CN107954817A - A kind of method for preparing odorlessness isomery dodecane - Google Patents
A kind of method for preparing odorlessness isomery dodecane Download PDFInfo
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- CN107954817A CN107954817A CN201711257873.0A CN201711257873A CN107954817A CN 107954817 A CN107954817 A CN 107954817A CN 201711257873 A CN201711257873 A CN 201711257873A CN 107954817 A CN107954817 A CN 107954817A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- 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
- B01J20/28014—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 form
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- 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
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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- 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
- B01J20/28078—Pore diameter
- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
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- 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
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/72—Copper
Abstract
The present invention relates to a kind of method for preparing odorlessness isomery dodecane.Isobutylene trimer (TIB) prepares thick isomery dodecane, thick isomery dodecane finished product isomery dodecane after dehydrating laggard level-one deodorization adsorption tower and protection deodorization tower in hydrogenation reactor with hydrogen reaction.Level-one deodorization tower parallel connection is changeable, deodorization adsorbent uses the bifunctional adsorbent with absorption hydrogenating reduction, regeneration desorption is using the method for hydrogenating reduction, and regeneration temperature is low, sorbent life length, equipment material is required low, replaced before regeneration without using hot nitrogen or steam blowing, energy consumption is low, regenerates without using oxygen, without burning and explosion danger, the basic free of losses of effective material adsorbed in adsorbent.Efficiently solve the contradiction between the factors such as the three wastes, energy consumption, material consumption, material and security.
Description
Technical field
The present invention relates to a kind of method for preparing odorlessness isomery dodecane, and in particular to be hydrogenated with by isobutylene trimer,
The method that deodorization prepares odorlessness isomery dodecane.
Background technology
Isomery dodecane is a kind of highly branched 12 carbon alkane of saturation, and the petroleum hydrocarbon gas of low-carbon alkanes is not present in itself
Taste, while also faster evaporation rate, can be as the substituent of volatile silicone oils, and skin sense is extremely salubrious during for cosmetics, can
It is widely used in the fields such as various cosmetics, skin care/treatment, aerosol.
Isomery dodecane is usually from the hydrogenation of isobutylene trimer (TIB), but hydrogenation products generally have certain gas
Taste, patent CN200480006931 think that the material for producing smell is lower polyolefins and the micro oxygen containing of oxygen haptoreaction generation
Aldehyde, alcohol, the impurity such as ester.The content of these impurity is extremely low, and the big alkyl in molecule make it that its polarity is weaker, it is difficult to pass through one
As rectifying the methods of removed from alkane.Generally odorous material is handled using solid absorbent, such as patent
CN200480006931 is taken off using the silica/alumina adsorbent isoparaffin standby to butene low polymers Hydrogenation
Taste.Practical study finds that for adsorbent under conditions of ensureing that outlet isomery dodecane smell is less than 1 grade, alkane treatment amount is general
No more than 50 times of adsorbent volume, if adsorbent is not regenerated and recycled, often produce 1 ton of product and just produce
The solid waste of 20kg, every 10,000 tons of products will produce 200 tons of solid waste, and in order to reduce solid waste yield, preferably adsorbent is carried out again
It is raw, but the prior art does not announce isomery dodecane adsorbent of smell removal renovation process.
In other technologies field, the inorganic adsorbent such as aluminium oxide, molecular sieve is after carbon distribution, generally by way of roasting again
It is raw, but the temperature roasted is higher, and usually between 350-450 DEG C, at the very high and long-term high temperature of requirement to equipment material
Comprehend the pore passage structure for destroying adsorbent.Meanwhile oxygen is used during roasting, for adsorbing the hydrocarbons in adsorbent easily
Produce burning and explosion danger, especially in the device of hydrogenation of olefins class, therefore, before roasting must also use hot nitrogen or
Steam carries out purging displacement, this needs to consume substantial amounts of nitrogen and steam, and the water in steam is to the steady of alumina adsorption structure
It is qualitative totally unfavorable.In addition, the odoring substance adsorbed in adsorbent often only accounts for the relatively little of ratio of the material adsorbed, also
It is effective product or raw material to have quite a few, but is difficult to separate the material in duct from adsorbent in regenerative process,
The material adsorbed in adsorbent must be disposed together, cause the greater loss of active principle.
In short, when being difficult to solve product taste removal in isomery dodecane production process by the prior art, the three wastes, energy consumption, thing
Contradiction between the factors such as consumption, equipment material and security.
The content of the invention
The object of the present invention is to provide a kind of method for preparing odorlessness isomery dodecane.On the one hand this method can pass through
Smell in adsorbent removing isomery dodecane, does not use oxygen high-temperature roasting, no when and regenerating, and regenerating to adsorbent
Using nitrogen and steam blowing, while reducing solid waste, the loss of effective material is reduced, reduces material requirement, reduces operation wind
Danger, and ensure the service life of adsorbent, finally reduce product cost.
To reach above goal of the invention, the technical solution adopted by the present invention is as follows：
A kind of method for preparing odorlessness isomery dodecane, including：
Isobutylene trimer (TIB, triisobutylene) prepares isomery dodecane in hydrogenation reactor with hydrogen reaction；Add
The thick isomery dodecane of hydrogen reactor outlet is made through dehydrating laggard level-one deodorization adsorption tower subsequently into protection deodorization tower
Finished product isomery dodecane.
As a kind of perferred technical scheme the TIB hydrogenation reactions in autoclave, fixed bed or tower reactor into
OK, catalyst for support type or matrix type group VIII transition metal element simple substance or copper, zinc, the oxide of chromium, autoclave or
Tower hydrogenation catalyst dosage is the 0.1-10wt% of TIB, and hydrogenation reaction temperature is 100~300 DEG C, pressure for 0.5~
10MPaG, reaction time are 0.5~10h.
In the method for the present invention, the conversion ratio that the isobutylene trimer (TIB) reaches in hydrogenation reactor is
More than 99.99%, i.e. alkene residual is less than 100ppm.Due to oxygenate impurity, meeting hydrogenolysis produces a small amount of water in hydrogenation process,
And the polarity of water is larger, Preferential adsorption is generally in adsorbent, therefore, into first will using gas-liquid separator before adsorption tower
Free water is separated, then into molecular sieve drying tower by moisture removal to below 100ppm, preferably below 30ppm.Described is different
Butene trimer (TIB) prepares the method referred to described in publication 201710259135.3 and obtains.
In the method for the present invention, the adsorbent of filling is the activity for having loaded metallic element in the level-one deodorization adsorption tower
Aluminium oxide.Metallic element be Ni, Pt, Pd, Cu, Mo, Zn in one or more combinations, preferably one kind in Ni, Pt, Pd or
A variety of combinations；The load capacity of metallic element is 0.1~25wt%, preferably 1~10wt%, based on activated alumina gross weight.Institute
The adsorbent stated prepares the activated alumina purity used and is more than >=99.99%；The sorbent shapes for spherical, bar shaped,
One kind in sheet, clover, bunge bedstraw herb, Raschig ring, it is preferably spherical.
In the method for the present invention, the activated alumina can be prepared by conventionally known method, as a kind of preferable
Specific technical solution, its preparation method are：The aluminium isopropoxide of hydrolysis >=99.99%, stirring while, add nitre at 80 DEG C
The molar ratio 1 of acid, wherein aluminium isopropoxide, water and nitric acid：100：0.2.After the transparent colloidal sol of solution, pore is added thereto
The molar ratio of agent, pore-foaming agent and aluminium isopropoxide is 0.001~0.05：1.Polytetrafluoroethyllining lining is put into after stirring 0.5-2h
In autoclave, cool drying is taken out after constant temperature 18-36h at 100-110 DEG C, is molded by means such as spin, tabletting or extrusions
3-5h is roasted at 450-550 DEG C, you can obtain shape as spherical, bar shaped, sheet, clover, bunge bedstraw herb, the load of Raschig ring afterwards
Body, preferably ball type carrier.
The pore-foaming agent for the sulfonate of TIB (triisobutylene), the benzene sulfonate of TIB, TIB carbonyl compounds into it is different
Structure tridecanol polyoxyethylene ether, TIB carbonyl compounds into isomerous tridecanol polyoxyethylene ether sulfate, TIB trimethyl bromination
The sulfonate of ammonium, preferably TIB；The TIB sulfonate, the benzene sulfonate of TIB, TIB carbonyl compounds into isomerous tridecanol gather
The counter ion of ethylene oxide ether sulfate is sodium ion, potassium ion, ammonium ion, is preferably sodium ion；The TIB carbonyl compounds into
Isomerous tridecanol polyoxyethylene ether, TIB carbonyl compounds into the ethylene oxide of isomerous tridecanol polyoxyethylene ether sulfate add
It is 2~7, preferably 2~3 into number.
The method that various pore-foaming agents are produced by TIB is as follows：The method referenced patent of alkylsulfonate, alkylbenzenesulfonate
CN200810163942, CN201510641102 and CN01136653, are referred to by the method for TIB carbonyl compounds into isomerous tridecanol
Patent CN201580035318.6, isomerous tridecanol polyoxyethylene ether and isomerous tridecanol are prepared by isomerous tridecanol ethoxylation
Method the referenced patent CN201210069147 and CN201611092863 of polyoxyethylene ether sulfate, dodecane is prepared by TIB
The method referenced patent CN201410019264 of base trimethylammonium bromide.
The preparation of the activated alumina of carried metal element uses conventional impregnation method, and preparation method refers to patent
CN201611202310.7, CN200710107266.6.
The average grain diameter of the adsorbent is 0.1~10mm, preferably 1~5mm；The average pore size of adsorbent for 1~
20nm, preferably 2~10nm；The specific surface area of adsorbent is 100~500m2/ g, preferably 200~400m2/g。
With the sulfonate of TIB, the benzene sulfonate of TIB, TIB carbonyl compounds into isomerous tridecanol polyoxyethylene ether and its sulphur
Hydrochlorate, the trimethylammonium bromide of TIB are pore-foaming agent pore-creating, are to be self-assembly of organic micella using the feature of its surface-active,
The pore structure of organic gel bundle branch support is left in alumina precursor preparation process, the pore-foaming agent that TIB itself is derived can be protected
The micelle diameters that card is formed are slightly larger than the molecular diameter of the oxygenatedchemicals of TIB, isomery dodecane and TIB generations, to ensure
Duct can smoothly be diffused into by adsorbing medium, but the channel diameter formed at the same time with above-mentioned pore-foaming agent again will not be than TIB, isomery
The oxygenatedchemicals molecule of dodecane and TIB are too many greatly, and the specific surface area caused by channel diameter is excessive will not be caused to drop
It is low.Meanwhile the hydrophobic group of pore-foaming agent is the alkyl that TIB is formed, the alkyl is to before outer support alumina support when forming micella
Body so that the surface appearance feature for the aluminium oxide pore passage structure being finally prepared and oxygenate impurity molecule derived from TIB double bonds
Structure feature height agree with, be very beneficial for the absorption of oxygenate impurity, each cycle can handle the thick of 400~2000 times of volumes
Isomery dodecane.The group of suction-operated is played in the adsorbent to odoring substance (oxygenate impurity of polarized, fatty aldehyde, alcohol, ester)
It is the very strong activated alumina of surface polarity to divide；The metallic element of load is reduction-state (0 valency metal), substantially nonpolarity, to pole
Property odoring substance do not play suction-operated, it is also difficult to odoring substance react, be not adsorb odoring substance component；Metallic element
Main function is in regeneration desorption stage, and the polarity oxygenate impurity catalysis adsorbed in oxidation aluminium surface is reduced to nonpolar alkane
Hydrocarbon, so that from aluminium oxide surface desorption.
In the method for the present invention, the level-one deodorization adsorption tower is changeable fixed bed in parallel, and quantity is 2~4,
It is preferred that 3, ensure that at least one deodorization adsorption tower is deodorized online, at least one deodorization adsorption tower is spare；Deodorization process conditions are as follows：
For thick isomery dodecane from absorption tower bottom charging of deodorizing, liquid hourly space velocity (LHSV) is 0.1~5h-1, preferably 0.5~2h-1；Operation temperature for-
20~60 DEG C, preferably 0~40 DEG C；Ratio of height to diameter is 10000：1~2：1, preferably 100：1~10：1；Operating pressure is 0~5MPaG,
It is preferred that 0~1MPaG.Adsorption column outlet sampling evaluation and test oder levels, when oder levels reach 1 grade, (0 grade is not smell any gas
Taste, without any reaction；1 grade, for that can smell smell reluctantly, is not easy to recognize adour properties, feels that it doesn't matter；2 grades weaker for that can smell
Smell, can recognize adour properties；3 grades are energy taste smell, unhappy, but are not disliked；4 grades are to have very strong smell, very
Dislike, wants to leave；5 grades, to there is extremely strong smell, can not endure, leave immediately), charging is switched into stand-by still, to having used
Deodorization adsorption tower regenerated, due to after level-one deodorization tower also have protection deodorization tower ensure product odour grade be less than 1 grade, because
This, smell reaches 1 grade the smell of final products can't be had an impact the outlet of level-one deodorization tower in a short time.
In the method for the present invention, adsorbent is renewable in the level-one deodorization adsorption tower, and renovation process is as follows：By thick isomery
Dodecane charging switches to spare deodorization adsorption tower by deodorization adsorption tower to be regenerated；By hydrogen by the top of adsorption tower and after deodorization
Isomery dodecane product be passed through adsorption tower to be regenerated by way of drip by top together, the gas-liquid mixed of bottom of towe discharging
Thing gas-liquid separation in gas-liquid separator, then liquid enter hydrogenation reactor after gas-liquid separator and drying tower moisture is taken off
Except laggard spare deodorization tower, hydrogen circulating and recovering.Technological condition of regeneration is as follows：100~300 DEG C of temperature, preferably 150~250 DEG C；
1~10MPaG of pressure, preferably 2~6MPag；The molar ratio 0.1~10 of hydrogen and charging isomery dodecane, preferably 1~5；Isomery
0.1~5h of dodecane liquid hourly space velocity (LHSV)-1, preferably 0.5~2h-1；When liquid sampling smell is reduced to 0 grade in bottom of towe gas-liquid separator,
Cut-out deodorize after isomery dodecane stream stock, in a hydrogen atmosphere to reactor decompression, cooling, the water of micro absorption in decompression and
Continue to be desorbed under conditions of hydrogen displacement, then cut off hydrogen, regeneration finishes, spare.Treat next adsorption column outlet material gas
Taste grade repeats aforesaid operations when reaching 1 grade, and regeneration is switched over to adsorbent.
Since odoring substance is generally the oxygenatedchemicals of polarity, triisobutylene (TIB) is micro with oxygen reaction generation
The possible structure of oxygenatedchemicals is shown below, these polarity material stronger than isomery dodecane can be preferentially adsorbed on adsorbent
Surface.Meanwhile be not hydrogenated with complete residual TIB because of double bond polarization easier than isomery dodecane, also can partial adsorbates in adsorbent table
Face.The present invention is under the catalytic action of hydrogen and the metallic element with catalysis reduction, by the oxygenatedchemicals quilt of absorption
Hydrogenolysis for saturation isomery dodecane and micro water, the suction-operated of water at high temperature also die down, therefore, isomery dodecane and
Water can be desorbed from adsorbent, meanwhile, the residual TIB of absorption can also be hydrogenated to the complete non-polar isomery 12 of saturation
Alkane, and then be desorbed from adsorbent surface, adsorbent is reduced.Hydroformylation product solution isomery dodecane and the isomery ten being adsorbed in duct
Dioxane not discharge system, caused loss of material when air or oxygen will not be caused to roast.The present invention is avoided in hydrogenation plant
Region uses high-temperature oxygen, can effectively avoid and fires risk, and regeneration temperature is also than relatively low, the influence to alumina adsorbant form
Also it is smaller, significantly extend sorbent life, reduce adsorbent cost, reduce solid waste yield and processing cost.
What is loaded in protection deodorization tower is the one or more in Kiselgel A, Type B silica gel, c-type silica gel, preferably Type B silicon
Glue, the isomery dodecane oder levels handled through overprotection deodorization tower can reach 0 grade.
The positive effect of the present invention is：
The adsorbent being prepared by the method for the present invention is good to the adsorptive selectivity of odoring substance in isomery dodecane, can be again
Life, long lifespan, solid waste yield are small；Regeneration temperature is low, to the of less demanding of equipment material；Regeneration without using oxygen, no burning and
Explosion danger, carries out purging displacement, energy consumption is low without using hot nitrogen or steam；The effective material adsorbed in adsorbent substantially without
Loss.Efficiently solve the contradiction between the factors such as the three wastes, energy consumption, material consumption, equipment material and security.
Brief description of the drawings
Fig. 1 is 2 triisobutylene Hydrogenation isomery dodecane of embodiment and deodorization process flow diagram
Embodiment
The following examples will be further described method provided by the present invention, but the invention is not restricted to listed
The embodiment gone out, should also be included in other any known changes in interest field of the presently claimed invention.
Analytical conditions for gas chromatography is as follows：The DB-5 capillary chromatographic columns of 30m × 0.3mm, fid detector, gasify room temperature
280 DEG C of degree, 50-300 DEG C of post case temperature, 280 DEG C of detector temperature, argon carrier flow 20ml/min, hydrogen flowing quantity 30ml/
Min, air mass flow 300ml/min, 1 microlitre of sample size, split ratio 10:1.
Embodiment 1
It is prepared by pore-foaming agent：Carry out TIB's and SO in falling film sulfonator3Sulfonating reaction, TIB and SO3Molar ratio be
1:1.1, sulfonating reaction temperature is 30 DEG C, SO3Gas concentration is 5%；Product after sulfonation with the NaOH solution of 20wt% in
The sodium sulfonate of TIB is obtained when hydrolysis 1.5 is small at 135 DEG C.
It is prepared by adsorbent：The aluminium isopropoxide of hydrolysis >=99.99%, stirring while, add nitric acid at 80 DEG C, wherein different
The molar ratio 1 of aluminium propoxide, water and nitric acid：100：0.2.After the transparent colloidal sol of solution, the sodium sulfonate pore of TIB is added thereto
The molar ratio of agent, TIB sodium sulfonates and aluminium isopropoxide is 0.05：1.The autoclave of polytetrafluoroethyllining lining is put into after stirring 1h
In, cool drying is taken out after constant temperature 24h at 105 DEG C, roasting 4h at 500 DEG C after roller forming can obtain average grain diameter
0.1mm, average pore size 2nm, specific surface area 500m2The spheric active alumina support of/g, measures the water absorption rate of activated alumina
For 1.51g water/g aluminium oxide；100g activated aluminas are weighed, by 0.21g chloroplatinic acids H2PtCl2It is dissolved in 151g water and solution is made,
Platinum acid chloride solution is uniformly sprayed to load weighted active oxidation aluminium surface, is dried after standing 5h at 120 DEG C under air atmosphere
No longer change to weight, precursor is made；0.03g hydrazine hydrates are dissolved in 200g water solution is made, the precursor after drying is poured into
In hydrazine hydrate aqueous solution, washing is up to Cl in washings after reductase 12 h-Residual is less than 1ppm, is then dried at nitrogen and 120 DEG C
Do to weight and no longer change, obtain the adsorbent of the Pt of load 0.1%.
Isobutylene trimer (TIB) prepares isomery dodecane in autoclave hydrogenation reactor with hydrogen reaction, and catalyst is
The skeletal copper of 2wt%, the 5wt% of the dosage position TIB of catalyst, reaction pressure 10MPaG, 100 DEG C of reaction temperature, reaction stop
Time 10h, alkene residual 100ppm.Into first free water being separated using gas-liquid separator before adsorption tower, then into point
Son sieves drying tower by moisture removal to 100ppm.
For dewatered thick isomery dodecane into the changeable level-one deodorization adsorption tower of 4 parallel connections, the ratio of height to diameter of tower is 2：1,
Thick isomery dodecane is fed from bottom, and feed rate is 1.5 cubic meters/hour, the adsorbent of 15 cubes of filling in each tower, during liquid
Air speed is 0.1h-1, operation temperature is 60 DEG C, atmospheric operation.
When the thick isomery dodecane of accumulative 30000 cubes of processing, adsorption column outlet sample oder levels reach 1 grade, this
When charging switched into stand-by still, used deodorization adsorption tower is regenerated：By hydrogen by the top of adsorption tower and after deodorization
Isomery dodecane product be passed through adsorption tower to be regenerated by way of drip by top together, the gas-liquid mixed of bottom of towe discharging
Thing gas-liquid separation in gas-liquid separator, then liquid enter hydrogenation reactor after gas-liquid separator and drying tower moisture is taken off
Except laggard spare deodorization tower, hydrogen circulating and recovering.Technological condition of regeneration is as follows：100 DEG C, pressure 1MPaG of temperature, hydrogen and charging
The molar ratio 0.1 of dodecane, isomery dodecane liquid hourly space velocity (LHSV) 0.1h-1, liquid sampling smell is reduced to 0 in bottom of towe gas-liquid separator
During level, the isomery dodecane stream stock after cut-out deodorization, in a hydrogen atmosphere to cutting off hydrogen after reactor decompression, cooling, regenerates
Finish.
What is loaded in protection deodorization tower is 7.5 cubes of Kiselgel A, it is ensured that is begun in finished product isomery dodecane smell
0 grade is maintained at eventually.
Embodiment 2
It is prepared by pore-foaming agent：By molar ratio 1.5:1 benzene and TIB is placed in reaction kettle, is added equivalent to substrate 1wt%'s
Alchlor is reacted when reaction 1.5 is small at 85 DEG C and terminated, after alchlor is quenched using water, by oil phase as catalyst
In benzene and TIB removed by distilling, the detergent alkylate of gained uses SO in falling film sulfonator3Sulfonation, detergent alkylate
With SO3Molar ratio be 1:1.2, sulfonating reaction temperature is 35 DEG C, SO3Gas concentration is 5%；Product after sulfonation is with 20%
KOH solution hydrolyzed at 135 DEG C 2 it is small when obtain the benzene sulfonic acid potassium of TIB.
It is prepared by adsorbent：The preparation process of carrier is same as Example 1, and pore-foaming agent is changed to the benzene sulfonic acid potassium of TIB, TIB
Benzene sulfonic acid potassium and aluminium isopropoxide molar ratio be 0.045：1, obtain average grain diameter 1mm, average pore size 5nm, specific surface area
430m2The bar shaped activated alumina of/g is carrier, and the water absorption rate for measuring activated alumina is 1.45g water/g aluminium oxide；Weigh
100g activated aluminas, by tetra- ammino palladium bichloride monohydrate Pd (NH of 2.48g3)4Cl2·H2O, which is dissolved in 145g water, is made chlorination
Palladium chloride solution, is uniformly sprayed at load weighted active oxidation aluminium surface by palladium solution, stands after 6h the air atmosphere at 150 DEG C
Under be dried to weight and no longer change, precursor is made；0.52g hydrazine hydrates are dissolved in 200g water solution is made, before after drying
Body is poured into hydrazine hydrate aqueous solution, and washing is up to Cl in washings after reducing 3h-Residual is less than 1ppm, then in nitrogen and 120
Weight is dried at DEG C no longer to change, and obtains the adsorbent of the Pd of load 1wt%.
As shown in Figure 1, isobutylene trimer (TIB) prepares isomery 12 in fixed bed hydrogenation reactor with hydrogen reaction
Alkane, catalyst are skeleton nickel, and reaction pressure 0.5MPa, temperature is 200 DEG C, liquid hourly space velocity (LHSV) 1h-1, alkene residual 80ppm.Into
First free water is separated using gas-liquid separator before adsorption tower, then into molecular sieve drying tower by moisture removal to 60ppm.
For dewatered thick isomery dodecane into the changeable level-one deodorization adsorption tower of 2 parallel connections, the ratio of height to diameter of tower is 10：
1, thick isomery dodecane is fed from bottom, and feed rate is 1.5 cubic meters/hour, the adsorbent of 3 cubes of filling, liquid in each tower
When air speed be 0.5h-1, operation temperature is 60 DEG C, operating pressure 0.5MPaG.
When the thick isomery dodecane of accumulative 5400 cubes of processing, adsorption column outlet sample oder levels reach 1 grade, this
When charging switched into stand-by still, used deodorization adsorption tower is regenerated, operation step sequence is same as Example 1, regeneration
Process conditions are as follows：150 DEG C, pressure 2MPaG of temperature, the molar ratio 1 of hydrogen and charging dodecane, dodecane liquid hourly space velocity (LHSV)
0.5h-1。
What is loaded in protection deodorization tower is 3 cubes of Type B silica gel, it is ensured that is protected all the time in finished product isomery dodecane smell
Hold at 0 grade.
Embodiment 3
It is prepared by pore-foaming agent：TIB in reaction kettle with synthesis gas (CO:H2=1:1) react, using the rhodium caprylate of 0.01wt% as
Catalyst, at 150 DEG C of temperature and pressure 15MPa after reaction time 20h, then by synthesis gas switches to hydrogen, at 150 DEG C and
The mixture that 5h obtains the isomery dodecane of the sum containing isomerous tridecanol is hydrogenated with 15MPa, is removed isomery dodecane by rectifying
After obtain isomerous tridecanol.In reaction kettle, the isomerous tridecanol prepared using TIB is initiator, using 0.2% KOH as catalysis
Agent reacts 5h for the ethylene oxide of 3 times of isomerous tridecanol with mole at 0.5MPa and 85 DEG C, then cures 1 at 120 DEG C
Hour postcooling obtains the isomerous tridecanol polyoxyethyl ether that ethoxymer distribution is 3.
It is prepared by adsorbent：The preparation process of carrier is same as Example 1, by pore-foaming agent be changed to TIB carbonyl compounds into it is different
Structure tridecanol polyoxyethylene ether (ethoxymer distribution 3), TIB carbonyl compounds into isomerous tridecanol polyoxyethylene ether (ring
Oxidative ethane adduct number is 0.02 for the molar ratio 3) with aluminium isopropoxide：1, average grain diameter 10mm is obtained, average pore size 12nm, compares table
Area 100m2The sheet activated alumina of/g is carrier, and the water absorption rate for measuring activated alumina is 1.11g water/g aluminium oxide；Claim
100g activated aluminas are taken, by 26.9g nickel sulfate hexahydrates NiSO4·6H2O, which is dissolved in 111g water, is made nickel sulfate solution, by sulfuric acid
Nickel solution is uniformly sprayed at load weighted active oxidation aluminium surface, and weight is dried under air atmosphere at 280 DEG C after standing 10h
No longer change, precursor is made；11.3g hydrazine hydrates are dissolved in 200g water solution is made, the precursor after drying is poured into hydrazine hydrate
In aqueous solution, after reductase 12 0h washing until washings in sulfate radical residual be less than 1ppm, then dried at nitrogen and 120 DEG C
No longer change to weight, obtain the adsorbent of the Ni of load 6wt%.Isobutylene trimer (TIB) is in bubble tower hydrogenation reactor
In with hydrogen reaction prepare isomery dodecane, catalyst is the palladium carbon of 0.5wt%, reaction pressure 6MPa, 150 DEG C of reaction temperature,
Residence time 6h, alkene residual 60ppm.Into first free water being separated using gas-liquid separator before adsorption tower, then into
Molecular sieve drying tower is by moisture removal to 50ppm.
Dewatered thick isomery dodecane is into the changeable level-one deodorization adsorption tower of 3 parallel connections, the ratio of height to diameter of tower
10000：1, thick isomery dodecane is fed from bottom, and feed rate is 1.5 cubic meters/hour, the suction of 0.3 cube of filling in each tower
Attached dose, liquid hourly space velocity (LHSV) 5h-1, operation temperature is -20 DEG C, operating pressure 5MPaG.
When the thick isomery dodecane of accumulative 120 cubes of processing, adsorption column outlet sample oder levels reach 1 grade, at this time
Charging is switched into stand-by still, used deodorization adsorption tower is regenerated, operation step sequence is same as Example 1, regenerates work
Skill condition is as follows：300 DEG C, pressure 4MPaG of temperature, the molar ratio 3 of hydrogen and charging dodecane, dodecane liquid hourly space velocity (LHSV) 1h-1。
What is loaded in protection deodorization tower is 3 cubes of c-type silica gel, it is ensured that is protected all the time in finished product isomery dodecane smell
Hold at 0 grade.
Embodiment 4
It is prepared by pore-foaming agent：TIB is placed in blistering reaction kettle, is heated to 40 DEG C, is passed through the bromine containing 0.5vol% air
Change hydrogen, TIB bromos finish after reacting 15min, after cooling, are added dropwise in the quaterisation kettle equipped with trimethylamine and reacted,
Reaction temperature maintains 35 DEG C, and the molar ratio of final TIB bromo-derivatives and trimethylamine is 1.1:1, insulated and stirred 1 is small after completion of dropwise addition
When, after crystallisation by cooling with acetone wash it is dry after obtain target pore-foaming agent.
It is prepared by adsorbent：The preparation process of carrier is same as Example 1, and pore-foaming agent is changed to the trimethylammonium bromide of TIB,
The trimethylammonium bromide of TIB and the molar ratio of aluminium isopropoxide are 0.025：1, average grain diameter 2mm, average pore size 2nm are obtained, than
Surface area 200m2The sheet activated alumina of/g is carrier, and the water absorption rate for measuring activated alumina is 1.35g water/g aluminium oxide；
100g activated aluminas are weighed, by 98g cupric sulfate pentahydrates CuSO4·5H2Sulfuric acid is made in the hot water of 135g (90 DEG C) is dissolved in O
Copper-bath, is uniformly sprayed at load weighted active oxidation aluminium surface by copper solution, stand under conditions of 90 DEG C after 12h
Weight is dried under air atmosphere no longer to change, precursor is made at 200 DEG C；47g hydrazine hydrates are dissolved in 200g water solution are made,
Precursor after drying is poured into hydrazine hydrate aqueous solution, reduce 72h after washing until washings in sulfate radical residual be less than 1ppm,
Then it is dried to weight at nitrogen and 120 DEG C no longer to change, obtains the adsorbent of the Cu of load 25wt%.
Isobutylene trimer (TIB) prepares isomery dodecane in bubbling column reactor with hydrogen reaction, and catalyst is
The ruthenium carbon of 1wt%, reaction pressure 4MPa, 220 DEG C, residence time 4h of reaction temperature, alkene residual 40ppm.Into adsorption tower it
It is preceding first to be separated free water using gas-liquid separator, then into molecular sieve drying tower by moisture removal to 30ppm.
For dewatered thick isomery dodecane into the changeable level-one deodorization adsorption tower of 3 parallel connections, the ratio of height to diameter of tower is 20：
1, thick isomery dodecane is fed from bottom, and feed rate is 1.5 cubic meters/hour, the adsorbent of 1.5 cubes of filling in each tower,
Liquid hourly space velocity (LHSV) is 1h-1, operation temperature is 30 DEG C, operating pressure 1MPaG.
When the thick isomery dodecane of accumulative 1200 cubes of processing, adsorption column outlet sample oder levels reach 1 grade, this
When charging switched into stand-by still, used deodorization adsorption tower is regenerated, operation step sequence is same as Example 1, regeneration
Process conditions are as follows：200 DEG C, pressure 10MPaG of temperature, the molar ratio 10 of hydrogen and charging dodecane:1, dodecane liquid hourly space velocity (LHSV)
5h-1。
What is loaded in protection deodorization tower is 4.5 cubes of Type B silica gel, it is ensured that in finished product isomery dodecane smell all the time
It is maintained at 0 grade.
Embodiment 5
It is prepared by pore-foaming agent：Except in ethoxylation by the ratio setting of isomerous tridecanol and ethylene oxide be 1:Outside 7, by
The method that TIB prepares isomerous tridecanol polyoxyethylene ether is same as Example 3.Obtained isomerous tridecanol polyoxyethylene ether is dropping
SO is used in membrane reactor3Sulfonation, isomerous tridecanol polyoxyethylene ether and SO3Molar ratio be 1:1.2, sulfonating reaction temperature is 40
DEG C, SO3Gas concentration is 5%；Product after sulfonation hydrolyzed with the KOH solution of 20wt% at 110 DEG C 2 it is small when obtain epoxy
Ethane adduct number is 7 isomerous tridecanol polyoxyethylene ether potassium sulfate.
It is prepared by adsorbent：The preparation process of carrier is same as Example 1, by pore-foaming agent be changed to TIB carbonyl compounds into it is different
Structure tridecanol polyoxyethylene ether potassium sulfate (ethoxymer distribution 7), TIB carbonyl compounds into isomerous tridecanol polyoxyethylene
The molar ratio of ether potassium sulfate (ethoxymer distribution 7) and aluminium isopropoxide is 0.03：1, obtain selecting purity >=99.99%,
Average grain diameter 3mm, average pore size 20nm, specific surface area 370m2The sheet activated alumina of/g is carrier, measures active oxidation
The water absorption rate of aluminium is 1.39g water/g aluminium oxide；100g activated aluminas are weighed, by 79g cupric sulfate pentahydrates CuSO4·5H2O and
10.5g ZnCl2It is dissolved in the hot water (90 DEG C) of 139g and copper sulphate-liquor zinci chloridi is made, which is uniformly sprayed at title
Measured active oxidation aluminium surface, weight is dried to no longer after 12h is stood under conditions of 90 DEG C at 200 DEG C under air atmosphere
Change, is made precursor；47g hydrazine hydrates are dissolved in 200g water solution is made, the precursor after drying is poured into hydrazine hydrate aqueous solution
In, reduce 72h after washing until washings in sulfate radical residual be less than 1ppm, be then dried to weight at nitrogen and 120 DEG C
No longer change, obtain the adsorbent of the Zn of the Cu and 5wt% of load 20wt%.
Isobutylene trimer (TIB) prepares isomery dodecane, catalyst in fixed bed hydrogenation reactor with hydrogen reaction
For copper Zinc-aluminium, reaction pressure 2MPa, 220 DEG C of reaction temperature, liquid hourly space velocity (LHSV) 1h-1, alkene residual 20ppm.Into absorption
First free water is separated using gas-liquid separator before tower, then into molecular sieve drying tower by moisture removal to 20ppm.
For dewatered thick isomery dodecane into the changeable level-one deodorization adsorption tower of 3 parallel connections, the ratio of height to diameter of tower is 50：
1, thick isomery dodecane is fed from bottom, and feed rate is 1.5 cubic meters/hour, the absorption of 0.75 cube of filling in each tower
Agent, liquid hourly space velocity (LHSV) 2h-1, operation temperature is 0 DEG C, operating pressure 2MPaG.
When the thick isomery dodecane of accumulative 800 cubes of processing, adsorption column outlet sample oder levels reach 1 grade, at this time
Charging is switched into stand-by still, used deodorization adsorption tower is regenerated, operation step sequence is same as Example 1, regenerates work
Skill condition is as follows：200 DEG C, pressure 6MPaG of temperature, the molar ratio 5 of hydrogen and charging dodecane:1, isomery dodecane liquid hourly space velocity (LHSV)
2h-1。
What is loaded in protection deodorization tower is 3.75 cubes of Type B silica gel, it is ensured that is begun in finished product isomery dodecane smell
0 grade is maintained at eventually.
Embodiment 6
The preparation of pore-foaming agent：Except in ethoxylation by the ratio setting of isomerous tridecanol and ethylene oxide be 1:2nd, by sulphur
Product after change is outer with the NaOH solution hydrolysis of 25wt%, and preparing the isomerous tridecanol that ethoxymer distribution is 2 by TIB gathers
The method of ethylene oxide ether sodium sulfate is same as Example 5.
It is prepared by adsorbent：The preparation process of carrier is same as Example 1, by pore-foaming agent be changed to TIB carbonyl compounds into it is different
Structure sodium tridecethsulfate (ethoxymer distribution 2), TIB carbonyl compounds into isomerous tridecanol polyoxyethylene
The molar ratio of ether potassium sulfate (ethoxymer distribution 2) and aluminium isopropoxide is 0.04：1, average grain diameter 5mm is obtained, average hole
Footpath 10nm, specific surface area 400m2The sheet activated alumina of/g is carrier, measure the water absorption rate of activated alumina for 1.41g water/
G aluminium oxide；100g activated aluminas are weighed, by 40.3g nickel sulfate hexahydrates NiSO4·6H2The molybdenum chloride MoCl of O and 2.8g5It is dissolved in
Nickel sulfate-chlorination molybdenum solution is made in 141g water, which is uniformly sprayed at load weighted active oxidation aluminium surface, stands
Weight is dried under air atmosphere no longer to change, precursor is made after 36h at 280 DEG C；19.7g hydrazine hydrates are dissolved in 200g water
In solution is made, the precursor after drying is poured into hydrazine hydrate aqueous solution, reduce 36h after washing until washings in sulfate radical it is residual
Stay and be less than 1ppm, being then dried to weight at nitrogen and 120 DEG C no longer changes, and obtains the Mo of the Ni and 1wt% of load 9wt%
Adsorbent.
Isobutylene trimer (TIB) prepares isomery dodecane in fixed bed reactors with hydrogen reaction, catalyst for nickel-
Aluminium oxide catalyst, reaction pressure 0.5MPa, 300 DEG C of reaction temperature, liquid hourly space velocity (LHSV) 2h-1, residual olefin do not detect.Into absorption
First free water is separated using gas-liquid separator before tower, then into molecular sieve drying tower by moisture removal to 10ppm.
For dewatered thick isomery dodecane into the changeable level-one deodorization adsorption tower of 3 parallel connections, the ratio of height to diameter of tower is 100：
1, thick isomery dodecane is fed from bottom, and feed rate is 1.5 cubic meters/hour, the adsorbent of 0.3 cube of filling in each tower,
Liquid hourly space velocity (LHSV) is 5h-1, operation temperature is 20 DEG C, operating pressure 3MPaG.
When the thick isomery dodecane of accumulative 420 cubes of processing, adsorption column outlet sample oder levels reach 1 grade, at this time
Charging is switched into stand-by still, used deodorization adsorption tower is regenerated, operation step sequence is same as Example 1, regenerates work
Skill condition is as follows：250 DEG C, pressure 4MPaG of temperature, the molar ratio 3 of hydrogen and charging dodecane:1, dodecane liquid hourly space velocity (LHSV) 1h-1。
What is loaded in protection deodorization tower is 3 cubes of Type B silica gel, it is ensured that is protected all the time in finished product isomery dodecane smell
Hold at 0 grade.
Comparative example
Except the activated alumina of load is changed to active aluminium oxide (specific surface area 275m2/ g, average grain diameter
5mm, the spheric granules of average pore size 9nm, Dongying Cole spy's new material Co., Ltd) it is used to adsorb and regenerate outer, other conditions
It is same as Example 6, i.e., when handling thick isomery dodecane with 1.5 cubic meters/hour of inlet amount, when only operation 8 is small, 0.3 cube
Adsorbent add up handle 12 cubes of thick isomery dodecanes when, the oder levels of adsorption column outlet sample just reach 1 grade, it is necessary to again
It is raw.The thick isomery dodecane sample in deodorization tower is drained before regeneration, then the water vapor purging using 120 DEG C is to exporting lime set
Middle no oil droplet produces, and then water vapour is switched to 120 DEG C of hot nitrogen, vapor is displaced deodorization tower.It is dilute using nitrogen
The air gas purge (oxygen content must control below 5% to avoid explode) released, by operation temperature in 12h
Improved by 120 DEG C to 400 DEG C, when can't detect CO and CO in exit gas2When, oxygen-containing gas is switched to nitrogen, in 4h
Temperature is progressively reduced to room temperature, completes regeneration, cut-out nitrogen is spare.
Claims (12)
1. a kind of method for preparing odorlessness isomery dodecane, including：
Isobutylene trimer prepares thick isomery dodecane in hydrogenation reactor with hydrogen reaction；Hydrogenation reactor exports thick different
Structure dodecane is through dehydrating laggard level-one deodorization adsorption tower, subsequently into protection deodorization tower finished product isomery dodecane.
2. the according to the method described in claim 1, it is characterized in that, conversion that isobutylene trimer reaches in hydrogenation reactor
Rate is more than 99.99%, and alkene residual is less than 100ppm.
3. method according to claim 1 or 2, it is characterised in that thick isomery dodecane into level-one deodorization adsorption tower it
It is preceding first to be separated free water using gas-liquid separator, then by moisture removal to below 100ppm in molecular sieve drying tower,
It is preferred that below 30ppm.
4. method according to claim 1 or 2, it is characterised in that the absorption of filling in the level-one deodorization adsorption tower
Agent is to have loaded the activated alumina of metallic element.
5. according to the method described in claim 4, it is characterized in that, the metallic element is in Ni, Pt, Pd, Cu, Mo, Zn
One or more, preferred one or more in Ni, Pt, Pd；The load capacity of the metallic element is 0.1~25wt%,
It is preferred that 1~10wt%, based on activated alumina gross weight.
6. method according to claim 4 or 5, it is characterised in that the preparation of activated alumina is with the sulfonate of TIB, TIB
Benzene sulfonate, TIB carbonyl compounds into isomerous tridecanol polyoxyethylene ether, TIB carbonyl compounds into isomerous tridecanol polyoxy
Ethene ether sulfate, the trimethylammonium bromide of TIB are pore-foaming agent pore-creating, preferably with the sulfonate pore-creating of TIB；The TIB sulphurs
Hydrochlorate, the benzene sulfonate of TIB, TIB carbonyl compounds into isomerous tridecanol polyoxyethylene ether sulfate counter ion for sodium ion,
Potassium ion, ammonium ion, are preferably sodium ion；It is preferred that the TIB carbonyl compounds into isomerous tridecanol polyoxyethylene ether, TIB
Carbonyl compound into isomerous tridecanol polyoxyethylene ether sulfate ethoxymer distribution be 2~7, more preferably 2~3；It is described
The average grain diameter of activated alumina be 0.1~10mm, preferably 1~5mm.
7. according to the method any one of claim 4-6, it is characterised in that the average pore size of the adsorbent is 2
~20nm, preferably 5~10nm；The specific surface area of the adsorbent is 100~500m2/ g, preferably 200~400m2/g。
8. according to the described method of any one of claim 1-7, it is characterised in that the level-one deodorization adsorption tower is parallel connection
Changeable fixed bed, quantity are 2~4, preferably 3, ensure that at least one deodorization adsorption tower is deodorized online, at least one is deodorized
Adsorption tower is spare；The ratio of height to diameter of deodorization adsorption tower is 10000：1~2：1, preferably 100：1~10：1.
9. according to the method any one of claim 1-8, it is characterised in that deodorization process conditions are：Thick isomery 12
Alkane is deodorized from level-one adsorbs tower bottom charging, and liquid hourly space velocity (LHSV) is 0.1~5h-1, preferably 0.5~2h-1；Operation temperature is -20~60
DEG C, preferably 0~40 DEG C；Operating pressure is 0~5MPaG, preferably 0~1MPaG.
10. according to the method any one of claim 1-9, it is characterised in that further include to deodorize to the level-one and inhale
In attached tower the step of adsorbent reactivation, including：Thick isomery dodecane is fed switched to by deodorization adsorption tower to be regenerated it is spare
Deodorization tower；Hydrogen is passed through adsorption tower to be regenerated together with the isomery dodecane product after deodorization by top, bottom of towe discharging
Gas-liquid mixture carries out gas-liquid separation, and the liquid after separation enters spare deodorization adsorption tower after dehydration and drying, and hydrogen is recycled back to
With.
11. according to the method described in claim 10, it is characterized in that, the regeneration step process conditions are as follows：Temperature 100
~300 DEG C, preferably 150~250 DEG C；1~10MPaG of pressure, preferably 2~6MPaG；Mole of hydrogen and charging isomery dodecane
Than 0.1~10, preferably 1~5；Isomery dodecane 0.1~5h-1 of liquid hourly space velocity (LHSV), preferably 0.5~2h-1.
12. according to the method any one of claim 1-11, it is characterised in that filling in the protection deodorization tower
It is the one or more in Kiselgel A, Type B silica gel, c-type silica gel, preferably Type B silica gel.
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