CN100364941C - Process for preparing 2.6-naphthalene diisoproply by essential naphthalene critical hydrogen isopropylation - Google Patents
Process for preparing 2.6-naphthalene diisoproply by essential naphthalene critical hydrogen isopropylation Download PDFInfo
- Publication number
- CN100364941C CN100364941C CNB2005101347123A CN200510134712A CN100364941C CN 100364941 C CN100364941 C CN 100364941C CN B2005101347123 A CNB2005101347123 A CN B2005101347123A CN 200510134712 A CN200510134712 A CN 200510134712A CN 100364941 C CN100364941 C CN 100364941C
- Authority
- CN
- China
- Prior art keywords
- naphthalene
- reaction
- isopropylation
- diisopropylnaphthalene
- dipn
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention discloses a method for preparing 2, 6-diisopropyl naphthalene from refined naphthalene by hydrogen isopropylation for improving the purity and the yield of 2, 6-diisopropyl naphthalene products. The method comprises three steps of the hydrogen isopropylation of refined naphthalene, the separating purification of 2, 6-diisopropyl naphthalene and the cyclic utilization of isopropylnaphthalene. The continuous multi-kettle average conversion of the hydrogen isopropylation is larger than 90%, and the average content of the 2, 6-diisopropyl naphthalene in a product is larger than 35%; 2, 6-diisopropyl naphthalene crystals with the purity which is not smaller than 99% can be obtained after the isopropylation product is separated and purified; more target products are obtained after other isopropyl naphthalene mixtures are cyclically used. The 2, 6-diisopropyl naphthalene is the precursor of 2, 6-naphthalenedicarboxylic acid which is an important organic macromolecular monomer. The 2, 6-naphthalenedicarboxylic acid is used for preparing a high polymer of a thermotropic liquid crystal and new generational polyester poly naphthalenedicarboxylic acid ethyl diester (PEN).
Description
Technical field
The present invention relates to the preparation method of high polymer monomer, especially a kind ofly face hydrogen isopropylation preparation 2, the method for 6-diisopropylnaphthalene by refined naphthalene
Background technology
2, (2,6-Diisopropylnaphthalene is called for short 2 to the 6-diisopropylnaphthalene, 6-DIPN) is important organic polymer monomer 2, the precursor of 6-naphthalic acid.The latter is used to prepare high performance thermotropic liquid crystal superpolymer and polyester Polyethylene Naphthalate of new generation (PEN).PET compares with general purpose polyester, PEN has better physical and mechanical properties, resistance toheat, gas barrier property and ultra-violet radiation resisting performance, be used to make ultra-thin video tape base, F class B insulation film, electronic component and food drug packages film etc., application prospect is very wide.
The naphthalene isopropylation is consecutive reaction, and an isopropyl naphthalene (MIPN), diisopropylnaphthalene (DIPN) and many isopropyl naphthalenes (PIPN) are a large amount of with depositing in the product.As reacting with traditional Friedel-Crafts catalyst, target product 2,6-DIPN only account for about 39%～40% and (promptly select form quotient in all DIPN, massfraction), 2,6-DIPN and 2, the mol ratio of 7-DIPN is near 1, and both boiling points (b.p.) only differ from 2 ℃, separation difficulty.Before and after the nineties in 20th century, people bring into use the shape-selective catalyst zeolite molecular sieve to carry out the decalin base reaction with the control response location, and will isolate 2 in the resultant, other isopropyl naphthalene recycle that obtains behind the 6-DIPN.U.S. Pat P4950824 has reported the preparation 2 that a kind ofly comprises isopropylation, transalkylation and distillation, step such as separates, the method for 6-DIPN.Owing in isopropylation, adopted non-shape-selective catalyst, make 2, the form quotient of selecting of 6-DIPN reduces greatly, also only brings up to 40% by transalkylation, causes 2, and the productive rate of 6-DIPN has only 23%, 2,6-/2,7-DIPN mol ratio is near 1, and effect is very undesirable.U.S. Pat P5003120 has reported improved method, with shape-selective catalyst mordenite catalysis isopropylation, has improved 2, and 6-DIPN selects form quotient and 2,6-/2,7-DIPN mol ratio.But in transalkylation process, the transformation efficiency that DIPN and naphthalene reaction generate MIPN is less than 60%, and reaction conditions also need be adjusted.The easy coking and deactivation of mordenite, the influence reaction is carried out smoothly, and this patent does not propose innovative approach.In addition, to 2, the method for purification of 6-DIPN is only mentioned fractional crystallization, does not specify process, so last purity and the yield of target product is all unclear.
Summary of the invention
The object of the present invention is to provide a kind of is raw material with industrial refined naphthalene and propylene, preparation 2, the method for 6-diisopropylnaphthalene, the purity and the yield of raising product.
Content of the present invention comprises three steps, promptly refined naphthalene face hydrogen isopropylation, 2, the 6-diisopropylnaphthalene separates purifies and the recycle of isopropyl naphthalene.Refined naphthalene or MIPN face the hydrogen isopropylation with propylene in the presence of shape-selective catalyst.Products therefrom is divided into behind atmospheric and vacuum distillation based on the low boiler cut of unreacted naphthalene and MIPN, DIPN cut and based on three and the PIPN high boiling fraction of tetra isopropyl naphthalene.Isolate from the DIPN mixed solution by cooling, crystallization highly purified 2, the 6-DIPN crystal.Again remaining other DIPN and above-mentioned PIPN are mixed with the unreacted naphthalene, in the presence of solid acid catalyst, carry out transalkylation reaction, generate enrichment MIPN material.The MIPN that the latter and distillation obtain mixes, and further isopropylation can obtain more multiple goal product.Thereby set up the process recycling that reclaims component.Through repeatedly circulation, the utilization ratio of refined naphthalene improves greatly, in fact almost can all be converted into 2,6-DIPN.
Method provided by the invention is described in detail in detail below:
One, refined naphthalene faces the hydrogen isopropylation
Add refined naphthalene and catalyzer in stainless steel autoclave, catalyst levels accounts for 5～7% of refined naphthalene amount.Use H
2Catching up with most air and keeping the hydrogen first pressing is 0.4～0.6MPa.Being heated to temperature of reaction is 270 °～300 ℃, under agitation feeds the propylene of purity＞99.5%.Refined naphthalene is 1: 1.8～2.0 with the mol ratio of propylene; Reaction times is 6～8 h.Reaction finishes to take out immediately reactant, rapidly cooling.Reaction product is filtered, and filtrate is carried out gas-chromatography (GC) analysis, and the catalyzer that leaches is used for next still reaction.
In above-mentioned reaction system, catalyst system therefor is synthetic h-mordenite (HM), and shape selectivity is good, but easy inactivation.Major cause is that the polycondensation of decalin base product is dehydrogenated to coke, has covered the acid site of HM and has stopped up its one-dimensional channels.If can slow down dehydrogenation, just might reduce the deactivation rate of catalyzer.Therefore the isopropylation of naphthalene is carried out than favourable under the nitrogen atmosphere under the hydrogen atmosphere.HM removes Cl at 450 °～500 ℃ through steam dealuminzation, weak acid scrubbing, washing
-After, oven dry promptly can be used for above-mentioned reaction in 4～6 hours 450 °～500 ℃ following calcinations again, was labeled as SDHM.
Two, 2, the 6-diisopropylnaphthalene separates purifies
Naphthalene isopropylation product is the mixture of various isopropyl naphthalenes.At first need product is carried out rectifying separation, cut into the different various components of alkylation degree, then from the DIPN cut further with 2,6-DIPN separates purification.
Naphthalene isopropylation product filtrate is carried out air distillation, successively obtain naphthalene and MIPN and (comprise the low boiler cut of α-IPN and β-IPN).Carry out rectification under vacuum again, can obtain the DIPN mixed fraction (wherein 2,6-DIPN content is between 50-60%) of content＞90% and content＞95% based on three and the PIPN high boiling fraction of tetra isopropyl naphthalene.Remaining a small amount of residue.
Above-mentioned DIPN cut is cooled to-18 °～-20 ℃, makes 2, the 6-DIPN sufficient crystallising comes out.Can obtain 2 of purity＞90% through centrifugation, the thick product of 6-DIPN, filtrate is with 2,7-DIPN is main mixture, recyclable utilization.
With thick 2, pour into behind the 6-DIPN crystal melting and carry out static fusion-crystallization in the classifying crystallizer.By slow cooling crystallization is separated out, and under-15 °～-20 ℃ low-temperature conditions sufficient crystallising.Heat up gradually then and make crystal layer sweating (partial melting discharge impurity).The sweating process is the committed step of purifying, and should slowly carry out.At last temperature is brought up to 2, more than the 6-DIPN fusing point (69 ℃), make it fine melt, obtain the crystal of purity＞99%.The melt of the purity that obtains in the sweating process≤99% can repeat above-mentioned " crystallization-sweating-fine melt " process and obtain again 〉=99% crystal.Above-mentioned crystallization and purification method can be carried out in order repeatedly crystal refining by the melt to the different concns level in same crystallizer, not only improved the purity of product but also increased yield, and equipment is simple, easy to operate.
Three, the recycle of isopropyl naphthalene
With the isopropylation product in unreacted naphthalene, PIPN cut and the DIPN cut mother liquor and static fusion-crystallization process behind freezing partial crystallization that rectifying separation is come out≤35 ℃ sweating liquid mixing, in the presence of solid acid catalyst, carry out transalkylation reaction, generate the material of enrichment MIPN.The latter and propylene reaction can obtain 2 again, 6-DIPN.Therefore the recycling of above these components to the utilization ratio that improves raw naphthalene material, reduce production costs extremely important.
Two above sec.-propyls (have the naphthalene nucleus of four sec.-propyls less) are arranged on the naphthalene nucleus in DIPN and the PIPN molecule, and intermolecular transalkylation reaction can take place with naphthalene in them, thereby obtains MIPN.Reaction also needs acid catalysis, need not select shape, therefore can use amorphous aluminum silicide.The factor that influences transalkylation reaction mainly contains mol ratio (IP/N), temperature of reaction, reaction times and the catalyst consumption etc. of sec.-propyl and naphthyl in the system.IP in the IP/N mol ratio refers to the sec.-propyl mole number on all isopropyl naphthalenes in the reactant, and N refers to the mole number summation of naphthalene and all isopropyl naphthalenes.Suitable IP/N is 0.5～1: 1, can add fresh refined naphthalene in case of necessity.Temperature of reaction is 300 °～350 ℃, and the reaction times is 4～6 h, and catalyzer amorphous aluminum silicide consumption is 3～5% of a reactant weight.Be reflected under the nitrogen atmosphere and carry out, pressure influence is little, N
2First pressing maintains 0.2～0.4MPa.Under these conditions, the transformation efficiency of PIPN and DIPN is respectively greater than 95% and 74%.Their transformation efficiencys in blending ingredients are low slightly, but also near 90% and 70%.In the equilibrium products that obtains, the content of MIPN is all above 40%, and β-/ratio 〉=10 of α-MIPN, promptly product is the material of enrichment β-MIPN, and this generates β to next step isopropylation, and β-product is highly beneficial.
The present invention compares with class methods with existing, and its beneficial effect is embodied in:
Refined naphthalene face the continuous many stills average conversion of hydrogen isopropylation＞90%, in the product 2,6-DIPN average content＞35%, 2,6-DIPN/DIPN＞63%, 2,6-DIPN/2,7-DIPNmol is than＞2.2;
2. the isopropylation product can obtain 2 of purity 〉=99% after separating purification, the 6-DIPN crystal, and productive rate is not less than 87%;
3. other isopropyl naphthalene mixtures are after a recycle, and the utilization ratio of refined naphthalene has improved 47%.
Embodiment
Below in conjunction with embodiment the present invention is done further statement.
1. refined naphthalene faces the hydrogen isopropylation
In the 0.5L stainless steel autoclave, add 100g coal tar refined naphthalene and 7g catalyst activated SDHM, use H
2Purging is also kept pressure at 0.4MPa.The heating high-pressure still starts stirring, when rising to 275 ℃, open micro pump in still by C
3H
6/ C
10H
8=1.8: 1 (mol ratio) input propylene.Stopped reaction after 7 hours, the sucking-off reaction mass leaches that still uses continuously under the catalyst supply, filtrate is carried out GC analyze.Because above reaction needed is carried out 7 stills continuously, catalyzer has loss inevitably when filtering.For fear of the catalytic amount minimizing reaction is exerted an influence, play the every still of the 7th still from the 2nd still and append 0.5g SDHM, under the situation that every still catalytic amount remains unchanged, observe the effect of isopropylation.More than the GC data of seven stills list in table 1.
The GC data (mass percent) of the continuous 7 still isopropylations of refined naphthalene under the table 1. hydrogen atmosphere
| Run NO. | Conv. (％) | Product Distribution(％) | 2，6-DIPN Yield (％) | DIPN Yield (％) | 2，6-/ 2，7- | 2，6-/ DIPN (％) | ||
| IPN | DAN | PAN | ||||||
| 1 2 3 4 5 6 7 Aver | 96.51 94.34 91.51 91.21 91.97 92.17 90.19 92.56 | 24.47 29.93 34.07 34.12 34.00 34.75 37.44 32.68 | 64.22 62.23 59.16 59.20 60.20 59.93 57.65 60.37 | 10.56 7.86 6.79 6.70 5.81 5.32 4.99 6.86 | 36.13 36.49 35.14 35.44 35.84 35.48 34.08 35.52 | 61.78 58.56 53.81 53.62 54.94 54.97 51.55 55.60 | 1.79 2.11 2.40 2.44 2.33 2.24 2.39 2.24 | 58.37 62.30 65.31 66.09 65.23 64.55 66.11 63.99 |
Annotate: Run No.: reaction times Conv.: naphthalene transformation efficiency Product Distribution: products distribution
DAN: dialkyl group naphthalene PAN: many alkylnaphthalenes Yield: yield Aver: mean value
As shown in Table 1, the naphthalene transformation efficiency of continuous 7 stills has only reduced by 6.32%, 2 under the hydrogen atmosphere, and the 6-DIPN yield has reduced by 2.05%.And under the nitrogen atmosphere, react 7 stills by similarity condition, but reduced by 22.4% and 15.62% relatively.The carbon deposit speed that this explanation hydrogen can effectively slow down catalyzer is carried out reacting balance.
2.2 the 6-diisopropylnaphthalene separates purifies
With 2 of purity＞90%, 6-DIPN coarse-grain heat fused is injected classifying crystallizer.Temperature with low temperature thermostat bath control heat-transfer medium is slowly lowered the temperature crystallizer, and is complete until-18 °～-20 ℃ crystallizations.The sweating that slowly heats up subsequently, despumation.Collect melt from 35 ℃～68 ℃ by different temperature intervals, obtain the crystal of different concns level.Be warming up at last more than 69 ℃, make the crystallizing layer fine melt, at this moment crystal purity＞99%.The impure melt that the differing temps section is obtained has been isolated straight product again by said process crystal refining once more again, and productive rate is significantly improved.Experimental data sees Table 2.
Table 2. obtains the productive rate of pure product from 2 of different content among the 6-DIPN
| The source | 2,6-DIPN content/% | Crystal yield/% of 〉=99% | Crystal yield/% of 〉=99.5% |
| Raw material sweating melt sweating melt sweating melt sweating melt | 96.42 98.35 95.77 90.94 83.02 | 63.20 75.99 51.63 37.34 34.24 | 63.20 75.99 37.09 0 0 |
Content be 96～97% 2, the 6-DIPN material can only obtain the pure product of yield about 63% through primary crystallization.Underproof melt once more after the crystallization, has been isolated 2 of purity 〉=99% from the 153.1g raw material, 6-DIPN 133.1g, productive rate has brought up to 86.94%.
3. the recycle of isopropyl naphthalene
(1) transalkylation reaction of PIPN and naphthalene
Get the isopropylation product through the PIPN of rectifying gained cut 45g.It consists of trialkyl naphthalene (TriAN) 6.4%, triisopropyl naphthalene (TriIPN) 80.4%, tetraalkyl naphthalene (TetAN) 10.3% and DIPN 2.6% (former three general name PIPN).Add naphthalenes in IP/N mol ratio=0.9: 1 and 0.8: 1 two kinds of ratio, be mixed with two parts of mixtures.Each dropped into the amorphous aluminum silicide of mixture weight 5% and makes catalyzer, 325 ℃ of reactions 5 hours.Reaction result sees Table 3.
The product of table 3.PIPN mixture and naphthalane group-transfer is formed
| IP/N mol ratio | Naph. (％) | MIPN (％) | DAN (％) | DIPN (％) | TriAN (％) | TriIPN (％) | TetAN (％) | Conv. of PIPN (％) | |
| β- | α- | ||||||||
| 0.8∶1 0.9∶1 | 29.8 26.1 | 39.3 40.6 | 3.9 3.7 | 2.8 2.4 | 19.8 22.4 | 1.4 1.7 | 1.2 1.8 | 0 0.5 | 97.3 95.9 |
When beginning reaction, PIPN and naphthalene generate DIPN earlier, and the latter generates MIPN with naphthalene again, wherein β-/α-mol is than 〉=10.By data in the table 2 as can be known, the easy and naphthalene generation transalkylation reaction of PIPN.IP/N mol helps PIPN and transforms than little.
(2) transalkylation reaction of diisopropylnaphthalene and naphthalene
Get the mother liquor 50g behind the partial crystallization, it consists of DIPN 94.9%, MIPN 0.93% and PIPN4.14%.DIPN comprises 2, and 6-DIPN 32.2%, 2, and 7-DIPN 54.2%.Press IP/N mol and add naphthalene, and add the amorphous silicon Al catalysts of mixture weight 5% than=0.9: 1.After 4 hours, leach catalyzer 325 ℃ of reactions.Successive reaction three stills.Filtrate is analyzed with GC, and data are listed in table 4.
The product of table 4.DIPN mixture and naphthalane group-transfer is formed
| Run NO. | Naph. (％) | MIPN (％) | DAN (％) | DIPN (％) | PIPN (％) | 2，6-DIPN (％) | 2，7-DIPN (％) | Conv. of DIPN (％) | |
| β- | α- | ||||||||
| 1 2 3 Aver | 29.0 29.3 28.1 28.8 | 40.3 38.0 36.9 38.4 | 3.9 3.8 3.6 3.8 | 1.57 1.02 0.86 1.15 | 21.6 24.0 27.3 24.3 | 2.00 2.68 3.15 2.61 | 9.39 10.1 11.3 10.3 | 8.53 10.2 11.6 10.1 | 77.3 74.7 71.3 74.4 |
Compare with table 3, the transformation efficiency of DIPN is lower than PIPN, and it is easier to illustrate that PIPN and naphthalene generate DIPN, and the reaction of DIPN and naphthalene generation MIPN is limited by reversible equilibrated, and it is difficult to transform.But the MIPN that generates amount is very approaching, all greater than 40%.Relatively in raw material and the product 2,6-DIPN and 2, the variation of 7-DIPN content can find out 2,7-DIPN is than 2, the easier MIPN that changes into of 6-DIPN.β among the MIPN-/α-mol is than 〉=10, generates 2,6-DIPN when helping further isopropylation.
Claims (1)
1. refined naphthalene faces hydrogen isopropylation preparation 2, and the method for 6-diisopropylnaphthalene is characterized in that this method comprises following three steps:
One, refined naphthalene faces the hydrogen isopropylation
Add refined naphthalene and catalyzer in stainless steel autoclave, catalyst levels accounts for 5～7% of refined naphthalene amount, uses H
2Catching up with most air and keeping the hydrogen first pressing is 0.4～0.6MPa, being heated to temperature of reaction is 270 °～300 ℃, under agitation feed the propylene of purity＞99.5%, refined naphthalene is 1: 1.8～2.0 with the mol ratio of propylene, reaction times is 6～8h, reaction finishes to take out immediately reactant, cooling rapidly, reaction product is filtered, filtrate is carried out gas chromatographic analysis, and the catalyzer that leaches is used for next still reaction, in above-mentioned reaction system, catalyst system therefor is the synthetic h-mordenite, and this catalyzer is before use through following processing: at 450 °～500 ℃ through the steam dealuminzation, weak acid scrubbing, washing removes Cl
-After, oven dry is again 450 °～500 ℃ following calcinations 4～6 hours;
Two, 2, the 6-diisopropylnaphthalene separates purifies
Refined naphthalene is faced hydrogen isopropylation product filtrate carry out air distillation, successively obtain a naphthalene and an isopropyl naphthalene low boiler cut, carry out rectification under vacuum again, can obtain the diisopropylnaphthalene mixed fraction of content＞90% and content＞95% based on three and many isopropyl naphthalenes high boiling fraction of tetra isopropyl naphthalene, above-mentioned diisopropylnaphthalene cut is cooled to-18 °～-20 ℃, make 2,6-diisopropylnaphthalene sufficient crystallising comes out, can obtain 2 of purity＞90% through centrifugation, the thick product of 6-diisopropylnaphthalene, filtrate is with 2, the 7-diisopropylnaphthalene is main mixture, with thick 2, pour into behind the 6-diisopropylnaphthalene crystal melting and carry out static fusion-crystallization in the classifying crystallizer, by slow cooling crystallization is separated out, and under-15 °～-20 ℃ low-temperature conditions sufficient crystallising, heat up gradually then and make the crystal layer sweating, at last temperature is brought up to 2, more than the 6-isopropyl naphthalene fusing point, make it fine melt, obtain the crystal of purity 〉=99%, the melt of the purity that obtains in the sweating process＜99% repeats above-mentioned " crystallization-sweating-fine melt " process, obtains the crystal of purity 〉=99% again;
Three, the recycle of isopropyl naphthalene
To face the unreacted naphthalene that hydrogen isopropylation product comes out through rectifying separation, in many isopropyl naphthalenes cut and the diisopropylnaphthalene cut mother liquor and static fusion-crystallization process behind freezing partial crystallization≤35 ℃ sweating liquid mixing, in the presence of the catalyzer amorphous aluminum silicide, carry out transalkylation reaction, generate the material of enrichment one isopropyl naphthalene, the latter and propylene reaction get back 2, the 6-diisopropylnaphthalene, transalkylation reaction conditions is: the IP/N mol ratio is 0.5～1: 1, IP in the IP/N mol ratio refers to the sec.-propyl mole number on all isopropyl naphthalenes in the reactant, N refers to the mole number summation of naphthalene and all isopropyl naphthalenes, temperature of reaction is 300 °～350 ℃, reaction times is 4～6h, catalyst levels is 3～5% of a reactant weight, be reflected under the nitrogen atmosphere and carry out N
2First pressing maintains 0.2～0.4MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101347123A CN100364941C (en) | 2005-12-19 | 2005-12-19 | Process for preparing 2.6-naphthalene diisoproply by essential naphthalene critical hydrogen isopropylation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101347123A CN100364941C (en) | 2005-12-19 | 2005-12-19 | Process for preparing 2.6-naphthalene diisoproply by essential naphthalene critical hydrogen isopropylation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1793088A CN1793088A (en) | 2006-06-28 |
| CN100364941C true CN100364941C (en) | 2008-01-30 |
Family
ID=36804754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101347123A Expired - Fee Related CN100364941C (en) | 2005-12-19 | 2005-12-19 | Process for preparing 2.6-naphthalene diisoproply by essential naphthalene critical hydrogen isopropylation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100364941C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130478B (en) * | 2006-08-25 | 2013-04-10 | 北京石油化工学院 | Method for preparing high purity 2, 6-diisopropyl naphthalene |
| CN103539624B (en) * | 2012-07-12 | 2015-10-21 | 中国石油化工股份有限公司 | The method of decalin base |
| CN103755661B (en) * | 2014-02-08 | 2016-09-21 | 山东省农药科学研究院 | A kind of separation and refining method of 2-chloro-5-chloromethyl thiazole |
| CN106608810A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Method for refining 2,6-diisopropylnaphthalene |
| CN106608809A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Separation and purification method for 2,6-diisopropylnaphthalene |
| CN106831295B (en) * | 2015-12-03 | 2020-08-07 | 中国石油化工股份有限公司 | Production method of 2, 6-diisopropyl naphthalene |
| CN107840775B (en) * | 2016-09-19 | 2020-12-01 | 中国石油化工股份有限公司 | Method for purifying 2, 6-diisopropyl naphthalene |
| CN107840776B (en) * | 2016-09-19 | 2021-02-09 | 中国石油化工股份有限公司 | Method for separating and preparing high-purity 2,6-diisopropyl naphthalene |
| CN114591135B (en) * | 2022-03-24 | 2023-09-15 | 中国科学院大连化学物理研究所 | Method for preparing 2, 6-diisopropyl naphthalene by naphthalene shape-selective alkylation |
| CN114558611A (en) * | 2022-03-24 | 2022-05-31 | 中国科学院大连化学物理研究所 | Catalyst, preparation method thereof and application thereof in preparation of 2, 6-diisopropyl naphthalene |
| CN114736089B (en) * | 2022-03-24 | 2023-08-08 | 中国科学院大连化学物理研究所 | Method for producing 2, 6-diisopropyl naphthalene |
-
2005
- 2005-12-19 CN CNB2005101347123A patent/CN100364941C/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 萘异丙基化制备2，6-二异丙基萘及其择形催化研究[D]. 张晓辉.鞍山钢铁学院化学化工学院. 1997 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1793088A (en) | 2006-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100364941C (en) | Process for preparing 2.6-naphthalene diisoproply by essential naphthalene critical hydrogen isopropylation | |
| CN101573314B (en) | Low temperature process for recovering and producing para-xylene and heat exchange network therefore | |
| EP0812813A2 (en) | Process for preparing dialkylnaphthalenes | |
| CN110937968B (en) | Device and process for producing aromatic hydrocarbon product | |
| KR100338424B1 (en) | Process for preparing 2,6-dialkylnaphthalene | |
| EP0889016B1 (en) | Process for preparing dialkylnaphthalene | |
| KR100721442B1 (en) | A method for obtaining 2,6-dimethylnaphthalene using isomerization and crystallization processes | |
| KR101520523B1 (en) | Apparatus and method for producing cumene for low consumption of energy | |
| CN110937973B (en) | Device and process for producing paraxylene | |
| CN110937972B (en) | Production device and process of p-xylene | |
| US6018087A (en) | Isomerization of dimethylnaphthalene to produce 2,6-dimethylnaphthalene | |
| CN1962577A (en) | Method for producing propylene ethane by catalytic cracking carbon-containing olefin | |
| CN104109065B (en) | A kind of method by benzene and methanol alkylation dimethylbenzene | |
| CN102701899A (en) | Energy conservation and emission reduction process for producing p-xylene through alkylation of tolylcarbinol | |
| US11236028B2 (en) | Production and use of 3,4′ and 4,4′-dimethylbiphenyl isomers | |
| CN115745750B (en) | O-phenylphenol, preparation method and application thereof | |
| CN114736089B (en) | Method for producing 2, 6-diisopropyl naphthalene | |
| RU2786739C1 (en) | Method for producing 3,5-xylenol | |
| CN112194549B (en) | Device and process for producing aromatic hydrocarbon product | |
| CN87101646A (en) | Use a kind of isomerization/transalkylation section of economic benefits and social benefits and produce dimethylbenzene | |
| CN111187133B (en) | Method for preparing p-xylene and co-producing ethylbenzene and propylene from methanol and/or dimethyl ether and benzene | |
| CN110937974B (en) | Production device and process of p-xylene | |
| CN101668723A (en) | Process for selective aromatics disproportionation with increased conversion | |
| WO2020018253A1 (en) | Preparation and purification of dimethylbiphenyl compounds | |
| CN114716293A (en) | Process system and process method for increasing yield of p-xylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080130 Termination date: 20111219 |