CN104610026B - A kind of double-reactor produces the method and system of polymethoxy dimethyl ether - Google Patents
A kind of double-reactor produces the method and system of polymethoxy dimethyl ether Download PDFInfo
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- CN104610026B CN104610026B CN201510058474.6A CN201510058474A CN104610026B CN 104610026 B CN104610026 B CN 104610026B CN 201510058474 A CN201510058474 A CN 201510058474A CN 104610026 B CN104610026 B CN 104610026B
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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 discloses a kind of double-reactor and produce the method and system of polymethoxy dimethyl ether (DMMn).The method includes: reaction raw materials is inputted the first reaction member by (1), using ionic liquid as catalyst, carries out initial reaction under conditions selected, and reaction raw materials includes paraformaldehyde, dimethoxym ethane；(2) after the catalyst in removing step (1) won the first place reactant liquor, then input the second reaction member, and using superpower solid acid as catalyst, carry out secondary response under conditions selected, it is thus achieved that comprise second reactant liquor of DMMn.Preferably, it is also with separative element and isolates target DMMn in the second reactant liquor；And reaction raw materials unreacted in the second reactant liquor or part the second reactant liquor are inputted the first reaction member again participate in reaction.This system includes first, second reaction member etc..The continuous prodution of the low cost of DMMn, high efficiency, environmental protection can be realized by the present invention.
Description
Technical field
The present invention relates to a kind of anhydrous new reaction system preparing polymethoxy dimethyl ether continuously and process, relate to especially
And one is with acidic ion liquid and solid acid as catalyst, with paraformaldehyde with dimethoxym ethane as raw material, raw through double-reactor
Produce new technology and the system of polymethoxy dimethyl ether.
Background technology
Polymethoxy dimethyl ether (DMMn) receives much attention as the novel fuel oil substitute of a kind of clean environment firendly.This
Alternative fuel is sufficiently close to the physicochemical property of traditional diesel fuel, can be directly appended to conventional diesel and use, Er Qiewu
Existing diesel engine need to be carried out the transformation in frame for movement, be ideal diesel fuel additives.Polymethoxy dimethyl ether has
Having higher Cetane number generally more than 63, specifically, its Cetane number is respectively as follows: DMM2 63, DMM3 78,
DMM490、DMM5 100.DMMn oxygen content is higher, it is possible to increase efficiency of combustion, reduces particulate matter and NOx, hydrocarbonization in tail gas
The discharge of compound VOC, meanwhile, it is good with the blending performance of diesel oil, can dissolve each other, and has self lubricity, can extend diesel oil
Mechanical life.
According to the record of CN 103772164 A, diesel oil adds 10%～20% polymethoxy dimethyl ether, can be notable
Improve the combustion characteristics of diesel oil, be effectively improved the thermal efficiency, the discharge of pollutant is greatly decreased.(the Zhu.et such as Huang Zuohua
Al.Proceedings of the Combustion Institute, 2013 (34): 3013-3020.) report diesel oil with
DMM mixture aptitude to burn, wherein, when DMM volume fraction is 15%～50%, blends and is conducive to improving the thermal efficiency, subtract
Few flue dust (smoke), CO, nanoparticles (nanoparticles), superfine particulate matter (ultrafine particles)
Discharge.And when using absolutely polymethoxy dimethyl ether as fuel time (with reference to US7235113B2, EP1422285B1),
The emissions such as particulate matter are below harsh Europe V standard (Euro V limit).
At present, polymethoxy dimethyl ether reaction raw materials has formalin, metaformaldehyde, paraformaldehyde, methyl alcohol, first to contract
Aldehyde, dimethyl ether etc. are multiple.Wherein, when using formalin or methyl alcohol as raw material, inevitably by water in raw material
Or the impact of water in products, makes side reaction increase, increase separating difficulty.WO 2006/045506A1、US
20080207954A1 etc. report metaformaldehyde and generate DMMn and water byproduct, reactant liquor warp under liquid acid is catalyzed with methyl alcohol
Deacidification separates with removing entrance rectifying column after water processes, and above-mentioned reactant liquor separation process need to use the acid of substantial amounts of sorbent treatment
With water, and the separation of methyl alcohol, water and DMMn still suffers from difficulty in actual mechanical process.
US13164677, US 1315439 etc. reports and produces under presence of acidic ionic liquid catalyst with methyl alcohol and metaformaldehyde
The method of DMMn, still contains a small amount of water and catalyst in thick product DMM3-8 in this technique, needs by silica gel or anion
Exchanger resin absorption abjection, could realize the refined of product DMM3-8.
When using anhydrous solid formaldehyde (such as metaformaldehyde, paraformaldehyde) as raw material, minimizing water can be prevented effectively from
Impact.Wherein, the price of paraformaldehyde is much lower relative to metaformaldehyde price.It is currently used for producing polymethoxy dimethyl ether
Catalyst have multiple, including liquid acid, solid acid, ionic liquid etc..But, when the liquid acid such as sulfuric acid, hydrochloric acid is catalyst,
More serious to equipment corrosion, and the later stage separate with product and have any problem, SO4 2-/TiO2Etc. superpower solid acid as catalyst
Time, metaformaldehyde and dimethoxym ethane are reacted and has preferable effect, but when use paraformaldehyde is raw material, superpower solid acid
Reactivity difference conversion ratio is the lowest.And when using ionic liquid as catalyst with polyformaldehyde reaction, although there is product easy
In separation, good selective, but relative price is higher, and reaction temperature is more higher than superpower solid acid, and can produce one
Quantitative formaldehyde.
In sum, the equal existing defects of the production technology of existing polymethoxy dimethyl ether, it would be highly desirable to improve.
Summary of the invention
Present invention is primarily targeted at a kind of method providing double-reactor to produce polymethoxy dimethyl ether, existing to overcome
There is the deficiency in technology.
A further object of the present invention also resides in the production system providing a kind of polymethoxy dimethyl ether.
For achieving the above object, the technical solution used in the present invention includes:
A kind of double-reactor produces the method for polymethoxy dimethyl ether, including:
(1) reaction raw materials is inputted the first reaction member, using ionic liquid as catalyst, is 80～150 DEG C in temperature,
Pressure is to carry out initial reaction under conditions of 0.1～8.0MPa, and wherein said reaction raw materials includes paraformaldehyde, dimethoxym ethane, and
Ionic liquid accounts for the 0.1～30wt% of overall reaction material；
(2) after the catalyst in removing step (1) won the first place reactant liquor, then the second reaction member is inputted, and with superpower
Solid acid, as catalyst, is 35～110 DEG C in temperature, and pressure is to carry out secondary response under conditions of 0.1～8.0MPa, it is thus achieved that
Comprise the second reactant liquor of polymethoxy dimethyl ether.
Further, described double-reactor produces the method for polymethoxy dimethyl ether and also includes: by defeated for the second reactant liquor
Entering separative element, to isolate target polymethoxy dimethyl ether therein, described separative element includes rectifying column.
As one of preferred embodiment, described double-reactor produces the method for polymethoxy dimethyl ether and also includes: will
In described second reactant liquor, unreacted reaction raw materials re-enters the first reaction member and again participates in reaction.
As one of preferred embodiment, described double-reactor produces the method for polymethoxy dimethyl ether and also includes: extremely
Major general's part the second reactant liquor inputs the first reactor and again participates in reaction.
As one of preferred embodiment, in step (1), the condition of initial reaction includes: temperature is 90～130 DEG C, pressure
Being 0.5～3.0MPa, ionic liquid accounts for the 0.1～5wt% of overall reaction material.
Wherein, described ionic liquid has a structure shown in formula (I):
Wherein, R is H or CH3-(CH2)n-, n=0～10；X-For CF3SO3 -, tetrafluoro boron F4 -、HSO4 -Or PTA-(p-
Toluenesulfonic Acid, p-methyl benzenesulfonic acid) anion.
Preferably, described ionic liquid has a structure shown in formula (II):
Wherein, X-For CF3SO3 -、HSO4 -、BF4 -Or PTA-(p-Toluenesulfonic Acid) anion.
Being more highly preferred to, described ionic liquid has a structure shown in formula (III):
Wherein, X-For CF3SO3 -、HSO4 -, tetrafluoro boron F4 -Or PTA-(p-Toluenesulfonic Acid) anion.
As one of preferred embodiment, in step (2), the condition of secondary response includes: temperature is 50～90 DEG C, pressure
Being 0.5～3.0MPa, superpower solid acid accounts for the 0.05～50wt% of overall reaction material.
Wherein, described superpower solid acid is at least to contain SO4 2-、S2O8 2-Or Cl-SO4 2-/MxOy、S2O8 2-/MxOyOr Cl-/
MxOyThe superpower solid acid of form, wherein M is at least selected from Fe, Zr, Al, Ti, Si, and the span of x/y is 0.2 to 1.
Preferably, M in described superpower solid acidxOyIncluding ZrO2、Fe2O3、Cl-/TiO2、Al2O3、ZrO2、SiO2、Fe3O4
In the combination of any one or more.
It is applied to the polymethoxy dimethyl ether production system in any one method aforementioned, including:
First reaction member, in order to make reaction raw materials under ionic liquid-catalyzed, is 80～150 DEG C in temperature, and pressure is
Initial reaction is carried out under conditions of 0.1～8.0MPa；
Second reaction member, in order to make the first reactant liquor that be removed ionic liquid, that step (1) is obtained at superpower solid
Under acid catalysis, being 35～110 DEG C in temperature, pressure is to carry out secondary response under conditions of 0.1～8.0MPa, thus obtains and comprise
Second reactant liquor of polymethoxy dimethyl ether；
Separative element, in order to isolate target polymethoxy dimethyl ether from the second reactant liquor.
More preferred, the material outlet of described second reaction member and/or the material outlet of separative element are also with first
The material inlet connection of reaction member.
Postscript, also can arrange the pretreatment list with functions such as filtrations between described second reaction member and separative element
Unit.
Compared with prior art, the beneficial effect comprise that the polymethoxy dimethyl ether production technology of offer is with honest and clean
The paraformaldehyde of valency as the source of aldehyde, and have employed under anhydrous system successively using ionic liquid with solid acid as catalysis
Agent, in two reactor system, the method for substep circular response, both can avoid the negative effect of water, may utilize again cheap
Paraformaldehyde is as raw material, simultaneously because successively using ionic liquid and solid acid as catalyst, the most fully combine both
Advantage, but also ionic liquid consumption can be greatly decreased, it is to avoid the shortcoming that solid acid is extremely low to polyformaldehyde reaction, significantly carry
Rise the conversion rate of dimethoxym ethane and paraformaldehyde.
Accompanying drawing explanation
For the technical scheme being illustrated more clearly that in the embodiment of the present invention, in embodiment being described below required for make
Accompanying drawing be briefly described, it should be apparent that, below describe in accompanying drawing for the present invention be only the one of the present invention
A little embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to according to these
Accompanying drawing obtains other accompanying drawing.
Fig. 1 is a kind of process principle figure preparing polymethoxy dimethyl ether continuously among the present invention one typical embodiments；
Fig. 2 is the knot of a kind of production system preparing polymethoxy dimethyl ether continuously among the present invention one typical embodiments
Structure schematic diagram；
Fig. 3 is a kind of production system preparing polymethoxy dimethyl ether continuously among another typical embodiments of the present invention
Structural representation.
Detailed description of the invention
Technical scheme in the embodiment of the present invention will be described in detail below, it is clear that described embodiment is only
It is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, ordinary skill
The every other embodiment that personnel are obtained on the premise of not making creative work, broadly falls into the model of present invention protection
Enclose.
In view of the deficiencies in the prior art, inventor, through studying for a long period of time and putting into practice in a large number, is proposed the skill of the present invention
Art scheme, it is a kind of method that double-reactor produces polymethoxy dimethyl ether, and saying more precisely, is that a kind of anhydrous system is continuous
The technique producing polymethoxy dimethyl ether, i.e. using dimethoxym ethane and paraformaldehyde as reaction raw materials, successively with ionic liquid with
Solid acid as catalyst, in two reactor system substep circular response and produce polymethoxy dimethyl ether.
Referring to shown in Fig. 1, among a typical embodiments of the present invention, this production technology may include that
(1) under the catalysis of ionic liquid, the raw material such as paraformaldehyde and dimethoxym ethane enter reaction member 1 80～150 DEG C,
Carrying out initial reaction under conditions of 0.1～8.0MPa, wherein, it is 0.1～30wt% that ionic liquid accounts for the mass fraction of total material；
(2) step (1) reacted reactant liquor enters reaction member 2 with catalyst after separating, at superpower solid acid
Catalysis under, under conditions of 35～110 DEG C, 0.1～8.0MPa, carry out secondary response；Reactant liquor can be partly recycled to reaction
Unit 1；
(3) reactant liquor that step (2) reaction member 2 obtains enters separative element, suitably separates, i.e. can get target
Product-polymethoxy dimethyl ether, a part circulates unreacted material and gently component, heavy constituent Returning reacting system continue anti-
Should.
Wherein, the composition of ionic liquid, superpower solid acid etc. can be as it was noted above, here is omitted.
Below in conjunction with some more specifically embodiments, present disclosure is illustrated.
Embodiment 1 refers to shown in Fig. 2, in conjunction with actual chemical industry equipment, The present invention gives an overall ionic liquid
Body and solid acid participate in catalysis, paraformaldehyde and dimethoxym ethane as the process flow system of the polymethoxy dimethyl ether processed of raw material
Concrete example.
Specifically, the present embodiment includes: first, is entered instead through pipeline 002 by pump P by the dimethoxym ethane in storage tank STR002
Answer device R001, meanwhile, paraformaldehyde through drier DRY001 after drying through measuring tank STR001 through conveying worm
SCRW001 through respective lines S4 also in reactor R001, and at the tank reactor equipped with ionic-liquid catalyst
R001 quickly stirs mixing.Thus, dimethoxym ethane and paraformaldehyde carry out initial reaction under the catalysis of catalyst.
In the present embodiment, the temperature in reactor R001 can be set as or 80 DEG C or 90 DEG C or 100 DEG C or 110 DEG C,
Or in the interval between 120 DEG C or 130 DEG C or 140 DEG C or 150 DEG C or these temperature；Pressure may be set in
0.1MPa or 1.0MPa or 2.0MPa or 3.0MPa or 4.0MPa or 5.0MPa or 6.0MPa or 7.0MPa or
In the interval of 8.0MPa or above-mentioned pressure；Catalyst can be fourth sulfonic group glyoxaline cation, 1-methyl-3-fourth sulfonic group miaow
Azoles cation, 1-ethyl-3-fourth sulfonic group glyoxaline cation, 1-propyl group-3-fourth sulfonic group glyoxaline cation, 1-butyl-3-fourth
Sulfonic group glyoxaline cation, 1-amyl group-3-fourth sulfonic group glyoxaline cation, 1-hexyl-3-fourth sulfonic group glyoxaline cation, 1-heptan
Base-3-fourth sulfonic group glyoxaline cation, 1-octyl group-3-fourth sulfonic group glyoxaline cation, 1-nonyl-3-fourth sulfonic group imidazoles sun from
Son, 1-decyl-3-fourth sulfonic group glyoxaline cation or above several mixture；Can also selected from fourth sulfonic group pyridine sun from
Son, or 1,1'-fourth sulfonic group-4,4'-bipyridine cation；Anion can be selected from TFMS root anion, sulfuric acid
Hydrogen radical anion, p-methyl benzenesulfonic acid anion, chlorion or a combination thereof；Catalyst amount can be 0.1wt% or
In the interval of 1wt% or 2wt% or 5wt% or 10wt% or 20wt% or 30wt% or above-mentioned consumption.
Liquid after dimethoxym ethane and paraformaldehyde carry out initial reaction under the catalysis of catalyst enters after pipeline 003
Continuing deep reaction in being filled with the reactor R002 of solid acid catalyst, outlet streams can be partly refluxed to reactor R001
Secondary response the most again；
In the present embodiment, the temperature in reactor R002 is set as or 35 DEG C or 40 DEG C or 50 DEG C or 60 DEG C or 70
DEG C or 80 DEG C or 90 DEG C or 110 DEG C or these temperature between interval in；Pressure be set in 0.1MPa or 1.0MPa,
Or the district of 2.0MPa or 3.0MPa or 4.0MPa or 5.0MPa or 6.0MPa or 7.0MPa or 8.0MPa or above-mentioned pressure
In；Catalyst is SO4 2-/TiO2, or SO4 2-/Fe2O3, or SO4 2-/ZrO2, or SO4 2-/Al2O3, or SO4 2-/Fe2O3-SiO2、
Or SO4 2-/TiO2-SiO2, or SO4 2-/TiO2-Al2O3, or SO4 2-/ZrO2-Al2O3, or SO4 2-/ZrO2-SiO2, or SO4 2-/
Al2O3-SiO2, or S2O8 2-/TiO2, or S2O8 2-/Fe2O3, or S2O8 2-/ZrO2, or S2O8 2-/Al2O3, or S2O8 2-/Fe2O3-
SiO2, or S2O8 2-/TiO2-SiO2, or S2O8 2-/TiO2-Al2O3, or S2O8 2-/ZrO2-Al2O3, or S2O8 2-/ZrO2-SiO2, or
S2O8 2-/Al2O3-SiO2, or Cl-/TiO2, or Cl-/Fe2O3, or Cl-/ZrO2, or Cl-/Al2O3, or Cl-/Fe2O3-SiO2, or
Cl-/TiO2-SiO2, or Cl-/TiO2-Al2O3, or Cl-/ZrO2-Al2O3, or Cl-/ZrO2-SiO2, or Cl-/Al2O3-SiO2, or
Person's a combination thereof；Wherein catalyst amount be 0.1wt% or 1wt% or 2wt% or 5wt% or 10wt% or 20wt% or
In the interval of 30wt% or 40wt% or 50wt% or above-mentioned consumption.
The product reacting generation in reaction member R002 enters separative element rectifying column SP001, light component through pipeline 004
In a small amount of methyl alcohol, formaldehyde and DMM and DMM2 isolate from tower top, and be back to reactor R001, heavy constituent is from tower
End discharging also enters rectifying column SP002 through pipeline 005 and separates, DMMn, n > heavy constituent of 8 is from discharging at the bottom of tower, and it is back to reaction
Device R001 reacts.Isolate DMM3-8 from tower top and can be used as product.
Embodiment 2 refers to shown in Fig. 3, in conjunction with actual chemical industry equipment, The present invention gives the ion of another entirety
Liquid and solid acid participate in catalysis, paraformaldehyde and dimethoxym ethane as the technological process system of the polymethoxy dimethyl ether processed of raw material
System concrete example.
Specifically, first the present embodiment may include that, is entered through pipeline 002 by pump P by the dimethoxym ethane in storage tank STR001
Enter reactor R001, meanwhile, wear into the paraformaldehyde after fine powder (200 mesh) and sprayed into reactor R001 through S1 line by nozzle NOZZLE
In, and quickly stirring mixes with unclassified stores in equipped with the tank reactor R001 of ionic-liquid catalyst.Thus, dimethoxym ethane
Under the catalysis of catalyst, initial reaction is carried out with paraformaldehyde.Nozzle is by compressing N2There is provided power, the N of excess in reactor2By
Relief valve is discharged.
Liquid after reactor R001 initial reaction enters the reactor equipped with solid acid catalyst after pipeline 003
Continuing deep reaction in R002, the extent of reaction can be passed through temperature, the time of staying, catalyst concn etc. and control, such as, work as reaction
Device temperature 50 C, time of staying 30min, catalyst concn 1.0%, can be manipulated by outlet thing comprising only DMMn, n
< the material of 8.Outlet streams can be partly the most anti-in pipeline 007 is back to reactor R001 after filter FLTR filters
Should, the solid filtered out is through can reuse as catalyst in 009 Returning reactor R002；In reaction member R002 instead
The product that should generate enters separative element rectifying column SP001 through pipeline 006, methyl alcohol, formaldehyde and DMM a small amount of in light component,
And DMM2 isolates from tower top, and being back to reactor R001, heavy constituent, from discharging at the bottom of tower and through pipeline 005 discharging, separates
The DMM3-8 gone out is product.
Embodiment 3 is by 12.2kg dimethoxym ethane, 7.2kg paraformaldehyde and 0.2kg ionic liquid [1-butyl-3-fourth sulfonic group
Glyoxaline cation] [TFMS root anion] join in the stainless steel cauldron continuously stirred, and to compress N2Arrive
2.0MPa, temperature 120 DEG C, enter into after stopping 30min in reactor in next stainless steel cauldron, there is 0.6kg inside
SO4 2-/TiO2Catalyst, keeps pressure 1.8MPa, and temperature 80 DEG C, after quickly stirring material stops 30min in reactor.
Now recording outlet dimethoxym ethane conversion ratio is 55%, and paraformaldehyde conversion ratio is 76%, DMM3-8Selectivity is 62%.
Wherein, dimethoxym ethane conversion ratio Conv1 computing formula is:
Dimethoxym ethane quality X 100% of the dimethoxym ethane quality that Conv1=has converted/feed intake.
Wherein, metaformaldehyde conversion ratio Conv2 computing formula is:
Metaformaldehyde quality X 100% of the metaformaldehyde quality that Conv2=has converted/feed intake.
Wherein DMM3-8Selective S3-8For computing formula it is:
S3-8DMM in=product3-8DMM in quality/product2-nQuality X 100%.
Embodiment 4 is by 12.2kg dimethoxym ethane, 7.2kg paraformaldehyde and 0.5kg ionic liquid [1-methyl-3-fourth sulfonic group
Glyoxaline cation] [anion hydrogen sulphate] join in the stainless steel cauldron continuously stirred, and to compress N2To 1.0MPa,
Temperature 110 DEG C, enters into after stopping 30min in next stainless steel cauldron in reactor, and there is the SO of 0.2kg inside4 2-/
ZrO2Catalyst, keeps pressure 0.8MPa, and temperature 85 DEG C, after quickly stirring material stops 60min in reactor.Now record
Outlet dimethoxym ethane conversion ratio is 56%, and paraformaldehyde conversion ratio is 78%, DMM3-8Selectivity is 62%.
Embodiment 5 is by 12.2kg dimethoxym ethane, 7.2kg paraformaldehyde and 0.02kg ionic liquid [1-amyl group-3-fourth sulfonic group
Glyoxaline cation] [anion hydrogen sulphate] join in the stainless steel cauldron continuously stirred, and to compress N2It is pressurized to
8.0MPa, temperature 130 DEG C, enter into after stopping 60min in reactor in next stainless steel cauldron, there is 0.5kg inside
SO4 2-/Fe2O3-SiO2Catalyst, keeps pressure 7.8MPa, temperature 50 C, and quickly stirring material stops in reactor
After 60min.Now recording outlet dimethoxym ethane conversion ratio is 51%, and paraformaldehyde conversion ratio is 55%, DMM3-8Selectivity is
52%.
Embodiment 6 by 12.2kg dimethoxym ethane, 7.2kg paraformaldehyde and 2.0kg ionic liquid [fourth sulfonic group pyridine sun from
Son] [TFMS root anion] join in the stainless steel cauldron continuously stirred, and to compress N2It is pressurized to 3.0MPa,
Temperature 100 DEG C, enters into after stopping 40min in next stainless steel cauldron in reactor, and there is the Cl of 0.02kg inside-/
ZrO2-SiO2Catalyst, keeps pressure 2.8MPa, and temperature 35 DEG C, after under agitation material stops 120min in reactor.This
Time record outlet dimethoxym ethane conversion ratio be 52%, paraformaldehyde conversion ratio is 59%, DMM3-8Selectivity is 55%.
Embodiment 7 by 12.2kg dimethoxym ethane, 7.2kg paraformaldehyde and 6.0kg ionic liquid [1,1'-fourth sulfonic group-4,
4'-bipyridine cation] [p-methyl benzenesulfonic acid anion] join in the stainless steel cauldron continuously stirred, and to compress N2Add
It is pressed onto 3.0MPa, temperature 80 DEG C, enters in next stainless steel fixed bed reactors after stopping 30min in reactor, interior
There is the S of 10kg in portion2O8 2-/TiO2-SiO2Beds, keeps pressure 2.8MPa, temperature 35 DEG C, and quickly stirring material is in reaction
After stopping 10min in device.Now recording outlet dimethoxym ethane conversion ratio is 49%, and paraformaldehyde conversion ratio is 48%, DMM3-8Select
Property is 43%.
Embodiment 8 is by 12.2kg dimethoxym ethane, 7.2kg paraformaldehyde and 0.8kg ionic liquid [1-decyl-3-fourth sulfonic group
Glyoxaline cation] [TFMS root anion] join in the stainless steel cauldron continuously stirred, and to compress N2Pressurization
To 8.0MPa, temperature 150 DEG C, entering in next stainless steel cauldron in reactor after stopping 30min, inside has
The SO of 0.8kg4 2-/Fe2O3Beds, keeps pressure 7.8MPa, temperature 65 DEG C, and quickly stirring material stops in reactor
After 30min.Now recording outlet dimethoxym ethane conversion ratio is 58%, and paraformaldehyde conversion ratio is 85%, DMM3-8Selectivity is
65%.
Embodiment 9 is by 13.9kg dimethoxym ethane, 5.4kg paraformaldehyde and 0.4kg ionic liquid [1-methyl-3-fourth sulfonic group
Glyoxaline cation] [p-methyl benzenesulfonic acid anion] join in the stainless steel cauldron continuously stirred, and to compress N2Arrive
2.0MPa, temperature 120 DEG C, enter into after stopping 30min in reactor in next stainless steel cauldron, there is 0.4kg inside
S2O8 2-/TiO2-Al2O3Catalyst, keeps pressure 1.8MPa, temperature 110 DEG C, and quickly stirring material stops in reactor
After 15min.Now recording outlet dimethoxym ethane conversion ratio is 42%, and paraformaldehyde conversion ratio is 95%, and DMM3-8 is selectively
58%.
Embodiment 10 is by 8.88kg dimethoxym ethane, 10.5kg paraformaldehyde and 0.4kg ionic liquid [1-methyl-3-fourth sulfonic acid
Base glyoxaline cation] [chlorion] join in the stainless steel cauldron continuously stirred, and to compress N2To 2.0MPa, temperature
120 DEG C, entering in next stainless steel cauldron in reactor after stopping 30min, there is the S of 0.4kg inside2O8 2-/
Fe2O3-SiO2Catalyst, keeps pressure 1.8MPa, and temperature 110 DEG C, after quickly stirring material stops 15min in reactor.This
Time record outlet dimethoxym ethane conversion ratio be 83%, paraformaldehyde conversion ratio is 64%, and DMM3-8 selectivity is 77%.
Embodiment 11 is by 15.0kg dimethoxym ethane, 4.3kg paraformaldehyde and 0.2kg ionic liquid [1-methyl-3-N-morpholinopropanesulfonic acid base
Glyoxaline cation] [anion hydrogen sulphate] join in the stainless steel cauldron continuously stirred, and with N2Set after displaced air
Constant-pressure is 0.1MPa, temperature 100 DEG C, enters in next stainless steel cauldron in reactor after stopping 30min, internal
There is the SO of 0.4kg4 2-/TiO2-ZrO2-SiO2Catalyst, keeps temperature 0.1MPa, temperature 110 DEG C, and quickly stirring material is in reaction
After stopping 15min in device.Now recording outlet dimethoxym ethane conversion ratio is 24%, and paraformaldehyde conversion ratio is 98%, and DMM3-8 selects
Selecting property is 43%.
Embodiment 12 (reference examples) is by 12.2kg dimethoxym ethane, 7.2kg paraformaldehyde and 0.6kg ionic liquid [1-butyl-3-
Fourth sulfonic group glyoxaline cation] [TFMS root anion] join in the stainless steel cauldron continuously stirred, and with pressure
Contracting N2To 2.0MPa, temperature 120 DEG C, in reactor, stop 60min.Now recording outlet dimethoxym ethane conversion ratio is 53%, many
Polyformaldehyde conversion ratio is 60%, DMM3-8Selectivity is 57%.
Embodiment 13 (reference examples) is by 12.2kg dimethoxym ethane, 7.2kg paraformaldehyde and 0.6kg SO4 2-/TiO2Catalyst adds
Entering in stainless steel cauldron, keep pressure 1.8MPa, temperature 80 DEG C, under rapid mixing conditions, material stops in reactor
After 60min.Now recording outlet dimethoxym ethane conversion ratio is 0.8%, and paraformaldehyde conversion ratio is 0.6%, DMM3-8Selectivity is
13%.
Embodiment 14 (reference examples) is by 12.2kg dimethoxym ethane, 7.2kg paraformaldehyde and 0.6kg SO4 2-/ZrO2Catalyst adds
Entering in stainless steel cauldron, keep pressure 2.8MPa, temperature 110 DEG C, under rapid mixing conditions, material stops in reactor
After staying 60min.Now recording outlet dimethoxym ethane conversion ratio is 5%, and paraformaldehyde conversion ratio is 7%, DMM3-8Selectivity is
22%.
Comparing embodiment 3 finds with embodiment 12, embodiment 13, embodiment 14, and the reactant liquor containing paraformaldehyde passes through
Ionic liquid reacts with solid acid after first activating again, can obtain higher conversion ratio and target product selectivity.And approximate bar
Under part the poorest using ionic liquid as effect during catalyst merely.And during merely using solid acid as catalyst, then less than 110 DEG C
Reacting hardly, target selectivity is the poorest.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of the spirit or essential attributes of the present invention, it is possible to realize the present invention in other specific forms.Therefore, no matter
From the point of view of which point, all should regard embodiment as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires rather than described above limits, it is intended that all by fall in the implication of equivalency and scope of claim
Change is included in the present invention.
Although moreover, it will be appreciated that this specification is been described by according to embodiment, but the most each embodiment only wraps
Containing an independent technical scheme, this narrating mode of specification is only that for clarity sake those skilled in the art should
Specification can also be formed those skilled in the art through appropriately combined as an entirety, the technical scheme in each embodiment
May be appreciated other embodiments.
Claims (7)
1. the method that a double-reactor produces polymethoxy dimethyl ether, it is characterised in that including:
(1) reaction raw materials is inputted the first reaction member, using ionic liquid as catalyst, be 80～150 DEG C in temperature, pressure
Being to carry out initial reaction under conditions of 0.1～8.0MPa, wherein said reaction raw materials contains paraformaldehyde, dimethoxym ethane, and ion
Liquid accounts for the 0.1～30wt% of overall reaction material, and it is shown that described ionic liquid has in formula (I), (II), (III) any one
Structure:
Wherein, R is H or CH3-(CH2)n-, n=0～10, X-For CF3SO3 -、BF4 -、HSO4 -Or p-methyl benzenesulfonic acid anion；
(2) after the catalyst in removing step (1) won the first place reactant liquor, then the second reaction member is inputted, and with superpower solid
Acid, as catalyst, is 35～110 DEG C in temperature, and pressure is to carry out secondary response under conditions of 0.1～8.0MPa, it is thus achieved that comprise
Second reactant liquor of polymethoxy dimethyl ether, described superpower solid acid is SO4 2-/MxOy、S2O8 2-/MxOyOr Cl-/MxOyForm
Superpower solid acid, wherein M is selected from Fe, Zr, Al, Ti or Si, and the span of x/y is 0.2～1.
Double-reactor the most according to claim 1 produces the method for polymethoxy dimethyl ether, it is characterised in that also include: will
Second reactant liquor input separative element, to isolate target polymethoxy dimethyl ether therein, described separative element includes rectifying
Tower.
Double-reactor the most according to claim 1 and 2 produces the method for polymethoxy dimethyl ether, it is characterised in that also wrap
Include: unreacted reaction raw materials in described second reactant liquor is re-entered the first reaction member and again participates in reaction.
Double-reactor the most according to claim 1 produces the method for polymethoxy dimethyl ether, it is characterised in that also include: extremely
Major general's part the second reactant liquor inputs the first reactor and again participates in reaction.
Double-reactor the most according to claim 1 produces the method for polymethoxy dimethyl ether, it is characterised in that in step (1)
The condition of initial reaction includes: temperature is 90～130 DEG C, and pressure is 0.5～3.0MPa, and ionic liquid accounts for overall reaction material
0.1～5wt%.
Double-reactor the most according to claim 1 produces the method for polymethoxy dimethyl ether, it is characterised in that in step (2)
The condition of secondary response includes: temperature is 50～90 DEG C, and pressure is 0.5～3.0MPa, and superpower solid acid accounts for overall reaction material
0.05～50wt%.
Double-reactor the most according to claim 1 produces the method for polymethoxy dimethyl ether, it is characterised in that: described superpower
M in solid acidxOySelected from ZrO2、Fe2O3、TiO2、Al2O3、ZrO2、SiO2、Fe3O4In the combination of any one or more.
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| CN106278836A (en) * | 2016-08-16 | 2017-01-04 | 鄂尔多斯市易臻石化科技有限公司 | Intermediate concentration formaldehyde and the apparatus and method of methylal synthesis polymethoxy dimethyl ether |
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| CN102320941A (en) * | 2011-07-14 | 2012-01-18 | 河南煤业化工集团研究院有限责任公司 | Method for synthesizing polyformaldehyde dimethyl ether by taking methanol and methanal as raw materials |
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