CN107840775A - The method of purification of 2,6 diisopropyl naphthalenes - Google Patents
The method of purification of 2,6 diisopropyl naphthalenes Download PDFInfo
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- CN107840775A CN107840775A CN201610831245.8A CN201610831245A CN107840775A CN 107840775 A CN107840775 A CN 107840775A CN 201610831245 A CN201610831245 A CN 201610831245A CN 107840775 A CN107840775 A CN 107840775A
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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
- C07C7/04—Purification; Separation; Use of additives by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/14—Purification; Separation; Use of additives by crystallisation; Purification or separation of the crystals
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Abstract
The present invention relates to one kind 2, the method of purification of 6 diisopropyl naphthalenes, high-purity 2 is produced using two-stage levitation melting crystallisation, 6 diisopropyl naphthalenes, first pass through rectifying and pre-separation is carried out to raw material, boiling point is isolated than 2, the low light component of 6 diisopropyl naphthalenes and boiling point ratio 2, the high heavy constituent of 6 diisopropyl naphthalenes, the intermediate species containing 2,6 diisopropyl naphthalenes is obtained as crystallization raw material, 2 are obtained by first order fusion-crystallization, the coarse-grain of 6 diisopropyl naphthalenes, then 2,6 diisopropyl naphthalene crystal products are obtained by second level fusion-crystallization.The technical solution adopted in the present invention preferably solves the problems, such as that product purity present in prior art is low, high energy consumption, in the production available for 2,6 diisopropyl naphthalenes.
Description
Technical field
The present invention relates to a kind of method of purification of 2,6- diisopropyl naphthalenes.
Background technology
2,6-DIPN (2,6-DIPN) is a kind of important Organic Chemicals, and 2,6- naphthalenes two are generated after oxidized
Formic acid (2,6-NDA) is esterified with ethylene glycol, and PEN (PEN) made from polycondensation is a kind of new high property
Can polyester material.High symmetry in PEN structures makes it have the characteristic of straight chain polymer, compared with phenyl polymer PET,
It is more superior in gas barrier property, heat resistance, mechanical performance, radiation resistance, chemical stability and dimensional stability etc., will be by
Step substitution PET commonly used at present.
The synthesis of 2,6-DIPN (2,6-DIPN) is usually that reaction product is single isopropyl using naphthalene and propylene as raw material
Base naphthalene (MIPN), diisopropyl naphthalene (DIPN), the mixture of triisopropyl naphthalene and more isopropyl naphthalenes (TIPN and PIPN), meet
Produce high-purity requirement of the NDA to raw material, it is necessary to which separating-purifying is carried out to 2,6-DIPN.Due to reaction product group
Into complexity, only diisopropyl naphthalene just has 10 kinds of isomers, and boiling point difference is seldom between each isomer, particularly target
Product 2,6-DIPN and 2,7-DIPN boiling point differ only by 2 DEG C, therefore rectification method can not obtain high-purity, in high yield 2,6-
DIPN, studying more separation method at present mainly has crystallisation, absorption method etc..
Chinese patent " refined naphthalene faces the method that hydrogen isopropylation prepares 2,6- diisopropyl naphthalenes " (number of patent application：
200510134712.3) a kind of method for crystallising for purifying 2,6-DIPN is proposed, the technical scheme is first carried out to raw material
Pre-separation, then 2,6-DIPN is purified by two-stage Crystallization Separation, first order crystallization category fusion-crystallization, it is different to obtain 2,6- bis-
Propyl group naphthalene coarse-grain, the second level are static fusion-crystallization, obtain the 2,6-DIPN product of high-purity.The technical scheme second
Level crystallization uses static fusion-crystallization, has following weak point：1) crystal growth is very slow, crystallization time length, required crystallizer
It is sufficiently bulky；2) needing, which increases sweating step, can just make crystal reach product purity requirement, add the complexity and difficulty of operation
Degree, and can only be intermittently operated, it is unfavorable for the production of industrial-scale；3) crystallized, sweating, fusing three steps are cut
, it is necessary to configure multiple surge tank storage materials when changing, equipment investment is added；4) same static melting crystallizer crystallization,
During sweating, melt operation, the circulate operation that constantly cooled, heats up, energy consumption is larger；5) it is quiet to realize continuous operation
State fusion-crystallization process need to configure two sets of identical crystal systems and switch over operation, add cost of investment and the complexity of operation
Property and difficulty.
A kind of Chinese patent " preparation method of high purity 2,6-diisopropyl naphthalene " (number of patent application：
200610111721.5) method for crystallising of another purification 2,6-DIPN is proposed, the technical scheme is equally first right
Raw material carry out pre-separation, then again by two-stage Crystallization Separation purify 2,6-DIPN, difference be the first order crystallization and
Second level crystallization is solution crystallization process, is required for using solvent.The deficiency of the technical scheme is：1) first order crystallization process
Crystallized using solution, although raw material has carried out pre-separation, but in the raw material of the first order crystallization 2,6-DIPN concentration
Still it is relatively low, it can typically be less than 50%, still containing substantial amounts of other impurities, such as 2,7- diisopropyl naphthalenes etc., be crystallized in the first order
Process adds solvent, it is necessary to dissolve other impurity with a large amount of solvents, therefore the utilization ratio of solvent is not high；2) two-stage crystallized
Journey all uses solvent, and solvent-oil ratio is big, and the cost of solvent recovery is high, causes separating energy consumption to increase；3) first order crystallization raw material
The concentration of middle 2,6-DIPN is low, and after adding solvent, the concentration of 2,6-DIPN further reduces, therefore the first order
Crystallization time is grown, and is 20~30 hours, causes crystalliser volume very big, crystalline rate is low, and energy consumption can increase therewith.
The content of the invention
The technical problems to be solved by the invention are that product present in the production method of existing 2,6- diisopropyl naphthalenes is pure
A kind of the problems such as spending low, high energy consumption, there is provided method of purification of new 2,6-DIPN.
In order to solve the above technical problems, the present invention is as follows using technical scheme：The mixed material of the diisopropyl naphthalene containing 2,6-
Rectifying through at least one pre-separation tower, the boiling point light component lower than 2,6-DIPN and boiling point ratio 2 are isolated, 6- bis- is different
The high heavy constituent of propyl group naphthalene, obtains the intermediate species containing 2,6-DIPN；The intermediate species of the diisopropyl naphthalene containing 2,6- enters
Enter progress levitation melting crystallization in first degree crystalline device, obtained magma I obtains 2,6- diisopropyls after the separation of solid-liquid separator I
Naphthalene coarse-grain and first degree crystalline mother liquor；2,6-DIPN coarse-grain enters in melting tank, and secondary crystallization is entered after heated fusing
In device carry out levitation melting crystallization, obtained magma II through solid-liquid separator II separation after obtain 2,6-DIPN crystal and
Secondary crystallization mother liquor, 2,6-DIPN crystal are returned in first degree crystalline device as final products, secondary crystallization mother liquor.
In above-mentioned technical proposal, the concentration of 2,6-DIPN is 5% in the mixed material containing 2,6-DIPN
~35%, more preferably 10~35%.
In above-mentioned technical proposal, the concentration of 2,6-DIPN is preferably in the intermediate species containing 2,6-DIPN
35%~60%, more preferably 35%~50%, in one embodiment of the invention, the concentration of 2,6-DIPN in intermediate species
For 40%.
In above-mentioned technical proposal, it is preferably 70% that solid-liquid separator I obtains 2,6-DIPN coarse-grain purity after separating
~99%, more preferably 80%~95%, in one embodiment of the invention, the purity of 2,6-DIPN coarse-grain is 85%.
In above-mentioned technical proposal, the purity of 2,6-DIPN crystal product is preferably 99%~99.9%, more preferably
For 99.5%~99.9%.
In above-mentioned technical proposal, the temperature of first degree crystalline device is preferably -15 DEG C~45 DEG C, more preferably -12 DEG C~40 DEG C,
In one embodiment of the invention, crystallization temperature is -12 DEG C.
In above-mentioned technical proposal, the temperature of secondary crystallizer is preferably 0 DEG C~69 DEG C, more preferably 20 DEG C~60 DEG C, this
Invent in an embodiment, crystallization temperature is 40 DEG C.
In above-mentioned technical proposal, the 2,6-DIPN crystal in preferred pair solid-liquid separator II is carried out using cleaning solution
Washing, more preferably cleaning solution is liquid 2,6-DIPN product.
In above-mentioned technical proposal, preferably at least some first degree crystalline mother liquor is returned in pre-separation tower.
In above-mentioned technical proposal, pre-separation first is carried out to the mixed material containing 2,6-DIPN, removes light, restructuring
Point, it is therefore an objective to the material concentration of crystallization process is improved, so as to improve the rate of recovery of crystallization process, and reduces energy consumption；Again to rich in
The intermediate species of 2,6-DIPN carries out two-stage suspension crystallization separation, obtains 2,6-DIPN crystal product, the skill
The benefit of art scheme is：1) two-stage crystallization all belongs to fusion-crystallization process, without adding solvent, without solvent recovery step, simplifies
Flow, reduce energy consumption；2) two-stage crystallization all belongs to suspension crystallization process, and mass-and heat-transfer effect is tied better than static in crystal growing process
Brilliant process, crystal purity is high, can operate continuously, and is adapted to industrialized large-scale production；3) rational crystallization temperature section is set,
First order crystallization process mainly ensures the rate of recovery, and second level crystallization process mainly ensures product purity, and two-stage crystallization process respectively has
Stress.It is reasonable that crystallization temperature section is set, and reduces energy consumption.
The production of 2,6-DIPN is carried out using the method for purification of the 2,6-DIPN of the present invention, first to containing 2,
The raw materials of 6- diisopropyl naphthalenes carries out pre-separation, then crystallizes to obtain 2,6-DIPN crystal by two-stage levitation melting and produce
Product, product purity reach 99.5~99.8%, and energy consumption reduces about 5~15%, achieves preferable technique effect.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of the method for purification of 2,6- diisopropyl naphthalenes of the present invention.
A-pre-separation tower, A '-pre-separation tower, B-first degree crystalline device, C-solid-liquid separator I, D-melting tank, E-bis-
Level crystallizer, F-solid-liquid separator II.
As described in Figure 1, rectifying of the mixed material 1 containing 2,6-DIPN through at least one pre-separation tower A, is isolated
The boiling point light component 2 lower than 2,6-DIPN and the boiling point heavy constituent 3 higher than 2,6-DIPN, obtain containing 2,6- bis-
The intermediate species 4 of isopropyl naphthalene；The intermediate species 4 of the diisopropyl naphthalene containing 2,6-, which enters in first degree crystalline device B, carries out levitation melting
Crystallization, obtained magma I 5 obtain 2,6-DIPN coarse-grain 6 and first degree crystalline mother liquor 7 after the C of solid-liquid separator I separation；
2,6-DIPN coarse-grain 6 enters in melting tank D, enters after heated fusing and levitation melting knot is carried out in secondary crystallizer E
Crystalline substance, obtained magma II 8 obtain 2,6-DIPN crystal 9 and secondary crystallization mother liquor 10 after the F of solid-liquid separator II separation,
2,6-DIPN crystal 9 is used as final products, and secondary crystallization mother liquor 10 is returned in first degree crystalline device B.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
The method of purification of 2,6- diisopropyl naphthalenes of the present invention.
As described in Figure 1, the mixed material 1 containing 2,6-DIPN, concentration containing 2,6-DIPN is 10%, through two
Platform pre-separation tower A and A ' rectifying, isolate the boiling point light component 2 lower than 2,6-DIPN and boiling point ratio 2,6- diisopropyls
The high heavy constituent 3 of base naphthalene, obtains the intermediate species 4 containing 2,6-DIPN；In the intermediate species 4 of the diisopropyl naphthalene containing 2,6-
The concentration of 2,6-DIPN is 40%, and levitation melting crystallization is carried out into first degree crystalline device B, and crystallization temperature is -12 DEG C,
Obtained magma I 5 obtains 2,6-DIPN coarse-grain 6 and first degree crystalline mother liquor 7,2,6- bis- after the C of solid-liquid separator I separation
The purity of isopropyl naphthalene coarse-grain 6 is 85%；2,6-DIPN coarse-grain 6 enters in melting tank D, and two are entered after heated fusing
Levitation melting crystallization is carried out in level crystallizer E, crystallization temperature is 40 DEG C, and obtained magma II 8 is after the F of solid-liquid separator II separation
2,6-DIPN crystal 9 and secondary crystallization mother liquor 10 are obtained, 2,6-DIPN crystal 9 is used as final products, purity
For 99.5%, secondary crystallization mother liquor 10 is returned in first degree crystalline device B.
【Embodiment 2】
The method of purification of 2,6- diisopropyl naphthalenes of the present invention.
As described in Figure 1, according to the operating condition of embodiment 1, wherein, the concentration of 2,6-DIPN in intermediate species 4
For 45%, the results are shown in Table 1 for it.
【Embodiment 3】
The method of purification of 2,6- diisopropyl naphthalenes of the present invention.
As described in Figure 1, according to the operating condition of embodiment 1, wherein, the concentration of 2,6-DIPN in intermediate species 4
For 50%, the results are shown in Table 1 for it.
【Embodiment 4】
The method of purification of 2,6- diisopropyl naphthalenes of the present invention.
As described in Figure 1, according to the operating condition of embodiment 3, wherein, the purity of 2,6-DIPN coarse-grain is 95%,
The results are shown in Table 1 for it.
【Comparative example 1】
Chinese patent " refined naphthalene faces the method that hydrogen isopropylation prepares 2,6- diisopropyl naphthalenes " (number of patent application：
200510134712.3) production methods of the 2,6- diisopropyl naphthalenes.
According to the operating condition of embodiment 3, using patent, " refined naphthalene faces the side that hydrogen isopropylation prepares 2,6-DIPN
The method of the method " 2,6-DIPN, the results are shown in Table 1 for it.
Table 1
| Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Intermediate species concentration (%) | 50 | 40 | 45 | 50 | 50 |
| First degree crystalline | Levitation melting crystallizes | Levitation melting crystallizes | Levitation melting crystallizes | Levitation melting crystallizes | Levitation melting crystallizes |
| First degree crystalline temperature (DEG C) | -15 | -12 | -10 | -15 | -12 |
| Coarse-grain purity (%) | 90 | 85 | 90 | 90 | 95 |
| Secondary crystallization | Static fusion-crystallization | Levitation melting crystallizes | Levitation melting crystallizes | Levitation melting crystallizes | Levitation melting crystallizes |
| Secondary crystallization temperature (DEG C) | 50 | 40 | 45 | 50 | 60 |
| The secondary crystallization time (h) | 30 | 6 | 6 | 5 | 5 |
| Product purity (%) | 99.5 | 99.6 | 99.6 | 99.7 | 99.8 |
| Energy consumption of unit product | Benchmark | - 5% | - 10% | - 12% | - 15% |
Claims (9)
1. a kind of method of purification of 2,6-DIPN, comprises the following steps：
A) rectifying of the mixed material containing 2,6-DIPN through at least one pre-separation tower, it is more different than 2,6- bis- to isolate boiling point
The low light component of propyl group naphthalene and the boiling point heavy constituent higher than 2,6-DIPN, obtain the middle groups containing 2,6-DIPN
Point；
B) intermediate species containing 2,6-DIPN, which enters, carries out levitation melting crystallization, obtained magma I in first degree crystalline device
2,6- diisopropyl naphthalenes coarse-grain and first degree crystalline mother liquor are obtained after the separation of solid-liquid separator I；
C) 2,6-DIPN coarse-grain enters in melting tank, enters after heated fusing in secondary crystallizer and carries out levitation melting
Crystallization, obtained magma II obtain 2,6-DIPN crystal and secondary crystallization mother liquor after the separation of solid-liquid separator II, and 2,
6- diisopropyl naphthalenes crystal is returned in first degree crystalline device as final products, secondary crystallization mother liquor.
2. the method for purification of 2,6-DIPN according to claim 1, it is characterised in that containing 2,6-DIPN
Mixed material in 2,6- diisopropyl naphthalenes concentration be 5%~35%.
3. the method for purification of 2,6-DIPN according to claim 1, it is characterised in that containing 2,6-DIPN
Intermediate species in 2,6- diisopropyl naphthalenes concentration be 35%~60%.
4. the method for purification of 2,6-DIPN according to claim 1, it is characterised in that after solid-liquid separator I separates
2,6- diisopropyl naphthalene coarse-grains purity is obtained as 70%~99%.
5. the method for purification of 2,6-DIPN according to claim 1, it is characterised in that 2,6-DIPN is brilliant
The purity of body product is 99%~99.9%.
6. the method for purification of 2,6-DIPN according to claim 1, it is characterised in that the temperature of first degree crystalline device
For -15~45 DEG C.
7. the method for purification of 2,6-DIPN according to claim 1, it is characterised in that the temperature of secondary crystallizer
For 0~69 DEG C.
8. the method for purification of 2,6-DIPN according to claim 1, it is characterised in that in solid-liquid separator II
2,6- diisopropyl naphthalene crystal washed using cleaning solution.
9. the method for purification of 2,6-DIPN according to claim 1, it is characterised in that at least part of one-level
Crystalline mother solution is returned in pre-separation tower.
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| CN201610831245.8A CN107840775B (en) | 2016-09-19 | 2016-09-19 | Method for purifying 2, 6-diisopropyl naphthalene |
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| CN201610831245.8A CN107840775B (en) | 2016-09-19 | 2016-09-19 | Method for purifying 2, 6-diisopropyl naphthalene |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5447542A (en) * | 1993-04-22 | 1995-09-05 | Hoechst Aktiengesellschaft | Process for separating and purifying substances by crystallization from the melt |
| CN1793088A (en) * | 2005-12-19 | 2006-06-28 | 鞍山科技大学 | Process for preparing 2.6-naphthalene diisoproply by essential naphthalene critical hydrogen isopropylation |
| CN101130478A (en) * | 2006-08-25 | 2008-02-27 | 北京石油化工学院 | Method for preparing high purity2, 6-diisopropyl naphthalene |
| KR20110077803A (en) * | 2009-12-30 | 2011-07-07 | 주식회사 효성 | Method of separation and purification of 1,5-dimethylnaphthalene |
-
2016
- 2016-09-19 CN CN201610831245.8A patent/CN107840775B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5447542A (en) * | 1993-04-22 | 1995-09-05 | Hoechst Aktiengesellschaft | Process for separating and purifying substances by crystallization from the melt |
| CN1793088A (en) * | 2005-12-19 | 2006-06-28 | 鞍山科技大学 | Process for preparing 2.6-naphthalene diisoproply by essential naphthalene critical hydrogen isopropylation |
| CN101130478A (en) * | 2006-08-25 | 2008-02-27 | 北京石油化工学院 | Method for preparing high purity2, 6-diisopropyl naphthalene |
| KR20110077803A (en) * | 2009-12-30 | 2011-07-07 | 주식회사 효성 | Method of separation and purification of 1,5-dimethylnaphthalene |
Non-Patent Citations (2)
| Title |
|---|
| 刘海岛等: "熔融结晶及其耦合技术研究的进展", 《化学工业与工程》 * |
| 王琰等: "混合二甲苯结晶分离的新工艺", 《石油化工》 * |
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