CN1197055A - 2,6-isopropyl-phenol preparing method - Google Patents
2,6-isopropyl-phenol preparing method Download PDFInfo
- Publication number
- CN1197055A CN1197055A CN 98112478 CN98112478A CN1197055A CN 1197055 A CN1197055 A CN 1197055A CN 98112478 CN98112478 CN 98112478 CN 98112478 A CN98112478 A CN 98112478A CN 1197055 A CN1197055 A CN 1197055A
- Authority
- CN
- China
- Prior art keywords
- phenol
- tower
- diisopropyl
- temperature
- diisopropyl phenol
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing 2,6-isopropylphenol includes alkylating reaction of phenol on propylene under existance of phenol aluminium as catalyst at 220-290 deg.C and 1.5-2.5 MPa and two-tower vacuum rectification separation, and features high product purity (99.5%) and output rate (over 82%). A formula for keeping 2,6-isopropylphenol stable in storage procedure is disclosed.
Description
The present invention relates to the manufacture method of alkylphenol, is raw material with phenol and propylene especially, is catalyzer with phenol aluminium, and industrialization makes 2, the method for 6-diisopropyl phenol.
2, the 6-diisopropyl phenol is a kind of broad-spectrum chemical, content be 99.5% 2, the 6-diisopropyl phenol can be used for the intravenous anesthesia agent, from 1986 since Britain comes out, at present more than 40 country's listings, this medicine has accounted for 50% of surgical anesthesia medicine in English, method two countries, have effect steadily, rapidly, clear-headed fast, do not have dependence, do not have characteristics such as obviously accumulate, domestic application still is in the development phase.2, the 6-diisopropyl phenol can also be used for Chemicals such as synthetic perfume, and its application prospect is very wide.At present domestic also do not have industrialization to make 2, the method for 6-diisopropyl phenol.
The object of the present invention is to provide a kind of being raw material with phenol and propylene, with phenol aluminium is catalyzer, and industrialization is made purity and reached 2 more than 99.5%, the method for 6-diisopropyl phenol, and wherein add a certain amount of oxidation inhibitor or stopper, to keep stay in grade.
The objective of the invention is to realize by the following technical solutions: with phenol and propylene is raw material, is catalyzer with phenol aluminium, and the third phenol alkylated reaction, alkylated product are again through the secondary rectification under vacuum, and its process mainly comprises:
(1) phenol and propylene are with 1.2～2.6: 1 mole proportioning, with phenol aluminium peg-raking catalyst, phenol aluminium is 0.5～5: 100 with respect to the mass ratio of phenol, in temperature is 220～290 ℃, pressure is under 1.5～2.5MPa, 1.5～4.5 hours reaction times, the alkylation of phenol reaction, get 2,6-diisopropyl phenol content is 30%～60%, phenol 20%～30%, o-isopropyl phenol 10%, 2, other many alkylphenols such as 4-diisopropyl phenol, cumylphenol account for the first distillate of 10% alkylphenol mixture, again
(2) it is 180～260 ℃ in tower still temperature, tower top temperature is 100～140 ℃, the top vacuum degree is under 0.01～0.08MPa condition first distillate to be carried out the first tower rectification under vacuum, separate 2, the impurity (2 that 6-diisopropyl phenol boiling point is following, 242 ℃ of 6-diisopropyl phenol boiling points), one cat head is adopted liquid and is mainly contained phenol, 2,6-diisopropyl phenol content only is 0～5%, circulation enters the alkylation reaction still, it is 190～270 ℃ in tower still temperature that still is adopted liquid (low boiling mixture content is 0～1.0%), tower top temperature is 150～190 ℃, and the top vacuum degree is to carry out the second tower rectification under vacuum under 0.01～0.08MPa, with selected pressure condition corresponding 2, under the 6-diisopropyl phenol boiling point, from overhead collection 2,6-diisopropyl phenol cut, its purity reaches 99.5%, 2,6-diisopropyl phenol yield is more than 82%, and boiling point is than 2, and the component that the 6-diisopropyl phenol is high flows out from the tower still.Be in the rectification under vacuum process, the tower internal pressure can be an a certain pressure selected in the above-mentioned pressure range, also can gradually change in above-mentioned pressure range on demand.Remove boiling point in the rectifying earlier than 2, the component that the 6-diisopropyl phenol is low collects 2 then, the 6-diisopropyl phenol, and than 2, the component that the 6-diisopropyl phenol is heavy is discharged at the bottom of two towers.In whole rectifying process, control of reflux ratio is in 1～20 scope.
The rectifying tower that described rectification under vacuum process is adopted can be a packing tower, also can be the tower of sieve-tray tower or other type, and the material of rectifying tower can be carbon steel or other available materials, but stainless steel preferably.
Described rectifying can be the gap, also can be successive, and whole rectifying process needs to carry out under secluding air or nitrogen protection.
The present invention's technical scheme preferably is: the alkylation of phenol temperature of reaction is 240～260 ℃, pressure is 1.6～1.8MPa, i.e. phenol heat temperature raising to 240～260 ℃, logical again propylene, at pressure is under 1.6～1.8MPa alkylated reaction to take place, and operational condition was kept 1.5～4.5 hours during reaction.Promptly do not rise when temperature of reaction, and system pressure is when beginning to go up, reaction to terminal.Reaction temperature is spent low, and raw material can not complete reaction, and the too high then by product of temperature of reaction increases, and 2,6-diisopropyl phenol speed reduces; Hypotony, level of response are not high, and hypertonia increases unsafe factor.
The present invention's technical scheme preferably can also be: alkylated product is through the secondary rectification under vacuum, and tower still temperature is 200～220 ℃ during a tower rectifying, and tower top temperature is 100～120 ℃, and the top vacuum degree is 0.02～0.06MPa; Tower still temperature is 220～260 ℃ during two tower rectifying, and tower top temperature is 160～180 ℃, and the top vacuum degree is 0.02～0.06MPa.The temperature of rectifying tower, pressure must change in the control condition scope, otherwise Tower System can't be operated balance, do not have utmost point end product to collect.
The raffinate that the present invention also can utilize the 2-isopropyl-phenol to produce is raw material, through the secondary rectification under vacuum, separates making 2, the 6-diisopropyl phenol.2-isopropyl-phenol raffinate is meant the raffinate after the 2-isopropyl-phenol is removed in the first distillate separation after the 2-isopropyl-phenol synthesizes, include 5% o-isopropyl phenol, 3%2,4-diisopropyl phenol, 50%2,6-diisopropyl phenol, 1～3% cumylphenol, many alkylates of about 40%.
The catalyzer that alkylated reaction of the present invention adopted can be selected from the set of following catalyzer:
(a) acid catalyst: as hydrofluoric acid, sulfuric acid, phosphoric acid or other organic acids;
(b) amberlite ester catalyst is as sulfonated phenylethylene and divinyl multipolymer etc.;
(c) alumina catalyst is as Y-Al
2O
3, oxygen handles Al
2O
3, CaSO
4Deng vitriol and Al
2O
3The blended composite catalyst;
(d) phenates catalyzer is as Al, Mg, Fe, Zn, the As salt of phenol; But preferably the aluminium salt of phenol, i.e. phenol aluminium.
Especially, 2, the 6-diisopropyl phenol very easily absorbs water, oxidation, therefore product adds a certain amount of oxidation inhibitor or stopper in wrapping process, can overcome 2 significantly, the polymerization of 6-diisopropyl phenol and oxidation, guarantee 2,6-diisopropyl phenol quality in 2 years does not produce obvious variation.The consumption of oxidation inhibitor or stopper is with respect to 2, and 6-diisopropyl phenol mass ratio is 0.01～1.0: 100.Oxidation inhibitor that is adopted or stopper are selected from the set of following substances or wherein a kind of or surpass a kind of mixture: acidic cpd, complex compound or reductibility compound.As phosphoric acid, tartrate, citric acid and ammonium salt thereof, phosphorous acid and its esters and ester class, rosin Amine D derivative, amino acid, pyrogallol, hydrazine hydrate or sodium bisulfite etc., best with the preservation and effect of oxidation inhibitor pyrogallol or sodium bisulfite.
It is simple that the present invention has technology, and flow process is short, and facility investment is few, the quality product height, and characteristics such as stay in grade, 2 of manufacturing, 6-diisopropyl phenol content is 99.5%, yield is higher than 82%, is domestic project of plugging a gap.
The present invention is described in further detail below by specific embodiment:
Embodiment 1:
900kg phenol is dropped in the reactor, and heat temperature raising to 130 ℃ adds aluminum shot 0.5kg then, stops to heat up, and the limit is stirred and reached 0.8MPa until pressure.Begin logical propylene, exothermic heat of reaction keeps 260 ℃ of extremely logical alkene 300kg to finish.Through gas chromatographic analysis 2,6-diisopropyl phenol 54.1%.Above-mentioned product is 190 ℃ of still temperature, and 138 ℃ of top temperature are carried out a tower rectifying under the top vacuum degree 0.06MPa, and still is adopted liquid through gas chromatographic analysis 2,6-diisopropyl phenol 70.5%.Continuation is 210 ℃ of still temperature, and 149 ℃ of top temperature are carried out two tower rectifying under the top vacuum degree 0.08MPa, and 6-diisopropyl phenol 99.6% is adopted through gas chromatographic analysis 2 on the top.2,6-diisopropyl phenol yield 83.5%.
Embodiment 2～9:
Operation steps is with embodiment 1, its process control condition, reactant ratio, quality product and 2, and 6-diisopropyl phenol yield sees table 1, table 2 for details.
Embodiment 10:
With known content is 99.66%, outward appearance is the water white transparency homogeneous liquid, colourity be 20 (platinum-cobalt method) 2, a 0.2% sodium bisulfite that adds of 6-di-isopropyl phenolic product is stored in normal temperature storage in the airtight container, and 2 years test its content is 99.51%, slightly yellow, the determination of colority value is 40, and control sample drops to 98.93%, and outward appearance is red-brown.
Embodiment 11～14:
Operation steps and testing method are with embodiment 10, and its added quantity of antioxidant and quality product see Table 3.
Table 1 alkylation reaction process control condition, reactant ratio and quality product table
| Embodiment | The alkanisation temperature (℃) | Pressure (MPa) | The reactant consumption | Reactant ratio | 2,6-diisopropyl phenol content % | |||
| Phenol (kg) | Propylene (kg) | Aluminum shot (kg) | Phenol: propylene (mol ratio) | Phenol aluminium/phenol mass percent | ||||
| 2 | ??220 | ??1.6 | ??2070 | ?500 | ?0.91 | ??1.85∶1 | ?0.5 | ??32.5 |
| 3?? | ??235 | ??2.4 | ??1477 | ?400 | ?3.65 | ??1.65∶1 | ?2.8 | ??48.9 |
| 4 | ??250 | ??2.1 | ??1609 | ?580 | ?4.40 | ??1.24∶1 | ?3.1 | ??51.2 |
| 5 | ??240 | ??2.5 | ??1740 | ?540 | ?4.45 | ??1.44∶1 | ?2.9 | ??45.6 |
| 6 | ??275 | ??1.7 | ??1558 | ?580 | ?5.50 | ??1.20∶1 | ?4.0 | ??53.0 |
| 7 | ??240 | ??1.9 | ??2095 | ?360 | ?6.65 | ??2.60∶1 | ?3.6 | ??55.1 |
| 8 | ??290 | ??2.4 | ??1816 | ?390 | ?8.01 | ??2.08∶1 | ?5.0 | ??45.4 |
| 9 | ??264 | ??1.8 | ??1762 | ?450 | ?4.67 | ??1.75∶1 | ?3.0 | ??49.5 |
Table 2 rectification process control condition, quality product and yield table
| Embodiment | One tower process condition | Two tower process conditions | 2,6-diisopropyl phenol total recovery % | ||||||||
| Inlet amount kg/h | Tower still temperature (℃) | Tower top temperature (℃) | Top vacuum degree (MPa) | 2,6 content % in the still liquid | Inlet amount kg/h | Tower still temperature (℃) | Tower top temperature (℃) | Top vacuum degree (MPa) | 2,6 content % in the liquid are adopted on the top | ||
| 2 | ??210 | ??193 | ??105 | ??0.03 | ??76.3 | ?198 | ?226 | ?158 | ?0.08 | ??99.5 | ??84.2 |
| 3 | ??200 | ??185 | ??100 | ??0.03 | ??70.4 | ?192 | ?243 | ?160 | ?0.06 | ??99.6 | ??82.9 |
| 4 | ??230 | ??240 | ??131 | ??0.06 | ??73.0 | ?214 | ?270 | ?190 | ?0.01 | ??99.7 | ??82.2 |
| 5 | ??180 | ??187 | ??106 | ??0.08 | ??78.6 | ?168 | ?197 | ?150 | ?0.02 | ??99.7 | ??83.6 |
| 6 | ??175 | ??224 | ??125 | ??0.07 | ??77.1 | ?163 | ?190 | ?164 | ?0.03 | ??99.6 | ??85.5 |
| 7 | ??185 | ??260 | ??139 | ??0.01 | ??72.8 | ?172 | ?239 | ?185 | ?0.06 | ??99.7 | ??82.0 |
| 8 | ??205 | ??208 | ??122 | ??0.05 | ??70.4 | ?190 | ?260 | ?177 | ?0.05 | ??99.6 | ??84.4 |
| 9 | ??196 | ??180 | ??109 | ??0.01 | ??76.6 | ?178 | ?245 | ?170 | ?0.05 | ??99.8 | ??85.9 |
Table 32,6-diisopropyl phenol add oxidation inhibitor and store synopsis
| Embodiment | Sodium bisulfite % | Pyrogallol % | 2, the 6-diisopropyl phenol | |||
| Content % | Outward appearance | Test after 2 years | ||||
| Content % | Outward appearance | |||||
| ??10 | ??0.2 | ??0 | ?99.66 | Water white transparency | 99.51 | Slightly yellow |
| ??11 | ??0.9 | ??0 | ?99.66 | Water white transparency | 99.61 | Water white transparency |
| ??12 | ??0 | ??0.01 | ?99.66 | Water white transparency | 99.50 | Little yellow |
| ??13 | ??0 | ??0.10 | ?99.66 | Water white transparency | 99.62 | Water white transparency |
| 14 (contrasts) | ??0 | ??0 | ?99.66 | Water white transparency | 98.93 | Red-brown |
Claims (4)
1, a kind of 2, the manufacture method of 6-diisopropyl phenol is a raw material with phenol and propylene, is catalyzer with phenol aluminium, the third phenol alkylated reaction, and alkylated product through the secondary rectification under vacuum, is characterized in that again:
(1) phenol and propylene are with 1.2～2.6: 1 mole proportioning, with phenol aluminium peg-raking catalyst, phenol aluminium is 0.5～5: 100 with respect to the mass ratio of phenol, in temperature is 220～290 ℃, and pressure is under 1.5～2.5MPa, 1.5～4.5 hours reaction times, the alkylation of phenol reaction, 2,6-diisopropyl phenol content is the first distillate of 30%～60% alkylphenol mixture, again
(2) it is 180～260 ℃ in tower still temperature, tower top temperature is 100～140 ℃, the top vacuum degree is under 0.01～0.08MPa condition first distillate to be carried out the first tower rectification under vacuum, separate 2, the impurity that 6-diisopropyl phenol boiling point is following, one cat head is adopted liquid and is mainly contained phenol, circulation enters the alkylation reaction still, it is 190～270 ℃ in tower still temperature that still is adopted liquid, tower top temperature is 150～190 ℃, the top vacuum degree is to carry out the second tower rectification under vacuum under 0.01～0.08MPa, corresponding 2 with selected pressure condition, under the 6-diisopropyl phenol boiling point, from overhead collection 2,6-diisopropyl phenol cut, its purity reaches 99.5%, 2,6-diisopropyl phenol yield is more than 82%, boiling point is than 2, and the component that the 6-diisopropyl phenol is high flows out from the tower still, and control of reflux ratio is in 1～20 scope in the rectifying.
2, according to claim 12, the manufacture method of 6-diisopropyl phenol is characterized in that: the alkylated reaction temperature is 240～260 ℃, and pressure is 1.6～1.8MPa.
3, according to claim 12, the manufacture method of 6-diisopropyl phenol is characterized in that: tower still temperature is 200～220 ℃ during a tower rectifying, and tower top temperature is 100～120 ℃, and the top vacuum degree is 0.02～0.06MPa; Tower still temperature is 220～260 ℃ during two tower rectifying, and tower top temperature is 160～180 ℃, and the top vacuum degree is 0.02～0.06MPa.
4, according to claim 12, the manufacture method of 6-diisopropyl phenol, it is characterized in that: 2, the 6-diisopropyl phenol adds a certain amount of antioxidant in wrapping process, oxidation inhibitor is pyrogallol or sodium bisulfite, the consumption of oxidation inhibitor is with respect to 2, and 6-diisopropyl phenol mass ratio is 0.01～1.0: 100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98112478 CN1197055A (en) | 1998-05-13 | 1998-05-13 | 2,6-isopropyl-phenol preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98112478 CN1197055A (en) | 1998-05-13 | 1998-05-13 | 2,6-isopropyl-phenol preparing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1197055A true CN1197055A (en) | 1998-10-28 |
Family
ID=5222327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98112478 Pending CN1197055A (en) | 1998-05-13 | 1998-05-13 | 2,6-isopropyl-phenol preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1197055A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081804B (en) * | 2007-06-04 | 2010-08-25 | 西安力邦制药有限公司 | Refining method for propofol injection |
| WO2011161687A1 (en) | 2010-06-23 | 2011-12-29 | Harman Finochem Limited | Process for preparing extra pure 2, 6-diisopropyl phenol |
| CN101538191B (en) * | 2009-05-06 | 2012-01-18 | 西安力邦制药有限公司 | Synthetic method of high-purity propofol |
| CN102039059B (en) * | 2009-10-10 | 2012-11-07 | 中国石油化工股份有限公司 | Method for controlling top of fine propylene tower |
| CN105218323A (en) * | 2015-08-13 | 2016-01-06 | 赤峰博元科技有限公司 | A kind of method suppressing crude phenol refining product variable color |
-
1998
- 1998-05-13 CN CN 98112478 patent/CN1197055A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081804B (en) * | 2007-06-04 | 2010-08-25 | 西安力邦制药有限公司 | Refining method for propofol injection |
| CN101538191B (en) * | 2009-05-06 | 2012-01-18 | 西安力邦制药有限公司 | Synthetic method of high-purity propofol |
| CN102039059B (en) * | 2009-10-10 | 2012-11-07 | 中国石油化工股份有限公司 | Method for controlling top of fine propylene tower |
| WO2011161687A1 (en) | 2010-06-23 | 2011-12-29 | Harman Finochem Limited | Process for preparing extra pure 2, 6-diisopropyl phenol |
| US8664452B2 (en) | 2010-06-23 | 2014-03-04 | Harman Finochem Limited | Process for preparing extra pure 2, 6-diisopropyl phenol |
| CN105218323A (en) * | 2015-08-13 | 2016-01-06 | 赤峰博元科技有限公司 | A kind of method suppressing crude phenol refining product variable color |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5371304A (en) | Process for the production of bisphenol A | |
| JP4418589B2 (en) | Method and apparatus for producing butyl acetate and isobutyl acetate | |
| CN103709012B (en) | Industrialization processing method for tar crude phenols | |
| CN1068579C (en) | Method for separating (methyl) propenoic acid from low-grade aldehydes including mixture by using rectificating method | |
| CA2214141A1 (en) | Dimethyl ether production and recovery from methanol | |
| CN108586207A (en) | A kind of separating technology extracting 2,4- xylenols and 2,5- xylenols from crude phenols | |
| FI74701C (en) | FOERFARANDE FOER KONTINUERLIG FRAMSTAELLNING AV SEK-BUTYLALKOHOL. | |
| KR960002596B1 (en) | Process for producing highly pure phenol | |
| CN1197055A (en) | 2,6-isopropyl-phenol preparing method | |
| CN1064663C (en) | Process for preparation and fractionation of mixture of dimethyl ether and chloromethane with water as extractant | |
| CN207627959U (en) | Alkylation reaction product separator and alkylated reaction device | |
| CN101440015A (en) | Method for producing methane chloride by using dilute hydrochloric acid | |
| CN1329588A (en) | Method for purifying triethanolamine | |
| CN112538002B (en) | Process method for separating ethylene glycol and 1, 2-butanediol by azeotropic distillation | |
| CN112771015B (en) | Method for producing isopropyl alcohol | |
| CN100387563C (en) | Alkylphenol coproduction technology | |
| CN106365178B (en) | A kind of method of purification of hydrogen cyanide | |
| CN1107047C (en) | Method for producing (meth) acrylic acid | |
| CN209010426U (en) | A kind of furfural recyclable device of Production of Ceramics condensate liquid | |
| CN111909004A (en) | Method for separating m-cresol from p-cresol | |
| CN1043739C (en) | Catalyst and process for prodn. of dimethyl ether by using synthetic gas as raw material | |
| CN102976901A (en) | Synthetic method for hybrid tertiary butyl phenol | |
| CN104761434A (en) | Cyclohexanol | |
| CN109761767A (en) | A kind of separating formaldehyde, purification PODE2Method and apparatus | |
| CN111377799B (en) | 3-methyl-3-butene-1-ol dehydration method and device thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 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 |