CN1061020A - The purification process of vi-ny l aromatic monomers - Google Patents
The purification process of vi-ny l aromatic monomers Download PDFInfo
- Publication number
- CN1061020A CN1061020A CN91109195.5A CN91109195A CN1061020A CN 1061020 A CN1061020 A CN 1061020A CN 91109195 A CN91109195 A CN 91109195A CN 1061020 A CN1061020 A CN 1061020A
- Authority
- CN
- China
- Prior art keywords
- monomer
- aluminum oxide
- aromatic monomers
- scope
- volume
- 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.)
- Pending
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 31
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 10
- 238000000746 purification Methods 0.000 title claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 230000002779 inactivation Effects 0.000 description 3
- HIGRAKVNKLCVCA-UHFFFAOYSA-N alumine Chemical compound C1=CC=[Al]C=C1 HIGRAKVNKLCVCA-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SHKKTLSDGJRCTR-UHFFFAOYSA-N 1,2-dibromoethylbenzene Chemical compound BrCC(Br)C1=CC=CC=C1 SHKKTLSDGJRCTR-UHFFFAOYSA-N 0.000 description 1
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- -1 amine compound Chemical class 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/20—Use of additives, e.g. for stabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Polymerisation Methods In General (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to contain the purification process of the vi-ny l aromatic monomers of phenolic inhibitor, this method is with the fixed bed of monomer by aluminium oxide particles, and the scope that it is characterized in that size of particles is 0.5-3mm, and the scope of individual space speed is 0.5-7.5h
-1, the scope of monomer linear velocity is 0.125-45m/h.
Description
The present invention relates to the purification process of vi-ny l aromatic monomers, more particularly, relate to the method for from described monomer, removing phenolic inhibitor.As everyone knows, in order to store and to transport, the stopper that adds 5-50ppm in vi-ny l aromatic monomers is absolutely necessary, described monomer comprises for example vinylbenzene, vinyl toluene, alpha-methyl styrene, butylstyrene, Vinylstyrene, monobromo and Dowspray 9 etc. and composition thereof, the most frequently used stopper is p-ten.-butylcatechol (TBC), but also can use other stopper, for example quinhydrones-ethyl ether, dinitrophenol(DNP) and picric acid.But stopper influences the quality of the polymkeric substance of producing sometimes, thereby, must in advance it be removed from monomer sometimes.Several this purpose methods that are suitable for have been arranged, for example:
ⅰ) distillation monomer, purpose is to remove (heating up in a steamer tail) phenolic inhibitor; Owing to consuming energy high and needing complex apparatus, this method is very expensive;
ⅱ) wash with aqueous sodium hydroxide washes; In order to remove the sodium hydroxide that remains in the monomer, this method wants water to wash strongly subsequently, and needs final dry to remove residual moisture content usually;
ⅲ) with monomer by anionite-exchange resin (contain tertiary amine and/or quaternary amine end group, be free and two kinds of forms of salify); The shortcoming of this method is, if use with salifiable form, the life-span of material is short especially, if resin uses with the free form, owing to there is the amine compound of trace, the monomer of handling has one niff.
The known purification process that also has other, this method comprises vi-ny l aromatic monomers by the aluminum oxide fixed bed.Because life-span of sorbing material is short, this method is very economical always not, and process cost is very high usually.This method must often be changed bed, and this needs complicated operations, for example removes the monomer that adsorbs on the material, emits waste material and handle, and adds fresh material etc.
In order to prolong the life-span of aluminum oxide, change number of times thereby reduce it, there is a part document (Japanese patent laid-open publication gazette 57538/1988, this paper document incorporated by reference) suggestion that proper space speed and extremely low space velocity (monomer) are used alternatingly recently, for example, 0.8h
-1Space velocity be equal to or less than 0.01h
-1Speed be used alternatingly, the life-span of aluminum oxide prolongs as a result, like this, before the aluminum oxide inactivation, the monomeric amount of the aluminum oxide of unit weight (or volume) the obtainable purifying of institute improves greatly.For " normally " space velocity, the document points out that its value is 0.1-10h
-1But the principle that this method requires operator must follow complexity is carried out the operation of purification column; In addition, the monomeric total amount of obtainable purifying be at most the threshold value of aluminum oxide, this value and not really high, and (be lower than 0.1h in " low " space velocity
-1) during in the production loss of not expecting is arranged.
The applicant finds out now: accurately select the certain operations condition, can avoid being used alternatingly space velocity, eliminate low spatial speed, the monomeric total amount of the purifying that is obtained is shockingly high.
In a broad sense, the present invention relates to contain the purification process of the vi-ny l aromatic monomers with 8-12 carbon atom of phenolic inhibitor, this method is with the fixed bed of monomer by aluminium oxide particles, and the scope that it is characterized in that median size is 0.5-3mm, and the scope of individual space speed is 0.5-7.5h
-1, the scope of monomer linear velocity is 0.125-45, preferred 1.2-45m/h.Space velocity is meant following ratio:
W=(m
3/ h (monomer))/(M
3(apparent volume of aluminum oxide))
Wherein " apparent " volume was meant before being full of aluminum oxide, the volume of empty purifying chamber, and certainly, this volume is different from Al
2O
3The volume of particle own.Linear velocity is meant the ratio of monomeric volumetric flow rate and the vertical cross sections in purifying chamber." monomer " be meant independent a kind of monomer such as vinylbenzene and with the mixture of other vi-ny l aromatic monomers.The preferred stopper of the inventive method is a p-ten.-butylcatechol, and the amount ranges of stopper is the preferred 5-15ppm of 5-50ppm(in the monomer to be purified).The long-pending preferable range of alumina surface is 150-270m
2/ g.Monomeric purifier apparatus of the present invention can be diversified; Monomer to be purified supplied with to be filled with the aluminum oxide fixed bed and to have the preferred right circular cylinder tube in the bottom of inlet obtained fabulous result.Aluminum oxide can be spherical (friction loss is minimum) or grain (having irregular limit).The size of aluminum oxide is more little, and its life-span is long more, and the shape (sphere, small column, particle etc.) of this result and used aluminum oxide is irrelevant; Never observe this fact before this.
Embodiment given below only is used to the present invention is described and does not limit the scope of the invention.In test, through-flow threshold value (terminal point in sorbent material life-span or " inactivation threshold value ") is that p-ten.-butylcatechol equals 2ppm in the monomer of handling usually just.This ultimate value than Japanese patent laid-open publication gazette 57538/1988 pointed ultimate value (its threshold value equals 8ppm) can accept (with regard to the requirement of many polymerizable compounds) many.
Embodiment 1(simultaneous test)
With mean sizes is that particulate alumina [trade(brand)name is in " COMPALOX AN/V-850 ", Nartinswerk GmbH, Bergheim(Germany) company produce] diameter of packing into of 5-10mm is 2.5cm, highly is in the right cylinder of 25cm; Then, at room temperature, the styrene monomer that will contain the 12ppm p-ten.-butylcatechol is with 6h
-1Space velocity (linear velocity=1.5m/h) is supplied with, in 1.04 days time (fortunately before the inactivation threshold value), the vinylbenzene that every volume aluminum oxide only may purifying 150 volumes, data and the results are shown in Table 1.
Embodiment 2
Under the condition identical with embodiment 1, different is, and to adopt size range be that 1-3mm, surface-area are about 170m
2The aluminum oxide of/h (commodity are called " COMPALOX AN/V-813 "), in 12.50 days, can the much more styrene monomer (every volume aluminum oxide 1800 volume vinylbenzene) of purifying.
Embodiment 3
Under the condition identical with embodiment 2, different is at 0.5h
-1Space velocity (linear velocity=0.125m/h) operation down, in 375 days time, can every volume aluminum oxide 4, the 500 volume vinylbenzene of purifying.
Embodiment 4
Under the condition identical with embodiment 1, different is, and to adopt mean sizes be the aluminum oxide (quality is called " COMPALOX AN/V-802 ") of 0.5-2mm, and in more than 17.36 days time, every volume aluminum oxide purifying is more than the vinylbenzene of 2,500 volumes.
Embodiment 5(simultaneous test)
Under the condition identical with embodiment 2, that different is space velocity (14h
-1) (linear velocity=3.5m/h) much higher, in 4.61 days time, every volume aluminum oxide purifying 1,550 volume vinylbenzene.
Embodiment 6
With the particle of embodiment 2 pack into diameter be 4.5cm, highly in the pillar of 6m.With the space velocity of 7.1h (linear velocity=42.6m/h) add the styrene monomer that contains the 10ppm p-ten.-butylcatechol, in 12.91 days time, every volume aluminum oxide purifying 2,200 volume vinylbenzene.
Embodiment 7(simultaneous test)
With the particulate alumina that is of a size of 1-3mm, embodiment 2 pack into diameter be 4.5cm, highly in the pillar of 3m.With 14h
-1Space velocity (linear velocity=42.0m/h) adds the styrene monomer that contains the 10ppm p-ten.-butylcatechol, in 3.72 days time, every volume aluminum oxide purifying 1,250 volume aluminum oxide.
Embodiment 8(simultaneous test)
With particle diameter be 2-5mm ball-aluminium oxide [commodity by name " ALUMINE ACTIVEE A 2-5 is by Rhone Poulenc(France) preparation] diameter of packing into is 4.5cm, highly is in the pillar of 6m.With 6.4h
-1Space velocity (linear velocity=38.4m/h) adds the styrene monomer that on average contains the 9ppm p-ten.-butylcatechol, and in 7.81 days time, every volume aluminum oxide can purifying 1,200 volume aluminum oxide.
Embodiment 9
With particle diameter is that 1.5-2.5mm, surface-area are about 270m
2The ball-aluminium oxide of/g (commodity are called " ALUMINE ACTIVEE A the 1.5-2.5 ") diameter of packing into is 4.5cm, highly in the pillar of 6m.With 6.8h
-1Space velocity (linear velocity=40.8m/h) adds the styrene monomer that on average contains the 9ppm p-ten.-butylcatechol; In 13.4 days time, the vinylbenzene that the aluminum oxide of every volume can purifying 2,200 volumes.
Embodiment 10(simultaneous test)
Ball-aluminium oxide [commodity are called Alcoa H151, by the Alcoa Chemicals Division(U.S.) produce] diameter of packing into that will be of a size of 1/4 inch (6.4mm) is 28mm, highly is in the pillar of 25cm.With 4h
-1Space velocity (linear velocity=1.0m/h) adds the styrene monomer that on average contains the 12ppm p-ten.-butylcatechol; In 1.56 days time, the vinylbenzene of an every volume aluminum oxide purifying 150 volumes.The data of all embodiment and outcome record are in table 1.
Claims (8)
1, the purification process that contains the vi-ny l aromatic monomers with 8-12 carbon atom of phenolic inhibitor, this method are with the fixed bed of monomer by aluminium oxide particles, it is characterized in that, the scope of individual space speed is 0.5-7.5h
-1, the size ranges of particle is 0.5-3.0mm, the scope of monomer linear velocity is 0.125-45m/h.
2, by the process of claim 1 wherein that the scope of described linear velocity is 1.2-45m/h.
3, by the method for claim 1 or 2, wherein said vi-ny l aromatic monomers is a vinylbenzene.
4, by the method for claim 1 or 2, wherein said stopper is a p-ten.-butylcatechol.
5, by the method for claim 1 or 2, wherein the content range of stopper is 5-50ppm.
6, by the method for claim 5, wherein said content range is 5-15ppm.
7, by the method for above-mentioned arbitrary claim, wherein alumina surface is long-pending is 150-270m
2/ h.
8, by the method for above-mentioned arbitrary claim, wherein aluminium oxide particles is spherical.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT02149590A IT1245845B (en) | 1990-09-17 | 1990-09-17 | PROCESS FOR THE PURIFICATION OF A VINYLAROMATIC MONOMER. |
| IT21495A/90 | 1990-09-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1061020A true CN1061020A (en) | 1992-05-13 |
Family
ID=11182672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91109195.5A Pending CN1061020A (en) | 1990-09-17 | 1991-09-17 | The purification process of vi-ny l aromatic monomers |
Country Status (5)
| Country | Link |
|---|---|
| CN (1) | CN1061020A (en) |
| GB (1) | GB2248627B (en) |
| HU (1) | HU209668B (en) |
| IT (1) | IT1245845B (en) |
| TN (1) | TNSN91079A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073977C (en) * | 1998-11-18 | 2001-10-31 | 中国石油化工集团公司 | Purification method of phenylethylene monomer |
| CN102307830A (en) * | 2009-02-05 | 2012-01-04 | 纳尔科公司 | Polymer inhibition of vinyl aromatic monomers using a quinone methide/alkyl hydroxylamine combination |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2758553B1 (en) * | 1997-01-22 | 1999-04-16 | Rhodia Chimie Sa | PROCESS FOR THE ELIMINATION OF INHIBITORS OF POLYMERIZATION OF MIXTURES OF MONOMERS USING A DOPED ALUMIN |
| FR2758552B1 (en) * | 1997-01-22 | 1999-04-16 | Rhodia Chimie Sa | PROCESS FOR THE ELIMINATION OF INHIBITORS OF POLYMERIZATION OF MIXTURES OF MONOMERS USING AN OPTIMIZED ALUMIN |
| FR2758554B1 (en) | 1997-01-22 | 1999-04-16 | Rhodia Chimie Sa | PROCESS FOR THE ELIMINATION OF INHIBITORS OF POLYMERIZATION OF MIXTURES OF MONOMERS USING AN ALUMIN OF OPTIMIZED FORM |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0717528B2 (en) * | 1986-08-28 | 1995-03-01 | 三井東圧化学株式会社 | Method for purifying aromatic vinyl monomer |
-
1990
- 1990-09-17 IT IT02149590A patent/IT1245845B/en active IP Right Grant
-
1991
- 1991-09-16 HU HU912978A patent/HU209668B/en not_active IP Right Cessation
- 1991-09-16 GB GB9119728A patent/GB2248627B/en not_active Expired - Fee Related
- 1991-09-17 CN CN91109195.5A patent/CN1061020A/en active Pending
- 1991-09-17 TN TNTNSN91079A patent/TNSN91079A1/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073977C (en) * | 1998-11-18 | 2001-10-31 | 中国石油化工集团公司 | Purification method of phenylethylene monomer |
| CN102307830A (en) * | 2009-02-05 | 2012-01-04 | 纳尔科公司 | Polymer inhibition of vinyl aromatic monomers using a quinone methide/alkyl hydroxylamine combination |
| CN102307830B (en) * | 2009-02-05 | 2014-10-22 | 纳尔科公司 | Polymer inhibition of vinyl aromatic monomers using a quinone methide/alkyl hydroxylamine combination |
Also Published As
| Publication number | Publication date |
|---|---|
| TNSN91079A1 (en) | 1992-10-25 |
| IT1245845B (en) | 1994-10-25 |
| HU912978D0 (en) | 1992-01-28 |
| HU209668B (en) | 1994-10-28 |
| GB2248627B (en) | 1994-05-18 |
| IT9021495A0 (en) | 1990-09-17 |
| IT9021495A1 (en) | 1992-03-17 |
| HUT59897A (en) | 1992-07-28 |
| GB2248627A (en) | 1992-04-15 |
| GB9119728D0 (en) | 1991-10-30 |
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|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |