant catalyst.And, above-mentioned industrial catalyst there is a problem of certain, such as desulfurization depth not enough, is only closed
Note deodorizing effect, using temperature heating etc. is needed.As requirement of the people to quality of the life is improved, hydrogenation industrial at present is urged
Agent can not meet isopropanol deep desulfuration and deodorant requirement.Therefore a kind of low-cost efficient isopropanol is sought at present
Deep desulfuration and deodorant adsorbent are particularly significant and necessary.
The content of the invention
The present invention is directed to the deficiencies in the prior art, from isopropanol deep absorption desulfurization (mercaptan, thioether, thiophene) and
Cooling step and adsorbent pores structure and auxiliary agent set out for key factor after deodorant essential and nickel-based sorbent melting, it is proposed that
One kind proposes the adsorbent for isopropanol deep desulfuration (mercaptan, thioether, thiophene) and deodorant nickel-based sorbent
Preparation method and applications.Nickel-based sorbent of the present invention has the active material outer surface layer of abundant suitable institutional framework composition
With the metal alloy kernel of high strength dense structure composition.Relative to the industrial hydrogenation catalyst for using at present, the present invention is Ni-based
Adsorbent has deep desulfuration (mercaptan, thioether, thiophene) function, and while there are obvious deodorization functions, absorption Sulfur capacity is big,
Can use at normal temperatures, long service life.
On the one hand, embodiments of the present invention provide a kind of for isopropanol deep desulfuration and deodorant nickel-based sorbent,
The nickel-based sorbent includes nickel, aluminium and optional auxiliary agent；
Wherein, on the basis of the percetage by weight of the nickel-based sorbent, nickel content is 40-80 weight %, and aluminium content exists
20-60 weight %, auxiliary agent content 0-10 weight %；
The auxiliary agent is selected from one or more element in Pd, Ru, Ag, Cu, Zn, Fe, Mn and Co.
In the embodiment of some, nickel content is 40-70 weight %, and aluminium content is in 30-60 weight %, auxiliary agent content 0-
10 weight %；Or, nickel content is 45-75 weight %, and aluminium content is in 25-55 weight %, auxiliary agent content 0-10 weight %.
In the embodiment of some, the nickel-based sorbent is graininess, or the nickel-based sorbent is spherical in shape, bar
The graininess of shape, cylinder and their combinations；Granular size 2.0-8.0mm；Preferably, the nickel-based sorbent has appearance
Surface layer and kernel, wherein, outer surface layer described in the outer surface layer has loose structure, and total pore volume is adsorbed more than 0.1ml/ml
Agent, the mesopore and macropore in the loose structure accounts for volume ratio 20%-50%, micro pore volume accounting 80%-50%.In the present invention
In, the micropore refers to hole of the average pore size less than 2nm, and mesopore refers to the hole more than 2nm less than 50nm, and macropore is referred to and is more than
The hole of 50nm.In some embodiments, the mean intensity of the kernel is that side pressure is more than 300N.
In the embodiment of some, the nickel-based sorbent is the nickel-based sorbent activated by aqueous slkali.
On the other hand, embodiments of the present invention provide a kind of for isopropanol deep desulfuration and deodorant nickel-based sorbent
Preparation method, methods described includes：
(1) mixture comprising nickel, aluminium and auxiliary agent is provided,
Wherein, nickel content is 40-80 weight %, and aluminium content is in 20-60 weight %, auxiliary agent content 0-10 weight %；It is described
Auxiliary agent is selected from one or more element in Pd, Ru, Ag, Cu, Zn, Fe, Mn and Co；
(2) after by the mixture pelleting, activation process is carried out to alloying pellet with aqueous slkali；
(3) particle after activation process is washed；
(4) optionally, dipping moditied processing is carried out to the particle after washing using the auxiliary agent water soluble salt aqueous solution,
Graininess nickel-based sorbent is obtained after washing again.
In the embodiment of some, in step (1), carried by the way that metallic nickel, metallic aluminium and auxiliary agent are carried out into melting
For the mixture；Preferably, the temperature of the melting is 1000-1800 DEG C, and the time, the type of cooling was rapid in 0.5-3 hours
Cold either ladder cooling naturally cools to normal temperature.
In the embodiment of some, in step (2), by broken particle is formed, particle is cast into or is broken into powder
It is last to be granulated by beating piece or extrude；Preferably, the granulation includes that brush choosing granulation, fused solution are closed after Mechanical Crushing
Forming agent is added to carry out beating piece or extrude granulation after gold casting granulation, fused solution alloy rotating granulation or crushing.
In the embodiment of some, in step (2), carrying out activation process to alloying pellet with aqueous slkali includes using nothing
Machine aqueous slkali carries out activation process to the alloying pellet, and preferably alloying pellet is placed in after fixed bed reactors carries out original position
Activation process；Preferably, the inorganic alkali solution be NaOH or KOH, wherein, alkaline concentration be 0.1-10 weight %, alkali soluble
The weight space velocity of liquid is 5-100 hours-1, activating treatment temperature is -100 DEG C of room temperature, and the activation process time is 1-8 hours.
In the embodiment of some, the aqueous slkali is KOH, wherein, KOH alkaline concentrations are 0.5-5 weight %,
The weight space velocity of KOH aqueous slkalis is 10-50 hours-1, activating treatment temperature is -80 DEG C of room temperature, and the activation process time is that 2-6 is little
When.
In the embodiment of some, in step (3), the aqueous slkali is switched into deionized water, until after washing
The pH value of solution is 7-9, wherein, wash temperature is -80 DEG C of room temperature.
In the embodiment of some, in step (4), the auxiliary agent water soluble salt aqueous solution is included containing zinc salt, molysite
Or the aqueous solution of ruthenium salt, wherein, zinc salt and molysite aqueous solution concentration are 0.5-10 weight %, and ruthenium saline solution concentration is 0.001-
0.1 weight %, the weight space velocity of the auxiliary agent water soluble salt aqueous solution is 0.5-5 hours-1, impregnate modification temperature be room temperature-
80 DEG C, the time is 0.5-3 hours.
In the embodiment of some, in step (4), the zinc salt is selected from zinc acetate, zinc sulfate and zinc nitrate；Molysite
Selected from ferric sulfate, ferric acetate, ferrous sulfate and frerrous chloride；Ruthenium salt is selected from acetic acid ruthenium, ruthenium trichloride and nitric acid ruthenium.
In the embodiment of some, in step (4), the auxiliary agent water soluble salt aqueous solution is switched into deionization
Water, until the pH value of solution is 7-9 after washing, wherein, wash temperature is -80 DEG C of room temperature.
On the other hand, embodiments of the present invention offer is described is used for isopropanol deep desulfuration and deodorant nickel-based sorbent
In technical grade, cosmetics-stage and pharmaceutical grade isopropanol deep desulfuration and the deodorant middle application as adsorbent.
On the other hand, embodiments of the present invention offer is described is used for isopropanol deep desulfuration and deodorant nickel-based sorbent
As the application of desulfuration adsorbent in isopropanol desulfurization.
In the embodiment of some, sulfur content is 0.5-5mg/kg in isopropyl raw polyol, Jing after nickel-based sorbent absorption
It is reduced to ＜ 0.025mg/kg；The temperature of absorption is 20-50 DEG C；And the effective Sulfur capacity for isopropanol deep absorption desulfurization is up to
3.50g sulphur/L adsorbents；Oder levels reach 1 grade after deodorization.
In the embodiment of some, the nickel-based sorbent after the failure of isopropanol deep desulfuration is used as isopropanol depth
Desulfurization pretreatment adsorbent is used, and sulfur content is 0.5-5mg/kg in isopropyl raw polyol, and the temperature of absorption is 20-50 DEG C；It is Ni-based
Adsorbent saturation Sulfur capacity is 100g sulphur/L adsorbents.
In the present invention, sulfur content is 0.5-5mg/kg in isopropyl raw polyol.Jing after nickel-based sorbent absorption, sulfur content is pressed
Do not detect according to microcoulomb method, i.e., less than 0.025mg/Kg, isopropanol deep desulfuration quality requirement can be met.And for isopropanol depth
Effective Sulfur capacity of degree absorption desulfurization is up to 3.50g sulphur/L adsorbents.Meanwhile, after nickel-based sorbent absorption, oder levels can
To 1 grade, meet the odor requirements of cosmetics-stage and medical level isopropanol.Meanwhile, there is the nickel-based sorbent saturation Sulfur capacity to be up to
100g sulphur/L adsorbents, can meet the application of general isopropanol desulfurization.And, the nickel-based sorbent is after deep desulfuration failure
Can continue to be used as general desulfurization, or as deep desulfuration pre-treatment, can further reduce use cost.
Compared to existing technology, nickel-based sorbent of the present invention has following advantage：
(1) nickel-based sorbent of the present invention can reach isopropanol deep desulfuration (less than 0.025mg/Kg), effective sulphur
Hold and be up to 3.50g sulphur/L adsorbents and the deodorant requirement to oder levels less than 1；
(2) nickel-based sorbent of the present invention can be used at normal temperatures, it is not necessary to which system is additionally heated, and energy consumption is low；
(3) there is nickel-based sorbent of the present invention saturation Sulfur capacity to be up to 100g sulphur/L adsorbents, can meet general different
The application of propyl alcohol desulfurization, deep desulfuration failure after can continue to be used as general desulfurization, or as deep desulfuration before
Process, can further reduce use cost；And
(4) preparation process is simple of nickel-based sorbent of the present invention, it is easy to industrialize, have a good application prospect and
Huge economic benefit.
By detailed description below and claim, other features and aspect can be made apparent from.
Specific embodiment
Unless otherwise defined, the technical term or scientific terminology used in claims and specification should be this
The ordinary meaning that the personage with general technical ability is understood in bright art.
With reference to specific embodiment, the present invention will be further described, but the invention is not restricted to following being embodied as
Mode.
The invention provides a kind of for isopropanol deep desulfuration and deodorant nickel-based sorbent, the nickel adsorbent for
Granular nickel-based sorbent, including the active material outer surface layer with abundant suitable institutional framework composition and high strength dense knot
The metal alloy kernel of structure composition.Wherein, the adsorbent consists of NiAlX, and Ni contents are 40-80 weight %, Al content
For 20-60 weight %, X is auxiliary agent, including a kind of element or various complex elements, and auxiliary agent total content is 0-10 weight %.
Preferably, the Ni contents of the graininess nickel-based sorbent are 45-75 weight %, and Al content is 25-55 weight %,
Auxiliary element X contents are 0-10 weight %.
In the present invention, by the original proportion of composing in adjustment metal alloy raw material and the addition of auxiliary agent, after melting
Through quenching, either ladder is cooled down or natural cooling, then either molten state cast molding or the rotation balling-up of broken particle
Type adds after grinding binding agent to play piece or extrusion molding；Then in lower Jing aqueous slkalis activation process, the deionization of imposing a condition
The washing of water and follow-up auxiliary agent dipping moditied processing, obtain the graininess nickel adsorbent of heterogeneity.
In the present invention, the absorbent particles shape can be irregular shape, spherical, hemispherical, column type, rod, tooth
Shape, hollow rod, the particle diameter be 0.5mm-12mm, height 0.5mm-12mm, more preferably diameter 2mm-6mm, height
2mm-8mm。
In the present invention, the auxiliary agent can be Pd, Ru, Ag, Cu, Zn, Fe, Mn and Co etc.；The Ni-based suction of the graininess
Attached dose of Ni contents are 45-75 weight %, and Al content is 25-55 weight %, and auxiliary element X contents are 0-10 weight %.
In the present invention, the activation process of the metal alloy particle is specially using aqueous slkali：By the gold of predetermined amount
Category alloying pellet raw material is placed in fixed bed reactors, is adopted inorganic alkali solution with default flow velocity and is passed through the metal alloy
Grain carries out activation process.
Preferably, the inorganic alkali solution is NaOH or KOH, and the aqueous slkali passes through alloying pellet with default flow velocity
Activation process is carried out, wherein alkaline concentration is 0.1-10 weight %, and the weight space velocity of aqueous slkali is 5-100 hours-1, at activation
Reason temperature is -100 DEG C of room temperature, and the activation process time is 1-8 hours.
It is further preferred that the aqueous slkali is KOH, the KOH aqueous slkalis are carried out with default flow velocity by alloying pellet
Activation process, wherein KOH alkaline concentrations are 0.5-5 weight %, and the weight space velocity of KOH aqueous slkalis is 10-50 hours-1, activation
Treatment temperature is -80 DEG C of room temperature, and the activation process time is 2-6 hours.
In the present invention, the use deionized water carries out washing tool to the metal alloy particle through activation process
Body is：The aqueous slkali is switched into deionized water, the deionized water with default flow velocity by the metal alloy particle,
Until the pH value of solution is 7-9 after washing.
Preferably, the deionized water is washed to the metal alloy particle, until the pH value of solution is after washing
7-9, wherein wash temperature are -80 DEG C of room temperature.
In the present invention, the metal alloy particle through carrying out washing treatment is entered using auxiliary agent water-soluble salt solution
Row auxiliary agent dipping moditied processing is specially：The deionized water is switched into the auxiliary agent water soluble salt aqueous solution, the auxiliary agent is water-soluble
Property saline solution carries out moditied processing with default flow velocity by the metal alloy particle.The auxiliary agent be Pd, Ru, Ag, Cu,
Zn, Fe, Mn and Co one or more mix.
Preferably, the follow-up dipping addition of described auxiliary element Zn, Fe or Ru, refers to zinc, iron or ruthenium saline solution
Moditied processing, wherein zinc salt are subsequently impregnated with alloying pellet NiAlX of the default flow velocity after activation process and washing
Or molysite aqueous solution concentration is 0.5-10 weight %, ruthenium saline solution concentration is 0.001-0.1 weight %, auxiliary agent saline solution
Weight space velocity is 0.5-5 hours-1, moditied processing temperature is -80 DEG C of room temperature, and the moditied processing time is 0.5-3 hours.
Preferably, the follow-up dipping addition of the auxiliary element, refers to zinc salt, molysite or ruthenium saline solution with default
Alloying pellet NiAlX of the flow velocity after activation process and washing is subsequently impregnated moditied processing, wherein zinc salt be zinc acetate,
Zinc sulfate and/or zinc nitrate；Molysite is ferric sulfate, ferric acetate, ferrous sulfate and/or frerrous chloride；Ruthenium salt is acetic acid ruthenium, trichlorine
Change ruthenium and/or nitric acid ruthenium.
Preferably, the deionized water is entered to metal alloy particle NiAlX that the follow-up dipping of the auxiliary element adds
Row washing, until the pH value of solution is 7-9 after washing, wherein wash temperature is -80 DEG C of room temperature.
The preparation method of isopropanol deep desulfuration of the present invention and deodorant normal-temperature efficient nickel-based sorbent includes following
Step：
(1) melting of metal alloy, granulation or shaping；
(2) activation process using aqueous slkali to the metal alloy particle；
(3) metal alloy particle through activation process is washed using deionized water；
(4) it is optional, the metal alloy particle through carrying out washing treatment is soaked using auxiliary agent water soluble salt
Stain moditied processing；
(5) it is optional, the particle that (4) step is obtained is washed using deionized water, obtain graininess Ni-based
Adsorbent.
In a preferred embodiment, step (1) melting of metal alloy and the preparation of particle includes：Metallic nickel,
The melting of aluminium or auxiliary agent, be crushed to certain granules using or carry out being cast to certain shape shaping, or broken pulverized powder
Shape is then by playing piece or extrusion molding.
Preferably, the metallic nickel and aluminium are included or the smelting temperature without auxiliary agent is at 1000-1800 DEG C, and the time exists
0.5-3 hours, for quenching, either ladder cools down or naturally cools to normal temperature to the type of cooling.
Shaping after the melting includes Mechanical Crushing shaping, using mechanical jaw crusher or impact crusher or
Hammer stone disintegrating machine is crushed, and the particle for choosing certain particle size by screen cloth obtains shaped granule, or the liquid by melting
Through cast molding, shape includes dome-type, rod or cuboid-type to alloy, or passes through rotation by the liquid alloy for melting
Turn granulation and form ball-type, or the fine powder that the modes such as ball milling yield less than 100 mesh is again passed by by the particle after broken, then
The forming agents such as aluminum oxide, water, binding agent are added, including carrying out playing piece, drying, roasting, diameter 1mm-6mm, height 1mm- is obtained
The cylindrical pellet of 6mm, or extruded, dry, roasting shaping, obtain cylinder, profile of tooth, hollow cylinder shape and or according to mill
Tool obtains different shape particle, and between 1mm-6mm, length is in 1mm-5mm for diameter.Wherein crushing and screening particle is irregular shape
Shape, between 1mm-8mm, in 1mm-12mm, melting rotating granulation size is in 1mm-8mm for fusion-cast particle for size.
It is highly preferred that the auxiliary agent is Pd, Ru, Ag, Cu, Zn, Fe, Mn and Co etc.；The content of the aluminium in 30-70%,
, in 30-60%, single auxiliary agent or mixed aid content are in 0-10% for the content of nickel.
In a preferred embodiment, in step (2), the activation process of the metal alloy particle is had using aqueous slkali
Body is：The metal alloy particle raw material of predetermined amount is placed in fixed bed reactors, inorganic alkali solution is adopted with default flow velocity
Activation process is carried out by the metal alloy particle.
It is highly preferred that the inorganic alkali solution is NaOH or KOH, the aqueous slkali passes through alloy with default flow velocity
Grain carries out activation process, and wherein alkaline concentration is 0.1-10 weight %, and the weight space velocity of aqueous slkali is 5-100 hours-1, activation
Treatment temperature is -100 DEG C of room temperature, and the activation process time is 1-8 hours.
It is highly preferred that the aqueous slkali is KOH, the KOH aqueous slkalis are lived with default flow velocity by alloying pellet
Change is processed, and wherein KOH alkaline concentrations are 0.5-5 weight %, and the weight space velocity of KOH aqueous slkalis is 10-50 hours-1, at activation
Reason temperature is -80 DEG C of room temperature, and the activation process time is 2-6 hours.
In a preferred embodiment, in step (3), the use deionized water is to the metal through activation process
Alloying pellet is washed, specially：The KOH aqueous slkalis are switched into deionized water, the deionized water is with default stream
Speed is by the metal alloy particle, until the pH value of solution is 7-9 after washing.Wherein wash temperature is -80 DEG C of room temperature.
In a preferred embodiment, in step (4), using auxiliary agent water-soluble salt solution to described through carrying out washing treatment
The metal alloy particle carries out auxiliary agent dipping moditied processing, specially：The deionized water is switched into auxiliary agent water soluble salt
The aqueous solution, the auxiliary agent water soluble salt aqueous solution carries out moditied processing with default flow velocity by the metal alloy particle.Institute
Auxiliary agent is stated for one or more mixing of Pd, Ru, Ag, Cu, Zn, Fe, Mn and Co.
It is highly preferred that the follow-up dipping addition of described auxiliary element Zn, Fe or Ru, refers to that zinc, iron or ruthenium salt are water-soluble
Alloying pellet NiAlX of the liquid with default flow velocity after activation process and washing is subsequently impregnated moditied processing, wherein zinc
Salt and molysite aqueous solution concentration are 0.5-10 weight %, and ruthenium saline solution concentration is 0.001-0.1 weight %, auxiliary agent saline solution
Weight space velocity be 0.5-5 hours-1, moditied processing temperature is -80 DEG C of room temperature, and the moditied processing time is 0.5-3 hours.
Preferably, the follow-up dipping addition of described auxiliary element Zn, Fe or Ru, refers to auxiliary agent saline solution with default
Alloying pellet NiAlX of the flow velocity after activation process and washing is subsequently impregnated moditied processing, wherein zinc salt be zinc acetate,
Zinc sulfate, zinc nitrate；Molysite is ferric sulfate, ferric acetate, ferrous sulfate, frerrous chloride；Ruthenium salt is acetic acid ruthenium, ruthenium trichloride, nitre
Sour ruthenium.
In a preferred embodiment, in step (5), using deionized water to described through the auxiliary agent water soluble salt aqueous solution
The metal alloy particle of follow-up dipping moditied processing is washed specially：By auxiliary agent water soluble salt aqueous solution switching
Into deionized water, the deionized water with default flow velocity by the metal alloy particle, until washing after solution pH value
For 7-9.Wherein wash temperature is -80 DEG C of room temperature.
The nickel-based sorbent prepared according to above-mentioned steps is applied to isopropanol depth liquid desulfuration and deodorant.Desulfurization and deodorant
The use of temperature is 20-50 DEG C in technique, volume space velocity 0.5-5.0 hours-1, sulfur content is 0.5-5mg/kg in should keeping, and Jing inhales
It is attached to be reduced to ＜ 0.025mg/kg (not detecting by microcoulomb method).Effectively Sulfur capacity is up to 3.50g sulphur/L adsorbents.Saturation is adsorbed
Sulfur capacity is up to 100g sulphur/L adsorbents.
Below in conjunction with specific embodiment, the invention will be further described, it should be pointed out that embodiment described below purport
Being easy to the understanding of the present invention, and any restriction effect is not played to the scope of protection of present invention.
Embodiment 1
Accurately weigh 500 grams of the aluminium of nickel 500 gram of the purity more than 99% and purity more than 99%, be placed in intermediate frequency furnace in
1650 DEG C are melted, and the time, at 1 hour, is poured out in mould through natural cooling, is crushed through jaw crusher machine,
Sieve is obtained to 3-6mm particles.
Then, this is consisted of into Ni50Al50Metal alloy particle 200g, be placed in internal diameter be 50mm quartz glass tube
Interior, concentration is that the NaOH aqueous slkalis of 0.8 weight % are flowed into by metal conjunction with the speed of 5L/ hours from the bottom of quartz glass tube
Then gold grain bed flows out from top.The weight space velocity of NaOH aqueous slkalis is 25 hours-1.Bed temperature is 30 DEG C, at activation
The reason time is 4 hours.Washed with 50 DEG C of deionized water after aqueous slkali activation process, until the pH of solution is 7- after washing
9.Obtained granular adsorbent averagely consists of Ni55.4Al44.6。
Embodiment 2
Accurately weigh 500 grams of the aluminium of 450 grams of nickel of the purity more than 99% and purity more than 99%, iron of the purity more than 99%
50 grams, it is placed in intermediate frequency furnace and is melted in 1600 DEG C, the time, at 1.5 hours, is poured out through natural cooling in mould, is passed through
Jaw crusher machine and ball mill are obtained alloyed powder of the particle diameter less than 150 mesh, are subsequently adding water, boehmite, binding agent, stone
Ink, is obtained the cylindrical particle of 3 millimeters of 3 height of diameter after tablet machine plays piece, drying and roasting.
Then, this is consisted of into Ni45Al50Fe5Metal alloy particle 200g, be placed in internal diameter be 50mm quartz glass tube
Interior, concentration is that the KOH aqueous slkalis of 1.0 weight % are flowed into by metal conjunction with the speed of 5L/ hours from the bottom of quartz glass tube
Then gold grain bed flows out from top, and the weight space velocity of NaOH aqueous slkalis is 25 hours-1.Bed temperature is 40 DEG C, at activation
The reason time is 4 hours.Washed with 60 DEG C of deionized water after aqueous slkali activation process, until the pH of solution is 7- after washing
9.Obtained granular adsorbent averagely consists of Ni54.4Al40.1Fe5.5。
Embodiment 3
Accurately weigh 500 grams of the aluminium of 430 grams of nickel of the purity more than 99% and purity more than 99%, copper of the purity more than 99%
20 grams, iron 50 gram of the purity more than 99% is placed in intermediate frequency furnace and is melted in 1500 DEG C, and the time, at 1 hour, pours out mould
Middle to be crushed through jaw crusher machine through quenching cooling, sieve is obtained to 3-6mm particles.
Then, this is consisted of into Ni43Al50Cu2Fe5Metal alloy particle 200g, be placed in internal diameter be 50mm quartzy glass
In glass pipe, concentration is that the KOH aqueous slkalis of 0.6 weight % are flowed into by gold with the speed of 6L/ hours from the bottom of quartz glass tube
Then category alloying pellet bed flows out from top, and the weight space velocity of KOH aqueous slkalis is 30 hours-1.Bed temperature is 30 DEG C, activation
Process time is 5 hours.Washed with 70 DEG C of deionized water after aqueous slkali activation process, until the pH of solution is after washing
7-9.Obtained granular adsorbent averagely consists of Ni50.2Al43.5Cu1.5Fe4.8。
Embodiment 4
Accurately weigh 510 grams of the aluminium of nickel 490 gram of the purity more than 99% and purity more than 99%, be placed in intermediate frequency furnace in
1650 DEG C are melted, and the time, at 0.8 hour, is poured out in mould through natural cooling, is broken through jaw crusher machine
Broken, sieve is obtained to 3-6mm particles.
Then, this is consisted of into Ni49Al51Metal alloy particle 200g, be placed in internal diameter be 50mm quartz glass tube
Interior, concentration is that the KOH aqueous slkalis of 0.8 weight % are flowed into by metal conjunction with the speed of 5L/ hours from the bottom of quartz glass tube
Then gold grain bed flows out from top, and the weight space velocity of KOH aqueous slkalis is 25 hours-1.Bed temperature is 30 DEG C, activation process
Time is 4 hours.Washed with 50 DEG C of deionized water after aqueous slkali activation process, until the pH of solution is 7-9 after washing.
Then, ferrous sulfate aqueous solution carries out the follow-up addition agent modified process of Fe, and ferrous sulfate aqueous solution concentration is 5 weights
Amount %, weight space velocity is 1 hour-1, bed temperature is 70 DEG C, and the impregnation process time is 2 hours.After follow-up dipping moditied processing with
50 DEG C of deionized water is washed, until the pH of solution is 7-9 after washing.Obtained graininess Raney's nickel catalyst it is flat
Consist of Ni53.3Al43.7Fe3.0。
Embodiment 5
Accurately weigh 500 grams of the aluminium of 450 grams of nickel of the purity more than 99% and purity more than 99%, iron of the purity more than 99%
50 grams, it is placed in intermediate frequency furnace and is melted in 1600 DEG C, the time, at 1 hour, pours out in mould and cooled down through ladder, through jaw
Formula disintegrating machine machine and ball mill are obtained alloyed powder of the particle diameter less than 200 mesh, are subsequently adding water, boehmite, binding agent, pass through
It is extruded into after bar, drying and roasting and the rod-shaped particles of the mm length 2-5 millimeters of diameter 2 is obtained.
Then this is consisted of into Ni45Al50Fe5Metal alloy particle 200g, be placed in internal diameter be 50mm quartz glass tube
Interior, concentration is that the KOH aqueous slkalis of 1.0 weight % are flowed into by metal conjunction with the speed of 5L/ hours from the bottom of quartz glass tube
Then gold grain bed flows out from top, and the weight space velocity of KOH aqueous slkalis is 25 hours-1.Bed temperature is 40 DEG C, activation process
Time is 4 hours.Washed with 60 DEG C of deionized water after aqueous slkali activation process, until the pH of solution is 7-9 after washing.
Then zinc sulfate solution carries out the follow-up addition agent modified process of Zn, and zinc sulfate solution concentration is 4.5 weight %,
Weight space velocity is 1 hour-1, bed temperature is 60 DEG C, and the impregnation process time is 2.0 hours.With 50 after follow-up dipping moditied processing
DEG C deionized water washed, until washing after solution pH be 7-9.Obtained granular adsorbent is averagely consisted of
Ni54.4Al37.7Fe5.1Zn2.8。
Embodiment 6
Accurately weigh 510 grams of the aluminium of 450 grams of nickel of the purity more than 99% and purity more than 99%, zinc of the purity more than 99%
40 grams, it is placed in intermediate frequency furnace and is melted in 1650 DEG C, the time, at 1 hour, pours out in mould and cooled down through ladder, through jaw
Formula disintegrating machine machine is crushed, and sieve is obtained to 3-6mm particles.
Then this is consisted of into Ni45Al51Zn4Metal alloy particle 200g, be placed in internal diameter be 50mm quartz glass tube
Interior, concentration is that the KOH aqueous slkalis of 0.8 weight % are flowed into by metal conjunction with the speed of 5L/ hours from the bottom of quartz glass tube
Then gold grain bed flows out from top, and the weight space velocity of KOH aqueous slkalis is 25 hours-1.Bed temperature is 30 DEG C, activation process
Time is 4 hours.Washed with 50 DEG C of deionized water after aqueous slkali activation process, until the pH of solution is 7-9 after washing.
Then the nitric acid ruthenium aqueous solution carries out the follow-up addition agent modified process of Ru, and nitric acid ruthenium concentration of aqueous solution is 0.01 weight
Amount %, weight space velocity is 1 hour-1, bed temperature is 60 DEG C, and the impregnation process time is 2.5 hours.After follow-up dipping moditied processing
Washed with 50 DEG C of deionized water, until the pH of solution is 7-9 after washing.Obtained graininess Raney's nickel catalyst
Averagely consist of Ni52.7Al44.6Zn0.6Ru0.08。
Embodiment 7
Accurately weigh 500 grams of the aluminium of 430 grams of nickel of the purity more than 99% and purity more than 99%, copper of the purity more than 99%
20 grams, iron 50 gram of the purity more than 99% is placed in intermediate frequency furnace and is melted in 1500 DEG C, and the time, at 1 hour, pours out mould
Middle to be crushed through jaw crusher machine through ladder cooling, sieve is obtained to 3-6mm particles.
Then this is consisted of into Ni43Al50Cu2Fe5Metal alloy particle 200g, be placed in internal diameter be 50mm quartz glass
In pipe, concentration is that the KOH aqueous slkalis of 0.6 weight % are flowed into by metal with the speed of 6L/ hours from the bottom of quartz glass tube
Then alloying pellet bed flows out from top, and the weight space velocity of KOH aqueous slkalis is 30 hours-1.Bed temperature is 30 DEG C, at activation
The reason time is 5 hours.Washed with 70 DEG C of deionized water after aqueous slkali activation process, until the pH of solution is 7- after washing
9。
Then zinc sulfate solution carries out the follow-up addition agent modified process of Zn, and zinc sulfate solution concentration is 4.0 weight %,
Weight space velocity is 1 hour-1, bed temperature is 60 DEG C, and the impregnation process time is 2.5 hours.With 50 after follow-up dipping moditied processing
DEG C deionized water washed, until washing after solution pH be 7-9.Obtained graininess Raney's nickel catalyst it is average
Consist of Ni50.1Al40.8Cu1.5Fe4.5Zn3.1。
Embodiment 8
Accurately weigh 500 grams of the aluminium of 470 grams of nickel of the purity more than 99% and purity more than 99%, copper of the purity more than 99%
30 grams, it is placed in intermediate frequency furnace and is melted in 1550 DEG C, the time, at 1 hour, is poured out through natural cooling in mould, through jaw
Formula disintegrating machine machine is crushed, and sieve is obtained to 3-6mm particles.
Then this is consisted of into Ni47Al50Cu3Metal alloy particle 200g, be placed in internal diameter be 50mm quartz glass tube
Interior, concentration is that the KOH aqueous slkalis of 0.8 weight % are flowed into by metal conjunction with the speed of 4L/ hours from the bottom of quartz glass tube
Then gold grain bed flows out from top, and the weight space velocity of KOH aqueous slkalis is 20 hours-1.Bed temperature is 40 DEG C, activation process
Time is 5 hours.Washed with 50 DEG C of deionized water after aqueous slkali activation process, until the pH of solution is 7-9 after washing.
Then zinc acetate aqueous solution carries out the follow-up addition agent modified process of Zn, and zinc acetate aqueous solution concentration is 5 weight %, heavy
Amount air speed is 1 hour-1, bed temperature is 60 DEG C, and the impregnation process time is 2.0 hours.With 50 DEG C after follow-up dipping moditied processing
Deionized water washed, until washing after solution pH be 7-9.Obtained granular adsorbent is averagely consisted of
Ni53.3Al43.3Cu2.3Zn1.1。
Performance of the adsorbent is evaluated：
Isopropanol deep desulfuration and Deodorization Experiment are carried out on fixed bed reactors, adsorbent inventory 50ml, and liquid phase is inhaled
20-50 DEG C of enclosure temperature, volume space velocity 0.5-5.0 hours-1。
Adsorbent uses the front dried process in nitrogen atmosphere, the isopropanol of entrance sulfur content 0.5-5mg/kg, smell
Grade is 5-6 levels, and sulfur content is carried out according to microcoulomb method in isopropanol.
Oder levels assay method is：5 milliliters of isopropanol odorless distilled water dilutings are taken to 100 milliliters, after being well mixed
Hear its stink.With water as 0 grade, slightly alcohol taste is 1 grade, and it is 2 grades that alcohol taste is slightly dense, and slightly peculiar smell is 3 grades, and peculiar smell is evident as 4 grades, different
It is 5 grades that taste is heavier, has strong peculiar smell to be 6 grades.
In the present invention, obtain a result when effective Sulfur capacity refers to that sulphur is not detected in isopropanol after adsorbent bed.It is full
The total amount of adsorbent absorption sulphur draws when referring to that sulfur content is no longer reduced in isopropanol after adsorbent bed with Sulfur capacity.
The reaction condition and reaction result of each embodiment is shown in Table 1.
Table 1.
The total isopropanol of adsorbent is flow through when a) not detecting according to sulfur content in outlet isopropanol to measure out.
Flow through sulphur in the total isopropanol deduction outflow isopropanol of adsorbent when b) no longer adsorbing sulphur according to adsorbent to draw.
Embodiment described above has been described in detail to technical scheme, it should be understood that the above is only
For the specific embodiment of the present invention, be not limited to the present invention, it is all be made in the spirit of the present invention any modification,
Supplement or similar fashion is substituted, and nickel-based sorbent is directly or indirectly applied to other related adsorbing and removing organic sulfur fields, especially
It is low-carbon alcohols desulfurization and field of deodorization etc., be should be included within the scope of the present invention.
Claims (10)
1. it is a kind of to be used for isopropanol deep desulfuration (mercaptan, thioether, thiophene) and deodorant nickel-based sorbent, the nickel-based sorbent bag
Nickeliferous, aluminium and optional auxiliary agent；
Wherein, on the basis of the percetage by weight of the nickel-based sorbent, nickel content is 40-80 weight %, and aluminium content is in 20-60
Weight %, auxiliary agent content 0-10 weight %；
The auxiliary agent is selected from one or more element in Pd, Ru, Ag, Cu, Zn, Fe, Mn and Co；And
The nickel-based sorbent is activated by aqueous slkali, forms the outer surface layer with loose structure, and total pore volume is more than 0.1ml/
Ml adsorbents.
2. isopropanol deep desulfuration and deodorant nickel-based sorbent are used for as claimed in claim 1, it is characterised in that nickel content is
40-80 weight %, aluminium content is in 20-60 weight %, auxiliary agent content 0-10 weight %；Preferably, nickel content is 45-75 weights
Amount %, aluminium content is in 25-55 weight %, auxiliary agent content 0-10 weight %.
3. isopropanol deep desulfuration and deodorant nickel-based sorbent are used for as claimed in claim 1, it is characterised in that described Ni-based
Adsorbent is graininess, or the nickel-based sorbent is spherical in shape, bar shaped, cylinder and their graininess for combining；And/or
Granular size 2.0-8.0mm.
4. isopropanol deep desulfuration and deodorant nickel-based sorbent are used for as claimed in claim 1, it is characterised in that the porous
Mesopore and macropore volume accounting 20%-50% in structure, micro pore volume accounting 80%-50%；And/or the nickel-based sorbent
Also include kernel, the mean intensity of the kernel is preferably side pressure more than 300N.
5. a kind of for isopropanol deep desulfuration and the preparation method of deodorant nickel-based sorbent, methods described includes：
(1) mixture comprising nickel, aluminium and auxiliary agent is provided,
Wherein, on the basis of the percetage by weight of the nickel-based sorbent, nickel content is 40-80 weight %, and aluminium content is in 20-60
Weight %, auxiliary agent content 0-10 weight %；The auxiliary agent is selected from one or more yuan in Pd, Ru, Ag, Cu, Zn, Fe, Mn and Co
Element；
(2) after by the mixture pelleting, activation process is carried out to alloying pellet with aqueous slkali；
(3) particle after activation process is washed；
(4) optionally, dipping moditied processing is carried out to the particle after washing using the auxiliary agent water soluble salt aqueous solution, again
Graininess nickel-based sorbent is obtained after washing.
6. preparation method as claimed in claim 5, it is characterised in that in step (1), by by metallic nickel, metallic aluminium and
Auxiliary agent carries out melting to provide the mixture；Preferably, the temperature of the melting is 1000-1800 DEG C, and the time is little in 0.5-3
When, for quenching, either ladder cools down or naturally cools to normal temperature to the type of cooling；
In step (2), particle is formed, particle is cast into or is broken into after powder and carried out by beating piece or extrude by broken
Granulation；Preferably, the granulation includes brush choosing granulation, the granulation of fused solution alloy casting, fused solution alloy after Mechanical Crushing
Forming agent is added to carry out beating piece or extrude granulation after rotating granulation or crushing；
In step (2), activation process is carried out to alloying pellet with aqueous slkali includes entering the alloying pellet with inorganic alkali solution
Row activation process, preferably alloying pellet is placed in after fixed bed reactors carries out in-situ activation process；Preferably, it is described inorganic
Aqueous slkali is NaOH or KOH, wherein, alkaline concentration is 0.1-10 weight %, and the weight space velocity of aqueous slkali is 5-100 hours-1,
Activating treatment temperature is -100 DEG C of room temperature, and the activation process time is 1-8 hours；
It is highly preferred that the aqueous slkali be KOH, wherein, KOH alkaline concentrations be 0.5-5 weight %, the weight of KOH aqueous slkalis
Air speed is 10-50 hours-1, activating treatment temperature is -80 DEG C of room temperature, and the activation process time is 2-6 hours；
In step (3), the aqueous slkali is switched into deionized water, until the pH value of solution is 7-9 after washing, wherein, wash
Temperature is washed for -80 DEG C of room temperature；
In step (4), the auxiliary agent water soluble salt aqueous solution includes the aqueous solution containing zinc salt, molysite or ruthenium salt, wherein, zinc salt
It is 0.5-10 weight % with molysite aqueous solution concentration, ruthenium saline solution concentration is 0.001-0.1 weight %, and the auxiliary agent is water-soluble
The weight space velocity of saline solution is 0.5-5 hours-1, the temperature for impregnating modification is -80 DEG C of room temperature, and the time is 0.5-3 hours；
In step (4), the zinc salt is selected from zinc acetate, zinc sulfate and zinc nitrate；Molysite is selected from ferric sulfate, ferric acetate, sulfuric acid
Ferrous and frerrous chloride；Ruthenium salt is selected from acetic acid ruthenium, ruthenium trichloride and nitric acid ruthenium；
In step (4), the auxiliary agent water soluble salt aqueous solution is switched into deionized water, until the pH value of solution is after washing
7-9, wherein, wash temperature is -80 DEG C of room temperature.
7. isopropanol deep desulfuration and deodorant nickel-based sorbent are used for as described in any one of claim 1-4 in technical grade, change
Cosmetic level and pharmaceutical grade isopropanol deep desulfuration and the deodorant middle application as adsorbent.
8. isopropanol deep desulfuration and deodorant nickel-based sorbent are used for as described in any one of claim 1-4 in isopropanol desulfurization
The middle application as desulfuration adsorbent.
9. as claimed in claim 7 or 8 application, it is characterised in that sulfur content is 0.5-5mg/kg in isopropyl raw polyol, Jing nickel
＜ 0.025mg/kg are reduced to after base adsorbent absorption；The temperature of absorption is 20-50 DEG C；And for isopropanol deep absorption desulfurization
Effectively Sulfur capacity is up to 3.50g sulphur/L adsorbents；Oder levels reach 1 grade after deodorization.
10. application as claimed in claim 7 or 8, it is characterised in that the Ni-based absorption after the failure of isopropanol deep desulfuration
Agent is used as isopropanol deep desulfuration pretreatment adsorbent, in isopropyl raw polyol sulfur content be 0.5-5mg/kg, the temperature of absorption
Spend for 20-50 DEG C；Nickel-based sorbent saturation Sulfur capacity is 100g sulphur/L adsorbents.
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