CN108341898A - A method of removing unsaturated polymer adds the remaining hydrogenation catalyst after hydrogen - Google Patents
A method of removing unsaturated polymer adds the remaining hydrogenation catalyst after hydrogen Download PDFInfo
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- CN108341898A CN108341898A CN201710059774.5A CN201710059774A CN108341898A CN 108341898 A CN108341898 A CN 108341898A CN 201710059774 A CN201710059774 A CN 201710059774A CN 108341898 A CN108341898 A CN 108341898A
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Abstract
The present invention relates to polymer arts, the method for the remaining hydrogenation catalyst after hydrogen is added to include more particularly to a kind of removing unsaturated polymer：The polymer solution after hydrogen will be added to carry out stratification, respectively obtain oil phase and water phase；Then the oil phase is entered from material inlet pipe in the cyclone hydraulic separators and is further detached, isolated hydropolymer is drawn from overflow pipe, and part gained hydropolymer cycle is introduced to the cyclone hydraulic separators, hydropolymer obtained by remainder is drawn as qualified hydropolymer, is (1.2~6) for the hydropolymer of cycle and the ratio between the mass flow as qualified hydropolymer：1.Method provided by the invention is more simple and practicable compared with the method for the prior art, removing unsaturated polymer using the present invention adds the method for the remaining hydrogenation catalyst after hydrogen, equipment investment can not only be saved, moreover it is possible to which the catalyst metal ion content in polymer solution is reduced to 10ppm or less.
Description
Technical field
The present invention relates to polymer arts, and in particular, to a kind of removing unsaturated polymer adds the remnants after hydrogen to add hydrogen
The method of catalyst.
Background technology
For the unsaturated polymerization containing poly bis alkene chain link such as butylbenzene Type of Collective object such as SBS, SBR and polybutadiene, SIS
Object, due to containing unsaturated double-bond in wherein poly bis alkene segment, chemical property is more active, heat, oxidative stability and ageing-resistant
Property is poor, therefore is saturated frequently with the unsaturated double-bond for adding the method for hydrogen to make such polymer, steady to greatly increase its environment
It is qualitative, and make it have good thermal stability.
Hydrogenation of polymer usually carries out in the presence of heavy metal catalyst, and up to the present, industrial method of hydrotreating is main
Using homogeneous phase solution catalyst hydrogenation method and heterogeneous solution catalytic hydrogenation method.Correspondingly, the catalyst that both methods uses
System can be divided into homogeneous catalyst system and heterogeneous catalyst systems.Polymer is carried out using heterogeneous catalysis to add hydrogen
Afterwards, the separation removal of catalyst is easier, but the activity and selectivity of heterogeneous catalysis is poor.Therefore in the prior art
In, mostly use the relatively high homogeneous catalyst progress polymer of activity and selectivity adds hydrogen, but since hydrogenation solution viscosity is big,
Remaining homogeneous catalyst is set to be difficult to remove.
A kind of typical method used in the prior art is that the solution of polymer or lotion and acid is (usually inorganic
Acid) aqueous solution mixing.A kind of method handling the polymer solution after adding hydrogen with dilute sulfuric acid is disclosed in US4396761, point
From aqueous phase, water vapour boiling polymer solution is then used, polymer is obtained to displace polymer solvent.It is public in US3780138
A kind of method of removing metallic catalyst is opened, using in oxidant and dilute lemonade and lower aliphatic alcohols extraction polymerizate
Metal ion.A kind of method removing metallic catalyst from polymer solution is disclosed in US4595749, using oxidation
Agent and dicarboxylic acids, the solvent of lower aliphatic alcohols (carbon atom number is less than 4) or toluene as dicarboxylic acids.Using this method, work as polymerization
When object solution viscosity is high, removal effect is undesirable.It is disclosed in CN1062909A and CN1067898A and a kind of using precipitated metal
Agent removing adds the method for residual catalyst metal ion in hydrogen post-consumer polymer solution, contains organic solvent and organic one in precipitating reagent
First acid or inorganic monoacid.
Add in hydrogen post-consumer polymer solution in the method for residual metal ions in above-mentioned removing, remaining metallic catalyst is through oxygen
Enter in acid solution after agent oxidation, polymer solution, acid solution are then carried out by water-oil separating by stratification, make polymerization
Metal ion in object solution is extracted to as much as possible in water phase acid solution, and oil phase polymer solution subsequently enters centrifuge,
Further the residual metal ions in polymer solution are removed after being centrifuged clean.But directly continue to locate with centrifuge
When managing the polymer solution after oxidation, pickling, due to density contrast between the metal ion and polymer solution in polymer solution
It is smaller, therefore to the more demanding of centrifuge instrument, the equipment investment for being respectively used for purchase centrifuge is larger.
Invention content
The purpose of the present invention is the methods for the prior art to add the remnants after hydrogen that hydrogen is added to urge in removing unsaturated polymer
Defect of high cost, carries caused by must handling the polymer solution after oxidation and pickling using expensive centrifuge when agent
Add the method for the remaining hydrogenation catalyst after hydrogen for a kind of unsaturated polymer of removing at low cost.
The present inventor using cyclone hydraulic separators removing unsaturated polymer under study for action it was unexpectedly observed that after adding hydrogen
Remaining hydrogenation catalyst in obtained hydrogenated polymers solution, and recycle ratio is more than or equal to 1.2 and the warp less than or equal to 6
Hydrogenated polymers solution after the cyclone hydraulic separators separation can obtain significantly higher catalyst when being recycled to cyclone hydraulic separators
Removal efficiency.It, can be by hydrogenated polymers when particularly, by controlling the recycle ratio in operating process in certain preferred scope
Catalyst metal ion content in solution is reduced to 10ppm or less.
To achieve the goals above, the present invention provides a kind of removing unsaturated polymer and adds the remaining hydrogenation catalyst after hydrogen
Method, this method includes：Unsaturated polymer after oxidized and pickling is added the polymer solution after hydrogen carry out standing point
Layer respectively obtains the oil phase containing remaining hydrogenation catalyst and containing the water phase of metal ion；Then by the oil phase from positioned at
The material inlet pipe on the top in the top cylinder area of cyclone hydraulic separators, which enters in the cyclone hydraulic separators, further to be detached, point
From obtained hydropolymer from the overflow pipe extraction positioned at the top of the cyclone hydraulic separators, and partly gained hydrogenation is poly-
Conjunction object is introduced in the cyclone hydraulic separators from material inlet pipe cycle and is detached, hydropolymer obtained by remainder
It is drawn as qualified hydropolymer and the cyclone hydraulic separators further includes being flared the lower part being connect with cylinder area bottom
Circular cone area, the material inlet pipe are tangentially-arranged along the cylinder area, wherein the hydropolymer for cycle and conduct
The ratio between mass flow of qualified hydropolymer is (1.2~6)：1.
The recycle ratio of the hydropolymer of present invention liquid-liquid cyclone hydraulic separators and control for recycling is equal to 1.2
And less than or equal to 6 method replace the prior art centrifuge the polymer solution after oxidation and pickling is detached, with into
Remaining metallic catalyst in one-step removal polymer solution, method provided by the invention are simpler easy compared with the method for the prior art
Row.
Particularly, removing unsaturated polymer using the present invention adds the method for the remaining hydrogenation catalyst after hydrogen, not only
Equipment investment can be saved, moreover it is possible to which the catalyst metal ion content in polymer solution is reduced to 10ppm or less.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is shown for the structure of the cyclone hydraulic separators applied in a kind of method of preferred embodiment of the present invention
It is intended to.
Fig. 2 is the vertical view of cyclone hydraulic separators shown in FIG. 1.
Fig. 3 is a kind of process flow diagram of the method for preferred embodiment of the present invention.
Reference sign
1, cylinder area 2, circular cone area
3, material inlet pipe 4, overflow pipe
5, the polymer solution after underflow pipe 6, oxidation and pickling
7, knockout drum 8, the water phase containing metal ion
9, the oil phase containing remaining hydrogenation catalyst
10, qualified hydrogenated polymer solution
11, the residual organic acids and metal ion being removed
12, circulation fluid
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
" flaring " and " slot " of the present invention indicates the bottom and top of circular cone respectively, and is flared as where cone bottom
Opening.
Add the method for the remaining hydrogenation catalyst after hydrogen, this method packet the present invention provides a kind of removing unsaturated polymer
It includes：Unsaturated polymer after oxidized and pickling is added the polymer solution after hydrogen carry out stratification, respectively obtain containing
The oil phase of remaining hydrogenation catalyst and water phase containing metal ion；Then by the oil phase from positioned at the top of cyclone hydraulic separators
The material inlet pipe on the top in cylinder area, which enters in the cyclone hydraulic separators, further to be detached, isolated hydrogenation polymerization
Object from positioned at the top of the cyclone hydraulic separators overflow pipe extraction, and will part gained hydropolymer from the material into
Mouth pipe cycle, which is introduced in the cyclone hydraulic separators, to be detached, and hydropolymer obtained by remainder polymerize as qualified hydrogenate
Object is drawn and the cyclone hydraulic separators further includes being flared the lower cone area being connect with cylinder area bottom, the material
Inlet tube is tangentially-arranged along the cylinder area, wherein for the hydropolymer of cycle and as qualified hydropolymer
The ratio between mass flow be (1.2~6)：1.
In the method for the present invention, the unsaturated polymer after oxidized and pickling adds the polymer solution after hydrogen quiet in progress
After setting layering, obtained water phase organic acid soln preferably enters organic acid soln refining system, to remove in organic acid soln
Catalyst metal ion enables organic acid soln to recycle.
In the method for the present invention, the unsaturated polymer after oxidized and pickling adds the polymer solution after hydrogen quiet in progress
After setting layering, obtained oil phase polymer solution preferably enters in cyclone hydraulic separators, continues removing residual in a polymer solution
Catalyst metal ion and organic acid soln, improve the removal efficiency of catalyst metal ion.
Preferably, it is (3 to be used for the hydropolymer of cycle with the ratio between the mass flow as qualified hydropolymer
~5)：1.It was found by the inventors of the present invention that using the polymer solution after cyclone hydraulic separators separation hydrogenation to remove therein urge
Agent metal ion and organic acid soln, and especially control is used for the hydropolymer of cycle and gathers as qualification hydrogenation
It is (3~5) to close the ratio between mass flow of object：When 1, the catalyst in the grade polymer solution obtained after separation is enabled to
Metal ion content is reduced to 10ppm or less.
Preferably, the oil phase by the material inlet pipe to enter the flow velocity of the inner space of the cyclone hydraulic separators
For 1~3.2m/s；More preferably 1.8~2.7m/s.That is, the oil phase by the flow velocity of the material inlet pipe be 1~
3.2m/s；More preferably 1.8~2.7m/s.
The preferable configuration of the cyclone hydraulic separators of the present invention is described below：The cyclone hydraulic separators include top cylinder area and
It is flared the circular cone area for the lower part being connect with cylinder area bottom, the top in the cylinder area has tangentially-arranged material inlet
It is provided at the top of pipe and the cylinder area and is connected to the inner space of the cyclone hydraulic separators and the overflow pipe of exterior space,
The oil phase is introduced to from the material inlet pipe in the inner space of the cyclone hydraulic separators.
In the present invention, the oil phase eliminates residual organic acids and metal by what the cyclone hydraulic separators was isolated
The polymer solution of the water white transparency of catalyst ion is flowed out from overflow pipe.
Preferably, the internal diameter of the material inlet pipe be the cylinder area internal diameter 1/5~1/2, more preferably 1/4~
1/3。
Preferably, the internal diameter of the overflow pipe is 1/4~1/2, more preferably the 1/4~1/3 of the internal diameter in the cylinder area.
Preferably, the bottom of the cyclone hydraulic separators has the underflow pipe being connect with the slot in the circular cone area.The bottom
Flow tube is used to be introduced to the remaining organic acid and metal catalyst ion removal in the oil phase in the cyclone hydraulic separators, and
The polymer solution for eliminating the water white transparency of residual organic acids and metal catalyst ion is flowed out from overflow pipe.
Preferably, the internal diameter of the underflow pipe is 1/5~1/2, more preferably the 1/4~1/3 of the internal diameter in the cylinder area.
According to a kind of preferred embodiment, the material inlet pipe, overflow pipe are identical with the internal diameter of underflow pipe.
Preferably, the depth that the overflow pipe is inserted into the inner space of the cyclone hydraulic separators is the interior of the cylinder area
0.2~2 times of diameter, more preferably 0.5~1.6 times.It was found by the inventors of the present invention that being inserted into institute by controlling the overflow pipe
When the depth for stating the inner space of cyclone hydraulic separators is 0.5~1.6 times of the internal diameter in the cylinder area, method using the present invention
The catalyst residue of the hydrogenated polymer solution of acquisition is less.
Preferably, the ratio between the height in the cylinder area and the height in the circular cone area are 1/4~1, more preferably 1/3~3/
5。
According to a kind of preferred embodiment, the structure of the cyclone hydraulic separators is as shown in Figure 1, specifically：
The cyclone hydraulic separators includes the cylinder area 1 on top and the circular cone area for being flared the lower part being connect with cylinder area bottom
2, the top in the cylinder area, which has, is provided with connection institute at the top of tangentially-arranged material inlet pipe 3 and the cylinder area
The inner space of cyclone hydraulic separators and the overflow pipe 4 of exterior space are stated, the oil phase is introduced to described from the material inlet pipe
In the inner space of cyclone hydraulic separators, the bottom of the cyclone hydraulic separators has the underflow pipe being connect with the slot in the circular cone area
5。
It was found by the inventors of the present invention that control the material inlet pipe internal diameter be the cylinder area internal diameter 1/5~
1/2, more preferably 1/4~1/3, and the oil phase is controlled by the material inlet pipe to enter the cyclone hydraulic separators
The flow velocity of inner space is 1~3.2m/s；When more preferably 1.8~2.7m/s, the polymer obtained by the method for the present invention is molten
The removal efficiency higher of catalyst metal ion in liquid.
In the method for the present invention, after unsaturated polymer adds hydrogen, oxidant is added to adding in the polymer solution after hydrogen
Residual metal ions are aoxidized, and pickling is carried out with the polymer solution after organic acid soln pair plus hydrogen, after adding hydrogen
Polymer solution in residual metal ions be extracted in organic acid soln.The oxidant can be previously added to after adding hydrogen
Polymer solution in, also can be simultaneously added with organic acid soln to plus hydrogen after polymer solution in.
In the present invention, in method of the invention, oxidant can be any oxidation suitable for oxidized metal catalyst
Object, for example, oxygen, air, hydrogen peroxide, alkyl or aryl peroxide.Oxidant with plus hydrogen after polymer solution in
The molar ratio of metal ion is (0.1~100)：1, preferably (1~20)：1.
In the method for the invention, the organic acid is the organic compound with carboxyl, and is dissolved in water, therefore described is had
Machine acid solution is the aqueous solution that organic acid is formed with water.Organic acid in the aqueous solutions of organic acids can in polymer solution
Metal ion form relatively stable chelate, and gained chelate is dissolved in water.Finally by the polymer solution and water of oil phase
The aqueous solutions of organic acids of phase detaches to achieve the purpose that residual catalyst metal ion in the polymer solution after removing plus hydrogen.
Here, the aqueous solutions of organic acids applied is organic acid soln commonly used in the art, specific example includes but not limited to citric acid
Aqueous solution, preferably aqueous citric acid solution, and a concentration of 1~5 weight % of aqueous citric acid solution, preferably 2~3 weight %,
And aqueous citric acid solution with plus hydrogen after polymer solution volume ratio be (0.6~1.5)：1, preferably (0.8~1.2)：1.
In the method for the present invention, add the oxidation of the polymer solution after hydrogen and pickling can be simultaneously in setting with mixed function
Standby middle completion, specific example includes but not limited to stirred tank, preferably stirred tank.
Preferably, the condition of the oxidation and pickling includes：Temperature is 50~80 DEG C, more preferably 60~70 DEG C；Time
For 50~90min, more preferably 65~80min.
In the method for the present invention, the unsaturated polymer after oxidized and pickling adds the polymer solution after hydrogen to need to carry out
Stratification, to realize the separation of water-oil phase.Stratification can carry out in common standing separation equipment in the art,
Specific example includes but not limited to the horizontal knockout drum with partition board, preferably with the horizontal knockout drum of partition board.
Preferably, the condition of the stratification includes：Temperature is 20~80 DEG C, more preferably 25~40 DEG C；Time is
90~180min, more preferably 120~150min.
In the method for the invention, for adding the unsaturated polymer of hydrogen that can be key point conjugated diene homopolymers, carbon be former
Subnumber 4~8, such as butadiene, isoprene, cyclopentadiene, conjugation hexadiene, conjugation heptadiene, conjugation octadiene；It can also
It is the homopolymer of vinyl aromatic polymers such as styrene, α-methylstyrene, vinyl-dimethyl benzene, vinyl benzene；May be used also
Be 4~8 carbon atoms conjugated diene and vinyl aromatic compound copolymer, it can be random, can also be
Block, the method for polymerization may refer in US3792005 and US3431323.
Preferably, the unsaturated polymer after the oxidized and pickling adds the polymer in the polymer solution after hydrogen
A concentration of 5~16 weight %, more preferably 8~12 weight %.
According to a kind of preferred embodiment, the removing unsaturated polymer of the invention adds the remnants after hydrogen to add
The method of hydrogen catalyst is carried out using technological process shown in Fig. 3, specifically：
This method includes：Unsaturated polymer after oxidized and pickling is added to the polymer after the oxidation and pickling after hydrogen
Solution 6, which is introduced in knockout drum 7, carries out stratification, respectively obtains the oil phase 9 containing remaining hydrogenation catalyst (from separation
Tank) and water phase 8 containing metal ion；Then by described, the oil phase 9 containing remaining hydrogenation catalyst is introduced into cyclone hydraulic separators
Further being detached, isolated hydropolymer is drawn from the overflow pipe positioned at the top of the cyclone hydraulic separators, and
And it is introduced in the cyclone hydraulic separators from material inlet pipe cycle using part gained hydropolymer as circulation fluid 12
Detached, hydropolymer obtained by remainder is drawn as qualified hydropolymer 10, the residual organic acids that are removed and
Metal ion 11 is discharged from underflow pipe.
In case of no particular description, " recycle ratio " as described herein is the hydropolymer for cycle
With the ratio between the mass flow as qualified hydropolymer.
The present invention will be described in detail by way of examples below.
In following embodiment, in case of no particular description, the various raw materials used are all from commercially available.
Preparation example
In 5L polymeric kettles, using n-BuLi as initiator, the mixture (weight hundred of hexamethylene of hexamethylene and n-hexane
87%) it is that solvent synthesizes butadiene-styrene block copolymer to divide than being.In gained polymerizate, butadiene-styrene is embedding
It is 10 weight % that section copolymer concentration, which is based on entire polymerization system, and the number-average molecular weight of the block copolymer is 5.5 ten thousand, styrene
Weight ratio with butadiene monomer unit is 3：7.Gained butadiene-styrene block copolymer solution 1200mL is taken, then will
It is added for use in the purified high-pressure hydrogenation kettle of 2L high-purity hydrogens.
Hydrogenation catalyst is by major catalyst nickel naphthenate (Beijing Yanshan Mountain synthetic rubber plant, technical grade, concentration 4g/L) and three
Aluminium isobutyl (Beijing Yanshan Mountain synthetic rubber plant, technical grade, concentration 3g/L) is aged 30 minutes at 50 DEG C and is made, wherein nickel aluminium ratio
It is 1：4 (molar ratios).The 2L equipped with butadiene-styrene block copolymer solution is added in hydrogenation catalyst obtained and adds hydrogen kettle
In, catalyst charge is 0.07gNi/100g butadiene-styrene block copolymers.It is passed through hydrogen to adding in hydrogen kettle, is controlled
Hydrogenation reaction pressure is 4MPa (gauge pressure), and hydrogenation reaction temperature is 65 DEG C, speed of agitator 600rpm.Reaction 2 hours, polymer
Butadiene section degree of hydrogenation is more than 98% in object.
It will add in the hydrogen post-consumer polymer solution indentation closed stirred tanks of 2L, and carry out the oxidation and pickling of polymer solution：Pass through
Water bath with thermostatic control will add hydrogen post-consumer polymer solution to be heated to 60 DEG C, then be added 30 weight %'s into the polymer solution after heating
Hydrogen peroxide, dosage is the 1% of polymer solution volume, while the aqueous citric acid solution of 2 weight % is added, and dosage is poly-
0.8 times of polymer solution volume, speed of agitator 500rpm, reaction incorporation time are 65min.
Acquired solution is spare.
Embodiment 1
Mixture after oxidation and pickling that preparation example is obtained is pressed by oxidation/pickling kettle in knockout drum, using standing
Separation method makes obtained polymer solution and aqueous citric acid solution carry out standing separation.Standing separation temperature is 25 DEG C, when
Between be 120min.The aqueous citric acid solution (water phase) obtained after standing enters ion exchange resin refining system, removes wherein institute
Nickel, the aluminum metal ion contained, so that aqueous citric acid solution is recycled.Isolated polymer solution (oil phase) into
Enter in cyclone hydraulic separators, further the wherein remaining nickel of removing, aluminum metal ion.
The cylinder area internal diameter of cyclone hydraulic separators is 50mm, and cylinder section length is 100mm, and the height of tapered zone is 200mm, and
Cone angle is 15 DEG C；Material inlet bore, overflow bore, underflow bore are 15mm, and overflow pipe insertion depth is
25mm.Recycle ratio in operating process is 1.2, and polymer solution enters rotary filter press by the material inlet pipe of cyclone hydraulic separators
Flow velocity when device is 1m/s.After rotary filter press, obtain containing nickel, aluminum metal ion a small amount of organic acid soln from underflow pipe
The polymer solution of outflow, water white transparency is flowed out from overflow pipe.
Drying to constant weight in 50 DEG C of drying box after the polymer solution cohesion for being gone out overflow with ethyl alcohol, then use etc. from
Sub- emission spectrometry surveys the tenor in polymer, and the content for measuring nickel in qualified hydropolymer is 4.8ppm, and aluminium contains
Amount is 10ppm.
Embodiment 2
The present embodiment is carried out using method similar to Example 1, the difference is that in the present embodiment, by operating process
In recycle ratio improve to 2, polymer solution enters flow velocity when cyclone hydraulic separators by the material inlet pipe of cyclone hydraulic separators
For 1.4m/s.
Remaining is in the same manner as in Example 1.
As a result, the content for measuring nickel in qualified hydropolymer is 4.5ppm, the content of aluminium is 9ppm.
Embodiment 3
The present embodiment is carried out using method similar to Example 1, the difference is that in the present embodiment, by operating process
In recycle ratio improve to 3, polymer solution enters flow velocity when cyclone hydraulic separators by the material inlet pipe of cyclone hydraulic separators
For 1.8m/s.
Remaining is in the same manner as in Example 1.
As a result, the content for measuring nickel in qualified hydropolymer is 3.9ppm, the content of aluminium is 7ppm.
Embodiment 4
The present embodiment is carried out using method similar to Example 1, the difference is that in the present embodiment, by operating process
In recycle ratio improve to 4, polymer solution enters flow velocity when cyclone hydraulic separators by the material inlet pipe of cyclone hydraulic separators
For 2.3m/s.
Remaining is in the same manner as in Example 1.
As a result, the content for measuring nickel in qualified hydropolymer is 3.5ppm, the content of aluminium is 6ppm.
Embodiment 5
The present embodiment is carried out using method similar to Example 1, the difference is that in the present embodiment, by operating process
In recycle ratio improve to 5, polymer solution enters flow velocity when cyclone hydraulic separators by the material inlet pipe of cyclone hydraulic separators
For 2.7m/s.
Remaining is in the same manner as in Example 1.
As a result, the content for measuring nickel in qualified hydropolymer is 4.3ppm, the content of aluminium is 8.2ppm.
Embodiment 6
The present embodiment is carried out using method similar to Example 1, the difference is that in the present embodiment, by operating process
In recycle ratio improve to 6, polymer solution enters flow velocity when cyclone hydraulic separators by the material inlet pipe of cyclone hydraulic separators
For 3.2m/s.
Remaining is in the same manner as in Example 1.
As a result, the content for measuring nickel in qualified hydropolymer is 4.8ppm, the content of aluminium is 8.9ppm.
Embodiment 7
The present embodiment is carried out using method similar to Example 1, the difference is that in the present embodiment, cyclone hydraulic separators
Overflow pipe insertion depth be 80mm.
Remaining is in the same manner as in Example 1.
As a result, the content for measuring nickel in qualified hydropolymer is 4.7ppm, the content of aluminium is 9.5ppm.
Embodiment 8
The present embodiment is carried out using method similar to Example 1, the difference is that in the present embodiment, cyclone hydraulic separators
The internal diameter of material inlet pipe be 10mm, and overflow bore, underflow bore are 15mm.
Remaining is in the same manner as in Example 1.
As a result, the content for measuring nickel in qualified hydropolymer is 4.9ppm, the content of aluminium is 10ppm.
Comparative example 1
This comparative example is carried out using technological process similar to Example 1, the difference is that using disk in this comparative example
Cyclone hydraulic separators in formula centrifuge alternative embodiment 1 will also pass through the polymer solution that knockout drum standing separation obtains and send
Enter in disc centrifuge (trade mark DHC270 is purchased from jiangsu wuxi), rotating speed 7300r/min, separation factor is
10136。
According to the method for the comparative example, the content of nickel is 4.7ppm in the qualified hydropolymer of gained, and the content of aluminium is
10ppm。
Comparative example 2
This comparative example is carried out using method similar to Example 1, the difference is that in this comparative example, in operating process
Recycle ratio be 1.
Remaining is in the same manner as in Example 1.
As a result, the content for measuring nickel in qualified hydropolymer is 6.3ppm, the content of aluminium is 15.2ppm.
Comparative example 3
This comparative example is carried out using method similar to Example 1, the difference is that in this comparative example, in operating process
Recycle ratio be 7.
Remaining is in the same manner as in Example 1.
As a result, the content for measuring nickel in qualified hydropolymer is 5.6ppm, the content of aluminium is 14.2ppm.
By comparison as can be seen that the present invention can avoided using expensive centrifuge by using cyclone hydraulic separators
Under the premise of obtain the hydropolymer that tenor is met the requirements, specifically, the tenor in the hydropolymer obtained
It can reach suitable with the tenor in the hydropolymer obtained when being centrifuged using centrifuge.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (11)
1. a kind of method for removing unsaturated polymer and adding the remaining hydrogenation catalyst after hydrogen, this method include：By oxidized and
Unsaturated polymer after pickling adds the polymer solution after hydrogen to carry out stratification, respectively obtains containing remaining hydrogenation catalyst
Oil phase and water phase containing metal ion；Then by the oil phase from the top positioned at the top cylinder area of cyclone hydraulic separators
Material inlet pipe, which enters in the cyclone hydraulic separators, further to be detached, and isolated hydropolymer is from positioned at the rotation
The overflow pipe at the top of liquid/gas separator is drawn, and part gained hydropolymer is introduced to from material inlet pipe cycle
It is detached in the cyclone hydraulic separators, hydropolymer obtained by remainder is drawn as qualified hydropolymer, Yi Jisuo
It further includes the lower cone area that flaring is connect with cylinder area bottom to state cyclone hydraulic separators, and the material inlet pipe is along the circle
Cylinder area is tangentially-arranged, wherein the hydropolymer and the ratio between the mass flow as qualified hydropolymer for cycle
For (1.2~6)：1.
2. according to the method described in claim 1, wherein, the hydropolymer for cycle polymerize with as qualification hydrogenation
The ratio between mass flow of object is (3~5)：1.
3. method according to claim 1 or 2, wherein the oil phase is by the material inlet pipe to enter the rotation
The flow velocity of the inner space of liquid/gas separator is 1~3.2m/s；Preferably 1.8~2.7m/s.
4. according to the method described in any one of claim 1-3, wherein the internal diameter of the material inlet pipe is the cylinder
The 1/5~1/2 of the internal diameter in area, preferably 1/4~1/3.
5. according to the method described in any one of claim 1-3, wherein the internal diameter of the overflow pipe is the cylinder area
The 1/4~1/2 of internal diameter, preferably 1/4~1/3.
6. according to the method described in any one of claim 1-5, wherein the bottom of the cyclone hydraulic separators have with it is described
The underflow pipe of the slot connection in circular cone area；Preferably,
The internal diameter of the underflow pipe is 1/5~1/2, preferably the 1/4~1/3 of the internal diameter in the cylinder area.
7. according to the method described in claim 6, wherein, the material inlet pipe, overflow pipe are identical with the internal diameter of underflow pipe.
8. method according to any one of claims 1-7, wherein the overflow pipe is inserted into the cyclone hydraulic separators
The depth of inner space be 0.2~2 times of internal diameter of the cylinder area；Preferably 0.5~1.6 times.
9. according to the method described in any one of claim 1-3, wherein the height in the cylinder area and the circular cone area
The ratio between height is 1/4~1, preferably 1/3~3/5.
10. according to the method described in claim 1, wherein, the condition of the oxidation and pickling includes：Temperature is 50~80 DEG C,
Preferably 60~70 DEG C；Time is 50~90min, preferably 65~80min.
11. according to the method described in claim 1, wherein, the condition of the stratification includes：Temperature is 20~80 DEG C, excellent
It is selected as 25~40 DEG C；Time is 90~180min, preferably 120~150min.
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