CN104276933A - Process for synthesizing polyoxymethylene dimethyl ethers by using methanol and paraformaldehyde - Google Patents
Process for synthesizing polyoxymethylene dimethyl ethers by using methanol and paraformaldehyde Download PDFInfo
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- CN104276933A CN104276933A CN201310286165.5A CN201310286165A CN104276933A CN 104276933 A CN104276933 A CN 104276933A CN 201310286165 A CN201310286165 A CN 201310286165A CN 104276933 A CN104276933 A CN 104276933A
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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
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- C07C41/58—Separation; Purification; Stabilisation; Use of additives
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Abstract
The invention relates to a process for synthesizing polyoxymethylene dimethyl ethers by using methanol and paraformaldehyde. The process comprises a reaction area and a separation area. The reaction area comprises a methanol storage tank, a mixing tank with a heater, a drying tube and a liquid-phase reaction kettle, and the technological steps at the reaction area comprise: sending paraformaldehyde and methanol into the mixing tank, preheating the paraformaldehyde solid and methanol, outputting the material flow, removing water by using the drying tube, and then sending into the liquid-phase stirring reaction kettle, and under the effect of a solid acid catalyst, reacting with a recovered mixture introduced into the reaction kettle, so as to generate polyoxymethylene dimethyl ethers. The separation area comprises an anion exchange resin bed layer, a rectification module and a product storage tank, and the technological steps at the separation area comprise: discharging the material from the reaction kettle, removing acids by using the anion exchange resin bed layer, sending into the rectification module for separation, then sending trimer and tetramer of polyoxymethylene dimethyl ethers into the product storage tank, and cycling other compositions into the reaction kettle. The technical scheme has the characteristics of high yield and selectivity, and is applicable to industrial production of polyoxymethylene dimethyl ethers.
Description
Technical field
The present invention relates to the processing method with methyl alcohol and paraformaldehyde synthesizing polyoxymethylene dme.
Background technology
The feature that the resource general layout of China has " rich coal, few oil, have gas ", and the flourishing industrial development of China proposes to oil supply the requirement increasingly increased.But in recent years, China's oil resource day is becoming tight, oil supply pressure unprecedentedly increases.According to statistics, within 2011, China's oil external dependence degree reaches 56.5%, rises 1.7 percentage points than 2010.China is since 1993 become net import of oil state for the first time, and CNPC's external dependence degree, by 6% rising all the way then, breaks through the barrier line of 50% for 2009.The energy dilemma how utilizing the coal resources of China's abundant to solve China just becomes researcher urgent problem.Therefore be day by day subject to people's attention by coal-based development of new fuel oil substitute.
In addition, due to the dual-pressure of atmospheric pollution and energy scarcity, energy-saving and emission-reduction have become a great society development topic.Therefore, for a long time petrochemical industry be devoted to development of new reduce discharging diesel-fuel.The exploitation of many emerging substitute diesels is just arisen at the historic moment, and comprising: GTL diesel oil, biofuel, ethanol diesel fuel, dimethyl ether, diesel oil oxygenatedchemicals, emulsified diesel wet goods.They are need not produce with oil by synthetic method mostly, substantially the not impurity such as sulfur-bearing, nitrogen, aromatic hydrocarbons, and be the diesel oil or diesel oil blending component that extremely clean, paid much attention in recent years, each state is all putting forth effort to develop and apply.This wherein uses diesel oil blending component, without the need to increasing device in addition or changing engine structure, is therefore considered to a kind of convenient, effective measures.
Dme is suggested as a kind of procetane the earliest, adds appropriate dme and effectively can reduce particulate matter in tail gas and CO in diesel oil
xand NO
xdischarge.But also there are some defects due to himself physical property in dme, such as self cold starting performance is poor, high, the easy generation vapour lock of vapour pressure also has and stores under normal temperature, transport, low-pressure liquefied contour cost, these make dme obviously raise as the cost of vehicle alternative fuel.Polyoxymethylene dimethyl ether, i.e. Polyoxymethylene dimethyl ethers (PODE), be the common name of a class material, its skeleton symbol can be expressed as CH
3o (CH
2o)
ncH
3, there is higher cetane value (> 40) and oxygen level (42 ~ 51%).When the value of n is 1, polyoxymethylene dimethyl ether is methylal, although use methylal also can improve efficiency of energy utilization as vehicle fuel addO-on therapy, reduces exhaust emissions, but still easily causes vent plug.When n value is 2 ~ 6, its physical properties, combustionproperty and diesel oil closely, preferably resolve the defect that dme and methylal exist as derv fuel oil blend component.Therefore polyoxymethylene dimethyl ether can be used as novel clean diesel component, and the addition in diesel oil can reach more than 10% (v/v), can improve diesel oil combustion position within the engine, improves thermo-efficiency, reduces the particulate matter in tail gas and CO
xand NO
xdischarge.The optimum chain length of the polyoxymethylene dimethyl ether mixed with diesel oil is n=3,4.During 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 temperatures.It is reported, add the CH of 5 ~ 30%
3oCH
2oCH
3significantly can reduce NO
xdischarge.
Be paraformaldehyde section in the middle of PODE, two ends are by methyl blocking.Therefore it is general by providing the compound of paraformaldehyde (formaldehyde, trioxymethylene and paraformaldehyde etc.) and providing the compound of end-blocking methyl (methyl alcohol, dme and methylal etc.) to synthesize PODE.PODE can be synthesized by acid-catalyzed dehydration by methyl alcohol and formaldehyde or paraformaldehyde, trioxymethylene.By gasification preparing synthetic gas, by synthetic gas synthesizing methanol, to be prepared paraformaldehyde or trioxymethylene by methanol oxidation synthesizing formaldehyde, formaldehyde are all industrialized processes already.Synthesize PODE by coal-based methanol and not only can replace part diesel oil, the efficiency of combustion of diesel oil can also be improved, reduce diesel combustion to the harm of environment, there is important strategic importance and good economic worth.The coal resources of China's abundant can be converted into liquid alternative fuel by the development of PODE and synthesis, reduce China to the importation dependence of oil, and then are all of great importance to national energy security.
Prepared by the method that in laboratory, polyoxymethylene dimethyl ether is reacted in 150 ~ 180 DEG C of heating low polymerization degree paraformaldehyde or paraformaldehyde and methyl alcohol under can being existed by trace sulfuric acid or hydrochloric acid.Because polyoxymethylene dimethyl ether has huge using value in diesel-dope field, since a very long time, numerous companies and research institute are all at the practicable industrial production technology of research.
It is the processing method that initial feed prepares polyoxymethylene dimethyl ether by methyl alcohol that EP2228359A1 describes a kind of.It is catalyzer that the method uses through ammonium molybdate and Ferric nitrate modified molecular sieve, and methyl alcohol is obtained polyoxymethylene dimethyl ether with air (oxygen) oxidation step under temperature more than 200 DEG C conditions.The method production cost is relatively low, but catalyst preparation process is complicated, and the selectivity of polyoxymethylene dimethyl ether is unsatisfactory.
EP1070755 describes and a kind ofly under three fluosulfonic acid exist, reacts by methylal and paraformaldehyde the method preparing in per molecule the polyoxymethylene dimethyl ether with 2 ~ 6 formaldehyde units.WO2006/045506A1 describes BASF AG and uses sulfuric acid, trifluoromethanesulfonic acid as catalyzer, obtains the series product of n=1 ~ 10 with methylal, paraformaldehyde, trioxymethylene for raw material.Above method all adopts protonic acid as catalyzer, and this catalyzer is cheap and easy to get, but corrodibility is strong, and be difficult to be separated, environmental pollution is large, the shortcoming high to the requirement of equipment.
US6160174 and US6265528 describes BP company and adopts methyl alcohol, formaldehyde, dme and methylal to be raw material, and adopt Zeo-karb as catalyzer, gas-solid phase reaction obtains polyoxymethylene dimethyl ether.Although but this method has catalyzer is easily separated, be beneficial to the advantages such as circulation, reaction conversion ratio is low, and productive rate is not high, complex process.
CN 200910056819.9 with methyl alcohol and trioxymethylene for raw material is using solid super-strong acid as catalyst synthesizing polyoxymethylene dme, although achieve good feed stock conversion, but due to the acidity of solid super-strong acid strong, irregular pore structure makes the selectivity of by product methylal in product 20 ~ 50%, a large amount of existence of methylal can reduce the flash-point of diesel fuel mixtures and therefore damage its quality, make product not too be suitable as procetane.CN 101048357A describes a kind of synthesis technique being Material synthesis polyoxymethylene dimethyl ether with methylal and trioxymethylene.We also develop ourselves and adopt solid acid catalyst (molecular sieve CN 200910056820.1, solid super-strong acid CN 200910056819.9) with methyl alcohol and trioxymethylene for polyoxymethylene dimethyl ether prepared by raw material.
But these techniques all adopt trioxymethylene to be reaction raw materials, according to market study, the price of trioxymethylene is 14000 yuan/ton; The price of contrast paraformaldehyde, only has 5000 yuan/ton.We are not difficult to find, are that raw material production polyoxymethylene dimethyl ether can significantly reduce production cost with paraformaldehyde.
CN 101182367A describes and adopts acidic ionic liquid as catalyzer, is synthesizing triformol by formaldehyde, then with the processing method of trioxymethylene and methanol-fueled CLC polyoxymethylene dimethyl ether.Although the method once through yield is high, the ionic-liquid catalyst used is expensive, and not easily separated, operation easier is larger.US5,959,156 describe with the synthesis technique of dme and the methyl alcohol polyoxymethylene dimethyl ether that is raw material, adopt novel heterogeneous promotion condensation catalyst.Although this technique cost is lower, product yield is undesirable.
Summary of the invention
It is the problem that Material synthesis polyoxymethylene dimethyl ether handicraft product yield is low that the present invention will solve methyl alcohol and paraformaldehyde in prior art, provides a kind of processing method using methyl alcohol and paraformaldehyde synthesizing polyoxymethylene dme newly.The method has that raw material paraformaldehyde is cheap, and production cost is low, the advantage that yield is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the processing method using methyl alcohol and paraformaldehyde synthesizing polyoxymethylene dme, this technique is divided into reaction zone and disengaging zone, and reaction zone comprises methyl alcohol storage tank, the tempering tank being with well heater, drying tube and liquid phase reaction still; Reaction zone processing step is that paraformaldehyde and methanol feeding are to tempering tank, and preheating is carried out to paraformaldehyde solid and methyl alcohol, output flows through drying tube and dewaters rear feeding to liquid phase stirred autoclave, under the effect of solid acid catalyst, the mixture reaction passing into reactor with recovery generates polyoxymethylene dimethyl ether; Disengaging zone comprises anion exchange resin bed layer, rectifying module and product storage tank, the processing step of disengaging zone is that reactor discharging enters rectifying module after the deacidification of anion exchange resin bed layer, through the separation of rectifying module, polyoxymethylene dimethyl ether three, tetramer enters product storage tank, other components are circulated to reactor.
Mixture described in technique scheme preferably include by rectifying module be separated containing the first cut of methylal, the second cut containing methyl alcohol and polyoxymethylene dimethyl ether dipolymer, and the 4th cut containing the more polyoxymethylene dimethyl ether of high-polymerization degree (n>4); Rectifying module is also isolated containing three of polyoxymethylene dimethyl ether, the 3rd cut of tetramer.Described rectifying module is preferably made up of 3 rectifying tower.Described first cut preferably ejects material by the first rectifying tower, and the second cut is preferably by the discharging of Second distillation column tower top, and the 3rd cut preferably ejects material by the 3rd rectifying tower, and the 4th cut is preferably by discharging at the bottom of the 3rd rectifying tower.Described the first, the second, and the 4th cut is preferably recycled to reactive system through the water eliminator Posterior circle that dewaters.Described first rectifying tower working pressure be preferably 0.2 ~ 2MPa, the working pressure of Second distillation column is preferably 0.02 ~ 1.2MPa, and the working pressure of the 3rd rectifying tower is preferably 0.001 ~ 0.6MPa.The theoretical plate number of described first rectifying tower is preferably 15 ~ 25, and the theoretical plate number of Second distillation column is preferably 15 ~ 30, and the theoretical plate number of the 3rd rectifying tower is preferably 15 ~ 40.
Methyl alcohol in technique scheme: the mass ratio of paraformaldehyde is preferably 0.02 ~ 50: 1.Temperature of reaction is preferably 50 ~ 250 DEG C.Reaction pressure is preferably 0.01 ~ 20.0 MPa.The Heating temperature of tempering tank is preferably 250 ~ 300 DEG C.
Solid acid catalyst described in technique scheme is preferably from one or more components following: acidic cation-exchange resin, molecular sieve, dinitrobenzoic acid, ethylenediamine tetraacetic acid (EDTA), aluminum oxide, titanium dioxide; More preferably the mixture that the mixture that forms of HZSM-5 molecular sieve and titanium dioxide, or dinitrobenzoic acid and HZSM-5 molecular sieve form.
The siccative that drying tube described in technique scheme, water eliminator use is selected from following at least one siccative: ion exchange resin, molecular sieve, Silica hydrogel.
The present invention has the following advantages: the first, yield and selection rate high, n=3 and n=4 product sum accounts for n=2 ~ 5 product summation up to 96.5wt%; The second, production cost is lower; 3rd, adopt the way of rectifying to make by product circulation and stress, achieve good technique effect.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the present invention's methyl alcohol and paraformaldehyde synthesizing polyoxymethylene dme.
The present invention 1 further describes with reference to the accompanying drawings.
Paraformaldehyde solid (logistics 1) and methyl alcohol (logistics 3 is exported by methyl alcohol storage tank 2) are fed to tempering tank 4, and tempering tank 4 is connected with well heater 5, and preheating is carried out to paraformaldehyde solid and methyl alcohol, export logistics 25 (methyl alcohol, formaldehyde, the mixed solution of water).Logistics 25 dewaters rear feeding to liquid phase stirred autoclave 7 through moisture eliminator 6, simultaneously to the material 14 (main component is methylal) dewatered by rectifying tower 11 recovered overhead in addition of reactor 7 charging, moisture eliminator 18 is except the logistics 19 (main component is the dipolymer of methyl alcohol and polyoxymethylene dimethyl ether and the polyoxymethylene dimethyl ether of the polymerization degree higher (n>4)) of Water Sproading.Reactor discharging 8 obtains material 10 after anion exchange resin bed layer 9 deacidifies, and material 10 enters rectifying tower 11 and is separated.Unreacted methylal, from rectifying tower 11 tower top discharging (logistics 12), again passes into liquid phase stirred autoclave 7 after water eliminator 13 dewaters.Discharging at the bottom of rectifying tower 11 tower enters rectifying tower 16 and carries out next step separation.The polyoxymethylene dimethyl ether dipolymer of unreacted methyl alcohol and generation again passes into liquid phase stirred autoclave 7 from rectifying tower 16 tower top discharging (logistics 17) after water eliminator 18 dewaters.Discharging 20 at the bottom of rectifying tower 16 tower enters rectifying tower 21 and carries out next step separation.The trimer of polyoxymethylene dimethyl ether and tetramer, from rectifying tower 21 tower top discharging (logistics 22), enter product storage tank 23.The polyoxymethylene dimethyl ether of the polymerization degree higher (n>4), from discharging (logistics 24) at the bottom of rectifying tower 21 tower, again passes into liquid phase stirred autoclave 7 after water eliminator 18 dewaters.
Below by embodiment, the present invention is further elaborated.
embodiment
[embodiment 1]
In the process of reaction process shown in accompanying drawing, the volume of reactor 9 is 2L, and with electric mixing device, electric heating cover heats.
In liquid phase reaction still 7, load 300g HZSM-5 molecular sieve (Si/Al=15), with nitrogen purging device, in tempering tank, add 10000g paraformaldehyde continuously, in tempering tank, add methyl alcohol simultaneously, input speed is 62.5g/h, and tempering tank temperature is 250 DEG C, enters liquid phase reaction still after tempering tank discharging dewaters, in reactor, add the methylal of circulation and stress simultaneously, the mixed solution of methyl alcohol and polyoxymethylene dimethyl ether (n=2,5,6), input speed is respectively 50.8g/h, 60.75g/h.The operational condition of liquid phase reaction still 7 is temperature of reaction is 150 DEG C, and reaction pressure is 2.0MPa.Reaction discharging enters anion exchange resin bed layer.
Reactor discharging 8 enters rectifying tower 11 and is separated after anion exchange resin bed layer 9 deacidifies.Unreacted methylal is from rectifying tower 11 tower top discharging (logistics 12), and working pressure is 1.1MPa, and theoretical plate number is 20, after water eliminator 13 dewaters, again pass into liquid phase stirred autoclave 7.Discharging at the bottom of rectifying tower 11 tower enters rectifying tower 16 and carries out next step separation, and working pressure is 0.6MPa, and theoretical plate number is 20.The polyoxymethylene dimethyl ether dipolymer of unreacted methyl alcohol and generation again passes into liquid phase stirred autoclave 7 from rectifying tower 16 tower top discharging (logistics 17) after water eliminator 18 dewaters.Discharging 20 at the bottom of rectifying tower 16 tower enters rectifying tower 21 and carries out next step separation, and working pressure is 0.3MPa, and theoretical plate number is 20.The trimer of polyoxymethylene dimethyl ether and tetramer, from rectifying tower 21 tower top discharging (logistics 22), enter product storage tank 23.The polyoxymethylene dimethyl ether of the polymerization degree higher (n>4), from discharging (logistics 24) at the bottom of rectifying tower 21 tower, again passes into liquid phase stirred autoclave 7 after water eliminator 18 dewaters.Successive reaction 80h, On-line Product samples, and by gas chromatographic analysis, in product, n=3 and n=4 accounts for the 90wt% of n=2 ~ 5, and experimental result is listed in table 1.
[embodiment 2]
In liquid phase reaction still 7, load 300g dinitrobenzoic acid, with nitrogen purging device, in tempering tank, add 7500g paraformaldehyde continuously, in tempering tank, add methyl alcohol simultaneously, input speed is 93.75g/h, and tempering tank temperature is 250 DEG C, enters liquid phase reaction still after tempering tank discharging dewaters, in reactor, add the methylal of circulation and stress simultaneously, the mixed solution of methyl alcohol and polyoxymethylene dimethyl ether (n=2,5,6), input speed is respectively 40g/h, 69.5g/h.The operational condition of liquid phase reaction still 7 is temperature of reaction is 130 DEG C, and reaction pressure is 0.50MPa.Reaction discharging enters anion exchange resin bed layer.
Other operation is with embodiment 1, and successive reaction 80h, On-line Product samples, and by gas chromatographic analysis, in product, n=3 and n=4 accounts for the 88.2wt% of n=2 ~ 5, and experimental result is listed in table 2.
[embodiment 3]
In liquid phase reaction still 7, load 300g dinitrobenzoic acid, with nitrogen purging device, in tempering tank, add 10000g paraformaldehyde continuously, in tempering tank, add methyl alcohol simultaneously, input speed is 62.5g/h, and tempering tank temperature is 250 DEG C, enters liquid phase reaction still after tempering tank discharging dewaters, in reactor, add the methylal of circulation and stress simultaneously, the mixed solution of methyl alcohol and polyoxymethylene dimethyl ether (n=2,5,6), input speed is respectively 50.8g/h, 60.75g/h.The operational condition of liquid phase reaction still 7 is temperature of reaction is 130 DEG C, and reaction pressure is 2.0MPa.Reaction discharging enters anion exchange resin bed layer.
Other operation is with embodiment 1, and successive reaction 80h, On-line Product samples, and by gas chromatographic analysis, in product, n=3 and n=4 accounts for the 92.6wt% of n=2 ~ 5, and experimental result is listed in table 3.
[embodiment 4]
150g HZSM-5 molecular sieve (Si/Al=15) is loaded in liquid phase reaction still 7, with nitrogen purging device, 7500g paraformaldehyde is added continuously in tempering tank, in tempering tank, add methyl alcohol simultaneously, input speed is 93.75g/h, tempering tank temperature is 250 DEG C, tempering tank discharging does not dewater, directly enter liquid phase reaction still, in reactor, add the methylal of circulation and stress, methyl alcohol and polyoxymethylene dimethyl ether (n=2 simultaneously, 5,6) mixed solution, input speed is respectively 39.4g/h, 59.6g/h.The operational condition of liquid phase reaction still 7 is temperature of reaction is 130 DEG C, and reaction pressure is 0.50MPa.Reaction discharging enters anion exchange resin bed layer.
Other operation is with embodiment 1, and successive reaction 80h, On-line Product samples, and by gas chromatographic analysis, in product, n=3 and n=4 accounts for the 87wt% of n=2 ~ 5, and experimental result is listed in table 4.
[embodiment 5]
150g catalyzer is loaded in liquid phase reaction still 7, wherein HZSM-5 molecular sieve (Si/Al=50) and the massfraction of titanium dioxide are than being 50:50, with nitrogen purging device, 7500g paraformaldehyde is added continuously in tempering tank, in tempering tank, add methyl alcohol simultaneously, input speed is 93.75g/h, tempering tank temperature is 250 DEG C, enter liquid phase reaction still after tempering tank discharging dewaters, in reactor, add the methylal of circulation and stress, methyl alcohol and polyoxymethylene dimethyl ether (n=2 simultaneously, 5,6) mixed solution, input speed is respectively 37.7g/h, 75.6g/h.The operational condition of liquid phase reaction still 7 is temperature of reaction is 110 DEG C, and reaction pressure is 0.50MPa.Reaction discharging enters anion exchange resin bed layer.
Other operation is with embodiment 1, and successive reaction 80h, On-line Product samples, and by gas chromatographic analysis, in product, n=3 and n=4 accounts for the 94.2wt% of n=2 ~ 5, and experimental result is listed in table 5.
[embodiment 6]
300g catalyzer is loaded in liquid phase reaction still 7, wherein the massfraction of dinitrobenzoic acid and HZSM-5 molecular sieve (Si/Al=15) is than being 30:70, with nitrogen purging device, 7500g paraformaldehyde is added continuously in tempering tank, in tempering tank, add methyl alcohol simultaneously, input speed is 93.75g/h, tempering tank temperature is 250 DEG C, enter liquid phase reaction still after tempering tank discharging dewaters, in reactor, add the methylal of circulation and stress, methyl alcohol and polyoxymethylene dimethyl ether (n=2 simultaneously, 5,6) mixed solution, input speed is respectively 49.7g/h, 78.9g/h.The operational condition of liquid phase reaction still 7 is temperature of reaction is 130 DEG C, and reaction pressure is 0.50MPa.Reaction discharging enters anion exchange resin bed layer.
Other operation is with embodiment 1, and successive reaction 80h, On-line Product samples, and by gas chromatographic analysis, in product, n=3 and n=4 accounts for the 96.2wt% of n=2 ~ 5, and experimental result is listed in table 6.
[embodiment 7]
300g catalyzer is loaded in liquid phase reaction still 7, wherein the massfraction of dinitrobenzoic acid and HZSM-5 molecular sieve (Si/Al=15) is than being 50:50, with nitrogen purging device, 10000g paraformaldehyde is added continuously in tempering tank, in tempering tank, add methyl alcohol simultaneously, input speed is 62.5g/h, tempering tank temperature is 250 DEG C, enter liquid phase reaction still after tempering tank discharging dewaters, in reactor, add the methylal of circulation and stress, methyl alcohol and polyoxymethylene dimethyl ether (n=2 simultaneously, 5,6) mixed solution, input speed is respectively 50.8g/h, 60.75g/h.The operational condition of liquid phase reaction still 7 is temperature of reaction is 150 DEG C, and reaction pressure is 2.0MPa.Reaction discharging enters anion exchange resin bed layer.
Other operation is with embodiment 1, and successive reaction 80h, On-line Product samples, and by gas chromatographic analysis, in product, n=3 and n=4 accounts for the 96.5wt% of n=2 ~ 5, and experimental result is listed in table 7.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Claims (10)
1. use the processing method of methyl alcohol and paraformaldehyde synthesizing polyoxymethylene dme, this technique is divided into reaction zone and disengaging zone, and reaction zone comprises methyl alcohol storage tank, the tempering tank being with well heater, drying tube and liquid phase reaction still; Reaction zone processing step is that paraformaldehyde and methanol feeding are to tempering tank, and preheating is carried out to paraformaldehyde solid and methyl alcohol, output flows through drying tube and dewaters rear feeding to liquid phase stirred autoclave, under the effect of solid acid catalyst, the mixture reaction passing into reactor with recovery generates polyoxymethylene dimethyl ether; Disengaging zone comprises anion exchange resin bed layer, rectifying module and product storage tank, the processing step of disengaging zone is that reactor discharging enters rectifying module after the deacidification of anion exchange resin bed layer, through the separation of rectifying module, polyoxymethylene dimethyl ether three, tetramer enters product storage tank, other components are circulated to reactor.
2. the processing method of synthesizing polyoxymethylene dme according to claim 1, it is characterized in that described mixture comprise by rectifying module be separated containing the first cut of methylal, the second cut containing methyl alcohol and polyoxymethylene dimethyl ether dipolymer, and the 4th cut containing the more polyoxymethylene dimethyl ether of high-polymerization degree (n>4); Rectifying module is also isolated containing three of polyoxymethylene dimethyl ether, the 3rd cut of tetramer.
3. the processing method of synthesizing polyoxymethylene dme according to claim 2, is characterized in that described rectifying module is made up of 3 rectifying tower.
4. the processing method of synthesizing polyoxymethylene dme according to claim 3, it is characterized in that described first cut ejects material by the first rectifying tower, second cut is by the discharging of Second distillation column tower top, and the 3rd cut ejects material by the 3rd rectifying tower, and the 4th cut is by discharging at the bottom of the 3rd rectifying tower.
5. the processing method of synthesizing polyoxymethylene dme according to claim 4, is characterized in that described the first, the second, and the 4th cut is recycled to reactive system through the water eliminator Posterior circle that dewaters.
6. the processing method of synthesizing polyoxymethylene dme according to claim 4, it is characterized in that described first rectifying tower working pressure be 0.2 ~ 2MPa, the working pressure of Second distillation column is 0.02 ~ 1.2MPa, and the working pressure of the 3rd rectifying tower is 0.001 ~ 0.6MPa.
7. the processing method of synthesizing polyoxymethylene dme according to claim 4, is characterized in that the theoretical plate number of described first rectifying tower is 15 ~ 25, and the theoretical plate number of Second distillation column is the theoretical plate number of the 15 ~ 30, three rectifying tower is 15 ~ 40.
8. the processing method of synthesizing polyoxymethylene dme according to claim 1, is characterized in that methyl alcohol: the mass ratio of paraformaldehyde is 0.02 ~ 50: 1.
9. the processing method of synthesizing polyoxymethylene dme according to claim 1, is characterized in that temperature of reaction is 50 ~ 250 DEG C.
10. the processing method of synthesizing polyoxymethylene dme according to claim 1, is characterized in that reaction pressure is 0.01 ~ 20.0 MPa.
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| CN109651099A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | By the process of methanol and paraformaldehyde synthesizing polyoxymethylene dimethyl ether |
| CN109651096A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | By the process of dimethoxym ethane and paraformaldehyde synthesizing polyoxymethylene dimethyl ether |
| CN109651108A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | With the process of methanol and paraformaldehyde synthesizing polyoxymethylene dimethyl ether |
| CN109651097A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | With the process of methanol and paraformaldehyde production polyoxymethylene dimethyl ether |
| CN109651100A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | By the process of methanol-fueled CLC polyoxymethylene dimethyl ether |
| CN110090464A (en) * | 2019-04-16 | 2019-08-06 | 天津大学 | Partition wall reactive distillation method and device for polymethoxy dimethyl ether synthesis |
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| US6160174A (en) * | 1998-11-12 | 2000-12-12 | Bp Amoco Corporation | Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of dimethyl ether with formaldehyde formed by oxy-dehydrogenation of methanol |
| CN101048357A (en) * | 2004-10-25 | 2007-10-03 | 巴斯福股份公司 | Method for producing polyoxymethylene dimethyl ethers |
| CN102040490A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Synthesis method of polyformaldehyde dimethyl ether |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109651099A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | By the process of methanol and paraformaldehyde synthesizing polyoxymethylene dimethyl ether |
| CN109651096A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | By the process of dimethoxym ethane and paraformaldehyde synthesizing polyoxymethylene dimethyl ether |
| CN109651108A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | With the process of methanol and paraformaldehyde synthesizing polyoxymethylene dimethyl ether |
| CN109651097A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | With the process of methanol and paraformaldehyde production polyoxymethylene dimethyl ether |
| CN109651100A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | By the process of methanol-fueled CLC polyoxymethylene dimethyl ether |
| CN109651099B (en) * | 2017-10-10 | 2022-04-01 | 中国石油化工股份有限公司 | Process method for synthesizing polyformaldehyde dimethyl ether from methanol and paraformaldehyde |
| CN109651100B (en) * | 2017-10-10 | 2022-04-05 | 中国石油化工股份有限公司 | Process for synthesizing polyformaldehyde dimethyl ether from methanol |
| CN109651097B (en) * | 2017-10-10 | 2022-04-05 | 中国石油化工股份有限公司 | Process for producing polyformaldehyde dimethyl ether from methanol and paraformaldehyde |
| CN109651096B (en) * | 2017-10-10 | 2022-04-05 | 中国石油化工股份有限公司 | Process method for synthesizing polyformaldehyde dimethyl ether from methylal and paraformaldehyde |
| CN110090464A (en) * | 2019-04-16 | 2019-08-06 | 天津大学 | Partition wall reactive distillation method and device for polymethoxy dimethyl ether synthesis |
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