CN1067367C - Process for preparing phenol and ketone or aldehyde by catalysis decomposing aryl alpha-hydroperoxide - Google Patents
Process for preparing phenol and ketone or aldehyde by catalysis decomposing aryl alpha-hydroperoxide Download PDFInfo
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Abstract
The present invention relates to a method for preparing phenol and ketone or aldehyde by decomposing aryl alpha-hydroperoxide in a catalytic decomposition mode. The method comprises the following steps: under the conditions that the temperature is from 20 to 150 DEG C, and the pressure is from normal pressure to 70 megapascals, raw material which contains aryl alpha-hydroperoxide is in contact with a catalyst which loads one or more than one kind of anhydrous heteropoly acid acidic salt whose chemical expression is MnHk-mn XZ12O40 on porous carrier material, wherein M is selected from alkali metal, alkali earth metal or ammonium ions, H represents a hydrogen ion, X is selected from phosphorus, silicon, germanium or arsenic atoms, Z is selected from one kind or two kinds of tungsten, molybdenum and vanadium atoms, m is a valence state of M ions, K is 3 or 4, n is more than 0 but less than 4, and K-mn is not equal to 0.
Description
The invention relates to hydroxyl and be connected in the compound on the six-membered ring carbon atom and contain the C=O base, only connect the preparation method of the compound of carbon or hydrogen atom, more particularly, is the method for preparing phenol and ketone or aldehyde about the catalytic decomposition aryl alpha-hydroperoxide.
Following decomposition reaction can take place and generate phenol and ketone or aldehyde in aryl alpha-hydroperoxide under the acid catalyst effect:
Wherein Ar is the aryl that contains at least one phenyl ring, R
1And R
2Be alkyl or hydrogen, be sulfuric acid at industrial this reaction catalyst system therefor at present, its shortcoming is that by product is too much, as under the vitriolic katalysis, hydrogen phosphide cumene (hereinafter to be referred as CHP) decomposes can generate phenol and acetone, and one ton of phenol of every production can generate 100～200 kilograms phenol tar by product, this not only makes the yield of phenol reduce, and can have a strong impact on the quality of product, make in the product foreign matter content too high, thereby influence the purposes of product.In addition, adopt sulfuric acid to make the shortcoming that catalyzer also has contaminate environment, etching apparatus.Thereby emerged some in recent years and compared H
2SO
4The catalyzer that catalytic performance is superior, wherein adopting heteropolyacid is one of efficient manner comparatively wherein as catalyzer.
US3,187,052 disclose a kind of method of decomposing aryl alpha-hydroperoxide, and this aryl alpha-hydroperoxide has following general formula:
Wherein, Ar represents aromatic ring or chlorination aromatic ring, R
1And R
2It is respectively the hydrogen or alkyl group, an or group of naphthene base that constitutes with the intermediary carbon atom, the improvement of this method is that catalyst system therefor is a heteropolyacid catalyst, temperature of reaction is 40～90 ℃, a kind of alkaline matter of the product that obtains, handle as aqueous sodium carbonate, or handle, to remove the heteropolyacid catalyst in the product with a kind of strong basic ion exchange resin.Foreign matter content is reduced significantly in the product that this method obtains, but still have following shortcoming: (1) heteropolyacid is soluble in and contains in the oxygen organic solvent, with the product acetone of CHP decomposition reaction generation and the mixing solutions of phenol, acetone and isopropyl benzene is example, at normal temperatures 12 tungstophosphoric acid (H
3PW
12O
40), 12 molybdophosphate (H
3PMo
12O
40) and 12 tungstosilicic acid (H
4SiW
12O
40) saturation solubility in acetone reaches 84.46 respectively, 81.46, with 78.20 heavy %, containing 77 heavy % acetone, saturation solubility in the mixing solutions of 20 heavy % phenol and 3 heavy % isopropyl benzenes reaches 55.47 weights respectively, 51.31 heavy %, with 43.50% weight, containing 60 heavy % acetone, saturation solubility in the mixing solutions of 35 heavy % phenol and 5 heavy % isopropyl benzenes reaches 46.3 heavy % respectively, 44.7 heavy % and 41.6 heavy %, high like this solubleness has caused containing in the reaction product a large amount of heteropolyacid catalysts, this part catalyzer can not be stayed in the product and must be removed, thereby this method not only wasted a large amount of heteropolyacid catalysts, and operation steps is also comparatively complicated.(2) this method product yield is lower, has only 83.5～96.5 moles of % as phenol yield.
US4,898,987 disclose a kind of method by acid catalyzed decomposition reaction while synthesizing phenol and acetone, this method is included in 20～150 ℃ of temperature of reaction, under the condition of reaction pressure 0～1000psig CHP is reacted on a kind of acid montmorillonite catalyst, this acidity montmorillonite catalyst is with the acid montmorillonite catalyst of heteropolyacid, titanium, zirconium or aluminum modification, when making catalyzer with the heteropolyacid modified montmorillonoid, loses activity owing to heteropolyacid can run off gradually in the method.And when making catalyzer with titanium, zirconium or aluminium modified montmorillonoid, because what play katalysis is Lewis acid position, thereby the easy inactivation of this catalyzer, need frequent regeneration, in addition in this method the activity of catalyst system therefor and selectivity (being phenol yield) one of them or all not high enough, as the record according to the example 10～14, though transformation efficiency can reach more than 99%, its phenol yield is the highest can only to reach 97 moles of %.
US4,898,995 disclose another method by acid catalyzed decomposition reaction while synthesizing phenol and acetone, this method is included in 20～150 ℃ of temperature of reaction, under the condition of reaction pressure 0～1000psig, CHP is reacted on a kind of catalyzer, the catalyzer of described catalyzer for forming by the heteropolyacid that loads on the inert support basically, described carrier contains a kind of inert compound, this compound comprises the compound of periodic table of elements III and IV family element, suitable compounds can be the oxide compound of aluminium, the oxide compound of silicon, the oxide compound of titanyl compound and zirconium or their mixture, other suitable carrier can be a carbon, ion exchange resin and carbon-containing carrier.When adopting this method to make catalyzer with the heteropolyacid of load, the firmness of heteropolyacid load on carrier and the surface properties of catalytic activity and carrier have much relations, a tree name the applicant's experimental result, load on silica gel, titanium oxide, zirconium white, heteropolyacid catalyst on the carriers such as gac has shown good catalytic activity to the decomposition reaction of CHP, but the firmness of its load is very poor, with the phospho-wolframic acid that loads on the phospho-wolframic acid on the gac and load on the silicon oxide is example, insert them in the acetone respectively, stir a little, after 2 hours, the phospho-wolframic acid that 90 heavy % are arranged on the silicon oxide of load 50 heavy % phospho-wolframic acids solution-off from the carrier is got off, on the gac of the heavy % phospho-molybdic acids of load 20, the phospho-molybdic acid that 70 heavy % are arranged solution-off from the carrier is got off.Again for example, will be on silicon oxide the catalyzer of load 20 heavy % phospho-molybdic acids and 20 heavy % phospho-wolframic acids place the excessive mixing solutions that contains 60 heavy % acetone, 5 heavy % isopropyl benzenes and 35 heavy % phenol at normal temperatures respectively, stir after 2 hours, phospho-molybdic acid and the phospho-wolframic acid content in catalyzer drops to 3.70 heavy % and 3.20 heavy % respectively.Therefore with above-mentioned carried heteropoly acid during as catalyzer, be dissolved with the heteropolyacid that a large amount of solution-off are got off in the product on the one hand, these heteropolyacids still need to be removed, operate with alkaline matter still comparatively complicated, on the other hand since a large amount of heteropolyacids solution-off from the carrier get off, behind several secondary responses, the charge capacity of heteropolyacid descends very serious in the catalyzer, this has not only influenced activity of such catalysts and activity stability, and cause a large amount of wastes of heteropolyacid, reduced the yield of phenol, thereby can not apply in the industrial production.Though the heteropolyacid that loads on the aluminum oxide has firmness preferably, its catalytic activity is well below the heteropolyacid catalyst that loads on silicon oxide, gac, titanium oxide or the zirconium white, thereby neither a good catalyzer.
The objective of the invention is to overcome the prior art complicated operation, corrosion contamination is serious, serious and the not high shortcoming of phenol yield of catalyst loss, provide a kind of new simple to operate, catalyst loss is little, does not have the higher catalytic decomposition aryl alpha-hydroperoxide of yield of corrosion contamination and phenol to prepare the method for phenol and ketone or aldehyde.
Method provided by the invention is included in 20～150 ℃ of temperature of reaction, and under the condition of reaction pressure normal pressure～70 MPas, the raw material that will contain the aryl alpha-hydroperoxide with following general formula contacts with a kind of catalyzer:
Wherein, the Ar representative contains the aryl of at least one phenyl ring; R
1And R
2Can be the same or different, represent alkyl and hydrogen.Described catalyzer be a kind of on porous carrier materials the catalyzer of one or more heteropolyacid acid salt of load, described heteropolyacid acid salt has following anhydrous chemical expression:
M
nH
k-
MnXZ
12O
40Wherein, M is selected from a kind of in alkalimetal ion, alkaline-earth metal ions, the ammonium ion; H represents hydrogen ion; X is selected from a kind of in phosphorus atom, Siliciumatom, germanium atom, the arsenic atom; Z is selected from one or both in tungsten atom, molybdenum atom, the vanadium atom; M is a M ionic valence state; K is integer 3 or 4; N gets any number between 0＜n＜4, and it is non-vanishing to satisfy K-mn.
According to method provided by the invention, in the described aryl alpha-hydroperoxide general formula, the Ar representative contains the aryl of at least one phenyl ring, and these aryl can be (1) phenyl; (2) be connected with the phenyl of one or more alkyl groups, as p-methylphenyl, o-tolyl, a tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3, the 5-xylyl, to the various isomer of ethylbenzene base, adjacent ethylbenzene base, an ethylbenzene base, diethyl phenyl to various isomer of cumyl, adjacent cumyl, a cumyl, diisopropylbenzyl etc.; (3) be connected with the chlorination phenyl of one or more chlorine, as rubigan, Chloro-O-Phenyl, a chloro-phenyl-, 2,3-dichlorophenyl, 2,4 dichloro benzene base, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 3,5-dichlorophenyl etc., (4) contain the aryl of two above phenyl ring, as naphthyl etc.The preferred phenyl of Ar, be connected with the phenyl of an alkyl group or be connected with the chlorination phenyl of a chlorine, more preferred phenyl.R
1And R
2Can be the same or different, represent alkyl group or hydrogen, preferred C
1～C
5Alkyl group or hydrogen, C
1～C
5The alkyl group such as the isomer of methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, various amyl groups etc.R
1And R
2More preferable methyl or hydrogen.Described aryl alpha-hydroperoxide is hydrogen phosphide cumene (being CHP) preferably.
According to method provided by the invention, the reaction of the catalyst decomposes of aryl alpha-hydroperoxide can intermittently or continuously carried out in tank reactor, catalytic distillation reactor or the fixed-bed reactor.
The described raw material that contains aryl alpha-hydroperoxide can be used pure product, also available industrial without the work in-process of purifying, if described aryl alpha-hydroperoxide is pure product, the solution of available corresponding ketone, aldehyde, ketone and phenol or the solution dilution of aldehyde and phenol are to regulate its concentration.The concentration of aryl alpha-hydroperoxide can change in the scope of 20～90 heavy % in the raw material, and as when raw material is CHP, the solution dilution of available acetone or acetone and phenol is to regulate its concentration.
According to method provided by the invention, temperature of reaction can change in 20～150 ℃ scope, more preferred 40～100 ℃ of temperature of reaction; Reaction pressure can change in the scope of normal pressure～70 MPas, and for saving the energy, reaction pressure is preferably normal pressure.
Catalyst consumption changes with the different of reactor types and reaction raw materials because of reaction conditions, with the batch reactor is example, when raw material is CHP, catalyst levels can be selected the scope of 0.1～5.0 heavy %, the scope (described percentage ratio refers to that heteropolyacid acid salt is with respect to the weight percentage of CHP in the catalyzer) of more preferred 0.2～4.5 heavy %, can guarantee like this CHP at 2.5 hours with interior whole conversions.
The difference of time visual response raw material, temperature of reaction, catalyst levels and/or the reactor types of reaction and changing, when the higher and/or catalyst levels of temperature of reaction was big, the reaction times can be shorter, on the contrary the reaction times can be longer.As being CHP when reaction raw materials, reactor be a tank reactor intermittently, and temperature of reaction is 40～100 ℃, during catalyst levels 0.1～5.0 weight %, the reaction times be 30～150 minutes comparatively suitable.
According to method provided by the invention, described catalyzer is made up of a kind of porous carrier materials and one or more heteropolyacid acid salt that load in this solid support material, the charge capacity of heteropolyacid acid salt (with respect to catalyst weight) can be 0.1～99.9 heavy % in the described catalyzer, preferred 1～80 heavy %, more preferred 5～60 heavy %.Described porous carrier materials can be the combination of any non-alkaline porous carrier materials or multiple non-alkaline porous carrier materials, and it can be soild oxide, gac, various zeolite, molecular sieve, various stratiform or the non-laminated clay of group IIIA, IV A family, IV B family element.The oxide compound of described group IIIA element such as aluminum oxide, gallium oxide etc., IV A family's element oxide such as silicon oxide, IV B family's element oxide such as zirconium white, titanium oxide etc.Described zeolite, molecular sieve can be zeolite, the molecular sieves of various natural or synthetic, as A type zeolite, X type zeolite, y-type zeolite, ZSM-5 zeolite, Beta zeolite, mordenite, omega zeolite, HTS, phosphate aluminium molecular sieve etc., as described in clay as being kaolin, polynite, diatomite etc.Preferred porous carrier materials is gac, silicon oxide, aluminum oxide, zirconium white, titanium oxide and aluminosilicate zeolite, and more preferred porous carrier materials is gac, silicon oxide.
In the general formula of described heteropolyacid acid salt, a kind of or ammonium ion in the M preferred as alkali ion, more preferred cesium ion, potassium ion or ammonium ion; Preferred phosphorus atom of X or Siliciumatom; Preferred molybdenum atom of Z or tungsten atom; The value of n changes because of the difference of K value, and when K was 3, n got any number between 0＜n＜3, any number between preferred 0.1～2.9, any number between more preferred 0.5～2.5; When K was 4, n got any number between 0＜n＜4, any number between preferred 0.1～3.9, any number between more preferred 0.5～3.5.
Method catalyst system therefor provided by the invention can prepare with the following method:
(1) heteropolyacid that takes by weighing quantitative phosphorous, silicon, germanium or arsenic and tungsten, molybdenum or vanadium is dissolved in and is made into the aqueous solution that contains heteropolyacid in the quantitative deionized water.With quantitative porous carrier materials under about 0.1 normal atmosphere or lower vacuum tightness in 50～120 ℃ of drying treatment 0.5～2 hour, be cooled to room temperature, under the condition that keeps vacuum, add the aqueous solution that contains heteropolyacid for preparing, vacuum impregnation porous carrier materials 0.5～2 hour, drying is 3～10 hours under 50～120 ℃ of maintenance vacuum conditions, obtains the sample of carried heteropoly acid on porous carrier materials.
(2) taking by weighing quantitative alkaline carbonate, alkaline earth metal hydroxides, volatile salt or ammoniacal liquor by the stoichiometry requirement is dissolved in and is made into the aqueous solution in the deionization.With the sample of the carried heteropoly acid of step (1) preparation in 0.1 normal atmosphere or drying treatment 0.5～2 hour under low vacuum and 50～120 ℃ of temperature more, be cooled to room temperature, at the solution that keeps adding under the vacuum condition alkali metal containing ion, alkaline-earth metal ions or the ammonium ion that have prepared, under the maintenance vacuum condition, flooded 3～10 hours, 50～120 ℃ of vacuum-dryings 3～10 hours, promptly get method catalyst system therefor provided by the invention.
Method provided by the invention has following advantage:
(1) method provided by the invention can keep higher phenol yield when keeping aryl alpha-hydroperoxide all to transform.For example, adopt method provided by the invention, heteropolyacid acid salt with 10～50 heavy % of load on silicon oxide or gac is catalyzer, with the industrial raw material that contains CHP is reaction raw materials, under 40～80 ℃ of temperature of reaction and normal pressure, the transformation efficiency of CHP is 100 moles of %, and phenol yield is greater than 98 moles of %.
(2) solubleness of heteropolyacid acid salt in reaction product in the method catalyst system therefor provided by the invention is very low even insoluble, thereby can save in the prior art and must carry out the step that depickling is handled to product, has simplified operating process greatly.
(3) very low or insoluble at all because of the solubleness of heteropolyacid acid salt in reaction product in the method catalyst system therefor provided by the invention, thereby, on the one hand, heteropolyacid acid salt can not get off from solution-off on the carrier in the method catalyst system therefor provided by the invention, thereby the amount of active ingredient in the reduction catalyzer, on the other hand, method catalyst system therefor provided by the invention can guarantee that in long-time its activity can not descend, and promptly its activity stability is good.For example adopt the decomposition reaction of method provided by the invention catalysis CHP in batch reactor, adopt the Cs of load 20.80 heavy %
0.5H
25PMo
12O
40Heteropolyacid acid salt is catalyzer, 60 ℃ of temperature of reaction, reaction pressure normal pressure, reaction times 1 hour, under the reaction conditions of catalyst levels 1 heavy % (heteropolyacid acid salt is with respect to the weight percentage of CHP consumption in the catalyzer), react that heteropolyacid acid salt content does not fall as follows in 40 rear catalysts, CHP transformation efficiency and phenol yield all do not descend yet, and the employing prior art, with carried heteropoly acid on silica gel is catalyzer, under the same conditions, the reaction 3 times after the CHP transformation efficiency just drop to 24.5 moles of % from 100 moles of %.
(4) method provided by the invention also has the low advantage of foreign matter content in the product.
The following examples will the present invention will be further described, but not thereby limiting the invention.
Example 1～7
The preparation of method catalyst system therefor provided by the invention.
Step (1) takes by weighing quantitative phospho-molybdic acid (H
3PMo
12O
4024H
2O, analytical pure, Beijing chemical reagent work of Xinhua produces) be dissolved in the quantitative deionized water, be made into and contain H
3PMo
12O
40The aqueous solution.Quantitative porous carrier materials is placed filter flask, under 0.1 normal atmosphere vacuum tightness and 75 ℃ of temperature, handled 1 hour.Be cooled to room temperature, under the condition that keeps vacuum, add the H that contains for preparing
3PMo
12O
40The aqueous solution, vacuum impregnation 1 hour kept vacuum conditions dry 6 hours down in 70 ℃, obtained loading on the phospho-molybdic acid sample on the porous carrier materials.
Step (2) takes by weighing quantitative cesium carbonate (Cs
2CO
3, analytical pure, northern Tonghua factory produces) be dissolved in being made in the quantitative deionized water and contain Cs
2CO
3The aqueous solution.Take by weighing the phospho-molybdic acid sample on the porous carrier materials of loading on of quantitative step (1) preparation, under 0.1 normal atmosphere vacuum tightness and 90 ℃ of temperature, handled 1 hour, be cooled to room temperature, contain Cs keeping adding under the vacuum condition
2CO
3The aqueous solution, flooded 6 hours, liquid all is inhaled in the porous carrier materials.The product that obtains keeping under vacuum and the 70 ℃ of conditions dry 6 hours, is promptly got method catalyst system therefor provided by the invention.
Table 1 has provided the phospho-molybdic acid sample number into spectrum on the porous carrier materials of loading on of phosphorus molybdenum acid solution consumption, porous carrier materials and consumption thereof, step (1) preparation.Table 2 has provided the numbering of the catalyzer that the sample of load phospho-molybdic acid and consumption and cesium carbonate solution usage, step (2) thereof obtain.Table 3 item has provided resulting catalyzer and has formed.Adopt plasma emission spectrum elemental analyser (ICP) to measure metal content in the heteropolyacid acid salt, calculate the anhydrous chemical expression of heteropolyacid acid salt and the content in catalyzer thereof by measurement result.The porous carrier materials gac is produced by brilliance timber mill, Beijing, and its specific surface is 643 meters
2/ gram, silica gel is produced by the Dalian Chemistry and Physics Institute, and its specific surface is 488 meters
2/ gram.
Table 1
| Example number | Phosphorus molybdenum acid solution | Porous carrier materials | Gained load phospho-molybdic acid sample number into spectrum | ||
| The phospho-molybdic acid consumption, gram | Water consumption, gram | Type | Consumption, gram | ||
| 1 | 15.50 | 40.0 | Silica gel | 12.50 | A’ |
| 2 | 15.50 | 40.0 | Activated carbon | 12.50 | B’ |
| 3 | 1.72 | 40.0 | Silica gel | 12.50 | C’ |
| 4 | 3.88 | 40.0 | Silica gel | 12.50 | D’ |
| 5 | 15.50 | 40.0 | Activated carbon | 12.50 | E’ |
| 6 | 15.50 | 40.0 | Activated carbon | 12.50 | F’ |
| 7 | 15.50 | 40.0 | Activated carbon | 12.50 | G’ |
Table 2
| Example number | The sample of load phospho-molybdic acid | Cesium carbonate solution | Gained catalyzer numbering | ||
| Type | Consumption, gram | The cesium carbonate consumption, gram | Water consumption, gram | ||
| 1 | A’ | 25.00 | 0.1120 | 40.0 | A |
| 2 | B’ | 25.00 | 0.5603 | 40.0 | B |
| 3 | C’ | 13.89 | 0.0622 | 40.0 | C |
| 4 | D’ | 15.60 | 0.1403 | 40.0 | D |
| 5 | E’ | 25.00 | 1.1211 | 40.0 | E |
| 6 | F’ | 25.00 | 2.2405 | 40.0 | F |
| 7 | G’ | 25.00 | 2.8023 | 40.0 | G |
Table 3
| Example number | The catalyzer numbering | Catalyzer is formed | ||
| Acid salt ' anhydrous chemical formula | Acid salt content *, heavy % | Bearer type | ||
| 1 | A | Cs 0.1H 2.8PMo 12O 40 | 50.20 | Silica gel |
| 2 | B | Cs 0.5H 2.5PMo 12O 40 | 51.10 | Activated carbon |
| 3 | C | Cs 0.5H 2.5PMo 12O 40 | 10.30 | Silica gel |
| 4 | D | Cs 0.5H 2.5PMo 12O 40 | 20.80 | Silica gel |
| 5 | E | Cs 1.1H 1.9PMo 12O 40 | 52.10 | Activated carbon |
| 6 | F | Cs 2.0H 1.0PMo 12O 40 | 54.00 | Activated carbon |
| 7 | G | Cs 2.5H 0.5PMo 12O 40 | 55.00 | Activated carbon |
# acid salt refers to heteropolyacid acid salt, down together
*Heteropolyacid acid salt accounts for the percentage ratio of total catalyst weight, down together
Comparative Examples 1
US4, the preparation of 898,995 the used carried heteropoly acid catalyst of method.
Press US4, the method for 898,995 example B is dissolved in 40.0 grams with 3.88 gram phospho-molybdic acids (specification is with example 1～7) and is made in the deionized waters and contains H
3PMo
12O
40The aqueous solution, under agitation add 12.50 gram silica-gel carriers (specification is with example 4), continue to stir 2 hours, mixture that evaporate to dryness obtains and the product that in nitrogen atmosphere, obtains in 250 ℃ of roastings 2 hours, must be on silica-gel carrier the carried heteropoly acid catalyst of load 20.00 heavy % phospho-molybdic acids, be designated as H.
Example 8～10
The preparation of method catalyst system therefor provided by the invention.
Method by example 1～7 prepares catalyzer, just changes cesium carbonate into salt of wormwood (K
2CO
3, analytical pure, the Beijing Chemical Plant produces), table 4 has provided consumption, porous carrier materials and the consumption thereof of phosphorus molybdenum acid solution, the sample number into spectrum of load phosphorus aluminic acid that step (1) is prepared.Table 5 has provided the consumption of the load phospho-molybdic acid sample that step (1) prepares and the consumption of solution of potassium carbonate, the catalyzer numbering that step (2) obtains.Table 6 item has provided the catalyzer that obtains and has formed.
Table 4
| Example number | The phosphorescence molybdenum acid solution | Porous carrier materials | Gained load phospho-molybdic acid sample number into spectrum | ||
| The phospho-molybdic acid consumption, gram | Water consumption, gram | Type | Consumption, gram | ||
| 8 | 15.50 | 40.0 | Silica gel | 12.50 | I＇ |
| 9 | 3.88 | 40.0 | Activated carbon | 12.50 | J＇ |
| 10 | 15.50 | 40.0 | Activated carbon | 12.50 | K＇ |
Table 5
| Example number | The sample of load phospho-molybdic acid | Solution of potassium carbonate | Gained catalyzer numbering | ||
| Type | Consumption, gram | The salt of wormwood amount, gram | Water consumption, gram | ||
| 8 | I＇ | 25.00 | 0.2761 | 40.0 | I |
| 9 | J＇ | 15.60 | 0.1185 | 40.0 | J |
| 10 | K＇ | 25.00 | 1.3805 | 40.0 | K |
Table 6
| Example number | The catalyzer numbering | Catalyzer is formed | ||
| The anhydrous chemical formula of acid salt | Acid salt content, heavy % | Bearer type | ||
| 8 9 10 | I J K | K 0.5H 2.5PMo 12O 40K 1.0H 2.0PMo 12O 40K 2.5H 0.5PMo 12O 40 | 50.80 20.60 52.50 | Silica gel gac gac |
Example 11～13
The preparation of method catalyst system therefor provided by the invention.
Method by example 1～7 prepares catalyzer, and just cesium carbonate is changed to strong aqua (contains NH
326.5 heavy %, analytical pure, Beijing Yili Fine Chemicals Co., Ltd. produces).Table 7 has provided the numbering of phosphorus molybdenum acid solution consumption, porous carrier materials and consumption thereof, step (1) gained load phospho-molybdic acid sample.Table 8 has provided consumption, the ammonia soln consumption of step (1) gained load phospho-molybdic acid sample, the numbering of step (2) gained catalyzer.Table 9 has provided the composition of gained catalyzer.
Table 7
| Example number | Phosphorus molybdenum acid solution | Porous carrier materials | Gained load phospho-molybdic acid sample number into spectrum | ||
| The phospho-molybdic acid consumption, gram | Water consumption, gram | Type | Consumption, gram | ||
| 11 | 12.70 | 40.0 | Silica gel | 12.50 | L＇ |
| 12 | 6.64 | 40.0 | Gac | 12.50 | M＇ |
| 13 | 1.35 | 40.0 | Silica gel | 12.50 | N＇ |
Table 8
| Example number | The sample of load phospho-molybdic acid | Ammonia soln | Gained catalyzer numbering | ||
| Type | Consumption, gram | The strong aqua consumption, gram | Water consumption, gram | ||
| 11 | L＇ | 22.73 | 0.0902 | 40.0 | L |
| 12 | M＇ | 17.86 | 0.1415 | 40.0 | M |
| 13 | N＇ | 13.60 | 0.0480 | 40.0 | N |
Table 9
| Example number | The catalyzer numbering | Catalyzer is formed | ||
| The anhydrous chemical formula of acid salt | Acid salt content, heavy % | Bearer type | ||
| 11 | L | (NH 4) 0.5H 2.5PMo 12O | 45.10 | Silica gel |
| 12 | M | (NH 4) 1.5H 1.5PMo 12O | 30.20 | Gac |
| 13 | N | (NH 4) 2.6H 0.4PMo 12O | 8.00 | Silica gel |
Example 14～16
The preparation of method catalyst system therefor provided by the invention.
Prepare catalyzer by example 1～7 described method, just change phospho-molybdic acid into phospho-wolframic acid (H
3PW
12O
4021H
2O, analytical pure, Beijing chemical reagent work of Xinhua produces).Table 10 has provided the numbering of Salkowski's solution consumption, porous carrier materials and consumption thereof, step (1) gained load phosphotungstic acid sample.Table 11 has provided the consumption of step (1) gained load phosphotungstic acid sample, cesium carbonate solution usage, step (2) gained catalyzer numbering.Table 12 has provided the composition of gained catalyzer.
Table 10
| Example number | Salkowski's solution | Porous carrier materials | Gained load phosphotungstic acid sample number into spectrum | ||
| The phospho-wolframic acid consumption, gram | Water consumption, gram | Type | Consumption, gram | ||
| 14 | 14.14 | 40.0 | Silica gel | 12.50 | O＇ |
| 15 | 1.57 | 40.0 | Gac | 12.50 | P＇ |
| 16 | 3.54 | 40.0 | Silica gel | 12.50 | Q＇ |
Table 11
| Example number | The sample of load phosphotungstic acid | Cesium carbonate solution | Gained catalyzer numbering | ||
| Type | Consumption, gram | The cesium carbonate consumption, gram | Water consumption, gram | ||
| 14 | O＇ | 25.00 | 0.3535 | 40.0 | O |
| 15 | P＇ | 13.89 | 0.1178 | 40.0 | P |
| 16 | Q＇ | 15.60 | 0.4425 | 40.0 | Q |
Table 12
| Example number | The catalyzer numbering | Catalyzer is formed | ||
| The anhydrous chemical formula of acid salt | Acid salt content, heavy % | Bearer type | ||
| 14 | O | Cs 0.5H 2.5PW 12O 40 | 50.60 | Silica gel |
| 15 | P | Cs 1.5H 1.5PW 12O 40 | 10.70 | Gac |
| 16 | Q | Cs 2.5H 0.5PW 12O 40 | 21.80 | Silica gel |
Example 17
Prepare catalyzer by example 1 described method, just change phospho-molybdic acid into phospho-wolframic acid (specification is with example 14～16) in the step (1), the phospho-wolframic acid consumption is 3.54 grams, and the silica-gel carrier consumption is 12.50 grams, and the sample number into spectrum of gained load phosphotungstic acid is R '.In the step (2) cesium carbonate is changed to salt of wormwood (specification is with example 8～10), the salt of wormwood consumption is 0.0375 gram, and the sample R ' consumption of load phosphotungstic acid is 15.60 grams, and the catalyzer that obtains is numbered R, and catalyzer R contains 20.00 heavy %K
0.5H
25PW
12O
40, carrier is a silica gel.
Example 18
Prepare catalyzer by example 1 described method, just change phospho-molybdic acid into phospho-wolframic acid (specification is with example 14～16) in the step (1), the phospho-wolframic acid consumption is 9.43 grams, and the silica gel consumption is 12.50 grams, and the sample number into spectrum of gained load phosphotungstic acid is S '.In the step (2) cesium carbonate is changed to strong aqua (specification is with example 11～13), the strong aqua consumption is 0.1850 gram, and the sample S ' consumption of load phosphotungstic acid is 20.80 grams, and the catalyzer that obtains is numbered S, and catalyst S contains 40.00 heavy % (NH
4)
2.0H
1.0PW
12O
40, carrier is a silica gel.
Comparative Examples 2
US4, the preparation of 898,995 the used carried heteropoly acid catalyst of method.
Press US4,898, the method of 995 example A, 3.54 gram phospho-wolframic acids (specification is with example 14～16) are dissolved in the 40.0 gram deionized waters, under agitation add 12.50 gram silica-gel carriers (specification is with example 4), continue to stir 2 hours, the mixture that evaporate to dryness obtains, in the following 250 ℃ of roastings of nitrogen atmosphere 2 hours, must be on silica gel the carried heteropoly acid catalyst of load 20.00 heavy % phospho-wolframic acids, be designated as T.
Example 19～20
The preparation of method catalyst system therefor provided by the invention.
Prepare catalyzer by example 2 described methods, just change phospho-molybdic acid into silicotungstic acid (H
4SiW
12O
415H
2O, analytical pure, chemical reagent factory in Shanghai produces), table 13 has provided the numbering of the load silicotungstic acid sample of silicotungstic acid solution usage, absorbent charcoal carrier consumption, step (1) preparation.Table 14 has provided the numbering of the catalyzer that consumption, cesium carbonate solution usage and the step (2) of the load silicotungstic acid sample of step (1) preparation obtain.Table 15 has provided the composition of catalyzer.
Table 13
| Example number | Silicotungstic acid solution | The absorbent charcoal carrier consumption, gram | Gained load silicotungstic acid sample number into spectrum | |
| The silicotungstic acid consumption, gram | Water consumption, gram | |||
| 19 | 13.68 | 40.0 | 12.50 | U＇ |
| 20 | 13.68 | 40.0 | 12.50 | V＇ |
Table 14
| Example number | The sample of load silicotungstic acid | Cesium carbonate solution | The catalyzer numbering | ||
| Numbering | Consumption, gram | The cesium carbonate consumption, gram | Water consumption, gram | ||
| 19 | U＇ | 25.00 | 0.3544 | 40.0 | U |
| 20 | V＇ | 25.00 | 2.1233 | 40.0 | V |
Table 15
| Example number | The catalyzer numbering | Catalyzer is formed | ||
| The anhydrous chemical formula of acid salt | Acid salt content, heavy % | Bearer type | ||
| 19 | U | Cs 0.5H 3.5SiW 12O 40 | 50.60 | Gac |
| 20 | V | Cs 3.0H 1.0SiW 12O 40 | 53.70 | Gac |
Example 21～22
The preparation of method catalyst system therefor provided by the invention.
Prepare catalyzer by example 1 described method, just change phospho-molybdic acid into tungstosilicic acid (specification is with example 19～20), change cesium carbonate into salt of wormwood (specification is with example 8～10).Table 16 has provided silicotungstic acid solution usage, silica-gel carrier consumption, step (1) gained load silicotungstic acid sample number into spectrum.Table 17 has provided the resultant catalyzer numbering of consumption, solution of potassium carbonate consumption, step (2) of load silicotungstic acid sample.Table 18 has provided the catalyzer composition.
Table 16
| Example number | Silicotungstic acid solution | The silica-gel carrier consumption, gram | Load silicotungstic acid sample number into spectrum | |
| The silicotungstic acid consumption, gram | Water consumption, gram | |||
| 21 | 3.42 | 40.0 | 12.50 | W＇ |
| 22 | 13.68 | 40.0 | 12.5 | X＇ |
Table 17
| Example number | The sample of load silicotungstic acid | Solution of potassium carbonate | The catalyzer numbering | ||
| Numbering | Consumption, gram | The salt of wormwood consumption, gram | Water consumption, gram | ||
| 21 | W＇ | 15.62 | 0.0749 | 40.0 | W |
| 22 | X＇ | 25.00 | 1.0489 | 40.0 | X |
Table 18
| Example number | The catalyzer numbering | Catalyzer is formed | ||
| The anhydrous chemical formula of acid salt | Acid salt content, heavy % | Bearer type | ||
| 21 | W | K 1.0H 3.0SiW 12O 40 | 20.00 | Silica gel |
| 22 | X | K 3.5H 0.5SiW 12O 40 | 51.90 | Silica gel |
Example 23
The preparation of method catalyst system therefor provided by the invention.
Prepare catalyzer by example 2 described methods, just change phospho-molybdic acid into tungstosilicic acid (specification is with example 19～20) in the step (1), the silicotungstic acid consumption is 13.68 grams, the absorbent charcoal carrier consumption is 12.5 grams, the sample number into spectrum of step (1) gained load silicotungstic acid is Y ', sample Y ' the consumption of load silicotungstic acid is 25.00 grams in the step (2), and cesium carbonate is changed to strong aqua (specification is with example 11～13), and the strong aqua consumption is 0.2786 gram.The catalyzer of step (2) gained is numbered Y, and catalyzer Y contains 50.30 heavy % (NH
4)
20H
20SiW
12O
40, carrier is a gac.
Example 24～46
Following example explanation the invention provides the solution-off situation of method catalyst system therefor in the acetone close with CHP degradation production composition, isopropyl benzene, phenol solution.
Take by weighing quantitative acetone, isopropyl benzene and phenol respectively, the three is mixed being made into the mixing solutions that contains 60 heavy % acetone, 5 heavy % isopropyl benzenes and 35 heavy % phenol.Take by weighing the catalyzer of quantitative example 1～23 preparation respectively, add in the excessive above-mentioned mixing solutions, stirred 2 hours, leave standstill, catalyst sedimentation is outwelled supernatant liquid in the solution bottom, with lower floor's catalyzer under 0.1 normal atmosphere vacuum tightness and 70 ℃ of temperature dry 10 hours, and, calculate heteropolyacid acid salt anhydrous chemical expression and the content in catalyzer thereof with the content of metallic element in plasma emission spectrum elemental analyser (ICP) analysis of catalyst, the results are shown in Table 19.
Comparative Examples 3～4
Following Comparative Examples explanation, the solution-off situation of carried heteropoly acid catalyst in the acetone close, isopropyl benzene, phenol solution with CHP degradation production composition.
Measuring method is with example 24～46, and just catalyst system therefor is respectively the catalyzer of Comparative Examples 1 and Comparative Examples 2 preparations, and the results are shown in Table 19.
The result of table 19 shows, the solubleness of activeconstituents heteropolyacid acid salt in the method catalyst system therefor provided by the invention in the solution close with CHP degradation production composition is very little, particularly when the n in the heteropolyacid acid salt general formula＞0.5, basically be insoluble to above-mentioned solution, thereby, in method provided by the invention, the active ingredient loss of catalyst system therefor is very little, when n＞0.5, there is not loss substantially, thereby adopt method provided by the invention, product does not need depickling to handle, and step greatly can simplify the operation.Because of not loss of active ingredient in the catalyzer, the catalyzer continuous several times is used becomes possibility.And the carried heteropoly acid salt catalyst of employing prior art, because of the solubleness of heteropolyacid in above-mentioned solution very big, thereby heteropolyacid can not load on the carrier securely, the solution-off result of experiment shows, after 2 hours solution-off, active component content drops to 3.70 and 3.20 heavy % respectively from 20 original heavy % in the catalyzer of Comparative Examples 1 and Comparative Examples 2 preparations, thereby existing carried heteropoly acid catalyst can not repeatedly use continuously, the product that obtains also needs depickling to handle complicated operation.
Table 19
Method catalysis aryl alpha-hydroperoxide provided by the invention decomposition reaction is adopted in following example and Comparative Examples explanation, can keep very high phenol yield under the prerequisites that keep aryl alpha-hydroperoxide all to transform.Used aryl alpha-hydroperoxide is hydrogen phosphide cumene (CHP) in the example, and reaction raw materials is the raw material of producing in second chemical plant, the Yanshan Mountain that contains CHP, and through efficient liquid phase chromatographic analysis, its composition is listed in the table 20.The CHP degradation production is formed the analysis of employing SP-3420 gas chromatograph in the example, and CHP is by chemical iodometric determination in the product.CHP transformation efficiency and phenol yield are defined as follows:
CHP mole number * 100% in CHP transformation efficiency=(in the charging in CHP mole number-product CHP mole number)/charging
CHP mole number * 100% in phenol mole number/charging in phenol yield=product
Table 20
| Component | CHP | Isopropyl benzene | Methyl phenyl ketone | Dimethyl benzyl alcohol | Alpha-methyl styrene |
| Content, heavy % | 88.5 | 8.9 | 1.3 | 1.2 | 0.1 |
Example 47～59
Carry out the decomposition reaction of CHP according to method provided by the invention.
In being 250 milliliters three-necked bottle, volume adds quantitative acetone respectively, filled with water cold reflux pipe, thermometer, in container, put into magnetic stick, the catalyzer that adds quantitative example 1～13 preparation respectively, starting magnetic stirrer stirs, place 60 ℃ water-bath to be heated to 60 ℃ three-necked bottle, drip reaction raw materials shown in the quantitative table 20, rate of addition so that in the three-necked bottle fluid temperature be no more than 70 ℃ and exceed, after adding, under the temperature of 60 ℃ of maintenances, continue to stir cooling in 60 or 90 minutes, catalyzer obtains sedimentation in the refrigerative process, weigh supernatant liquid and analyze its composition, table 21 has been listed acetone, catalyzer, the consumption that contains the CHP raw material, reaction times, CHP transformation efficiency and phenol yield.
Comparative Examples 5
With the loading type phospho-molybdic acid is the decomposition reaction that catalyzer carries out CHP.
Reaction unit, reaction raw materials, operational condition are with example 50, and just catalyst system therefor is the catalyzer H of Comparative Examples 1 preparation, after reacting end and being cooled to room temperature, isolate catalyzer, add 0.13 gram NaHCO in reaction product
3Powder leaves standstill with phospho-molybdic acid in the neutralized reaction product, the supernatant liquid and analyze its composition of weighing.Acetone, catalyzer, the consumption that contains the CHP raw material, reaction times, CHP transformation efficiency and phenol yield are listed in the table 21.
Table 21
Example 60～64
Carry out the cartalytic decomposition effect of CHP by method provided by the invention.
Reaction unit, reaction raw materials, operational condition are with example 47～59, and just catalyst system therefor is the catalyzer of example 14～18 preparations.Acetone consumption, catalyzer and consumption thereof, the consumption that contains the CHP raw material, reaction times, CHP transformation efficiency and phenol yield are listed in the table 22.
Comparative Examples 6
With the carried phospho-tungstic acid is the decomposition reaction that catalyzer carries out CHP.Reaction unit, reaction raw materials, operational condition are with example 62, and just catalyst system therefor is the catalyzer T of Comparative Examples 2 preparations, and reaction is cooled to room temperature after finishing, and add 0.09 gram NaHCO in reaction product
3Powder is with the phospho-wolframic acid in the neutralized reaction product, and supernatant liquid and analyze its composition leaves standstill, weighs.Acetone, catalyzer, contain the consumption of CHP raw material, reaction times, CHP transformation efficiency and phenol yield are listed in the table 22.
Table 22
| Example number | The acetone consumption, gram | Catalyzer | Contain CHP raw material consumption, gram | In the reaction times, divide | The CHP transformation efficiency, mole % | Phenol yield, mole % | |
| Numbering | Consumption, gram | ||||||
| 60 | 30.8 | O | 1.5 | 40.0 | 60 | 100.0 | 98.5 |
| 61 | 30.8 | P | 7.0 | 40.0 | 60 | 100.0 | 99.1 |
| 62 | 78.0 | Q | 4.0 | 40.0 | 90 | 100.0 | 98.9 |
| 63 | 30.8 | R | 3.5 | 40.0 | 60 | 100.0 | 99.3 |
| 64 | 78.0 | S | 5.0 | 40.0 | 90 | 100.0 | 98.6 |
| Comparative Examples 6 | 19.0 | T | 4.0 | 40.0 | 90 | 100.0 | 96.7 |
Example 65～69
Carry out the cartalytic decomposition effect of CHP by method provided by the invention.
Reaction unit, reaction raw materials, operational condition are with example 47～59, and just catalyst system therefor is the catalyzer of example 19～23 preparations.Acetone consumption, catalyzer and consumption thereof, the consumption that contains the CHP raw material, reaction times, CHP transformation efficiency and phenol yield are listed in the table 23.
Table 23
| Example number | The acetone consumption, gram | Catalyzer | Contain CHP raw material consumption, gram | In the reaction times, divide | The CHP transformation efficiency, mole % | Phenol yield, mole % | |
| Numbering | Consumption, gram | ||||||
| 65 | 30.8 | U | 2.5 | 40.0 | 60 | 100.0 | 99.1 |
| 66 | 78.0 | V | 10.0 | 40.0 | 90 | 100.0 | 99.4 |
| 67 | 30.8 | W | 3.0 | 40.0 | 60 | 100.0 | 98.7 |
| 68 | 19.0 | X | 12.0 | 40.0 | 90 | 100.0 | 99.0 |
| 69 | 30.8 | Y | 5.0 | 40.0 | 90 | 100.0 | 99.0 |
Table 21,22 and 23 result show that (1) adopts method provided by the invention, can be under the prerequisite that keeps CHP to transform fully, and keep phenol yield at 98.5 moles more than the %, be higher than the method that adopts carried heteropoly acid to make catalyzer.(2) can save the step of product being carried out the depickling processing in the method provided by the invention, thereby simplify the operation steps of prior art method therefor greatly, method provided by the invention is better than prior art.
Example 70～71
Following example explanation, method temperature of reaction provided by the invention and reaction times relation.
Reaction unit, each raw material consumption, catalyzer and consumption thereof are with example 52, and just temperature of reaction is different with the reaction times, and temperature of reaction, reaction times and reaction result are listed in the table 24.Be convenient contrast, listed file names with the result of example 52 in the table 24.Wherein temperature of reaction is 40 ℃, refers to begin to drip the raw material that contains CHP at 40 ℃, and rate of addition makes temperature of reaction be no more than 50 ℃.80 ℃ of temperature of reaction refer to begin to drip the raw material that contains CHP at 80 ℃, and rate of addition makes temperature of reaction be no more than 90 ℃, after the reaction times refers to contain CHP and drips, continue the time of stirring.
Table 24
| Example number | Temperature of reaction, ℃ | In the reaction times, divide | The CHP transformation efficiency, mole % | Phenol yield, mole % |
| 70 | 150 | 100 | 99.4 | |
| 52 | 60 | 60 | 100 | 99.5 |
| 71 | 80 | 45 | 100 | 99.2 |
The result of table 24 shows that in method provided by the invention, the higher the reaction time of temperature of reaction can be shorter, then answers the time of corresponding prolongation reaction when temperature of reaction is low.
Example 72～75
This example illustrates the activity stability and the product composition of catalyst system therefor in the method provided by the invention.
Carry out the decomposition reaction of CHP by example 50 described each material consumption, reaction unit and operational condition, after finishing, reaction isolates catalyzer, again used catalyst is used for the identical CHP decomposition reaction of another time, repeat 40 times continuously, table 25 has provided the 1st, 10,20,40 secondary response CHP transformation efficiencys, the composition of phenol yield and reaction product.
Comparative Examples 7～9
When the explanation of this Comparative Examples adopts carried heteropoly acid to make catalyzer, this activity of such catalysts stability.
Carry out the CHP decomposition reaction by the method identical with Comparative Examples 5, just catalyst system therefor is the catalyzer H of the load 20 heavy % phospho-molybdic acids of Comparative Examples 1 preparation, and reaction does not add NaHCO after finishing
3, directly isolate catalyzer and use it for the identical CHP decomposition reaction of another time.React the 1st time, the 3rd time and the 5th the results are shown in Table 25.
Table 25
| Example number | 72 | 73 | 74 | 75 | Comparative Examples 7 | Comparative Examples 8 | Comparative Examples 9 |
| Reaction times | 1 | 10 | 20 | 40 | 1 | 3 | 5 |
| The CHP transformation efficiency, mole % | 100 | 100 | 100 | 100 | 100 | 24.5 | 4.3 |
| Phenol yield, mole % | 99.3 | 99.5 | 99.2 | 99.4 | 97.5 | 24.5 | 4.3 |
| Product is formed, heavy % CHP acetone isopropyl benzene phenol alpha-methyl styrene methyl phenyl ketone dimethyl benzyl alcohol | 0.0 62.0 5.1 31.0 1.0 0.8 0.1 | 0.0 61.6 5.2 31.4 0.8 0.8 0.2 | 0.0 61.8 5.1 31.3 0.8 0.8 0.2 | 0.0 61.9 5.1 31.4 0.7 0.8 0.1 | 0.0 61.8 5.1 31.4 0.8 0.8 0.1 | 38.2 47.6 5.1 7.7 0.3 0.7 0.4 | 48.4 43.7 5.2 1.3 0.1 0.8 0.5 |
The result of table 25 shows, adopt method provided by the invention, with carried heteropoly acid salt is the decomposition reaction of catalyst CHP, reacting 40 rear catalyst activity does not fall as follows, and adopt carried heteropoly acid salt is catalyzer, the CHP transformation efficiency just drops to 24.5 moles of % from 100 moles of % after reacting 3 times, and method provided by the invention is better than prior art.
Claims (12)
1. a catalytic decomposition aryl alpha-hydroperoxide prepares the method for phenol and ketone or aldehyde, this method is included in 20～150 ℃ of temperature of reaction, under the condition of reaction pressure normal pressure～70 MPas, the raw material that will contain the aryl alpha-hydroperoxide with following general formula contacts with a kind of catalyzer:
Wherein, the Ar representative contains the aryl of at least one phenyl ring; R
1And R
2Can be the same or different, represent hydrogen or C
1～C
5Alkyl, it is characterized in that described catalyzer be a kind of on porous carrier materials the catalyzer of one or more heteropolyacid acid salt of load, described heteropolyacid acid salt has following anhydrous chemical expression:
M
nH
k-
MnXZ
12O
40Wherein, M is selected from a kind of in alkalimetal ion, alkaline-earth metal ions and the ammonium ion; H represents hydrogen ion; X is selected from a kind of in phosphorus atom, Siliciumatom, germanium atom and the arsenic atom; Z is selected from one or both in tungsten atom, molybdenum atom and the vanadium atom; M is a M ionic valence state, and K is integer 3 or 4, and n gets any number between 0＜n＜4, and it is non-vanishing to satisfy K-mn.
2. according to the described method of claim 1, it is characterized in that Ar is selected from phenyl in the described aryl alpha-hydroperoxide general formula.
3. according to the described method of claim 2, it is characterized in that described R
1And R
2Be selected from methyl or hydrogen respectively.
4. according to the described method of claim 1, it is characterized in that described aryl alpha-hydroperoxide refers to hydrogen phosphide cumene.
5. according to the described method of claim 1, it is characterized in that described temperature of reaction is 40～100 ℃, reaction pressure is a normal pressure.
6. according to the described method of claim 1, the charge capacity that it is characterized in that heteropolyacid acid salt in the described catalyzer is 5～60 heavy %.
7. according to the described method of claim 1, it is characterized in that described porous carrier materials refers to gac or silicon oxide.
8. according to the described method of claim 1, it is characterized in that M is selected from alkalimetal ion or ammonium ion in the described heteropolyacid acid salt anhydrous chemical expression.
9. described according to Claim 8 method is characterized in that described M is selected from potassium ion, ammonium ion or cesium ion.
10. according to the described method of claim 1, it is characterized in that the X in the described heteropolyacid acid salt anhydrous chemical expression is selected from phosphorus atom or Siliciumatom; Z is selected from molybdenum atom or tungsten atom.
11., it is characterized in that in described heteropolyacid acid salt catalyzer anhydrous chemical expression, when K=4, n is any number between 0.1～3.9 according to the described method of claim 1.
12., it is characterized in that in described heteropolyacid acid salt catalyzer anhydrous chemical expression, when K=4, n is any number between 0.5～3.5 according to the described method of claim 11.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3187052A (en) * | 1960-04-26 | 1965-06-01 | Allied Chem | Process for preparing phenols and carbonyl alkanes |
| CN1041581A (en) * | 1988-09-30 | 1990-04-25 | 三井石油化学工业株式会社 | Phenol preparation and the method that therefrom reclaims propylene |
| GB2269588A (en) * | 1992-08-15 | 1994-02-16 | Solvay Interox Ltd | Hydroxylation of aromatic hydrocarbons |
-
1997
- 1997-07-28 CN CN97115168A patent/CN1067367C/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3187052A (en) * | 1960-04-26 | 1965-06-01 | Allied Chem | Process for preparing phenols and carbonyl alkanes |
| CN1041581A (en) * | 1988-09-30 | 1990-04-25 | 三井石油化学工业株式会社 | Phenol preparation and the method that therefrom reclaims propylene |
| GB2269588A (en) * | 1992-08-15 | 1994-02-16 | Solvay Interox Ltd | Hydroxylation of aromatic hydrocarbons |
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