CN106622096B - Isopropanol deep desulfuration and the nickel-based sorbent of deodorization and its preparation method and application - Google Patents
Isopropanol deep desulfuration and the nickel-based sorbent of deodorization and its preparation method and application Download PDFInfo
- Publication number
- CN106622096B CN106622096B CN201611015181.0A CN201611015181A CN106622096B CN 106622096 B CN106622096 B CN 106622096B CN 201611015181 A CN201611015181 A CN 201611015181A CN 106622096 B CN106622096 B CN 106622096B
- Authority
- CN
- China
- Prior art keywords
- nickel
- weight
- auxiliary agent
- based sorbent
- isopropanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J20/0203—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
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J20/28—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
Abstract
The present invention provides isopropanol deep desulfuration (mercaptan, thioether, thiophene) and nickel-based sorbents of deodorization and its preparation method and application.The present invention includes nickel, aluminium and auxiliary agent for isopropanol deep desulfuration and the nickel-based sorbent of deodorization；Wherein, nickel content is 40-80 weight %, and aluminium content is in 20-60 weight %, auxiliary agent content 0-10 weight %；The auxiliary agent one or more elements in Pd, Ru, Ag, Cu, Zn, Fe, Mn and Co.Through nickel-based sorbent of the present invention treated isopropanol can satisfy cosmetics-stage and medical level isopropanol quality requirement.Compared with prior art, nickel-based sorbent desulfurization precision of the present invention is high, Sulfur capacity is high, deodorizing effect is significant, low energy consumption, price is low, simple production process, is easy to industrialize, and has a good application prospect and huge economic benefit.
Description
Technical field
The present invention relates to a kind of isopropanol deep desulfuration and nickel-based sorbents of deodorization and its preparation method and application, specifically
It is related to technical grade, cosmetics-stage and pharmaceutical grade isopropanol deep desulfuration and the nickel-based sorbent of deodorization and preparation method thereof and answers
With.
Technical background
Isopropanol is important chemical products and raw material.It is mainly used for pharmacy, cosmetics, plastics, fragrance, coating etc..Example
Such as in drug, it is mainly used for manufacture 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 to solubilized synthetic detergent.Currently, industrial isopropanol is basic
It is to be synthesized from propylene.Since propylene can bring different sulphur-containing substance and Ammonia substance into due to technological reason, will cause different
The sulfur content of propyl alcohol is exceeded and smell is abnormal, seriously affects the product quality of isopropanol and high-grade with application on the way.
General sulfur method has sulfuric acid treatment, extracting rectifying, freezing and crystallizing, catalytic hydrogenation, choosing in existing organic compound
Select oxidation, selection absorption, precipitating desulfurization and ionic liquid and biological desulphurization etc..And adsorb desulfurization with equipment investment it is small,
The advantages that simple process, condition be easy to control, significant effect, is currently the common method of domestic and international desulfurization.
The principle for adsorbing desulfurization is to be supported on porous solid carrier, using the adsorbent based on transition metal certain
Selectively make sulphur atom and metallic atom in the sulfur-containing compounds such as thiophene, mercaptan, thioether that phase occur under temperature and pressure
Interaction, so that sulfur-containing compound is adsorbed on the surface of adsorbent and is removed.In general, with the metallic element of 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 related with mercaptan, thioether sulfides, but between peculiar smell and sulfur content
There is no direct relationships.Therefore, it in order to be applicable to isopropanol in cosmetics-stage and the product of 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 other than sulfide by aldehyde
Class, amine etc. cause.Therefore it is required that adsorbent not only has the function of deep desulfuration, deodorization functions have also been needed.
United States Patent (USP) US4219685A discloses a kind of low-carbon alcohols deodour method: aoxidizing low-carbon alcohols and metal or metal
The deodorization contact that object or the two form together is in contact, and metal oxide party is reduced into metal.It is representative
Be stannous chloride, preferable granularity is about 0.79mm, preferably be deodorized contact have effective surface area be less than 1000m2/
g。
Zheng Kuishan (Liaoning chemical industry, 1984,03,27-31), which is described, selects skeleton nickel and carrier nickel for isopropanol deodorization
Method: deodorization condition is 60 DEG C and 80 DEG C, can be using fixed bed or fluidized bed, and thinks that hydrogenation catalyst can be used for
Isopropanol deodorization.And the document only focuses on deodorization, does not have related data to deep desulfuration.Meanwhile the document thinks at skeleton nickel
Product is muddy after reason, and isopropanol has dehydrogenation phenomenon after processing.
Yang Zhisheng (Liaoning chemical industry, 1985,12,14-16), which is reported, selects seven kinds of industrial catalysts that an isopropyl is fixed
Alcohol deodorization: catalyst preferably 804, process conditions are 50 DEG C, and normal pressure, air speed is 10 hours-1.However, sulfur content after its processing
In 0.2ppm or so.
In conclusion isopropanol deodorization at present generally uses industrial hydrogenation catalyst, there is no dedicated for isopropanol depth
Spend the catalyst of desulfurization and deodorization.Moreover, above-mentioned industrial catalyst has certain problems, for example desulfurization depth is inadequate, only closes
Deodorizing effect is infused, need to heat using temperature etc..Requirement with people to quality of the life improves, and industrial at present adds hydrogen to urge
Agent is not able to satisfy the requirement of isopropanol deep desulfuration and deodorization.Therefore seek a kind of cheap efficient isopropanol at present
Deep desulfuration and the adsorbent of deodorization are particularly significant and necessary.
Summary 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 after essence and the nickel-based sorbent melting of deodorization for key factor, propose
One kind being used for the nickel-based sorbent of isopropanol deep desulfuration (mercaptan, thioether, thiophene) and deodorization, and proposes the adsorbent
Preparation method and applications.Nickel-based sorbent of the present invention has the active material outer surface layer for enriching suitable institutional framework composition
With the metal alloy kernel of high strength dense structure composition.Relative to industrial hydrogenation catalyst used at present, the present invention is Ni-based
Adsorbent has the function of deep desulfuration (mercaptan, thioether, thiophene), and at the same time having apparent deodorization functions, absorption Sulfur capacity is big,
It can use at normal temperature, long service life.
On the one hand, embodiments of the present invention provide a kind of nickel-based sorbent for isopropanol deep desulfuration and deodorization,
The nickel-based sorbent includes nickel, aluminium and optional auxiliary agent；
Wherein, on the basis of the weight percent 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 one or more elements in Pd, Ru, Ag, Cu, Zn, Fe, Mn and Co.
In some embodiments, nickel content is 40-70 weight %, and aluminium content is in 30-60 weight %, auxiliary agent content 0-
10 weight %；Alternatively, nickel content is 45-75 weight %, aluminium content is in 25-55 weight %, auxiliary agent content 0-10 weight %.
In some embodiments, the nickel-based sorbent is graininess or the nickel-based sorbent is spherical in shape, item
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 porous structure, and total pore volume is adsorbed greater than 0.1ml/ml
Agent, mesoporous and macropore in the porous structure account for volume ratio 20%-50%, micro pore volume accounting 80%-50%.In the present invention
In, the micropore refers to that average pore size is less than the hole of 2nm, and mesoporous refers to the hole for being less than 50nm greater than 2nm, and macropore, which refers to, to be greater than
The hole of 50nm.In some embodiments, the mean intensity of the kernel is that side pressure is greater than 300N.
In some embodiments, 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 nickel-based sorbent for isopropanol deep desulfuration and deodorization
Preparation method, which comprises
(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 one or more elements in Pd, Ru, Ag, Cu, Zn, Fe, Mn and Co；
(2) by after the mixture pelleting, alloying pellet is activated with aqueous slkali；
(3) particle after activation processing is washed；
(4) optionally, dipping moditied processing is carried out to the particle after washing using auxiliary agent water soluble salt aqueous solution,
Graininess nickel-based sorbent is obtained after washing again.
In some embodiments, in step (1), mentioned by the way that metallic nickel, metallic aluminium and auxiliary agent are carried out melting
For the mixture；Preferably, the temperature of the melting is 1000-1800 DEG C, and the time, the type of cooling was rapid at 0.5-3 hours
Cold or ladder is cooling or naturally cools to room temperature.
In some embodiments, in step (2), particle is formed, particle is cast into or is broken into powder by broken
It is last to be granulated by beating piece or extruding；Preferably, described to be granulated including brush choosing is granulated, fused solution closes after Mechanical Crushing
Gold casting is granulated, addition forming agent carries out beating piece or extrudes granulation after fused solution alloy rotating granulation or crushing.
In some embodiments, in step (2), be activated to alloying pellet with aqueous slkali includes using nothing
Machine aqueous slkali is activated the alloying pellet, and preferably alloying pellet is placed in after fixed bed reactors and carries out original position
It is activated；Preferably, the inorganic alkali solution is NaOH or KOH, wherein alkaline concentration is 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 being activated the time is 1-8 hours.
In some embodiments, the aqueous slkali is KOH, wherein KOH alkaline concentration is 0.5-5 weight %,
The weight space velocity of KOH aqueous slkali is 10-50 hours-1, activating treatment temperature is -80 DEG C of room temperature, and being activated the time is that 2-6 is small
When.
In some embodiments, 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 some embodiments, in step (4), the auxiliary agent water soluble salt aqueous solution includes 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 are 0.5-5 hours-1, the temperature for impregnating modification is room temperature-
80 DEG C, the time is 0.5-3 hours.
In some embodiments, 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 some embodiments, 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 provide the nickel-based sorbent for being used for isopropanol deep desulfuration and deodorization
In the application of technical grade, cosmetics-stage and pharmaceutical grade in isopropanol deep desulfuration and deodorization as adsorbent.
On the other hand, embodiments of the present invention provide the nickel-based sorbent for being used for isopropanol deep desulfuration and deodorization
As the application of desulfuration adsorbent in isopropanol desulfurization.
In some embodiments, sulfur content is 0.5-5mg/kg in isopropyl raw polyol, after nickel-based sorbent adsorbs
It is reduced to < 0.025mg/kg；The temperature of absorption is 20-50 DEG C；And effective Sulfur capacity for isopropanol deep absorption desulfurization is up to
3.50g sulphur/L adsorbent；Oder levels reach 1 grade after deodorization.
In some embodiments, the nickel-based sorbent after the failure of isopropanol deep desulfuration is as isopropanol depth
Desulfurization pretreatment adsorbent uses, 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
It is 100g sulphur/L adsorbent that adsorbent, which is saturated Sulfur capacity,.
In the present invention, sulfur content is 0.5-5mg/kg in isopropyl raw polyol.After nickel-based sorbent adsorbs, sulfur content is pressed
It is not detected according to microcoulomb method, that is, is less than 0.025mg/Kg, isopropanol deep desulfuration quality requirement can be met.And it is deep for isopropanol
Effective Sulfur capacity of degree absorption desulfurization is up to 3.50g sulphur/L adsorbent.Meanwhile after nickel-based sorbent adsorbs, 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 adsorbent can meet the application of general isopropanol desulfurization.Moreover, the nickel-based sorbent is after deep desulfuration failure
It can continue to use as general desulfurization, or as deep desulfuration pre-treatment, use cost can be further decreased.
Compared with prior art, nickel-based sorbent of the present invention has the advantage that
(1) nickel-based sorbent of the present invention can achieve isopropanol deep desulfuration (being less than 0.025mg/Kg), effective sulphur
Hold and is up to the 3.50g sulphur/requirement of L adsorbent and deodorization to oder levels less than 1；
(2) nickel-based sorbent of the present invention can use at normal temperature, do not need system and additionally heat, low energy consumption；
(3) there is nickel-based sorbent of the present invention saturation Sulfur capacity to be up to 100g sulphur/L adsorbent, can meet general different
The application of propyl alcohol desulfurization, deep desulfuration failure after can continue to use as general desulfurization, or as deep desulfuration before
Processing, can further decrease use cost；And
(4) preparation process of nickel-based sorbent of the present invention is simple, is easy to industrialize, have a good application prospect and
Huge economic benefit.
By the following detailed description and claim, other features and aspect can become apparent.
Specific embodiment
Unless otherwise defined, technical term or scientific term used in claims and specification should be this hair
The ordinary meaning that personage in bright technical field with general technical ability is understood.
Below with reference to specific embodiment, the present invention will be further described, but the present invention is not limited to following specific implementations
Mode.
The present invention provides a kind of nickel-based sorbent for isopropanol deep desulfuration and deodorization, the nickel adsorbent is
Granular nickel-based sorbent, including having the active material outer surface layer and high strength dense knot that enrich suitable institutional framework composition
The metal alloy kernel of structure composition.Wherein, the group of the adsorbent becomes NiAlX, and Ni content is 40-80 weight %, Al content
It is auxiliary agent, including a kind of element or a variety of complex elements for 20-60 weight %, X, auxiliary agent total content is 0-10 weight %.
Preferably, the Ni content of the graininess nickel-based sorbent is 45-75 weight %, and Al content is 25-55 weight %,
Auxiliary element X content is 0-10 weight %.
In the present invention, by adjusting the additive amount of original composition ratio and auxiliary agent in metal alloy raw material, after melting
The particle or molten state cast molding that are then crushed by quenching or the cooling perhaps natural cooling of ladder or rotation balling-up
Type binder is added after grinding plays piece or extrusion molding；Then it is activated under setting condition through aqueous slkali, deionization
The washing of water and subsequent auxiliary agent impregnate moditied processing, obtain the graininess nickel adsorbent of heterogeneity.
In the present invention, the absorbent particles shape can be irregular shape, spherical shape, hemispherical, cylindrical type, stick, tooth
Shape, hollow stick, the particle diameter are 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 graininess
Attached dose of Ni content is 45-75 weight %, and Al content is 25-55 weight %, and auxiliary element X content is 0-10 weight %.
In the present invention, using aqueous slkali to the activation processing of the metal alloy particle specifically: by the gold of predetermined amount
Belong to alloying pellet raw material to be placed in fixed bed reactors, inorganic alkali solution is used to pass through the metal alloy with preset flow velocity
Grain is activated.
Preferably, the inorganic alkali solution is NaOH or KOH, and the aqueous slkali passes through alloying pellet with preset flow velocity
It is activated, wherein alkaline concentration is 0.1-10 weight %, and the weight space velocity of aqueous slkali is 5-100 hours-1, at activation
Managing temperature is -100 DEG C of room temperature, and being activated the time is 1-8 hours.
It is further preferred that the aqueous slkali is KOH, the KOH aqueous slkali is carried out with preset flow velocity by alloying pellet
It is activated, it is 10-50 hours that wherein KOH alkaline concentration, which is the weight space velocity of 0.5-5 weight %, KOH aqueous slkali,-1, activation
Treatment temperature is -80 DEG C of room temperature, and being activated the time is 2-6 hours.
In the present invention, described that washing tool is carried out to the metal alloy particle by being activated using deionized water
Body are as follows: the aqueous slkali is switched into deionized water, the deionized water with preset flow velocity by the metal alloy particle,
Until the pH value of solution is 7-9 after washing.
Preferably, the deionized water washs the metal alloy particle, until the pH value of solution is after washing
7-9, wherein wash temperature is -80 DEG C of room temperature.
In the present invention, using auxiliary agent water-soluble salt solution to the metal alloy particle by carrying out washing treatment into
Row auxiliary agent impregnates moditied processing specifically: the deionized water is switched to auxiliary agent water soluble salt aqueous solution, the auxiliary agent is water-soluble
Property saline solution with preset flow velocity pass through the metal alloy particle carry out moditied processing.The auxiliary agent be Pd, Ru, Ag, Cu,
The mixing of Zn, Fe, Mn and Co one or more.
Preferably, described auxiliary element Zn, Fe perhaps Ru subsequent dipping addition refer to zinc, iron or ruthenium saline solution
Subsequent dipping moditied processing is carried out by the alloying pellet NiAlX after being activated and washing with preset flow velocity, wherein zinc salt
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 subsequent dipping addition of the auxiliary element, refers to zinc salt, molysite or ruthenium saline solution with preset
Flow velocity by be activated and washing after alloying pellet NiAlX carry out subsequent dipping 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 to the metal alloy particle NiAlX of the subsequent dipping of auxiliary element addition into
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 the normal-temperature efficient nickel-based sorbent of deodorization includes following
Step:
(1) melting, granulation or molding of metal alloy；
(2) using aqueous slkali to the activation processing of the metal alloy particle；
(3) metal alloy particle by being activated is washed using deionized water；
(4) optionally, it is soaked to described by the metal alloy particle of carrying out washing treatment using auxiliary agent water soluble salt
Stain moditied processing；
(5) optionally, it is washed using the particle that deionized water obtains (4) step, it is Ni-based to obtain graininess
Adsorbent.
In a preferred embodiment, the melting of step (1) described metal alloy and the preparation of particle include: metallic nickel,
The melting of aluminium or auxiliary agent is crushed to certain granules use and perhaps carries out being cast to certain shape molding or broken pulverized powder
Shape is then by playing piece or extrusion molding.
Preferably, the metallic nickel and aluminium include or the smelting temperature without auxiliary agent is at 1000-1800 DEG C, and the time exists
0.5-3 hours, the type of cooling was quenching or ladder cooling or naturally cools to room temperature.
Molding after the melting includes Mechanical Crushing molding, using mechanical jaw crusher or impact crusher or
Hammer stone crusher is crushed, and obtains shaped granule, or the liquid for passing through melting by the particle that sieve chooses certain particle size
Alloy passes through cast molding, shape include dome-type, stick perhaps cuboid-type or by the liquid alloy of melting through overwinding
Turn to be granulated and form ball-type, or the modes such as ball milling are again passed by by broken particle and are obtained less than 100 targeted fine powders, then
The forming agents such as aluminium oxide, water, binder are added, including carry out beating piece, drying, roasting, obtain diameter 1mm-6mm, height 1mm-
The cylindrical pellet of 6mm, or formed through extrusion, drying, roasting, obtain cylinder, tooth form, hollow cylinder shape and according to mill
Tool obtains different shape particle, and diameter is between 1mm-6mm, and length is in 1mm-5mm.Wherein crushing and screening particle is irregular shape
Shape, for size between 1mm-8mm, fusion-cast particle melts rotating granulation size in 1mm-8mm in 1mm-12mm.
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%,
The content of nickel is in 30-60%, and single auxiliary agent or mixed aid content are in 0-10%.
In a preferred embodiment, in step (2), had using activation processing of the aqueous slkali to the metal alloy particle
Body are as follows: the metal alloy particle raw material of predetermined amount is placed in fixed bed reactors, uses inorganic alkali solution with preset flow velocity
It is activated 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 preset flow velocity
Grain is activated, 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 being activated the time is 1-8 hours.
It is highly preferred that the aqueous slkali is KOH, the KOH aqueous slkali is lived with preset flow velocity by alloying pellet
Change processing, it is 10-50 hours that wherein KOH alkaline concentration, which is the weight space velocity of 0.5-5 weight %, KOH aqueous slkali,-1, at activation
Managing temperature is -80 DEG C of room temperature, and being activated the time is 2-6 hours.
In a preferred embodiment, in step (3), the metal that process is activated using deionized water
Alloying pellet is washed, specifically: the KOH aqueous slkali is switched into deionized water, the deionized water is with preset 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 by carrying out washing treatment
The metal alloy particle carries out auxiliary agent and impregnates moditied processing, specifically: the deionized water is switched into auxiliary agent water soluble salt
Aqueous solution, the auxiliary agent water soluble salt aqueous solution carry out moditied processing by the metal alloy particle with preset flow velocity.Institute
Auxiliary agent is stated as the mixing of Pd, Ru, Ag, Cu, Zn, Fe, Mn and Co one or more.
It is highly preferred that described auxiliary element Zn, Fe perhaps Ru subsequent dipping addition refer to that zinc, iron or ruthenium salt are water-soluble
Liquid carries out subsequent dipping moditied processing by the alloying pellet NiAlX after being activated and washing with preset flow velocity, 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 subsequent dipping addition of described auxiliary element Zn, Fe or Ru, refers to auxiliary agent saline solution with preset
Flow velocity by be activated and washing after alloying pellet NiAlX carry out subsequent dipping 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), pass through auxiliary agent water soluble salt aqueous solution to described using deionized water
The metal alloy particle of subsequent dipping moditied processing is washed specifically: switches the auxiliary agent water soluble salt aqueous solution
At deionized water, the deionized water with preset flow velocity by the metal alloy particle, until after washing solution pH value
For 7-9.Wherein wash temperature is -80 DEG C of room temperature.
It is applied to isopropanol depth liquid desulfuration and deodorization according to the nickel-based sorbent of above-mentioned steps preparation.Desulfurization and deodorization
It the use of temperature is 20-50 DEG C, volume space velocity 0.5-5.0 hours in technique-1, should keep in sulfur content be 0.5-5mg/kg, through inhaling
It is attached to be reduced to < 0.025mg/kg (being not detected by microcoulomb method).Effective Sulfur capacity is up to 3.50g sulphur/L adsorbent.Saturation absorption
Sulfur capacity is up to 100g sulphur/L adsorbent.
Below in conjunction with specific embodiment, the invention will be further described, it should be pointed out that embodiment described below purport
It is being convenient for the understanding of the present invention, and is not playing any restriction effect to the scope of protection of present invention.
Embodiment 1
Accurately weigh nickel 500 gram of the purity greater than 99% and purity be greater than 500 grams of aluminium of 99%, be placed in intermediate frequency furnace in
1650 DEG C are melted, and the time at 1 hour, pours out in mold by natural cooling, is crushed by jaw crusher machine,
Sieve, which obtains, arrives 3-6mm particle.
Then, which is become into Ni50Al50Metal alloy particle 200g, be placed in internal diameter be 50mm quartz glass tube
Interior, concentration is that the NaOH aqueous slkali of 0.8 weight % was flowed into from the bottom of quartz glass tube through metal conjunction with 5L/ hours speed
Then gold particle bed is flowed out from top.The weight space velocity of NaOH aqueous slkali is 25 hours-1.Bed temperature is 30 DEG C, at activation
Managing the time is 4 hours.Aqueous slkali is washed after being activated with 50 DEG C of deionized water, until the pH of solution is 7- after washing
9.The average composition of obtained granular adsorbent is Ni55.4Al44.6。
Embodiment 2
500 grams of aluminium of 450 grams of nickel of the purity greater than 99% and purity greater than 99% are accurately weighed, purity is greater than 99% iron
It 50 grams, is placed in intermediate frequency furnace and is melted in 1600 DEG C, the time at 1.5 hours, pours out in mold by natural cooling, passes through
Alloyed powder of the partial size less than 150 mesh is made in jaw crusher machine and ball mill, and water, boehmite, binder, stone is then added
The cylindrical particle of 3 millimeters of 3 height of diameter is made in ink after tablet machine plays piece, drying and roasting.
Then, which is become into Ni45Al50Fe5Metal alloy particle 200g, be placed in internal diameter be 50mm quartz glass tube
Interior, concentration is that the KOH aqueous slkali of 1.0 weight % was flowed into from the bottom of quartz glass tube through metal conjunction with 5L/ hours speed
Then gold particle bed is flowed out from top, the weight space velocity of NaOH aqueous slkali is 25 hours-1.Bed temperature is 40 DEG C, at activation
Managing the time is 4 hours.Aqueous slkali is washed after being activated with 60 DEG C of deionized water, until the pH of solution is 7- after washing
9.The average composition of obtained granular adsorbent is Ni54.4Al40.1Fe5.5。
Embodiment 3
500 grams of aluminium of 430 grams of nickel of the purity greater than 99% and purity greater than 99% are accurately weighed, purity is greater than 99% copper
20 grams, 50 grams of iron of purity greater than 99% are placed in intermediate frequency furnace to be melted in 1500 DEG C, and the time at 1 hour, pours out mold
Middle to be crushed by quenching cooling by jaw crusher machine, sieve, which obtains, arrives 3-6mm particle.
Then, which is become into Ni43Al50Cu2Fe5Metal alloy particle 200g, be placed in internal diameter be 50mm quartzy glass
In glass pipe, concentration is flowed into 6L/ hours speed from the bottom of quartz glass tube for the KOH aqueous slkali of 0.6 weight % passes through gold
Belong to alloying pellet bed then to flow out from top, the weight space velocity of KOH aqueous slkali is 30 hours-1.Bed temperature is 30 DEG C, activation
Handling the time is 5 hours.Aqueous slkali is washed after being activated with 70 DEG C of deionized water, until the pH of solution is after washing
7-9.The average composition of obtained granular adsorbent is Ni50.2Al43.5Cu1.5Fe4.8。
Embodiment 4
Accurately weigh nickel 490 gram of the purity greater than 99% and purity be greater than 510 grams of aluminium of 99%, be placed in intermediate frequency furnace in
1650 DEG C are melted, and the time at 0.8 hour, pours out in mold by natural cooling, carries out brokenly by jaw crusher machine
Broken, sieve, which obtains, arrives 3-6mm particle.
Then, which is become into Ni49Al51Metal alloy particle 200g, be placed in internal diameter be 50mm quartz glass tube
Interior, concentration is that the KOH aqueous slkali of 0.8 weight % was flowed into from the bottom of quartz glass tube through metal conjunction with 5L/ hours speed
Then gold particle bed is flowed out from top, the weight space velocity of KOH aqueous slkali is 25 hours-1.Bed temperature is 30 DEG C, is activated
Time is 4 hours.Aqueous slkali is washed after being activated with 50 DEG C of deionized water, until the pH of solution is 7-9 after washing.
Then, ferrous sulfate aqueous solution carries out the subsequent addition agent modified processing of Fe, and ferrous sulfate aqueous solution concentration is 5 weights
% is measured, weight space velocity is 1 hour-1, bed temperature is 70 DEG C, and the impregnation time is 2 hours.After subsequent 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 is put down
Group becomes Ni53.3Al43.7Fe3.0。
Embodiment 5
500 grams of aluminium of 450 grams of nickel of the purity greater than 99% and purity greater than 99% are accurately weighed, purity is greater than 99% iron
It 50 grams, is placed in intermediate frequency furnace and is melted in 1600 DEG C, the time at 1 hour, pours out by ladder cooling in mold, by jaw
Alloyed powder of the partial size less than 200 mesh is made in formula crusher machine and ball mill, and water, boehmite, binder is then added, and passes through
Be extruded into item, drying and roasting after be made 2-5 millimeters of 2 mm length of diameter rod-shaped particles.
Then the group is become into Ni45Al50Fe5Metal alloy particle 200g, be placed in internal diameter be 50mm quartz glass tube
Interior, concentration is that the KOH aqueous slkali of 1.0 weight % was flowed into from the bottom of quartz glass tube through metal conjunction with 5L/ hours speed
Then gold particle bed is flowed out from top, the weight space velocity of KOH aqueous slkali is 25 hours-1.Bed temperature is 40 DEG C, is activated
Time is 4 hours.Aqueous slkali is washed after being activated with 60 DEG C of deionized water, until the pH of solution is 7-9 after washing.
Then zinc sulfate solution carries out the subsequent addition agent modified processing 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 time is 2.0 hours.With 50 after subsequent dipping moditied processing
DEG C deionized water washed, until washing after solution pH be 7-9.The average composition of obtained granular adsorbent is
Ni54.4Al37.7Fe5.1Zn2.8。
Embodiment 6
510 grams of aluminium of 450 grams of nickel of the purity greater than 99% and purity greater than 99% are accurately weighed, purity is greater than 99% zinc
It 40 grams, is placed in intermediate frequency furnace and is melted in 1650 DEG C, the time at 1 hour, pours out by ladder cooling in mold, by jaw
Formula crusher machine is crushed, and sieve, which obtains, arrives 3-6mm particle.
Then the group is become into Ni45Al51Zn4Metal alloy particle 200g, be placed in internal diameter be 50mm quartz glass tube
Interior, concentration is that the KOH aqueous slkali of 0.8 weight % was flowed into from the bottom of quartz glass tube through metal conjunction with 5L/ hours speed
Then gold particle bed is flowed out from top, the weight space velocity of KOH aqueous slkali is 25 hours-1.Bed temperature is 30 DEG C, is activated
Time is 4 hours.Aqueous slkali is washed after being activated with 50 DEG C of deionized water, until the pH of solution is 7-9 after washing.
Then nitric acid ruthenium aqueous solution carries out the subsequent addition agent modified processing of Ru, and nitric acid ruthenium concentration of aqueous solution is 0.01 weight
% is measured, weight space velocity is 1 hour-1, bed temperature is 60 DEG C, and the impregnation time is 2.5 hours.After subsequent dipping moditied processing
It is washed with 50 DEG C of deionized water, until the pH of solution is 7-9 after washing.Obtained graininess Raney's nickel catalyst
Average composition is Ni52.7Al44.6Zn0.6Ru0.08。
Embodiment 7
500 grams of aluminium of 430 grams of nickel of the purity greater than 99% and purity greater than 99% are accurately weighed, purity is greater than 99% copper
20 grams, 50 grams of iron of purity greater than 99% are placed in intermediate frequency furnace to be melted in 1500 DEG C, and the time at 1 hour, pours out mold
It is middle cooling by ladder, it is crushed by jaw crusher machine, sieve, which obtains, arrives 3-6mm particle.
Then the group is become into Ni43Al50Cu2Fe5Metal alloy particle 200g, be placed in internal diameter be 50mm quartz glass
In pipe, concentration is flowed into 6L/ hours speed from the bottom of quartz glass tube for the KOH aqueous slkali of 0.6 weight % passes through metal
Then alloying pellet bed is flowed out from top, the weight space velocity of KOH aqueous slkali is 30 hours-1.Bed temperature is 30 DEG C, at activation
Managing the time is 5 hours.Aqueous slkali is washed after being activated with 70 DEG C of deionized water, until the pH of solution is 7- after washing
9。
Then zinc sulfate solution carries out the subsequent addition agent modified processing 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 time is 2.5 hours.With 50 after subsequent dipping moditied processing
DEG C deionized water washed, until washing after solution pH be 7-9.Obtained graininess Raney's nickel catalyst is averaged
Group becomes Ni50.1Al40.8Cu1.5Fe4.5Zn3.1。
Embodiment 8
500 grams of aluminium of 470 grams of nickel of the purity greater than 99% and purity greater than 99% are accurately weighed, purity is greater than 99% copper
It 30 grams, is placed in intermediate frequency furnace and is melted in 1550 DEG C, the time at 1 hour, pours out by natural cooling in mold, by jaw
Formula crusher machine is crushed, and sieve, which obtains, arrives 3-6mm particle.
Then the group is become into Ni47Al50Cu3Metal alloy particle 200g, be placed in internal diameter be 50mm quartz glass tube
Interior, concentration is that the KOH aqueous slkali of 0.8 weight % was flowed into from the bottom of quartz glass tube through metal conjunction with 4L/ hours speed
Then gold particle bed is flowed out from top, the weight space velocity of KOH aqueous slkali is 20 hours-1.Bed temperature is 40 DEG C, is activated
Time is 5 hours.Aqueous slkali is washed after being activated with 50 DEG C of deionized water, until the pH of solution is 7-9 after washing.
Then zinc acetate aqueous solution carries out the subsequent addition agent modified processing of Zn, and zinc acetate aqueous solution concentration is 5 weight %, weight
Measuring air speed is 1 hour-1, bed temperature is 60 DEG C, and the impregnation time is 2.0 hours.With 50 DEG C after subsequent dipping moditied processing
Deionized water washed, until washing after solution pH be 7-9.The average composition of obtained granular adsorbent is
Ni53.3Al43.3Cu2.3Zn1.1。
Performance of the adsorbent evaluation:
Isopropanol deep desulfuration and Deodorization Experiment carry 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 is dried using preceding be used in nitrogen atmosphere, the isopropanol of entrance sulfur content 0.5-5mg/kg, smell
Grade is 5-6 grades, and sulfur content is carried out according to microcoulomb method in isopropanol.
Oder levels measuring method are as follows: take 5 milliliters of isopropanols to be diluted to 100 milliliters with odorless distilled water, after mixing
Hear its stink.With water for 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
Heavier taste is 5 grades, and having strong peculiar smell is 6 grades.
In the present invention, effective Sulfur capacity refers to obtains a result when sulphur is not detected in isopropanol after adsorbent bed.It is full
The total amount of adsorbent absorption sulphur obtains when referring to that sulfur content no longer reduces in isopropanol after adsorbent bed with Sulfur capacity.
The reaction condition and reaction result of each embodiment are shown in Table 1.
Table 1.
The total isopropanol of adsorbent is flowed through when a) being not detected according to sulfur content in outlet isopropanol to measure out.
Sulphur in the total isopropanol deduction outflow isopropanol of adsorbent is flowed through when b) no longer adsorbing sulphur according to adsorbent to obtain.
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, be not intended to restrict the invention, it is all be made in spirit of the invention it is any modification,
Supplement or similar fashion substitution and nickel-based sorbent are 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. a kind of nickel-based sorbent is used in isopropanol deep desulfuration and deodorization in technical grade, cosmetics-stage and pharmaceutical grade as absorption
The application of agent, wherein the nickel-based sorbent includes nickel, aluminium and optional auxiliary agent；
On the basis of the weight percent of the nickel-based sorbent, nickel content is 40-80 weight %, and aluminium content is in 20-60 weight
Measure %, auxiliary agent content 0-10 weight %；
The auxiliary agent one or more elements in Pd, Ru, Ag, Cu, Zn, Fe, Mn and Co；And
The nickel-based sorbent is activated by KOH aqueous slkali, forms the outer surface layer with porous structure；
Wherein, the mesoporous in the porous structure and macropore volume accounting 20%-50%, micro pore volume accounting 80%-50%；Institute
Stating nickel-based sorbent further includes kernel, and the mean intensity of the kernel is that side pressure is greater than 300N；
The total pore volume of the nickel-based sorbent is greater than 0.1ml/ml adsorbent；With
KOH alkaline concentration is that the weight space velocity of 0.5-5 weight %, KOH aqueous slkali is 10-50 hours-1, activating treatment temperature is
- 80 DEG C of room temperature, being activated the time is 2-6 hours.
2. application as described in claim 1, which is characterized in that sulfur content is 0.5-5mg/kg in isopropyl raw polyol, through Ni-based
< 0.025mg/kg is reduced to after adsorbent absorption；The temperature of absorption is 20-50 DEG C；And having for isopropanol deep absorption desulfurization
Effect Sulfur capacity is up to 3.50g sulphur/L adsorbent；Oder levels reach 1 grade after deodorization.
3. application as described in claim 1, which is characterized in that the nickel-based sorbent after the failure of isopropanol deep desulfuration is made
It is used for isopropanol deep desulfuration pretreatment adsorbent, sulfur content is 0.5-5mg/kg in isopropyl raw polyol, and the temperature of absorption is
20-50℃；It is 100g sulphur/L adsorbent that nickel-based sorbent, which is saturated Sulfur capacity,.
4. application as described in claim 1, which is characterized in that the desulfurization include removal of mercaptans, desulfurization ether, de- thiophene and it
Combination.
5. application as described in claim 1, which is characterized in that nickel content is 45-75 weight %, and aluminium content is in 25-55 weight
Measure %, auxiliary agent content 0-10 weight %.
6. application as described in claim 1, which is characterized in that the nickel-based sorbent is graininess；With granular size 2.0-
8.0mm。
7. application as described in claim 1, which is characterized in that the nickel-based sorbent be spherical in shape, bar shaped, cylinder and
The graininess that they are combined.
8. application as described in claim 1, which is characterized in that the nickel-based sorbent is prepared in the following manner:
(1) mixture comprising nickel, aluminium and auxiliary agent is provided,
Wherein, on the basis of the weight percent 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 one or more members in Pd, Ru, Ag, Cu, Zn, Fe, Mn and Co
Element；
(2) by after the mixture pelleting, alloying pellet is activated with KOH aqueous slkali；
(3) particle after activation processing is washed；
(4) optionally, dipping moditied processing is carried out to the particle after washing using auxiliary agent water soluble salt aqueous solution, again
Graininess nickel-based sorbent is obtained after washing.
9. application as claimed in claim 8, which is characterized in that in step (1), by by metallic nickel, metallic aluminium and auxiliary agent
Melting is carried out to provide the mixture；
In step (2), particle is formed, it is cast into particle by broken or is broken into after powder by beating piece or extruding progress
It is granulated；
In step (3), aqueous slkali is switched into deionized water, until the pH value of solution is 7-9 after washing, wherein washing temperature
Degree is -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, zinc salt
Selected from zinc acetate, zinc sulfate and zinc nitrate；Molysite is selected from ferric sulfate, ferric acetate, ferrous sulfate and frerrous chloride；Ruthenium salt is selected from vinegar
Sour ruthenium, ruthenium trichloride and nitric acid ruthenium；And/or
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.
10. application as claimed in claim 9, which is characterized in that in step (1), the temperature of the melting is 1000-1800
DEG C, the type of cooling was quenching or ladder cooling or naturally cooled to room temperature at 0.5-3 hours the time；Or
It is described to be granulated including brush choosing after Mechanical Crushing is granulated, fused solution alloy casting is granulated, fused solution conjunction in step (2)
Forming agent is added after golden rotating granulation or crushing to carry out beating piece or extrude granulation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611015181.0A CN106622096B (en) | 2016-11-18 | 2016-11-18 | Isopropanol deep desulfuration and the nickel-based sorbent of deodorization and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611015181.0A CN106622096B (en) | 2016-11-18 | 2016-11-18 | Isopropanol deep desulfuration and the nickel-based sorbent of deodorization and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106622096A CN106622096A (en) | 2017-05-10 |
| CN106622096B true CN106622096B (en) | 2019-06-14 |
Family
ID=58807521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611015181.0A Active CN106622096B (en) | 2016-11-18 | 2016-11-18 | Isopropanol deep desulfuration and the nickel-based sorbent of deodorization and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106622096B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1406914A (en) * | 2001-08-16 | 2003-04-02 | 中国石油化工股份有限公司 | Aromatic adsorption desulfurizing method |
| CN104673378A (en) * | 2015-02-04 | 2015-06-03 | 中国石油大学(北京) | Method for producing desulfurized gasoline |
| CN106140195A (en) * | 2015-04-22 | 2016-11-23 | 上海迅凯新材料科技有限公司 | The Hydrobon catalyst of caprolactam and the hydrofinishing process of caprolactam |
| CN106140196A (en) * | 2015-04-22 | 2016-11-23 | 上海迅凯新材料科技有限公司 | BYD Hydrogenation for the hydrogenation catalyst of BDO and BYD Hydrogenation for the method for BDO |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1179021C (en) * | 2002-08-09 | 2004-12-08 | 中国石油化工股份有限公司 | Diesel oil adsorption desulfurizing method |
| CN101032688A (en) * | 2007-04-11 | 2007-09-12 | 江苏工业学院 | Activator for producing glycol by catalytic hydrogenation method |
-
2016
- 2016-11-18 CN CN201611015181.0A patent/CN106622096B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1406914A (en) * | 2001-08-16 | 2003-04-02 | 中国石油化工股份有限公司 | Aromatic adsorption desulfurizing method |
| CN104673378A (en) * | 2015-02-04 | 2015-06-03 | 中国石油大学(北京) | Method for producing desulfurized gasoline |
| CN106140195A (en) * | 2015-04-22 | 2016-11-23 | 上海迅凯新材料科技有限公司 | The Hydrobon catalyst of caprolactam and the hydrofinishing process of caprolactam |
| CN106140196A (en) * | 2015-04-22 | 2016-11-23 | 上海迅凯新材料科技有限公司 | BYD Hydrogenation for the hydrogenation catalyst of BDO and BYD Hydrogenation for the method for BDO |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106622096A (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102806062B (en) | Preparation method of palladium adsorbent for benzene refining desulfurization as well as product and application of palladium adsorbent | |
| CN105214599B (en) | Sulphur arsenic adsorbent and preparation method thereof | |
| KR20140005218A (en) | Decontaminant, carbon/polymer composite, decontamination sheet member and filter material | |
| CN105777528A (en) | Hydrogenation Of Fatty Acids Using A Promoted Supported Nickel Catalyst | |
| CN104368307A (en) | Preparation method of special active carbon for ammonia adsorption | |
| CN104549143A (en) | Activated carbon desulfurization adsorbent and preparation method thereof | |
| CN106669604A (en) | Air purifying material capable of removing ammonia and secondhand smoke and preparation method thereof | |
| Sobhanardakani et al. | Removal of Ni (II) and Zn (II) from aqueous solutions using chitosan | |
| CN110142057A (en) | A kind of Ag/g-C3N4/ bamboo charcoal/montmorillonite composite material and its application | |
| CN106622096B (en) | Isopropanol deep desulfuration and the nickel-based sorbent of deodorization and its preparation method and application | |
| CN101628230A (en) | Filter medium for removing nickel in water and preparation method thereof | |
| CN102972864B (en) | Preparation method of catalyst for selectively reducing released amount of hydrogen cyanide in mainstream smoke of cigarette | |
| CN106732323B (en) | Nickel-based adsorbent for deeply removing thiophene from benzene and preparation method and application thereof | |
| CN111375419A (en) | Hydrogenation catalyst and preparation method thereof | |
| CN112191227B (en) | Mercury removing agent for natural gas and preparation method thereof | |
| CN106139216A (en) | A kind of refrigerator, the preparation method of refrigerator-freezer bactericidal deodoring materials | |
| JP3513346B2 (en) | Aroma-containing gas reforming method | |
| CN105080487A (en) | Active carbon desulphurization adsorbent loaded with cobalt phthalocyanine sulfonate and copper and preparation method thereof | |
| CN105080488B (en) | Load phthalocyanine cobalt sulfonate active carbon desulfurization adsorbent and preparation method thereof | |
| CN103447067A (en) | Composite type catalyst and preparation method thereof | |
| Boruah et al. | Removal of Ni (II) ions from aqueous solution by using low cost biosorbent prepared from jackfruit (Artocarpus heterophyllus) leaf powder | |
| JP5692671B2 (en) | Oxygen absorber | |
| CN104001524B (en) | A kind of non-mercury catalyst for acetylene hydrochlorination reaction | |
| CN100594964C (en) | Filtration medium for making water into negative potential, alkaline small micelle water and method for producing the same | |
| KR20010043030A (en) | Material for introducing physiologically-essential inorganic elements into drinkable water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |