CN104341279A - Method for preparing polyoxymethylene dimethyl ether from methanol and formaldehyde - Google Patents

Method for preparing polyoxymethylene dimethyl ether from methanol and formaldehyde Download PDF

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Publication number
CN104341279A
CN104341279A CN201310337587.0A CN201310337587A CN104341279A CN 104341279 A CN104341279 A CN 104341279A CN 201310337587 A CN201310337587 A CN 201310337587A CN 104341279 A CN104341279 A CN 104341279A
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pode
product
acetalation
unit
rectifying
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刘殿华
张建强
房鼎业
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East China University of Science and Technology
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East China University of Science and Technology
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Priority to CN201910027736.0A priority Critical patent/CN110028391B/en
Priority to CN201310337587.0A priority patent/CN104341279A/en
Publication of CN104341279A publication Critical patent/CN104341279A/en
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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

Abstract

The invention relates to a method for preparing PODE (polyoxymethylene dimethyl ether) from methanol and formaldehyde solution. The method comprises the following steps: (1) methanol is mixed with 37wt% formaldehyde water solution, and the mixture is dehydrated, such that a methanol and formaldehyde mixed liquid with water content no higher than 40wt% is obtained; (2) under the existence of a catalyst, the obtained methanol and formaldehyde mixed liquid with water content no higher than 40wt% is subjected to an acetalation reaction, such that polyoxymethylene dimethyl ether (PODEn=3-4) is obtained; and (3) the PODEn=3-4 crude product obtained in the step (2) is subjected to separation purification. According to the invention, low-concentration formaldehyde (37wt%) and methanol are adopted as raw material for preparing PODEn=3-4, such that raw material and operation costs are reduced. The PODE preparation method has higher commercial value.

Description

A kind of method being prepared polymethoxy dimethyl ether by methyl alcohol and formaldehyde
Technical field
The present invention relates to the method that one prepares polymethoxy dimethyl ether (Polyoxymethylene Dimethyl Ethers, referred to as PODE), specifically, relate to a kind of method being prepared PODE by methyl alcohol and formalin.
Background technology
PODE is a kind of oil dope, and average cetane value (CN) value is 76, and oxygen level is high.Under the condition not transforming vehicle engine fuel system, the PODE of mediation 10-20% is in diesel oil, and can improve the efficiency of combustion of diesel oil, smoke intensity is the highest reduces 80%-90%.Therefore, the concern of the preparation of PODE extremely scientists.
So far, the existing multiple method preparing PODE is revealed.A kind of method of PODE prepared by methyl alcohol and trioxymethylene is disclosed and CN102701923A discloses a kind of system and device (raw material is still formaldehyde and trioxymethylene) preparing PODE as CN102249869A.Due to the price factor of trioxymethylene, the commercial prospect of these class methods is also pessimistic.
CN101198630A provide a kind of with formalin and methyl alcohol for the method for PODE prepared by raw material, there is the defect that product separation is complicated and product yield is lower in the method.CN102249868A propose a kind of with formalin and methyl alcohol for improving one's methods of PODE prepared by raw material, comprise: A) having under catalyzer (acidic ion liquid IL I) existence condition, obtained the mixture of trioxymethylene, formaldehyde and water through polyreaction by the formalin of 50wt% ~ 60wt%; B) under the katalysis of acidic ion liquid IL II, by steps A) gained mixture and methyl alcohol obtains the steps such as PODE through acetalation.
In sum, prepare in the method for PODE existing, raw material generally adopts the mixture of methyl alcohol and trioxymethylene or trioxymethylene, formaldehyde and water.Due to trioxymethylene price more expensive (or its preparation cost is higher), the existing method preparing PODE is made to lack commercial value.
Therefore, provide a kind of syntheti c route succinct and the preparation method with the PODE of commercial value is the technical issues that need to address of the present invention.
Summary of the invention
The present inventor finds through extensive and deep research: be that catalyzer is (as styrene type acidic cation-exchange resin, ZSM molecular sieve, Al with solid acid 2o 3or other solid acid etc.), adopt suitable preparation technology, can realize adopting 37wt% formaldehyde and methyl alcohol to be that PODE prepared by raw material, reduce raw material and running cost, make it have more commercial value.
Preparation PODE(CH of the present invention 3o (CH 2o) xcH 3, 3≤X≤4, hereinafter referred to as PODE n=3 ~ 4) method, comprise the steps:
(1) methyl alcohol and the mixing of 37wt% formalin and dehydration are obtained water-content and be less than or equal to the methyl alcohol of 40wt% and the step of formaldehyde mixed solution;
(2) having under catalyzer existence condition, be less than or equal to the methyl alcohol of 40wt% by the water-content of gained and formaldehyde mixed solution obtains PODE through acetalation n=3 ~ 4step; With
(3) by the PODE that step (2) is obtained n=3 ~ 4the step of separation and purification.
As shown from the above technical solution, the present invention, while raw materials used (methyl alcohol and 37wt% formalin) mixes, carries out processed, and by the water content control of raw mixture for being less than or equal to 40wt%.So, can carry out acetalation smoothly and obtain PODE, and the selectivity of PODE increases significantly, the selectivity of (PODE(1-8) reaches as high as 99%, PODE(3-4) selectivity reach as high as 92%, product (CH 3o (CH 2o) xcH 3, 3≤X≤4) selectivity can improve 10% ~ 70%), one way methanol conversion reaches as high as 80%.
Accompanying drawing explanation
Fig. 1 is preparation PODE of the present invention n=3 ~ 4the schematic flow sheet of method;
Wherein, 3.-raw material dehydration unit, 5.-acetalation unit, 8.-product (PODE n=3 ~ 4) separating unit, 10.-product (PODE n=3 ~ 4) refined unit.
Embodiment
In invention, have no special requirements to the dewatering type of raw material (mixed solution of methyl alcohol and 37wt% formalin), the existing dewatering by absorption, rectifying or flash distillation is all applicable to the present invention.
In the present invention's preferred technical scheme, the concrete dehydration conditions of raw material (mixed solution of methyl alcohol and 37wt% formalin) (being applicable to absorption, rectifying or flash distillation mode dewatering type) is: dehydration temperaturre is 30 DEG C ~ 50 DEG C, and dewatering pressure is 1.0MPa ~ 1.5MPa.The water content control of raw mixture is for being less than or equal to 30wt%.
The present invention recommends to adopt dewatering agent (as water absorbent polymer, the super absorbent polymer of modified polyacrylic acid and polyacrylamide combination) to be carried out the dehydration of raw material by the mode of absorption.
In another preferred technical scheme of the present invention, the temperature of reaction 60 DEG C ~ 120 DEG C of acetalation described in step (2), reaction pressure 1.0MPa ~ 2.0MPa.The catalyzer that described acetalation adopts is solid acid catalyst, as (but being not limited to): the styrene type acidic cation-exchange resin of styrene type acidic cation-exchange resin (Amberlyst36, Rohm and Haas), modification, ZSM molecular sieve are or/and Al 2o 3;
Wherein, except the styrene type acidic cation-exchange resin of described modification, commercially available product is.And the preparation method of the vinylbenzene acidic cation-exchange resin of described modification comprises the steps:
Take Amberlyst36 resin 10g, be placed in 250ml beaker stand-by; Then the hydrophobizing agent GLYMO(silane of 4% is prepared) solution, after it dissolves each other completely, 10g GLYMO solution is poured in the 250ml beaker that Amberlyst36 resin 10g is housed, keep water-bath 50 DEG C, after dipping 24h, filter, and with after deionized water wash several, be placed in loft drier 110 DEG C of dry 12h, the styrene type acidic cation-exchange resin of modification can be obtained.
In a further preferred technical solution of the present invention, through the product (PODE that the acetalation described in step (2) obtains n=3 ~ 4with unreacting material) be separated and adopt flash distillation mode to carry out being separated (certainly, as long as other can make PODE n=3 ~ 4the separation method be separated with unreacting material is also applicable the present invention), concrete flash conditions is: flash vaporization point is 70 DEG C ~ 80 DEG C, and flashing pressure is 400KPa ~ 600KPa.
Be separated through flash distillation mode and obtain PODE n=3 ~ 4crude product enters PODE n=3 ~ 4refined unit refine further, be separated through flash distillation mode the water that the unreacted raw material that obtains and acetalation produce and then return raw material dehydration unit.
In a further preferred technical solution of the present invention, PODE n=3 ~ 4the refining mode by rectifying realize, the condition of concrete rectifying is: rectifying bottom temperature is 128 DEG C, and rectifying pressure is 0.4PMa.
In sum (and see Fig. 1), preparation PODE of the present invention n=3 ~ 4method, comprise the steps:
(1) 1. 2. mixed and dewater (mol ratio of formaldehyde and methyl alcohol is preferably 3:1) in raw material dehydration unit is 3. middle with 37wt% formalin by methyl alcohol, the water-content in making material is 4. less than or equal to the preferred water-content of 40wt%(and is less than or equal to 30wt%);
Wherein, concrete dehydration conditions is: dehydration temperaturre is 30 DEG C ~ 50 DEG C, and dewatering pressure is 1.0MPa ~ 1.5MPa.
(2) 4. material enters acetalation unit and 5. carries out acetalation, in described acetalation, catalyzer used is that solid acid catalyst is (as (but being not limited to): the styrene type acidic cation-exchange resin of styrene type acidic cation-exchange resin, modification, ZSM molecular sieve or/or Al 2o 3), the temperature of reaction 60 DEG C ~ 120 DEG C of described acetalation, reaction pressure 1.0MPa ~ 2.0MPa.
(3) 7. the product material 5. obtained by acetalation unit enters product (PODE n=3 ~ 4) separating unit 8., product (PODE n=3 ~ 4) 8. separating unit can be that 7. flashing tower (namely adopts flash distillation mode separated product material.Certainly, as long as other can make PODE n=3 ~ 4the separation method be separated with unreacting material is also applicable the present invention, and concrete flash conditions is: flash vaporization point is 70 DEG C ~ 80 DEG C, and flashing pressure is 400KPa ~ 600KPa, by product (PODE n=3 ~ 4) 8. separating unit be separated the PODE obtained n=3 ~ 4thick product material 9. enter product (PODE n=3 ~ 4) 10. refined unit refine; And by product (PODE n=3 ~ 4) separating unit be 8. separated the unreacted feed product obtained 6. then return raw material dehydration unit 3. in.
(4) PODE n=3 ~ 4thick product material 9. enter product (PODE n=3 ~ 4) refined unit 10., described product (PODE n=3 ~ 4) refined unit generally can adopt stuffing rectification column (certainly, other can refine PODE n=3 ~ 4equipment be equally applicable to the present invention), when adopt stuffing rectification column time, the condition of concrete rectifying is: rectifying bottom temperature is 128 DEG C, and rectifying pressure is 0.4PMa.
By product (PODE n=3 ~ 4) PODE that 10. obtains of refined unit n=3 ~ 4sterling material enter product (PODE n=3 ~ 4) storage tanks (not marking in Fig. 1), and by product (PODE n=3 ~ 4) the light constituent material that 10. obtains of refined unit then return acetalation unit 5. in.
Below by embodiment, the present invention is further elaborated, its object is to better understand content of the present invention.
Embodiment 1
(1) material benzenemethanol 1. with 37wt% formalin 2. (temperature 30 DEG C, pressure 1.55MPa), after mass flowmeter metering, mix (mol ratio of formaldehyde and methyl alcohol is 3:1) in raw material dehydration unit is 3. middle and dewaters, the water-content in making material is 4. less than or equal to 40wt%;
The dewatering agent wherein adopted is the water-absorbing resin (super absorbent polymer combined by modified polyacrylic acid and polyacrylamide, commercially available product), dehydration temperaturre 30 DEG C, dewatering pressure 1.5MPa, after dehydration, gained mixture water-content is 4. less than or equal to 40wt%.
(2) 4. material enters acetalation unit and 5. carries out acetalation, described acetalation is carried out in the fixed-bed reactor of filling solid acid catalyst, institute's filling solid acid catalyst is styrene type acidic cation-exchange resin (Amberlyst36, Rohm and Haas) and the mixture of styrene type acidic cation-exchange resin (preparation method is see above) of modification, the temperature of reaction 60 DEG C of described acetalation, reaction pressure 2.0MPa.
(3) 8. 7. the product material 5. obtained by acetalation unit enter product (PODE) separating unit, 8. product (PODE) separating unit adopts flash distillation mode separated product material, and 7. (concrete equipment is flashing tower, concrete flash conditions is: flash vaporization point is 70-80 DEG C, and flashing pressure is 400-600KPa).
By product (PODE n=3 ~ 4) 8. separating unit be separated the PODE obtained n=3 ~ 4thick product material 9. (by discharging at the bottom of flashing tower tower used) enter product (PODE n=3 ~ 4) 10. refined unit refine; And by product (PODE n=3 ~ 4) separating unit be 8. separated the unreacted feed product that obtains 6. (by flashing tower tower top used discharging) then return raw material dehydration unit 3. in.
(4) PODE n=3 ~ 4thick product material 9. enter product (PODE n=3 ~ 4) refined unit 10., described product (PODE n=3 ~ 4) refined unit employing filler (stainless steel structured packing) rectifying tower, the condition of concrete rectifying is: rectifying bottom temperature is 128 DEG C, and rectifying pressure is 0.4PMa.
By product (PODE n=3 ~ 4) PODE that 10. obtains of refined unit n=3 ~ 4sterling material (by discharging at the bottom of rectifying tower used) enters product (PODE n=3 ~ 4) storage tanks (not marking in Fig. 1), and by product (PODE n=3 ~ 4) the light constituent material that 10. obtains of refined unit (ejecting material by rectifying tower used) then return acetalation unit 5. in.Experimental result is in table 1.
Embodiment 2
(1) material benzenemethanol 1. with 37wt% formalin 2. (temperature 30 DEG C, pressure 1.55MPa), after mass flowmeter metering, mix (mol ratio of formaldehyde and methyl alcohol is 3:1) in raw material dehydration unit is 3. middle and dewaters, the water-content in making material is 4. less than or equal to 30wt%;
The dewatering agent wherein adopted is the water-absorbing resin (super absorbent polymer combined by modified polyacrylic acid and polyacrylamide, commercially available product), dehydration temperaturre 30 DEG C, dewatering pressure 1.5MPa, after dehydration, gained mixture water-content is 4. less than or equal to 40wt%.
(2) 4. material enters acetalation unit and 5. carries out acetalation, and described acetalation is carried out in the fixed-bed reactor of filling solid acid catalyst, and institute's filling solid acid catalyst is ZSM molecular sieve (commercially available product) and Al 2o 3the mixture of (commercially available product), the temperature of reaction 120 DEG C of described acetalation, reaction pressure 1.0MPa.
(3) 7. the product material 5. obtained by acetalation unit enters product (PODE n=3 ~ 4) separating unit 8., product (PODE n=3 ~ 4) 8. separating unit adopt flash distillation mode separated product material 7. (concrete equipment is flashing tower, and concrete flash conditions is: flash vaporization point is 70-80 DEG C, and flashing pressure is 400-600KPa).
By product (PODE n=3 ~ 4) 8. separating unit be separated the PODE obtained n=3 ~ 4thick product material 9. (by discharging at the bottom of flashing tower tower used) enter product (PODE n=3 ~ 4) 10. refined unit refine; And by product (PODE n=3 ~ 4) separating unit be 8. separated the unreacted feed product that obtains 6. (by flashing tower tower top used discharging) then return raw material dehydration unit 3. in.
(4) PODE n=3 ~ 4thick product material 9. enter product (PODE n=3 ~ 4) refined unit 10., described product (PODE n=3 ~ 4) refined unit employing filler (stainless steel structured packing) rectifying tower, the condition of concrete rectifying is: rectifying bottom temperature is 128 DEG C, and rectifying pressure is 0.4PMa.
By product (PODE n=3 ~ 4) PODE that 10. obtains of refined unit n=3 ~ 4sterling material (by discharging at the bottom of rectifying tower used) enters product (PODE n=3 ~ 4) storage tanks (not marking in Fig. 1), and by product (PODE n=3 ~ 4) the light constituent material that 10. obtains of refined unit (ejecting material by rectifying tower used) then return acetalation unit 5. in.Experimental result is in table 1.
Comparative example
Except middle without except raw material dehydration unit 3. (or without raw material dehydration step) in flow process (or step), all the other are identical with embodiment 1.Experimental result is in table 1.
Table 1
As shown in Table 1, in raw material the control of water-content to the transformation efficiency of methyl alcohol and PODE n=3 ~ 4selectivity improve play keying action.In addition, PODE can also be simplified to the control of water-content in raw material n=3 ~ 4purification procedures.

Claims (9)

1. prepare polymethoxy dimethyl ether (PODE for one kind n=3 ~ 4) method, comprise the steps:
(1) methyl alcohol and the mixing of 37wt% formalin and dehydration are obtained water-content and be less than or equal to the methyl alcohol of 40wt% and the step of formaldehyde mixed solution;
(2) having under catalyzer existence condition, be less than or equal to the methyl alcohol of 40wt% by the water-content of gained and formaldehyde mixed solution obtains polymethoxy dimethyl ether (PODE through acetalation n=3 ~ 4) step; With
(3) by the polymethoxy dimethyl ether (PODE that step (2) is obtained n=3 ~ 4) step of separation and purification.
2. the method for claim 1, is characterized in that, the dehydration conditions described in step (1) is: dehydration temperaturre is 30 DEG C ~ 50 DEG C, and dewatering pressure is 1.0MPa ~ 1.5MPa.
3. the method for claim 1, is characterized in that, the temperature of reaction 60 DEG C ~ 120 DEG C of acetalation described in step (2), reaction pressure 1.0MPa ~ 2.0MPa.
4. method as claimed in claim 3, it is characterized in that, in step (2), the catalyzer that described acetalation adopts is solid acid catalyst.
5. method as claimed in claim 4, is characterized in that, wherein said solid acid catalyst is that styrene type acidic cation-exchange resin, the styrene type acidic cation-exchange resin of modification, ZSM molecular sieve are or/and Al 2o 3;
Wherein, the preparation method of the vinylbenzene acidic cation-exchange resin of described modification comprises the steps:
Take styrene type acidic cation-exchange resin (Amberlyst36) 10g, be placed in 250ml beaker stand-by; Then the hydrophobizing agent GLYMO(silane of 4% is prepared) solution, after it dissolves each other completely, 10g GLYMO solution is poured in the 250ml beaker that Amberlyst36 resin 10g is housed, keep water-bath 50 DEG C, after dipping 24h, filter, and with after deionized water wash several, be placed in loft drier 110 DEG C of dry 12h, the styrene type acidic cation-exchange resin of modification can be obtained.
6. the method for claim 1, it is characterized in that, the separation of the product that the acetalation wherein described in step (2) obtains adopts flash distillation mode to be separated, and concrete flash conditions is: flash vaporization point is 70 DEG C ~ 80 DEG C, and flashing pressure is 400KPa ~ 600KPa.
7. the method for claim 1, is characterized in that, wherein PODE n=3 ~ 4the refining mode by rectifying realize, the condition of concrete rectifying is: rectifying bottom temperature is 128 DEG C, and rectifying pressure is 0.4PMa.
8. as the method in claim 1 ~ 7 as described in any one, it is characterized in that, described method comprises the steps:
(1) 2. 1. methyl alcohol mixed and dewatered in raw material dehydration unit is 3. middle with 37wt% formalin, the water-content in making material is 4. less than or equal to 30wt%;
Wherein, concrete dehydration conditions is: dehydration temperaturre is 30 DEG C ~ 50 DEG C, and dewatering pressure is 1.0MPa ~ 1.5MPa;
(2) 4. material enters acetalation unit and 5. carries out acetalation, and in described acetalation, catalyzer used is solid acid catalyst, the temperature of reaction 60 DEG C ~ 120 DEG C of described acetalation, reaction pressure 1.0MPa ~ 2.0MPa;
(3) 7. the product material 5. obtained by acetalation unit enters product (PODE n=3 ~ 4) separating unit 8., product (PODE n=3 ~ 4) 8. separating unit can be flashing tower, concrete flash conditions is: flash vaporization point is 70 DEG C ~ 80 DEG C, and flashing pressure is 400KPa ~ 600KPa, by product (PODE n=3 ~ 4) 8. separating unit be separated the PODE obtained n=3 ~ 4thick product material 9. enter product (PODE n=3 ~ 4) 10. refined unit refine; And by product (PODE n=3 ~ 4) separating unit be 8. separated the unreacted feed product obtained 6. then return raw material dehydration unit 3. in;
(4) PODE n=3 ~ 4thick product material 9. enter product (PODE n=3 ~ 4) refined unit 10., described product (PODE n=3 ~ 4) refined unit generally can adopt stuffing rectification column, the condition of concrete rectifying is: rectifying bottom temperature is 128 DEG C, and rectifying pressure is 0.4PMa;
By product (PODE n=3 ~ 4) PODE that 10. obtains of refined unit n=3 ~ 4sterling material enter product (PODE n=3 ~ 4) storage tanks, and by product (PODE n=3 ~ 4) the light constituent material that 10. obtains of refined unit then return acetalation unit 5. in.
9. method as claimed in claim 8, it is characterized in that, wherein the mol ratio of formaldehyde and methyl alcohol is 3:1.
CN201310337587.0A 2013-08-05 2013-08-05 Method for preparing polyoxymethylene dimethyl ether from methanol and formaldehyde Pending CN104341279A (en)

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US11236032B2 (en) 2017-08-24 2022-02-01 Bp P.L.C. Process for dehydrating methanol to dimethyl ether
US11427524B2 (en) 2017-08-24 2022-08-30 Bp P.L.C. Process for dehydrating methanol to dimethyl ether product
US11673851B2 (en) 2017-08-24 2023-06-13 Bp P.L.C. Process for dehydrating methanol to dimethyl ether product
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