CN109647516A - The catalyst of polyoxymethylene dimethyl ether preparation - Google Patents
The catalyst of polyoxymethylene dimethyl ether preparation Download PDFInfo
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- CN109647516A CN109647516A CN201710937995.8A CN201710937995A CN109647516A CN 109647516 A CN109647516 A CN 109647516A CN 201710937995 A CN201710937995 A CN 201710937995A CN 109647516 A CN109647516 A CN 109647516A
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- 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
- B01J31/10—Ion-exchange resins sulfonated
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/58—Separation; Purification; Stabilisation; Use of additives
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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
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Abstract
The present invention relates to the catalyst of polyoxymethylene dimethyl ether preparation, it solves the problems, such as low as Material synthesis polyoxymethylene dimethyl ether handicraft product yield using dimethoxym ethane with paraformaldehyde, by using the catalyst of polyoxymethylene dimethyl ether preparation, the catalyst is metal ion-modified cation exchange resin, the metal includes the technical solution of IB race metal, preferably solves the technical problem.
Description
Technical field
The present invention relates to the catalyst of polyoxymethylene dimethyl ether preparation.
Background technique
The resource pattern in China has the characteristics that " rich coal, has gas at few oil ", and the flourishing industrial development in China supplies petroleum
To proposing the requirement increased increasingly.But in recent years, China's oil resource day is becoming tight, and petroleum supply pressure unprecedentedly increases.
According to statistics, China's oil external dependence degree in 2011 reaches 56.5%, rises 1.7 percentage points than 2010.China since
Since 1993 become net import of oil state for the first time, for China Petroleum external dependence degree by 6% rising all the way of current year, 2009 prominent
Broken 50% warning line.How to be become using the energy crisis that China's coal resources abundant solve China as researcher urgency
Problem to be solved.Therefore the attention of people is increasingly subject to by coal base exploitation novel fuel substitute.
In addition to this, due to the dual-pressure of air pollution and energy shortages, energy-saving and emission-reduction have become great society development
Theme.Therefore, petrochemical industry is dedicated to developing the diesel fuel of novel emission reduction for a long time.Many emerging substitute diesels
Exploitation is just come into being, comprising: GTL diesel oil, biodiesel, ethanol diesel fuel, dimethyl ether, diesel oil oxygenatedchemicals, emulsified diesel
Oil etc..They are to be substantially free of the impurity such as sulphur, nitrogen, aromatic hydrocarbons without being produced with petroleum with synthetic method mostly, are pole cleanings
Diesel oil or diesel oil blending component, be highly valued in recent years, each state is all putting forth effort to be developed and promoted and applied.This its
In, using diesel oil blending component, without in addition increasing device or changing engine structure, therefore it is considered as that one kind is convenient, has
The measure of effect.
Dimethyl ether is proposed as a kind of procetane earliest, and appropriate dimethyl ether is added into diesel oil effectively to be subtracted
Particulate matter and CO in few tail gasxAnd NOxDischarge.However dimethyl ether is since there is also some defects for its own physical property, such as
Itself cold starting performance is poor, vapour pressure is high under room temperature, is easy to produce vapour lock there are also storing, transport, low-pressure liquefied contour cost,
These make dimethyl ether significantly raised as the cost of vehicle alternative fuel.Polyoxymethylene dimethyl ether, i.e. Polyoxymethylene
Dimethyl ethers (PODE), is the common name of a substance, and skeleton symbol can be expressed as CH3O(CH2O)nCH3, have higher
Cetane number (> 40) and oxygen content (42~51%).When the value of n is 1, polyoxymethylene dimethyl ether is dimethoxym ethane, is used
Although dimethoxym ethane can also improve efficiency of energy utilization as vehicle fuel addO-on therapy, exhaust emissions is reduced, but still easily causes gas
Plug.When n value is 2~6, physical property, combustibility and diesel oil are very close, preferably resolve dimethyl ether and first contracting
Aldehyde is as defect existing for derv fuel blend component.Therefore polyoxymethylene dimethyl ether can be used as novel cleaning diesel component,
Additive amount in diesel oil can improve the combustion position of diesel oil within the engine, improve the thermal efficiency up to 10% (v/v) or more,
Reduce the particulate matter and CO in tail gasxAnd NOxDischarge.The a length of n=3,4 of polyoxymethylene dimethyl ether optimal chain mixed with diesel oil.
When n=2, the flash-point of polyoxymethylene dimethyl ether is too low, and when n is excessive, polyoxymethylene dimethyl ether may precipitate blocking at low temperature.According to report
Road, the CH of addition 5~30%3OCH2OCH3NO can be greatly reducedxDischarge.
It is paraformaldehyde section among PODE, both ends are by methyl blocking.Therefore generally by the compound (first of offer paraformaldehyde
Aldehyde, metaformaldehyde and paraformaldehyde etc.) and provide sealing end methyl compound (methanol, dimethyl ether and dimethoxym ethane etc.) Lai Hecheng
PODE.PODE can be synthesized by dimethoxym ethane and formaldehyde or paraformaldehyde, metaformaldehyde by acid-catalyzed dehydration.It is synthesized by coal gasification system
Gas is synthesized by synthesis gas synthesizing methanol, dimethoxym ethane, by methanol oxidative synthesis formaldehyde, formaldehyde prepares paraformaldehyde or trimerization first
Aldehyde is industrialized process already.Part diesel oil can not only be replaced by synthesizing PODE by coal-based methanol, moreover it is possible to improve diesel oil
Efficiency of combustion, reduce harm of the diesel combustion to environment, there is important strategic importance and good economic value.PODE's
Develop and synthesis, China's coal resources abundant can be converted to liquid alternative fuel, reduce China to the import of petroleum according to
Degree of depositing, and then be of great importance to national energy security.
Polyoxymethylene dimethyl ether can be by oligomeric in 150~180 DEG C of heating in the presence of trace sulfuric acid or hydrochloric acid in laboratory
The method preparation that right paraformaldehyde or paraformaldehyde are reacted with methanol.Since polyoxymethylene dimethyl ether has in diesel fuel additives field
There is huge application value, since a very long time, practicable industry life is all being studied by numerous companies and research institute
Production technology.
EP2228359A1 describes a kind of process for preparing polyoxymethylene dimethyl ether for initial feed by methanol.The party
It is catalyst that method, which is used by ammonium molybdate and Ferric nitrate modified molecular sieve, by methanol under 200 DEG C of conditions above of temperature with sky
The oxidation of gas (oxygen) step obtains polyoxymethylene dimethyl ether.This method production cost is relatively low, but catalyst preparation process is complicated,
And the selectivity of polyoxymethylene dimethyl ether is unsatisfactory.
EP1070755 describes a kind of react in the presence of three fluosulfonic acid by dimethoxym ethane with paraformaldehyde and prepares per molecule
In with 2~6 formaldehyde units polyoxymethylene dimethyl ether method.WO2006/045506A1 describes BASF AG and uses sulphur
Acid, trifluoromethanesulfonic acid have obtained the series of n=1~10 using dimethoxym ethane, paraformaldehyde, metaformaldehyde as raw material as catalyst
Product.Above method is all made of Bronsted acid as catalyst, and this catalyst is cheap and easy to get, but corrosivity is strong, it is difficult to separate, ring
Border pollution is big, to the demanding disadvantage of equipment.
US6160174 and US6265528 describes BP company and uses methanol, formaldehyde, dimethyl ether and dimethoxym ethane for raw material,
Using cation exchange resin as catalyst, gas-solid phase reaction obtains polyoxymethylene dimethyl ether.Although but this method have urge
The advantages that agent can be easily separated, and be conducive to circulation, but reaction conversion ratio is low, and yield is not high, complex process.
CN 101768057A synthesizes poly- first using solid super-strong acid as catalyst using methanol and metaformaldehyde as raw material
Aldehyde dimethyl ether, although achieving preferable feed stock conversion, since the acidity of solid super-strong acid is strong, irregular pore structure
So that for the selectivity of by-product dimethoxym ethane 20~50%, a large amount of presence of dimethoxym ethane can reduce the sudden strain of a muscle of diesel fuel mixtures in product
Therefore point simultaneously damages its quality, so that product is unsuitable to be used as procetane.CN 101048357A describe it is a kind of with
Dimethoxym ethane and metaformaldehyde are the synthesis technology of Material synthesis polyoxymethylene dimethyl ether.We are also developed ourselves and are urged using solid acid
Agent (molecular sieve CN 200910056820.1, solid super-strong acid CN 200910056819.9) is original with methanol and metaformaldehyde
Material prepares polyoxymethylene dimethyl ether.
However it is reaction raw materials that these techniques, which are all made of metaformaldehyde, according to market survey it is found that the price of metaformaldehyde
It is 14000 yuan/ton；The price of comparison paraformaldehyde, only 5000 yuan/ton.We are it is not difficult to find that raw by raw material of paraformaldehyde
Production cost can be significantly reduced by producing polyoxymethylene dimethyl ether.
CN 101182367A is described using acidic ionic liquid as catalyst, is synthesizing triformol by formaldehyde, then
With the process of metaformaldehyde and methanol-fueled CLC polyoxymethylene dimethyl ether.Although this method one-way yield is high, the ion used
Liquid catalyst is expensive, is not readily separated, and operation difficulty is larger.US5,959,156 is described with dimethyl ether and methanol as original
The synthesis technology of the polyoxymethylene dimethyl ether of material promotes condensation catalyst using novel multiphase.Although cost is relatively low for the technique,
It is that product yield is undesirable.
Summary of the invention
The first technical problem to be solved by the present invention is that the prior art is poly- as Material synthesis using dimethoxym ethane and paraformaldehyde
The low problem of formaldehyde dimethyl ether handicraft product yield provides a kind of new polyoxymethylene dimethyl ether catalyst for preparing.The catalyst
Have the advantages that the selectivity of product of n=2-10 is high.
The second technical problem to be solved by the present invention is to provide a kind of using catalyst described in one of above-mentioned technical problem
Preparation method.
The third technical problem to be solved by the present invention is the application of catalyst described in one of above-mentioned technical problem.
One of in order to solve the above-mentioned technical problem, technical scheme is as follows:
The catalyst of polyoxymethylene dimethyl ether preparation, the catalyst are metal ion-modified cation exchange resin,
The metal includes IB race metal.The metal-modified sulfonic acid polystyrene cation exchange resin of IB race, significantly improves to n=
The selectivity of 2~10 PODE.
In above-mentioned technical proposal, IB race element preferably is selected from least one of Cu and Ag；More preferable Cu.
In above-mentioned technical proposal, the content of modified metal is not particularly limited in catalyst, such as, but not limited to catalyst
The content of middle modified metal is greater than 0 and to be less than or equal to 9.8w%.
In above-mentioned technical proposal, the full exchange capacity of the resin is 3.0~5.9mmol/g.
In above-mentioned technical proposal, the resin can be gel-type or macroporous type.
In above-mentioned technical proposal, the resin is preferably sulfonic acid polystyrene cation exchange resin.
In above-mentioned technical proposal, the sulfonic acid polystyrene includes crosslinked polystyrene skeleton and sulfonic acid group.
In above-mentioned technical proposal, the metal preferably includes VIIB metal.
In above-mentioned technical proposal, VIIB metal preferably is selected from selected from least one of Mn or Tc, Cu and Mn and Cu and Tc
There is synergistic effect in terms of improving to the selectivity of the PODE of n=2~10.Ratio between Cu and Mn and Cu and Tc does not have
There is special limitation, being such as, but not limited to independently selected from mass ratio is 0.01~100, within this range further non-restrictive
Such as 0.1,0.5,0.8,1,1.5,2,3,4,5,6,7,8,9,10 etc..
In above-mentioned technical proposal, VIIB metal more preferably includes Mn and Tc, and Mn and Tc are improving the PODE to n=2~10
Selectivity in terms of have synergistic effect.Ratio between Mn and Tc is not particularly limited, and is such as, but not limited to selected from mass ratio
Be 0.01~100, within this range further non-restrictive such as 0.1,0.5,0.8,1,1.5,2,3,4,5,6,7,8,
9,10 etc..
In order to solve the above-mentioned technical problem two, technical scheme is as follows:
The preparation method of catalyst described in any one of technical solution of one of above-mentioned technical problem, is included in catalytic amount
Acid in the presence of, the cation exchange resin and the suspension containing the modified metal-oxide and/or hydroxide are connect
Touching carries out ion exchange.
In above-mentioned technical proposal, the acid is not particularly limited, if can with containing the modified metal-oxide and/or
The salt that hydroxide reacts can be dissolved in solvent used in the suspension and be ok, under this principle such as, but not limited to
At least one of hydrochloric acid, nitric acid or carboxylic acid of C2~C10.
In above-mentioned technical proposal, the carboxylic acid can be hydroxyl substituted carboxylic acid, such as, but not limited to hydroxyacetic acid, lactic acid,
Tartaric acid, citric acid etc..
In above-mentioned technical proposal, the carboxylic acid can be the monoacid of C2~C10, such as, but not limited to acetic acid etc..
To solve above-mentioned technical problem three, technical scheme is as follows:
Application of any one of one of the above-mentioned technical problem catalyst in synthesizing polyoxymethylene dimethyl ethers.
Key problem in technology of the invention is the selection of catalyst, and to specific application method, those skilled in the art can be closed
Reason selects and need not pay creative labor.
Such as specific application method may is that
By the process of dimethoxym ethane and paraformaldehyde synthesizing polyoxymethylene dimethyl ether, this method includes reaction zone and separation
Area, reaction zone include nitrogen storage tank, dimethoxym ethane storage tank, the mixing channel with heater, drying tube and bubbling reactor, reaction zone work
Skill step is that paraformaldehyde is heated to be formaldehyde gas in mixing channel, after nitrogen purging is sent to drying tube water removal, into drum
Reaction kettle is steeped, under the action of solid acid catalyst, it is poly- to react generation with the mixture that dimethoxym ethane and recycling are passed through reaction kettle
Formaldehyde dimethyl ether, Disengagement zone include anion exchange resin bed layer, rectifying module and product storage tank, and the processing step of Disengagement zone is
Reactor discharging enters rectifying module after the deacidification of anion exchange resin bed layer, by the separation of rectifying module, polyformaldehyde
Dimethyl ether three, tetramer enter product storage tank, other components are recycled to reactor.
In above-mentioned technical proposal, dimethoxym ethane: the mass ratio of paraformaldehyde is preferably 0.02~50: 1.Reaction temperature is preferably
50~250 DEG C；Reaction pressure is 0.01~20.0MPa.Reaction time is preferably 0.5~10.0h.Mixing channel temperature is preferred
It is 200~300 DEG C, more preferably 240~280 DEG C.Recycling is passed through reaction kettle mixture and is preferably contained by what rectifying module separated
Have the first fraction of dimethoxym ethane, the second fraction containing methanol polyoxymethylene dimethyl ether dimer, and containing more high polymerization degree (n >
4) the 4th fraction of polyoxymethylene dimethyl ether；It is preferred that rectifying module also isolate containing polyoxymethylene dimethyl ether three, tetramer
Third fraction.The rectifying module is preferably made of 3 rectifying columns.First fraction is preferably discharged by first rectifying column tower top,
Second fraction is preferably discharged by Second distillation column tower top, and third fraction is preferably discharged by third distillation column tower top, and the 4th fraction is excellent
Choosing is discharged by third distillation column tower bottom.First, second and the 4th fraction preferably after dehydrater removes water circulation and stress to react
System.The operating pressure of first rectifying column is preferably 0.2~2MPa, and the operating pressure of Second distillation column is preferably 0.02~
1.2MPa, the operating pressure of third distillation column are preferably 0.001~0.6MPa.The theoretical cam curve of first rectifying column is preferably 15
~25, the theoretical cam curve of Second distillation column is preferably 15~30, and the theoretical cam curve of third distillation column is preferably 15~35.
In above-mentioned technical proposal, the solid acid catalyst is selected from above-mentioned metal-modified cation exchange resin.
In order to solve the above-mentioned technical problem two, technical scheme is as follows:
In above-mentioned technical proposal, the preparation method of the catalyst, including in the presence of the acid of catalytic amount, by the sulphur
Acid type polystyrene cation exchange resin contacts progress with the suspension containing the modified metal-oxide and/or hydroxide
Ion exchange.
In above-mentioned technical proposal, the acid is not particularly limited, if can with containing the modified metal-oxide and/or
The salt that hydroxide reacts can be dissolved in solvent used in the suspension and be ok, under this principle such as, but not limited to
At least one of hydrochloric acid, nitric acid or carboxylic acid of C2~C10.
In above-mentioned technical proposal, the carboxylic acid can be hydroxyl substituted carboxylic acid, such as, but not limited to hydroxyacetic acid, lactic acid,
Tartaric acid, citric acid etc..
In above-mentioned technical proposal, the carboxylic acid can be the monoacid of C2~C10, such as, but not limited to acetic acid etc..
In above-mentioned technical proposal, desiccant used in drying tube, dehydrater preferably is selected from following at least one desiccant: from
Sub-exchange resin, molecular sieve, Silica hydrogel.
In above-mentioned technical proposal, the rectifying column is preferably packed tower, and filler is preferably ordered structure stainless steel or ceramics.
The present invention has the following advantages: first, yield and selection rate are high, and the sum of n=3 and n=4 product accounts for the product of n=2~5
Summation is high；Second, lower production costs；Third makes by-product circulation and stress using the method for rectifying；Achieve preferable technology
Effect.
Detailed description of the invention
The present invention 1 is further described with reference to the accompanying drawings.Fig. 1 is process flow chart of the invention.
The nitrogen (logistics 2) that nitrogen storage tank 1 exports purges paraformaldehyde (logistics 3) to mixing channel 4, mixing channel 4 with plus
Hot device 5 is connected, and paraformaldehyde is heated to gas in mixing channel 4, the logistics 6 of output (for nitrogen, formaldehyde gas, vapor
Gaseous mixture) it is dry except vapor obtains material 8 by drying tube 7, material 8 is fed into bubbling reactor 9, at the same to reactor 9 into
The logistics 14 (liquid phase dimethoxym ethane) of material also exported by dimethoxym ethane storage tank 13, the material 19 removed water by 15 recovered overhead of rectifying column
(main component is dimethoxym ethane), and (main component is methanol and polyoxymethylene dimethyl ether by the material 24 after the water removal of dehydrater 23
Two, five, hexamer).Reactor discharging 10 obtains material 11 into rectifying after the deacidification of anion exchange resin bed layer 12
Tower 15 is separated.Unreacted dimethoxym ethane discharges (logistics 17) from 15 tower top of rectifying column, discharges after the water removal of dehydrater 18
19 are passed through bubbling reactor 9 again.The discharging of 15 tower bottom 16 of rectifying column enters rectifying column 20 and carries out next step separation.Unreacted first
Alcohol and the polyoxymethylene dimethyl ether dimer of generation discharge (logistics 22) from 20 tower top of rectifying column, the weight after the water removal of dehydrater 23
Newly it is passed through bubbling reactor 9.20 tower bottom of rectifying column discharging 21 enters rectifying column 25 and carries out next step separation.Polyoxymethylene dimethyl ether
Trimer and tetramer discharge (logistics 27) from 25 tower top of rectifying column, into product storage tank 28.The poly- first of the degree of polymerization higher (n > 4)
Aldehyde dimethyl ether discharges (logistics 26) from 25 tower bottom of rectifying column, is passed through bubbling reactor 9 again after the water removal of dehydrater 23.Charging
When bring the nitrogen of device into, by the incoagulable gas outlet discharge (figure of condenser after the condensation of the condenser of 15 tower top of rectifying column
In be not drawn into).
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
The Cu (OH) that acid type polystyrene cation exchange resin and 300ml are 2 grams containing Cu21 drop ice vinegar is added in aqueous suspension mixing
Acid, mixing stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtain the catalyst that Cu content is 2w%.
2, the synthesis of polyoxymethylene dimethyl ether
During the reaction process shown in attached drawing, the volume of reactor 9 is 2L, has electric mixing device, electric heating cover
Heating.
150g catalyst is loaded in bubbling reactor 9, and 10000g is continuously added in mixing channel with nitrogen purging device
Paraformaldehyde, mixing channel temperature are 250 DEG C, and the formaldehyde gas generated after heating enters bubbling reactor 9 after drying tube removes water；
While dimethoxym ethane being added into bubbling reactor 9, the mixed liquor (methanol, formaldehyde and PODEn=1,2,5,6) of circulation and stress,
Wherein reaction raw materials dimethoxym ethane and formaldehyde charging rate are respectively 76g/h, 90g/h.The operating condition of bubbling reactor 9 is reaction
Temperature is 110 DEG C, reaction pressure 2.0MPa.Reaction discharging enters anion exchange resin bed layer.
Reactor discharging 10 enters rectifying column 15 after the deacidification of anion exchange resin bed layer 12 and is separated, operation pressure
Power is 1.10MPa, theoretical cam curve 20.Unreacted dimethoxym ethane discharges (logistics 17) from 15 tower top of rectifying column, by water removal
Device 18 is passed through bubbling reactor 9 after removing water again.The discharging of 15 tower bottom of rectifying column enters rectifying column 20 and carries out next step separation, operation
Pressure is 0.56MPa, theoretical cam curve 20.Unreacted methanol and the polyoxymethylene dimethyl ether dimer of generation are from rectifying column
20 tower tops discharge (logistics 22), are passed through bubbling reactor 9 again after the water removal of dehydrater 23.20 tower bottom of rectifying column discharging 21 into
Enter rectifying column 25 and carries out next step separation, operating pressure 0.30MPa, theoretical cam curve 20.The trimerization of polyoxymethylene dimethyl ether
Object and tetramer discharge (logistics 27) from 25 tower top of rectifying column, into product storage tank 28.The polyformaldehyde two of the degree of polymerization higher (n > 4)
Methyl ether discharges (logistics 26) from 25 tower bottom of rectifying column, is passed through bubbling reactor 9 again after the water removal of dehydrater 23.Successive reaction
80h, On-line Product sampling, by gas chromatographic analysis, experimental result is listed in Table 1 below.
[embodiment 2]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin, the Mn (OH) for being 2 grams containing Mn with 300ml under nitrogen protection2Aqueous suspension mixing, adds
Enter 1 drop glacial acetic acid, mix, stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtaining Mn content is 2w%'s
Catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Other operations are the same as embodiment 1, successive reaction 80h, On-line Product sampling, by gas chromatographic analysis, experimental result column
In table 1.
[embodiment 3]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin, the Tc (OH) for being 2 grams containing Tc with 300ml under nitrogen protection2Aqueous suspension mixing, adds
Enter 1 drop glacial acetic acid, mix, stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtaining Tc content is 2w%'s
Catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Other operations are the same as embodiment 1, successive reaction 80h, On-line Product sampling, by gas chromatographic analysis, experimental result column
In table 1.
[embodiment 4]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin, with 300ml containing the Cu (OH) that Cu is 1 gram and Mn is 1 gram under nitrogen protection2And Mn
(OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, dry extremely in vacuum oven
Constant weight, obtaining Cu content is the catalyst that 1w% and Mn content is 1w%.
2, the synthesis of polyoxymethylene dimethyl ether
Other operations are the same as embodiment 1, successive reaction 80h, On-line Product sampling, by gas chromatographic analysis, experimental result column
In table 1.
[embodiment 5]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin, with 300ml containing the Cu (OH) that Cu is 1 gram and Tc is 1 gram under nitrogen protection2And Tc
(OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, dry extremely in vacuum oven
Constant weight, obtaining Cu content is the catalyst that 1w% and Tc content is 1w%.
2, the synthesis of polyoxymethylene dimethyl ether
Other operations are the same as embodiment 1, successive reaction 80h, On-line Product sampling, by gas chromatographic analysis, experimental result column
In table 1.
[embodiment 6]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin with 300ml containing Cu is 1 gram under nitrogen protection, Tc is 0.5 gram and Mn is 0.5 gram
Cu(OH)2、Tc(OH)2With Mn (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature,
Dry to constant weight in vacuum oven, it be 0.5w% and Mn content is urging for 0.5w% that obtain Cu content, which be 1w%, Tc content,
Agent.
2, the synthesis of polyoxymethylene dimethyl ether
150g catalyst is loaded in bubbling reactor 9, and 10000g is continuously added in mixing channel with nitrogen purging device
Paraformaldehyde, mixing channel temperature are 250 DEG C, and the formaldehyde gas generated after heating enters bubbling reactor 9 after drying tube removes water；
While dimethoxym ethane being added into bubbling reactor 9, the mixed liquor (methanol, formaldehyde and PODEn=1,2,5,6) of circulation and stress,
Wherein reaction raw materials dimethoxym ethane and formaldehyde charging rate are respectively 76g/h, 90g/h.The operating condition of bubbling reactor 9 is reaction
Temperature is 110 DEG C, reaction pressure 2.0MPa.Reaction discharging enters anion exchange resin bed layer.
Other operations are the same as embodiment 1, successive reaction 80h, On-line Product sampling, by gas chromatographic analysis, experimental result column
In table 1.
[embodiment 7]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin with 300ml containing Cu is 1.5 grams under nitrogen protection, Tc is 0.25 gram and Mn is 0.25
Gram Cu (OH)2、Tc(OH)2With Mn (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, it is small to stand 24 at room temperature for mixing
When, dry to constant weight in vacuum oven, it is that 0.25w% and Mn content is that obtain Cu content, which be 1.5w%, Tc content,
The catalyst of 0.25w%.
2, the synthesis of polyoxymethylene dimethyl ether
Other operations are the same as embodiment 1, successive reaction 80h, On-line Product sampling, by gas chromatographic analysis, experimental result column
In table 1.
Table 1
N is the degree of polymerization, product CH3O(CH2O)nCH3。
Claims (10)
1. the catalyst of polyoxymethylene dimethyl ether preparation, the catalyst is metal ion-modified cation exchange resin, institute
Stating metal includes IB race metal.
2. catalyst according to claim 1, it is characterized in that IB race element is selected from least one of Cu and Ag.
3. catalyst according to claim 1, it is characterized in that the content of modified metal is greater than 0 and to be less than etc. in catalyst
In 9.8w%.
4. catalyst according to claim 1, it is characterized in that the full exchange capacity of the resin is 3.0~5.9mmol/g.
5. catalyst according to claim 1, it is characterized in that the resin is gel-type or macroporous type.
6. catalyst according to claim 1, it is characterized in that the resin sulfonic acid polystyrene cation exchange resin.
7. catalyst according to claim 6, it is characterized in that sulfonic acid polystyrene cation described in the resin exchanges
Resin includes crosslinked polystyrene skeleton and sulfonic acid group.
8. the preparation method of catalyst according to any one of claims 1 to 7, including inciting somebody to action in the presence of the acid of catalytic amount
The sulfonic acid polystyrene cation exchange resin with contain the modified metal-oxide and/or the modified metal hydroxide
The suspension contact of object carries out ion exchange.
9. preparation method according to claim 8, it is characterized in that the acid is the carboxylic acid of hydrochloric acid, nitric acid or C2~C10
At least one of.
10. application of the catalyst according to any one of claims 1 to 7 in synthesizing polyoxymethylene dimethyl ethers.
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| CN106582834A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for preparation of polyoxymethylene dimethyl ether |
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| US7119153B2 (en) * | 2004-01-21 | 2006-10-10 | Jensen Michael D | Dual metallocene catalyst for producing film resins with good machine direction (MD) elmendorf tear strength |
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