CN1003644B - Catalytic synthesising of monoterpene ether from natural mordenite - Google Patents

Abstract

The present invention relates to a new technology for producing monoterpene ether from monoterpene olefin and alcohol through the directly catalysis of natural mordenite as a catalyst by a fixed bed counter flow type continuous process. The used monoterpene olefin is alpha-pinene, beta-pinene, camphene, dipentene (limonene), gamma-terpinene, etc. The alcohol additive to terpene can be methanol, ethanol, propanol, isopropanol, propenol, butanol, ethanediol, citronellol, phenylmethanol, etc. The ether obtained by the addition reaction comprises alpha-terpinyl ether, camplholytic ether (bornyl ether), isocampholytic ether, etc. The etherification rate of the reaction can reach 90 to 100%, and the maximal yield of the ether can reach more than 90%. The technology has the advantages of high conversion rate of the reaction, few products of a side isomerization reaction, high yield and low cost.

Description

Catalytic synthesising of monoterpene ether from natural mordenite

The invention belongs to the synthetic of single terpene base ether.

Some monoterpene alkene can carry out addition reaction with alcohol under acid catalysis, generate various single terpene base ethers, and a lot of single terpene base ethers can be used as spices and tensio-active agent etc.The technical report of past relevant monoterpene hydrocarbyl etherization, used catalyzer are various mineral acids or Zeo-karb.Burczxk Bogdan (C.A.7345613(1970) for example) make catalyzer with sulfuric acid, with α-Pai Xi respectively with methyl alcohol, ethanol, propyl alcohol and isopropanol reaction, obtain corresponding single terpene base ether, its maximum output is respectively 83.5%, 68%, 77% and 56%.And for example people such as Mnssinan C.J. report (U.S.Patent4,131,687(1978)) they with alkene and BF ₃.Et ₂O reacts in ethanol and has made this terpene base ether of 1.8-diethoxy-P-alkane, can be used as the spices and the pigment of food, medicine and makeup.With the synthetic more serious reaction isomerization of single terpene base ether ubiquity of aforesaid method, problems such as the low and equipment corrosion of productive rate.

1981 and 1985 we reported respectively with synthetic h-mordenite, catalysis geraniol and α-Pai Xi, amphene, alkene, with the alcohols reaction, make methoxyl group, oxyethyl group geraniol and α-terpinyl, positive bornyl, isobornyl and various ethers (Guangdong Province's chemistry meeting nd Annual Meeting (1981), chemical communication (86.4)), this method has the advantage that transformation efficiency is higher, isomerization is less, but artificial synthetic zeolite's price is expensive, and only be suitable for step production, so production cost is still higher.

At the problem in the aforesaid method, the present invention adopts cheap natural mordenite zeolite as catalyzer, use fixed bed adverse current, flow type reaction utensil, carry out the continous way catalyzed reaction, it is few that this reaction conversion ratio height, isomerization are paid reaction product, the product yield height, cost is low, is a kind of novel process of comparatively ideal production single terpene base ether.Core of the present invention is to make catalyzer with the natural mordenite zeolite through special processing, and with fixed bed adverse current successive reaction ware, catalysis monoterpene alkene and pure addition reaction obtain single terpene base ether.

The monoterpene alkene that is suitable for has: α-Pai Xi, beta-pinene, amphene, hesperidene (kautschin), terpinene etc.With the alcohol of terpenes addition can be methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, vinylcarbinol, ethylene glycol, geraniol, phenylcarbinol etc., the product of etherification reaction is α-pine oil ether, Borneolum Syntheticum base ether and isoborneol ether etc.Reaction conversion ratio is looked different material and reaction conditions (temperature, feed rate etc.) and is different, generally between 100～60%.The productive rate of ether is between 98～50%, and isomerization reaction is lower than 1～30%, can change method acquisition ideal results such as selectivity of catalyst by the control reaction conditions.

Embodiment of the present invention are as follows:

(1) Preparation of catalysts

Getting the natural mordenite zeolite (containing mordenite more than 50%) of Jinyun county, China Zhejiang Province natural zeolite mineral products handles as follows for raw material:

1. will sieve after the natural mordenite zeolite fragmentation, get 1～3mm magnitude range to make raw material stand-by, handle above-mentioned zeolites with hydrochloric acid or the sulfuric acid of 0.5～6N down at 90～100 ℃, the consumption of acid is four times (weight) of zeolite, during processing, heat while stirring, the treatment time is one hour.Repeat above-mentioned acid treatment process 4～12 times, wash with water above-mentionedly, be neutral until wash water through acid-treated mordenite, oven dry, place electric furnace or other process furnace to be heated to 400～600 ℃, roasting 3～8 hours repeats the operations process of above-mentioned acid treatment to roasting.

2. handling with ammoniacal liquor or ammonium bicarbonate soln through the mordenite of 1. handling; Ammonia concn is 0.5～2%, and ammonium bicarbonate soln concentration is 1～4%; The consumption of ammoniacal liquor or bicarbonate of ammonia is 4 times (weight) of zeolite consumption, at room temperature stirred 1 hour, wash with water to wash water and be neutral, oven dry, place electric furnace or other heating kiln roasting, maturing temperature is 350 ℃～450 ℃ (preferably 400 ℃), and the time is 3～8 hours, promptly makes the monoterpene catalyst for etherification.This catalyzer has stability and reproducibility preferably.

(2) the fixed bed countercurrent reactor synoptic diagram that carries out the etherification reaction fixed bed countercurrent reactor of monoterpene alkene is seen accompanying drawing 1.

Explanation about accompanying drawing 1:

1. feeder; 2. filling tube; 3. reactor; 4. heating jacket; 5. beds; 6. heat-carrier inlet; 7. heating medium outlet; 8. reflux exchanger; 9. condenser; 10. reaction product susceptor; 11. well heater; 12. thermal barrier circulation tube.

Reactor is Glass tubing (or stainless steel) the internal diameter 25mm that a heating jacket is arranged, 1.2 meters of length of tube, 1 meter of beds, fill the 1～3mm catalyzer for preparing in the reactor, reactor bottom has a sieve plate support catalyzer, reaction mass adds from the bottom, adverse current is passed through beds from top to bottom, reaction finishes and flows out by the condenser cooling from reactor head, reactor head is equipped with reflux exchanger, reflux for the lower boiling alcohols, the interlayer of reactor is by continuous round-robin thermal barrier, and visual response temperature requirement difference can water, oil or steam etc. are as thermal barrier.

Alkene and alcohols are made reaction mass according to certain proportioning, look different raw material and adopt different feed rates, and keep temperature of reaction by the thermal barrier in the reactor interlayer.

(3) regeneration of catalyzer

Catalyzer is through using more than half a year, activity descends gradually, can regenerate by laxative remedy: with slowly oven dry after the catalyzer with water flushing, place electric furnace slowly to be warming up to 550～600 ℃, kept 4～10 hours, repeat embodiment one described acid treatment process, use ammoniacal liquor (0.5～2%) or bicarbonate of ammonia (1～4%) re-treatment (treatment condition are described with embodiment one) again, wash with water to neutrality, oven dry, placed electric furnace or other heating kiln roasting 3～8 hours, 350～450 ℃ of maturing temperatures (preferably 400 ℃).After regeneration finishes, can recover original catalytic activity fully.

Example one

α-Pai Xi and ethanol etherificate system α-terpinyl ether and bornyl ether.

With industrial α-Pai Xi (containing α-Pai Xi 95%) and dehydrated alcohol is raw material, by α-Pai Xi: ethanol=1: the 10(mol ratio) prepare reaction mass and adopt the described fixed bed counter-current reactor of above-mentioned embodiment (two), react, fill the described catalyzer for preparing 550 grams of embodiment () in the reactor, temperature of reaction is 78 ℃ ± 2 ℃, the feed rate of reaction mass is 0.4 Grams Per Hour (weight space velocity, be that the reaction mass that every gram catalyzer per hour passes through is 0.4 gram), after fractionation, can obtain α-terpinyl ether and two products of bornyl ether simultaneously, α-Pai Xi transformation efficiency 100%, α-terpinyl ether productive rate is 45%, can obtain simultaneously 25% bornyl ether, carry out successive reaction by above-mentioned reaction conditions, catalyst life can keep must not regenerating more than half a year.

Example two

Amphene and methanol etherification synthetizing isoborneol base methyl ether

With industrial amphene (containing tricyclene alkene about 20%) and anhydrous methanol is raw material by amphene: methyl alcohol=1: the 20(mol ratio) reactant ligand material, for the dissolving amphene can suitably heat, adopt embodiment (two), described fixed bed counter-current reactor, fill the described catalyzer for preparing 550 grams of embodiment () in the reactor, temperature of reaction is 65 ℃ ± 2 ℃, the reaction mass feed rate is 0.2 Grams Per Hour (weight space velocity, be that every gram catalyzer is per hour by reaction mass 0.2 gram, after fractionation, can obtain purified isobornyl methyl ether, reaction result is that the amphene transformation efficiency is greater than 98%, isobornyl methyl ether productive rate is 95%, successive reaction, catalyzer can be used more than half a year, must not regenerate.

Example three

Kautschin and ethanol etherificate system α-terpinyl ether

Is raw material with industrial dipentene (content is more than 90%) with dehydrated alcohol, kautschin and ethanol proportioning are 1: the 10(mol ratio), adopt the described fixed bed counter-current reactor of embodiment (two), fill catalyzer 550 grams of the described preparation of embodiment () in the reactor, temperature of reaction is 78 ℃ ± 2 ℃, the reaction mass feed rate is 0.4 Grams Per Hour (weight space velocity, be that every gram catalyzer is per hour by reactant 0.4 gram), after fractionation, can obtain purified α-terpinyl ether, above-mentioned reaction double amylene transformation efficiency is more than 95%, α-terpinyl ether productive rate is more than 90%, and the successive reaction catalyst activity can keep must not regenerating more than half a year.

Claims (8)

1, a kind of directly method of synthetic single terpene base ether, this method comprises the steps:

1. the catalyzer of single terpene base ether is synthesized in preparation, natural mordenite zeolite was handled 1 hour at 90～100 ℃ with the acid of concentration 0.5～6N, acid is 4: 1 with the weight ratio of zeolite, repeat above-mentioned processing 4～12 times, in 400～600 ℃ of roastings 3～8 hours, ammoniacal liquor with 0.5～2% or 1～4% ammonium bicarbonate soln are handled the back in 350～450 ℃ of roastings 3～8 hours, make catalyzer.

2. be that raw material carries out etherification reaction in the fixed bed counter-current reactor with monoterpene alkene and alcohols, fill above-mentioned catalyzer in the reactor.

3. after catalyst activity reduction, can be after 4～10 hours 550～600 ℃ of roastings, repeat the acid treatment process of preparation catalyzer in the claim 1 and use ammoniacal liquor (or bicarbonate of ammonia) to handle again,, make catalyzer recover active at last in 350～450 ℃ of repetition roastings 3～8 hours.

2, method for preparing catalyst according to claim 1 is characterized in that the used acid of acid treatment mordenite is hydrochloric acid or sulfuric acid.

3, according to the method for preparing catalyst of claim 1, when it is characterized in that with ammoniacal liquor or ammonium bicarbonate soln processing, the consumption of ammoniacal liquor (or bicarbonate of ammonia) is four times of zeolite, one hour treatment time.

4,, it is characterized in that in the last roasting process that maturing temperature preferably is controlled at 400 ℃ according to the method for preparing catalyst of claim 1.

5, according to the etherification method of claim 1, the raw material terpene hydrocarbon that it is characterized in that etherification reaction can be: α-Pai Xi or beta-pinene or amphene, or hesperidene (kautschin), or terpinene, with the alcohol of terpenes addition can be: methyl alcohol or ethanol or n-propyl alcohol, or Virahol, or butanols or vinylcarbinol or ethylene glycol or phenylcarbinol, geraniol.

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