CN1146532C - Carboxylates in catalytic hydrolysis of alkylene oxides - Google Patents

Carboxylates in catalytic hydrolysis of alkylene oxides Download PDF

Info

Publication number
CN1146532C
CN1146532C CNB998156361A CN99815636A CN1146532C CN 1146532 C CN1146532 C CN 1146532C CN B998156361 A CNB998156361 A CN B998156361A CN 99815636 A CN99815636 A CN 99815636A CN 1146532 C CN1146532 C CN 1146532C
Authority
CN
China
Prior art keywords
acid
solid carrier
carboxyl
catalyzer
water
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
Application number
CNB998156361A
Other languages
Chinese (zh)
Other versions
CN1333738A (en
Inventor
E・M・G・A・范克鲁啻顿
E·M·G·A·范克鲁啻顿
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of CN1333738A publication Critical patent/CN1333738A/en
Application granted granted Critical
Publication of CN1146532C publication Critical patent/CN1146532C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
    • C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention relates to a process for the preparation of alkylene glycols by reacting an alkylene oxide with water in the presence of a catalytic composition including a polycarboxylic acid derivative, having in its chain molecule one or more carboxyl groups and one or more carboxylate groups, the individual carboxyl and/or carboxylate groups being separated from each other in the chain molecule by a separating group consisting of at least one atom. Preferably the polycarboxylic acid derivative is immobilised on a solid support.

Description

Carboxylate salt in catalytic hydrolysis of alkylene oxides
Technical field
The present invention relates in the presence of catalytic composition, react the method for preparing alkylene glycol by alkylene oxide and water.
Background of invention
Alkylene glycol, particularly single alkylene glycol are known commercial interesting products.For example, single alkylene glycol is used for anti-freezing composition, is used to prepare polyalkylene terephthalate as solvent with as base-material, as is used for fiber or bottle.
Knownly can prepare alkylene glycol by the alkylene oxide liquid-phase hydrolysis.This hydrolysis by adding a large amount of excessive waters such as every mole of alkylene oxide 20 to 25 mole of water are carried out, or is carried out with the excessive water of less degree in catalyst system under the situation of catalyst-free.Described reaction is considered to nucleophilic substitution reaction, and the cracking of alkylene oxide ring takes place thus, and water plays the nucleophilic reagent effect.Because the initial single alkylene glycol that forms also plays the nucleophilic reagent effect, so form the mixture of single alkylene glycol, two alkylene glycol and more senior alkylene glycol usually.In order to increase selectivity, must suppress at first the side reaction of competing mutually with hydrolysis alkylene oxide that take place between the product that generates and the alkylene oxide to single alkylene glycol.
A kind of effective way that suppresses side reaction is the relative populations that is increased in the water that exists in the reaction mixture.Though this method improvement to the selectivity of manufacture order alkylene glycol, the problem of its generation is must remove a large amount of water to reclaim product.
People have carried out sizable effort and have sought to need not to use a large amount of excessive waters to increase the replacement scheme of reaction preference.Usually these effort all concentrate on and select active higher hydrolyst, and disclose various catalyzer.
People all study to the bronsted lowry acids and bases bronsted lowry hydrolyst, this shows to use acid catalyst to increase speed of reaction, but selectivity is not had tangible disadvantageous effect, and use the lower selectivity to single alkylene glycol of the general acquisition of basic catalyst.
The known conversion to alkylene oxide of some negatively charged ion such as bicarbonate radical, bisulfite, formate and molybdate has good catalytic activity and single alkylene glycol is had good selectivity.Yet when using these anionic salt to be used as catalyzer in homogeneous system, a difficult problem can appear in the reaction product comprehensive process process of being undertaken by distillation, because described salt is indissoluble in described glycol, is easy to form semi-solid.Quaternary ammonium salt keeps solubility in the glycol reaction product.
Can obtain high conversion, good selectivity and low water/alkylene oxide ratio by disclosed method in EP-A 0156449 and EP-A 0160330 (being Union Carbide Corporation's application).According to these documents, the hydrolysis of alkylene oxide is carried out containing can improve in the presence of the anionic species that optionally metallizes, and this material is preferably has electropositive solid that the metallization negatively charged ion is had the coordination position of affinity.Described solid is anionite-exchange resin, particularly styrene diethylene benzene copoly mer preferably.Described electropositivity coordination position is quaternary ammonium, protonated tertiary amine Huo quaternary phosphine particularly.The metallization negatively charged ion is specially molybdate, wolframate radical, metavanadic acid root, pyrovanadic acid hydrogen root and pyrovanadium acid radical anion.The complicacy of this method is that the product logistics that contains alkylene glycol also comprises a large amount of metallization negatively charged ion that displaces from the electropositivity coordination position of containing the anionic solid matter that metallizes.For reducing the anionic quantity of metallization in the logistics of alkylene glycol product, this logistics is contacted with the solid with electropositivity coordination position, and described electropositivity coordination position with can be associated mutually by described metallization negatively charged ion metathetical negatively charged ion.
A kind of method for preparing alkylene glycol is disclosed in WO95/20559 (shell), wherein alkylene oxide and water react in the presence of catalyst composition, described catalyst composition comprises and has one or the solid matter at electropositivity position, many places, described position and one or more negatively charged ion such as coordination mutually of bicarbonate radical, bisulfite and carboxylate radical except that metallization or halide anion, condition be when described solid matter be quaternary ammonium salt type anionite-exchange resin and described negatively charged ion when being bicarbonate radical, described method exists and carries out there not being carbonic acid gas substantially.According to this document, the existence of carbonic acid gas is deleterious to the catalytic effect of the supercarbonate exchange resin of quaternary ammonium salt type in raw material.
The common shortcoming of conventional anionite-exchange resin is that they have limited tolerance to heat.Find when implementing the alkylene oxide method for hydrolysis of WO95/20559 using based on the catalyst composition of the organic quaternary ammonium ion exchanger of routine, under the alkylene oxide hydrolysis reaction condition of harshness (high temperature and/or long-time use), aggravate based on the catalytic activity (selectivity and/or transformation efficiency) of the catalyzer of conventional resin.In addition, under these reaction conditionss, these catalyzer generation swellings.
In EP-A 226799, disclose a kind of in the presence of the binary composition catalyzer of forming by monobasic or polycarboxylic acid and this carboxylic metal or ammonium salt, carry out the method that ethylene glycol or propylene glycol are produced in hydration by corresponding oxide compound.
The invention summary
The present invention relates in the presence of catalytic composition, react the method for preparing alkylene glycol by alkylene oxide and water, described catalytic composition comprises polycarboxylic acid derivatives, in the chain molecule of described derivative, have one or more carboxyl and one or more carboxylate groups, in chain molecule, make each carboxyl and/or carboxylate groups disconnected from each other by the separation group of forming by at least one atom.
The number of the carboxyl in described molecule is preferably the number that equals carboxylate groups at least.
In a preferred embodiment of the invention, polycarboxylic acid derivatives is fixed on the solid carrier as defined above.The solid catalyst that comprises this polycarboxylic acid derivatives that is fixed is novel.
Detailed description of the invention
But described carboxylate groups metal-salt such as basic metal and alkaline earth salt or ammonium salt.Preferred described carboxylate salt is an an alkali metal salt, most preferably is sodium salt.
Described separation group can comprise several atoms, and these atoms can be arranged in straight or branched or circlewise.Preferred described separation group is made up of single carbon atom.
The example of dicarboxylic acid derivatives of the present invention is single sodium salt of following acid, described acid is propanedioic acid, Succinic Acid, hexanodioic acid, tartrate, toxilic acid, terephthalic acid, oxysuccinic acid, suberic acid, phthalic acid, m-phthalic acid, quinolinic acid (2, the 3-pyridine dicarboxylic acid), 2, the 5-pyridine dicarboxylic acid, pyridine dicarboxylic acid (2, dipicolimic acid 2), 3, the 4-pyridine dicarboxylic acid, dinicotinic acid (3, the 5-pyridine dicarboxylic acid), tetrahydrobenzene-1,2-dicarboxylic acid (3,4,5, the 6-tetrahydrophthalic acid) and isomer, hexanaphthene-1,2-dicarboxylic acid (hexahydrophthalic acid) and isomer, hexanaphthene-1, the 1-dicarboxylic acid, thiophene-2, the 5-dicarboxylic acid, jervasic acid (4-oxa--4H-pyrans-2,6-dicarboxylic acid), thiophene-3,4-dicarboxylic acid etc.
The example of tricarboxylic acid derivative of the present invention is single sodium salt of citric acid, trimellitic acid (1,2, the 4-benzenetricarboxylic acid) and trimesic acid (1,3, the 5-benzenetricarboxylic acid).
The example of tetracarboxylic acid derivatives of the present invention is the single sodium and the double sodium salt of pyromellitic acid (1,2,4, the 5-benzene tertacarbonic acid).
So, here the polycarboxylic acid derivatives of Xian Dinging can be effective as the alkylene oxide hydrolyst in the homogeneous liquid reaction system.Yet when they used in the heterogeneous reaction system, these polycarboxylic acid derivatives showed special advantage, and wherein, they are fixed on the solid carrier, special but be as the solid matter with electropositivity position defined at WO95/20559 not exclusively.Particularly, when described solid carrier is strongly basic anion exchange resin, the exchange of its negatively charged ion and polycarboxylic acid derivatives of the present invention forms catalytic composition, described composition stable and keep its selectivity and stability and swelling more had tolerance under the reaction conditions of harshness.
Can use in numerous ion exchange resin (IER) any as solid carrier, particularly wherein basic group is strong basicity (anionic) IER of quaternary ammonium Huo quaternary phosphine, has the solid carrier at electropositivity coordination position of inorganic in nature such as the IER of carbon, silicon-dioxide, silicon-dioxide-aluminium sesquioxide, zeolite, glass and clay such as hydrotalcite based on vinyl pyridine, organopolysiloxane and other.In addition, immobilized coordination macrocylc compound such as crown ether etc. also can be used as solid carrier.
Be applicable to that the anionite-exchange resin in the inventive method itself is known, and many is commercial available, for example with trade name AMBERJET 4200, AMBERLITE 400, IRA 404, LEWATIT M 500WS, DOWEX 1 * 8, DOWEX MSA-1 (be based on polystyrene, with the product of divinyl benzene crosslinked), REILLEX HPQ (based on polyvinylpyridine, with divinyl benzene crosslinked) sold those.
The customization on different solid carrier materials such as polystyrene, acrylate and silicon-dioxide and the crown ether that wherein is fixed by IBC Advanced Technologies Inc., AmericanFork, Utah, USA sells with trade name SuperLig.
Catalyzer carboxylic acid derivative of the present invention can be secured on the described solid carrier by it is added in the solid carrier suspension with aqueous solution form, and can carry out or not carry out adaptation operation in the described carrier preparation step formerly.For example, when solid carrier is anionite-exchange resin, can single step by described resin is mixed in water-bearing media with catalyzer, washes with water subsequently carry out described fixing-or in two steps suddenly, at first with oxyhydroxide as aqueous sodium hydroxide solution with as described in resin be converted into its hydroxyl form, then add as described in catalyzer fix as described in carrying out.
Alkylene oxide as initial substance has their generic definition in the methods of the invention, that is, they are the compounds that have vicinal oxide compound (epoxy) group in its molecule.
Particularly suitable be the alkylene oxide of following general formula:
Figure C9981563600071
R wherein 1To R 4Represent hydrogen atom independently or have the randomly substituted alkyl of 1 to 6 carbon atom.By R 1, R 2, R 3And/or R 4Any alkyl of expression preferably has 1 to 3 carbon atom.As substituting group, can there be non-active portion, as oh group.Preferred R 1, R 2And R 3Represent hydrogen atom, R 4Represent unsubstituted C 1-C 3Alkyl, more preferably R 1, R 2, R 3And R 4All represent hydrogen atom.
Thereby the example of the alkylene oxide that is suitable for comprises oxyethane, propylene oxide, 1,2-butylene oxide ring, 2,3-butylene oxide ring and Racemic glycidol.Oxyethane and propylene oxide have special commercial significance.
As mentioned above, advantageously under the condition of not using excessive water, carry out the hydrolysis of alkylene oxide.In the method for the invention, the water yield scope that is fit to fully use is 1 to 15 mole of every mole of alkylene oxide, is 1 to 6 mole in the same datum preferable range.In the methods of the invention, when every mole of alkylene oxide only provides 4 or 5 mole of water, can realize highly selective usually to single alkylene glycol.
The inventive method can andnon-continuous operation manner be carried out.Yet, particularly in extensive embodiment, preferred this method of operate continuously.
This class continuation method can be carried out in fixed-bed reactor, operates with upper reaches or downward stream mode.Preferably operate with downward stream mode.
Described reactor can remain constant temperature, thermal insulation or its mixing condition.Isothermal reactor is the shell-tube type reactor normally, is the multitube type mostly, contains catalyzer in the wherein said pipe, and cooling agent flows outside pipe.Adiabatic reactor does not cool off, and leaves the product logistics of reactor and can independently cool off in the heat exchanger.
Under the situation of some selections, the catalytic conversion process of EO can be incomplete, and in this case, all the other EO can be at the reactor dead space thermal hydrolysis that is arranged under the catalyst bed.Because this thermal hydrolysis is less for the specificity degree that forms MEG, suggestion reduces to minimum with the liquid maintenance dose in reactor.Thereby can reducing its volume by arrangement internals or inert filler in the reactor outlet part, this realizes, and/or by in the reactor feed mixture, adding rare gas element such as nitrogen and under so-called drip condition, operating reactor and realize.
For obtaining reasonable time-yield value, suggestion is carried out described method under heating up and boosting.
The range of reaction temperature that is suitable for generally is 80 to 200 ℃, and wherein preferred range is 90 to 150 ℃.The common range of choice of reaction pressure is 200 to 3000, and preferred 200 to 2000kPa.For the periodical operation of described method, selected reaction pressure advantageously obtains by pressurizeing with rare gas element such as nitrogen.As needs, but the using gas mixture, and for example the mixture of carbonic acid gas and nitrogen is useful in some cases.
For adapting to any swelling of catalyzer, reactor volume can be advantageously greater than the occupied therein volume of catalyzer in operating process, and for example 10 to 70vol% or bigger.
Can understand the inventive method and be not limited to the operation in the presence of the catalyzer that is limited, carried out.In some cases, particularly when operating, find in the continuous flow mode, before finishing catalytic hydrolysis, make to small part according to appointment 30-60wt% alkylene oxide feed stream to stand the portion of hot hydrolysis under the condition that does not have catalyzer be favourable.Find, even the partial hydrolysis of carrying out under the condition that does not have catalyzer still has enough selectivity to forming single alkylene glycol, and this measure is effective for save catalyst on the other hand.
The problem that takes place sometimes in any method that oxyethane is hydrolyzed is to have small amount of amine and/or phosphine as impurity in the product logistics.When using strongly basic anion exchange resin to be used as the anionic solid carrier of catalysis, its basic group is quaternary ammonium or quaternary groups.Find that in operating process a spot of amine or phosphine are tending towards leaching in the product logistics from resin.In addition, the amine in the product logistics also can come from and add the sanitas in the employed water in the described method to.Though this class amine in the arrival final product and/or the quantity of phosphine pollutent are generally seldom, they can have a negative impact to the quality of final product, thereby may need to hold it in and be lower than detected value.For example, Trimethylamine 99 (TMA) and/or dimethylamine (DMA) can arrive in the final product up to the quantity of 10ppm, and quantity is low to moderate the TMA of 1ppb and just can produces fishy smell.
Any method that oxyethane is hydrolyzed, comprise the inventive method the product logistics in effective removal means of the amine that exists usually and/or phosphine be found in use and contain the guard bed of the strong-acid ion exchange resin that can effectively capture amine or phosphine.Strong-acid ion exchange resin is a sulfonic acid type.Commercially available example is with known those of trade mark AMBERLYST 15, AMBERJET 1500H, AMBERJET1200H, DOWEX MSC-1, DOWEX 50W, DIANON SK1B, LEWATIT VP OC1812, ELWATIT S 100 MB and ELWATIT S 100 G1.These strong-acid ion exchange resins can be H +With its salt form such as Na +Form obtains.When in guard bed, only using H +During the highly acidic resin of form, can be changed into tart therefrom flowing through the after product logistics.Use is H +The advantage that the strong-acid ion exchange resin mixture of form and its salt form is had is that the pH of product logistics keeps approaching neutrality.
Another guard bed additional advantage of strongly-acid is that any remaining alkylene oxide that still can be present in the product logistics is hydrolyzed to alkylene glycol, though it is lower to form the selectivity of single alkylene glycol.
In operating process, for adapting to the consumption of strong-acid ion exchange resin, advantageously guard bedly operate with two or more independently containers.
The strong-acid ion exchange resin of inactivation can be by using acid such as HCl and the H that is better than sulfonic acid group in the resin matrix 2SO 4Handle and regenerate.Equivalent concentration is that the hot sulfuric acid of 0.1-2 is proved to be effective.
Following examples explanation the present invention.
Embodiment
1. preparation catalyzer
I. test 1-12, in homogeneous catalysis system, carry out intermittent hydrolysis
In the reaction of EO intermittent hydrolysis, following carboxylic acid sample and sodium carboxylate salt are carried out the catalytic activity screening:
Dicarboxylic acid and carboxylate salt:
-oxalic acid HOOC-COOH and its list and disodium salt
-propanedioic acid HOOC-CH 2-COOH and its single sodium salt
-Succinic Acid HOOC-CH 2-CH 2-COOH and its list and disodium salt
-tartrate HOOC-CH (OH)-CH (OH)-COOH and its list and disodium salt
List and the disodium salt of-toxilic acid HOOC-CH=CH-COOH (cis);
-hexanodioic acid (HOOC-(CH 2) 4-COOH) and its single sodium salt
-terephthalic acid p-COOH-C 6H 4-COOH and its list and disodium salt
Tricarboxylic acid and carboxylate salt:
-citric acid HOOC-CH 2-C (OH) (COOH)-CH 2-COOH, it is single, two and trisodium salt
-trimellitic acid 1,2,4-C 6H 3(COOH) 3With its list and disodium salt
Tetracarboxylic acid and carboxylate salt:
-pyromellitic acid 1,2,4,5-C 6H 2(COOH) 4Single with it, two and trisodium salt
In the 250ml autoclave, pack into 30mmol polycarboxylic acid derivatives or correlated sodium bicarbonate and 5.55mol (100g) water.Some carboxylic acid derivative are the hydrate form to be bought and uses with this form.But be considered to not remarkable by the water yield that these hydrates (maximum value 210mmol) are introduced in reaction system, the add-on of water is not adjusted.
With nitrogen gas cap is purged 3 times, and adopt the 1000kPa original pressure.Described mixture heating up to 100 ℃.Stirring (500rpm) slow down oxyethane (44g that adds; 1 mole).Under continuously stirring, reaction mixture was kept 6 hours down at 100 ℃.The sample of gathering the end of run is used for GLC and analyzes.
Use homogeneous catalyst (carboxylic acid and carboxylic acid sodium) with the selective presentation that forms MEG carries out EO catalysis intermittent hydrolysis result of experiment and contrast experiment (catalyst-free and NaHCO 3) the results are shown in Table 1.
Table 1.
Experiment No. Catalyzer Selectivity (mol%) to MEG *
Acid Single sodium Disodium Trisodium
Contrast
1 - 67.8
2 NaHCO 3 85.0
Dicarboxylic acid derivatives
3 Oxalic acid 77.0 78.2 78.7
4 Propanedioic acid 73.7 83.1
5 Succinic Acid 72.2 82.7 53.1
6 Toxilic acid 83.2 48.9
7 Tartrate 72.5 82.4 66.0
8 Hexanodioic acid 72.3 80.3
9 Terephthalic acid 70.8 82.6 51.0
The tricarboxylic acid derivative
10 Citric acid 70.9 85.4 76.7 43.3
11 Trimellitic acid 74.5 84.3 64.8
Tetracarboxylic acid derivatives
12 Pyromellitic acid 74.7 83.9 84.6 72.7
* to selectivity (mol%)=100 * MEG/ (MEG+2DEG+3TEG) of MEG, under＞99.5%EO transformation efficiency, measure
The result shows that in all cases, polycarboxylic performance only slightly is better than uncatalyzed thermal response (selectivity to MEG is that 70.8-77.0% is to 67.8%).
Except that oxalic acid (not belonging to the present invention), when the single sodium salt that uses dicarboxylic acid obtains significantly to improve the MEG selectivity of (reaching 80.3-85.4%) during as catalyzer.Yet, when two carboxyls of dicarboxylic acid all are converted into carboxylate group, selectivity variation (48.9-66.0%).
Tricarboxylic acid is observed similar behavior: single sodium salt has best selective (84-85%), and trisodium analogue selectivity variation.Equally, when comparing with corresponding single sodium salt, tricarboxylic carboxylic acid disodium salt shows selectivity and reduces (though not remarkable) (64.8/76.7 is to 85%).
The performance of tetracarboxylic acid (pyromellitic acid) is similar, and carboxylic acid list and disodium salt all show best selective (83.9/84.6%) in this case.
II. test 13-17, the intermittent hydrolysis that in heterogeneous system, carries out
Use the strong basic ion exchange resin of two kinds of quaternary ammonium types:
-AMBERJET 4200, based on the resin of monodisperse cross-linked polystyrene/divinylbenzene, from Rohm﹠amp; Haas, the muriate form, exchange capacity 1.4mgq/ml and
-IRA 404, based on the resin of polydispersion crosslinked polystyrene/Vinylstyrene, from Rohm﹠amp; Haas, muriate form, exchange capacity 1.3mgq/ml.
By following described resin is handled with fixing described carboxylic acid derivative:
-the 150ml wet resin is slurried in the water filling Glass tubing;
(excessive 10 moles, in 2500g water) are to handle about 5 hours (LHSV:4l/h) with the exchange muriate in-usefulness sodium bicarbonate (contrast), monosodium citrate (the present invention) or trisodium citrate (contrast) aqueous solution;
2 hours (LHSV:4l/h) of resin washing that-usefulness 1200ml water will exchange;
-by this step, great majority (＞98%) cl anion is by required anionresin in the described resin.
In the 250ml autoclave, pack into catalyzer (30mmol) and water (1.00g, 5.55mol).With nitrogen gas cap is purged 3 times, and adopt the 1000kPa original pressure.Described mixture heating up to 100 ℃.Stirring (500rpm) slow down oxyethane (44g that adds; 1 mole).Under continuously stirring, reaction mixture was kept 6 hours down at 100 ℃.Take the sample of the end of run to be used for the GLC analysis.
Result's (EO transformation efficiency and MEG selective data) lists in the table 2.
Table 2
Experiment No. Catalyzer Catalyst amounts (mmol) EO transformation efficiency (%) * Selectivity (%) to MEG **
13 (contrasts) - - 99.2 67.8
15 (contrasts .) AMBERJET 4200 /HCO 3 - 30 99.0 88.3
16 AMBERJET 4200/ citrate single anion 30 99.5 79.3
17 IRA 404/ citrate single anion 30 99.6 79.8
18 (contrasts .) AMBERJET 4200/ citrate trianion 30 99.7 58.3
* EO transformation efficiency (%)=100% * (MEG+2DEG+3TEG)/(EO+MEG+2DEG+3TEG)
* is to selectivity (%)=100 * MEG/ (MEG+2DEG+3TEG) of MEG
The result shows in the table 2, and is similar to the discovery in homogeneous catalysis system, and same in heterogeneous system, polycarboxylic part salt is gratifying catalysts selective, and salt then is not completely.
III. test 19-20, the catalyst stability test
Estimate the thermostability of AMBERJET 4200/ carboxylate catalyst, and compare with the thermostability of AMBERJET4200/ supercarbonate.Test thermostability by the 20ml catalyzer being placed the 65cm Hoke pipe that is provided with the heating jacket that uses the deep fat system long, 0.5 inch wide.In 48 hours, under 150 ℃ and 1000kPa pressure, pump into current through catalyst bed with the LHSV of 1l/l.h with the HPLC pump.From described reactor, shift out catalyst samples then.By titration determination strong basicity capacity (quaternary ammonium group), weakly alkaline capacity (tertiary amine group) and total negatively charged ion capacity (aforementioned two kinds of capacity sums) in fresh and used catalyzer, and observe its difference % (variation in use).
The results are shown in Table 3.
Table 3
Strong basicity capacity (mmol/g) Weakly alkaline capacity (mmol/g) Total negatively charged ion capacity (mmol/g)
Experiment No. catalyzer 150 ℃ t=0 hour 150 ℃ t=48 hour Change % 150 ℃ t=0 hour 150 ℃ t=48 hour Change % 150 ℃ t=0 hour 150 ℃ t=48 hour Change %
19AMBERJET 4200/ bicarbonate radical 3.19 1.15 -64 0.27 0.68 +152 146 1.83 -47
20AMBERJET 4200/ citrate single anion 3.19 2.23 -30 0.27 0.46 +70 3.46 2.69 -22
These results show that in this harsh accelerated stability test, IER/ citrate single anion catalyzer is stable higher 2 times than corresponding bicarbonate radical catalyzer.
IV. test 21, continuous hydrolysis in heterogeneous catalytic system.
Use AMBERJET 4200/ citrate single anion catalyzer to carry out this test, (water: the EO molar ratio is 5.0 to 18.9 wherein to change the parameter of method; LHSV is 0.81-0.95, and the bed top temperature is 95-112 ℃).Regularly gather sample.
The results are shown in Table 4.
Table 4
Operating time (hour) H 2O/EO mol ratio LHSV(l/l.h) The bed top temperature (℃) EO transformation efficiency (mol%) * Selectivity (mol%) to MEG **
75 8.1 0.91 112 98.8 97.7
107 8.1 0.88 99.3 96.7
153 8.0 0.89 99.3 96.8
223 11.9 0.90 100.0 97.4
270 12.1 0.94 103 99.7 97.8
317 18.9 0.95 105 100.0 98.4
392 18.8 0.95 107 100.0 98.3
417 5.0 0.85 103 97.2 93.8
465 13.5 0.90 100.0 97.0
486 12.1 0.91 102 99.8 97.7
528 5.1 0.87 97.7 94.5
704 5.0 0.82 102 98.3 95.3
772 5.0 0.87 97.5 96.0
847 5.0 0.81 95 96.9 96.3
*: EO transformation efficiency (mol%)=100 * (MEG+2DEG+3TEG)/(EO+MEG+2DEG+3TEG)
*: to selectivity (mol%)=100 * MEG/ (MEG+2DEG+3TEG) of MEG
V. test 22 and 23, the EO continuous hydrolysis
Using AMBERJET 4200/ citrate single anion catalyzer in the fixture bed experiment continuously.Compare with the long-time performance of AMBERJET 4200/ bicarbonate radical under identical method condition.
This test is carried out in the one way mode.The long reactor of 24cm is made of the wide Glass tubing of the 20mm (internal diameter) in the wide stainless steel metal pipe of 34mm.Between glass reactor tubes and SS outer tube, use Teflon (PTFE) layer as isolator.The SS pipe uses electric heating system to compensate calorific loss outside; The temperature set-point of this heating unit is set at the temperature of water/EO reactor feed.The catalyzer of described reactor charge 60ml.With the water feeding preheating with reach required reactor inlet temperature before EO mixes.Use is arranged on the thermopair of reactor head and measures the temperature of described charging, uses to be arranged in the thermopair that reactor outlet just is lower than catalyst bed and to measure temperature out.
Method condition in these experimentations is listed in the table 5.1.
Table 5.1
Pressure (kPa) 1000
Reactor inlet temperature (℃) 65-90
The reactor outlet temperature (℃) 85-110
H 2O/EO flow velocity (ml/h) 130-150
H 2O/EO Mol ratio (mol/mol) 10-25
LHSV(l/l.h) 2.3-2.5
This contrast experiment the results are shown in table 5.2 and 5.3, shows that AMBERJET 4200/ citrate catalyzer has the life-span of remarkable increase under applied method condition when when corresponding bicarbonate radical catalyzer compares.
Table 5.2
AMBERJET 4200/ bicarbonate radical catalyzer
Operating time (hour) EO transformation efficiency (%)
90 99.8
425 99.7
670 99.9
750 98.3
1000 99.1
1200 99.2
1365 99.5
1400 96.2
1600 94.7
1675 76.3
Table 5.3
AMBERJET 4200/ citrate catalyzer
Operating time (hour) EO transformation efficiency (%)
90 99.9
425 99.9
670 99.8
750 99.9
1000 99.7
1200 99.9
1365 99.7
1400 99.7
1600 99.7
1745 99.6
1895 99.6
1944 99.6
2060 99.4
2350 99.3
2500 98.9

Claims (10)

1. in the presence of catalytic composition, react the method for preparing alkylene glycol by alkylene oxide and water, described catalytic composition comprises polycarboxylic acid derivatives, in the chain molecule of described derivative, have one or more carboxyl and one or more carboxylate group, in chain molecule, make each carboxyl and/or carboxylate group disconnected from each other by the separation group of forming by at least one atom.
2. the method for claim 1 is characterized in that described separation group is made up of single carbon atom.
3. claim 1 or 2 method is characterized in that described polycarboxylic acid derivatives is a citric acid derivant.
4. the method for claim 3 is characterized in that described citric acid derivant is the citric acid single anion.
5. claim 1 or 2 method is characterized in that described carboxylic acid derivative is fixed on the solid carrier.
6. the method for claim 5 is characterized in that described solid carrier is the carrier with electropositivity position.
7. the method for claim 6 is characterized in that described solid carrier is the anionite-exchange resin of quaternary ammonium Huo quaternary phosphine type.
8. the method for claim 5 is characterized in that described solid carrier is a clay.
9. the method for claim 5 is characterized in that described solid carrier comprises the big ring that is fixed.
10. be applicable to by alkylene oxide and water and react the catalyst composition for preparing alkylene glycol, described catalyst composition comprises polycarboxylic acid derivatives, in the chain molecule of described derivative, have one or more carboxyl and one or more carboxylate group, make each carboxyl and/or carboxylate group disconnected from each other by the separation group of being made up of at least one atom in chain molecule, this polycarboxylic acid derivatives is fixed on the solid carrier.
CNB998156361A 1998-12-14 1999-12-13 Carboxylates in catalytic hydrolysis of alkylene oxides Expired - Fee Related CN1146532C (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP98204234.3 1998-12-14
EP98204234 1998-12-14
EP99201348 1999-04-29
EP99201348.2 1999-04-29

Publications (2)

Publication Number Publication Date
CN1333738A CN1333738A (en) 2002-01-30
CN1146532C true CN1146532C (en) 2004-04-21

Family

ID=26150968

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB998156361A Expired - Fee Related CN1146532C (en) 1998-12-14 1999-12-13 Carboxylates in catalytic hydrolysis of alkylene oxides

Country Status (9)

Country Link
EP (1) EP1140750A1 (en)
JP (1) JP2002532448A (en)
KR (1) KR20010082339A (en)
CN (1) CN1146532C (en)
AU (1) AU759133B2 (en)
BR (1) BR9916242A (en)
CA (1) CA2354777A1 (en)
PE (1) PE20001571A1 (en)
WO (1) WO2000035842A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6562890B2 (en) * 2001-03-29 2003-05-13 Milliken & Company Disodium hexahydrophthalate salt compositions and nucleated polymers comprising such compositions
US6448456B1 (en) 2001-05-31 2002-09-10 The Dow Chemical Company Process for the preparation of alkylene glycols
NZ515366A (en) * 2001-11-08 2004-07-30 Univ Waikato Method for producing vicinal diols of compounds (especially lanosterol and cyclohexane derivatives) by reacting compounds with acids with pKa of less than or equal to 2 in the presence of one or more reagents capable of supplying hydroxy groups
US7435858B2 (en) 2004-12-23 2008-10-14 Shell Oil Company Process for the preparation of alkylene glycols
US7663005B2 (en) * 2007-05-30 2010-02-16 Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg Process for preparing an alkylene glycol
US8053609B2 (en) * 2007-10-15 2011-11-08 Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg Solid catalyst useful for converting an alkylene oxide to an alkylene glycol

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2256907C3 (en) * 1972-11-20 1982-03-18 Henkel KGaA, 4000 Düsseldorf Process for the production of vicinal di- and polyols
EP0226799B1 (en) * 1985-11-18 1992-01-02 MITSUI TOATSU CHEMICALS, Inc. Method for preparing ethylene glycol and/or propylene glycol

Also Published As

Publication number Publication date
CA2354777A1 (en) 2000-06-22
PE20001571A1 (en) 2001-01-26
CN1333738A (en) 2002-01-30
AU2098100A (en) 2000-07-03
WO2000035842A1 (en) 2000-06-22
JP2002532448A (en) 2002-10-02
AU759133B2 (en) 2003-04-03
BR9916242A (en) 2001-10-02
KR20010082339A (en) 2001-08-29
EP1140750A1 (en) 2001-10-10

Similar Documents

Publication Publication Date Title
RU2233261C2 (en) Method for preparing alkylene glycols and catalytic composition for their preparing
CN1023809C (en) Einc-containing solid catalyst, process of preparing same and process for preparing polyalkylene carbonate
CN1139916A (en) Process for the preparation of alkylene glycols
RU2222522C2 (en) Method for preparing alkylene glycols
JP5306200B2 (en) Method for producing alkylene carbonate
CN101528649B (en) Process for the preparation of alkylene glycol
CN1056865A (en) Be used to produce 1, the catalyzer of 3-glycol and/or 3-hydroxy aldehyde and preparation method and application thereof
CN1071411A (en) The purification process of carboxylic acid and/or its acid anhydrides
CN1202146A (en) Preparation of polyalcohols
CN1149186C (en) Quaternary phosphonium salt catalysts in catalytic hydrolsysi of alkylene oxides
CN86107894A (en) Prepare ethylene glycol and (or) method of propylene glycol
CN1146532C (en) Carboxylates in catalytic hydrolysis of alkylene oxides
CN1845785A (en) Method of producing unsaturated aldehyde and unsaturated acid in fixed-bed catalytic partial oxidation reactor with enhanced heat control system
CN1155550C (en) Catalyst stabilising additive in the hydrolysis of alkylene oxides
CN1239449C (en) Catalytic process for producing an alkylene glycol with reactor-output recycle
CN1272307C (en) Procdss for preparing hydroxyaldyl (meth) acrylate
JPH0737422B2 (en) Process for producing dialkyl carbonate
CN1467194A (en) Hydroxyalkyl(meth)acrylate and process for the preparation
RU2467995C2 (en) Method of producing alkylene glycol
CN1178718A (en) Method for producing diester carbonate
RU2230728C2 (en) Alkylene oxide hydrolysis method involving catalyst-stabilizing additive
CN1518529A (en) Process for preparation of alkylene glycols
CN1168699C (en) Prepn. of substituted aromatic amines
CN1216031C (en) Method of preparing valeryl acetate
CN1720220A (en) Method for inhibiting polymerization during the recovery and purification of unsaturated mononitriles

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination
PB01 Publication
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee