CN104610026A - Method and system for producing polyoxymethylene dimethyl ethers (DMMn) through dual reactor - Google Patents
Method and system for producing polyoxymethylene dimethyl ethers (DMMn) through dual reactor Download PDFInfo
- Publication number
- CN104610026A CN104610026A CN201510058474.6A CN201510058474A CN104610026A CN 104610026 A CN104610026 A CN 104610026A CN 201510058474 A CN201510058474 A CN 201510058474A CN 104610026 A CN104610026 A CN 104610026A
- Authority
- CN
- China
- Prior art keywords
- reaction
- dimethyl ether
- polymethoxy dimethyl
- ionic liquid
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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 method and a system for producing polyoxymethylene dimethyl ethers (DMMn) through a dual reactor. The method comprises the following steps: (1) inputting reaction raw materials into a first reaction unit, and performing initial reaction by using ionic liquid as a catalyst under a selected condition, wherein the reaction raw materials include paraformaldehyde and methylal; (2) removing the catalyst in a first reaction liquid obtained in the step (1), inputting into a second reaction unit, and reacting for a second time by using super solid acid as a catalyst under the selected condition to obtain a second reaction liquid containing DMMn; preferably separating target DMMn in the second reaction liquid through a separating unit; inputting the unreacted raw materials in the second reaction liquid or part of the second reaction liquid into the first reaction unit to react again. The system comprises the first reaction unit and the second reaction unit. By virtue of the method and the system, the low-cost, high-efficiency and environmentally-friendly continuous production of DMMn can be achieved.
Description
Technical field
The present invention relates to a kind of anhydrous new reaction system and processing method of continuous production polymethoxy dimethyl ether, in particular to one with acidic ion liquid and solid acid for catalyzer, with paraformaldehyde and methylal for raw material, produce novel process and the system of polymethoxy dimethyl ether through double-reactor.
Background technology
Polymethoxy dimethyl ether (DMMn) as a kind of clean environment firendly novel fuel oil substitute and receive much attention.The physicochemical property of this alternative fuel and traditional diesel oil fuel is very close, directly can add conventional diesel to and use, and without the need to carrying out the transformation in physical construction to existing diesel engine, be ideal diesel-dope.Polymethoxy dimethyl ether has higher cetane value usually more than 63, and specifically, its cetane value is as follows respectively: DMM2 63, DMM3 78, DMM490, DMM5 100.DMMn oxygen level is higher, can improve efficiency of combustion, reduces the discharge of particulate matter and NOx in tail gas, hydrocarbon polymer VOC, and meanwhile, the blending performance of itself and diesel oil is good, can dissolve each other, and has self lubricity, can extend diesel oil mechanical life.
According to the record of CN 103772164 A, in diesel oil, add 10% ~ 20% polymethoxy dimethyl ether, significantly can improve the combustioncharacteristics of diesel oil, effectively improve thermo-efficiency, significantly the discharge of decreasing pollution thing.(the Zhu.et al.Proceedings of theCombustion Institute such as Huang Zuohua, 2013 (34): 3013-3020.) characteristic of diesel oil and DMM mixture burns is reported, wherein, when DMM volume fraction is 15% ~ 50%, blending is conducive to improving thermo-efficiency, reduces the discharge of flue dust (smoke), CO, nanoparticles (nanoparticles), superfine particulate matter (ultrafine particles).And when using a hundred per cent polymethoxy dimethyl ether as (with reference to US7235113B2, EP1422285B1) during fuel, the discharges such as particulate matter are all lower than harsh Europe V standard (Euro V limit).
At present, polymethoxy dimethyl ether reaction raw materials has formalin, trioxymethylene, paraformaldehyde, methyl alcohol, methylal, dme etc. multiple.Wherein, when adopting formalin or methyl alcohol as raw material, be inevitably subject to the impact of water or water in products in raw material, side reaction is increased, increase separating difficulty.WO 2006/045506A1, US 20080207954A1 etc. report trioxymethylene and methyl alcohol generates DMMn and water byproduct under liquid acid catalysis, reaction solution through deacidification with except water treatment laggard enter rectifying column be separated, above-mentioned reaction solution separation process need adopt a large amount of sorbent treatment acid and water, and methyl alcohol, water still have difficulties with being separated of DMMn in actual mechanical process.
US13164677, US 1315439 etc. reports the method for producing DMMn with methyl alcohol and trioxymethylene under presence of acidic ionic liquid catalyst, still a small amount of water and catalyzer is contained in thick product DMM3-8 in this technique, need to be deviate from by silica gel or anionite-exchange resin absorption, the refining of product D MM3-8 could be realized.
When adopting anhydrous solid formaldehyde (such as trioxymethylene, paraformaldehyde) as raw material, can effectively avoid reducing water mitigation.Wherein, the price of paraformaldehyde is much lower relative to trioxymethylene price.Catalyzer at present for the production of polymethoxy dimethyl ether has multiple, comprises liquid acid, solid acid, ionic liquid etc.But, when the liquid acid such as sulfuric acid, hydrochloric acid is catalyzer, comparatively serious to equipment corrosion, and later stage and product separation are had any problem, SO
4 2-/ TiO
2during etc. superpower solid acid as catalyzer, trioxymethylene and methylal are reacted and has good effect, but when using paraformaldehyde for raw material, superpower solid acid reactive behavior difference transformation efficiency is very low.And when using ionic liquid as catalyzer and polyformaldehyde reaction, be easy to be separated although have product, good selective, relative price is higher, and temperature of reaction is more higher than superpower solid acid, and can produce a certain amount of formaldehyde.
In sum, the equal existing defects of production technique of existing polymethoxy dimethyl ether, urgently improves.
Summary of the invention
Main purpose of the present invention is to provide a kind of double-reactor to produce the method for polymethoxy dimethyl ether, to overcome deficiency of the prior art.
Another object of the present invention is also the production system providing a kind of polymethoxy dimethyl ether.
For achieving the above object, the technical solution used in the present invention comprises:
Double-reactor produces a method for polymethoxy dimethyl ether, comprising:
(1) reaction raw materials is inputted the first reaction member, using ionic liquid as catalyzer, it is 80 ~ 150 DEG C in temperature, pressure is carry out initial reaction under the condition of 0.1 ~ 8.0MPa, wherein said reaction raw materials comprises paraformaldehyde, methylal, and ionic liquid accounts for 0.1 ~ 30wt% of total reaction material;
(2) removing step (1) after the catalyzer of winning the first place in reaction solution, input the second reaction member again, and using superpower solid acid as catalyzer, it is 35 ~ 110 DEG C in temperature, pressure is carry out secondary reaction under the condition of 0.1 ~ 8.0MPa, obtains the second reaction solution comprising polymethoxy dimethyl ether.
Further, the method that described double-reactor produces polymethoxy dimethyl ether also comprises: by the second reaction solution input separating unit, to isolate target polymethoxy dimethyl ether wherein, described separating unit comprises rectifying tower.
As one of better embodiment, the method that described double-reactor produces polymethoxy dimethyl ether also comprises: unreacted reaction raw materials in described second reaction solution is re-entered the first reaction member and again participate in reaction.
As one of better embodiment, the method that described double-reactor produces polymethoxy dimethyl ether also comprises: input the first reactor to major general's part second reaction solution and again participate in reaction.
As one of better embodiment, in step (1), the condition of initial reaction comprises: temperature is 90 ~ 130 DEG C, and pressure is 0.5 ~ 3.0MPa, and ionic liquid accounts for 0.1 ~ 5wt% of total reaction material.
Wherein, described ionic liquid has structure shown in formula (I):
Wherein, R is H or CH
3-(CH
2)
n-, n=0 ~ 10; X
-for CF
3sO
3 -, tetrafluoro boron F
4 -, HSO
4 -or PTA
-(p-Toluenesulfonic Acid, tosic acid) negatively charged ion.
Preferably, described ionic liquid has structure shown in formula (II):
Wherein, X
-for CF
3sO
3 -, HSO
4 -, BF
4 -or PTA
-(p-Toluenesulfonic Acid) negatively charged ion.
More preferred, described ionic liquid has structure shown in formula (III):
Wherein, X
-for CF
3sO
3 -, HSO
4 -, tetrafluoro boron F
4 -or PTA
-(p-Toluenesulfonic Acid) negatively charged ion.
As one of better embodiment, in step (2), the condition of secondary reaction comprises: temperature is 50 ~ 90 DEG C, and pressure is 0.5 ~ 3.0MPa, and superpower solid acid accounts for 0.05 ~ 50wt% of total reaction material.
Wherein, described superpower solid acid is at least containing SO
4 2-, S
2o
8 2-or Cl
-sO
4 2-/ M
xo
y, S
2o
8 2-/ M
xo
yor Cl
-/ M
xo
ythe 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 acid
xo
ycomprise ZrO
2, Fe
2o
3, Cl
-/ TiO
2, Al
2o
3, ZrO
2, SiO
2, Fe
3o
4in the combination of any one or more.
Be applied to the polymethoxy dimethyl ether production system in any one method aforementioned, comprise:
First reaction member, in order to make reaction raw materials under ionic liquid-catalyzed, be 80 ~ 150 DEG C in temperature, pressure is carry out initial reaction under the condition of 0.1 ~ 8.0MPa;
Second reaction member, in order to make that be removed ionic liquid, that step (1) obtains the first reaction solution under superpower solid acid catalysis, it is 35 ~ 110 DEG C in temperature, pressure is carry out secondary reaction under the condition of 0.1 ~ 8.0MPa, thus obtains the second reaction solution comprising polymethoxy dimethyl ether;
Separating unit, in order to isolate target polymethoxy dimethyl ether from the second reaction solution.
Comparatively preferred, the material outlet of described second reaction member and/or the material outlet of separating unit are also communicated with the material inlet of the first reaction member.
Postscript, also can arrange the pretreatment unit with functions such as filtrations between described second reaction member and separating unit.
Compared with prior art, beneficial effect of the present invention comprises: the polymethoxy dimethyl ether production technique provided is using the paraformaldehyde of cheapness as the source of aldehyde, and to have employed under anhydrous system successively using ionic liquid and solid acid as catalyzer, the method of substep circulating reaction in two reactor system, both the negative impact of water can have been avoided, cheap paraformaldehyde can be utilized again as raw material, simultaneously due to successively using ionic liquid and solid acid as catalyzer, not only fully combine both advantages, but also can significantly reduce ionic liquid consumption, avoid the shortcoming that solid acid is extremely low to polyformaldehyde reaction, significantly improve the conversion rate of methylal and paraformaldehyde.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing for the present invention in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the process principle figure of a kind of continuous production polymethoxy dimethyl ether among the present invention one typical embodiments;
Fig. 2 is the structural representation of the production system of a kind of continuous production polymethoxy dimethyl ether among the present invention one typical embodiments;
Fig. 3 is the structural representation of the production system of a kind of continuous production polymethoxy dimethyl ether among another typical embodiments of the present invention.
Embodiment
Be described in detail to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under the prerequisite not making creative work, all belongs to the scope of protection of the invention.
In view of the deficiencies in the prior art, inventor is through studying for a long period of time and putting into practice in a large number, technical scheme of the present invention is proposed, it is a kind of method that double-reactor produces polymethoxy dimethyl ether, more specifically, be a kind of technique of anhydrous system continuous seepage polymethoxy dimethyl ether, namely using methylal and paraformaldehyde as reaction raw materials, successively using ionic liquid and solid acid as catalyzer, substep circulating reaction in two reactor system and produce polymethoxy dimethyl ether.
Refer to shown in Fig. 1, among a typical embodiments of the present invention, this production technique can comprise:
(1) under the catalysis of ionic liquid, the raw material such as paraformaldehyde and methylal enter reaction member 1 80 ~ 150 DEG C, carry out initial reaction under the condition of 0.1 ~ 8.0MPa, wherein, the massfraction that ionic liquid accounts for total material is 0.1 ~ 30wt%;
(2) step (1) reacted reaction solution through with catalyst separating after enter reaction member 2, under the catalysis of superpower solid acid, 35 ~ 110 DEG C, carry out secondary reaction under the condition of 0.1 ~ 8.0MPa; Reaction solution can be partly recycled to reaction member 1;
(3) reaction solution that step (2) reaction member 2 obtains enters separating unit, carry out appropriate separation, target product-polymethoxy dimethyl ether can be obtained, a part circulation unreacted material and light constituent, heavy constituent Returning reacting system continue reaction.
Wherein, the composition etc. of ionic liquid, superpower solid acid can as mentioned before, repeat no more herein.
Below in conjunction with some more specifically embodiments, content of the present invention 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 and solid acid participate in catalysis, paraformaldehyde and methylal be as the process flow system concrete example of the polymethoxy dimethyl ether processed of raw material.
Specifically, the present embodiment comprises: first, methylal in storage tank STR002 is entered reactor R001 by pump P through pipeline 002, simultaneously, paraformaldehyde also enters into reactor R001 through worm conveyor SCRW001 through respective lines S4 through test tank STR001 after moisture eliminator DRY001 drying, and rapid stirring mixing in the tank reactor R001 that ionic-liquid catalyst is housed.Thus methylal and paraformaldehyde carry out initial reaction under the catalysis of catalyzer.
In the present embodiment, the temperature in reactor R001 can be set as or in interval between 80 DEG C or 90 DEG C or 100 DEG C or 110 DEG C or 120 DEG C or 130 DEG C or 140 DEG C or 150 DEG C or these temperature, pressure can be set in the interval of 0.1MPa or 1.0MPa or 2.0MPa or 3.0MPa or 4.0MPa or 5.0MPa or 6.0MPa or 7.0MPa or 8.0MPa or above-mentioned pressure, catalyzer can be fourth sulfonic group glyoxaline cation, 1-methyl-3-fourth sulfonic group glyoxaline 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-heptyl-3-fourth sulfonic group glyoxaline cation, 1-octyl group-3-fourth sulfonic group glyoxaline cation, 1-nonyl-3-fourth sulfonic group glyoxaline cation, the mixture that 1-decyl-3-fourth sulfonic group glyoxaline cation or more is several, also fourth sulfonic group pyridylium can be selected from, or 1,1'-fourth sulfonic group-4,4'-bipyridine cation, negatively charged ion can be selected from trifluoromethanesulfonic acid root negatively charged ion, anion hydrogen sulphate, tosic acid negatively charged ion, chlorion or its combination, catalyst levels can be in the interval of 0.1wt% or 1wt% or 2wt% or 5wt% or 10wt% or 20wt% or 30wt% or above-mentioned consumption.
Liquid after methylal and paraformaldehyde carry out initial reaction under the catalysis of catalyzer enter after pipeline 003 be filled with solid acid catalyst reactor R002 in continue deep reaction, outlet streams can be partly refluxed in reactor R001 secondary response again;
In the present embodiment, the temperature in reactor R002 is set as or in interval between 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; Pressure setting is in the interval of 0.1MPa or 1.0MPa or 2.0MPa or 3.0MPa or 4.0MPa or 5.0MPa or 6.0MPa or 7.0MPa or 8.0MPa or above-mentioned pressure; Catalyzer is SO
4 2-/ TiO
2, or SO
4 2-/ Fe
2o
3, or SO
4 2-/ ZrO
2, or SO
4 2-/ Al
2o
3, or SO
4 2-/ Fe
2o
3-SiO
2, or SO
4 2-/ TiO
2-SiO
2, or SO
4 2-/ TiO
2-Al
2o
3, or SO
4 2-/ ZrO
2-Al
2o
3, or SO
4 2-/ ZrO
2-SiO
2, or SO
4 2-/ Al
2o
3-SiO
2, or S
2o
8 2-/ TiO
2, or S
2o
8 2-/ Fe
2o
3, or S
2o
8 2-/ ZrO
2, or S
2o
8 2-/ Al
2o
3, or S
2o
8 2-/ Fe
2o
3-SiO
2, or S
2o
8 2-/ TiO
2-SiO
2, or S
2o
8 2-/ TiO
2-Al
2o
3, or S
2o
8 2-/ ZrO
2-Al
2o
3, or S
2o
8 2-/ ZrO
2-SiO
2, or S
2o
8 2-/ Al
2o
3-SiO
2, or Cl
-/ TiO
2, or Cl
-/ Fe
2o
3, or Cl
-/ ZrO
2, or Cl
-/ Al
2o
3, or Cl
-/ Fe
2o
3-SiO
2, or Cl
-/ TiO
2-SiO
2, or Cl
-/ TiO
2-Al
2o
3, or Cl
-/ ZrO
2-Al
2o
3, or Cl
-/ ZrO
2-SiO
2, or Cl
-/ Al
2o
3-SiO
2, or its combination; Wherein catalyst levels is in the interval of 0.1wt% or 1wt% or 2wt% or 5wt% or 10wt% or 20wt% or 30wt% or 40wt% or 50wt% or above-mentioned consumption.
The product reacting generation in reaction member R002 enters separating unit rectifying tower SP001 through pipeline 004, methyl alcohol a small amount of in light constituent, formaldehyde and DMM and DMM2 isolate from tower top, and be back to reactor R001, heavy constituent is from discharging at the bottom of tower and enter rectifying tower SP002 through pipeline 005 and be separated, DMMn, the heavy constituent of n>8 from discharging at the bottom of tower, and is back to reactor R001 and reacts.Isolate DMM3-8 from tower top and namely 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 ionic liquid of another entirety and solid acid participate in catalysis, paraformaldehyde and methylal be as the process flow system concrete example of the polymethoxy dimethyl ether processed of raw material.
Specifically, the present embodiment can comprise: first, methylal in storage tank STR001 is entered reactor R001 by pump P through pipeline 002, simultaneously, wear into the paraformaldehyde after fine powder (200 order) to be sprayed in reactor R001 by nozzle NOZZLE through S1 line, and rapid stirring mixes with unclassified stores in the tank reactor R001 that ionic-liquid catalyst is housed.Thus methylal and paraformaldehyde carry out initial reaction under the catalysis of catalyzer.Nozzle is by compressing N
2there is provided power, N excessive in reactor
2discharged by pressure release valve.
Liquid after reactor R001 initial reaction enter after pipeline 003 solid acid catalyst is housed reactor R002 in continue deep reaction, level of response can pass through the controls such as temperature, the residence time, catalyst concn, such as when temperature of reactor 50 DEG C, residence time 30min, catalyst concn 1.0%, can control to export the material only containing DMMn, n<8 in thing by operation.Outlet streams part can be back in reactor R001 secondary response again through pipeline 007 after filter FLTR filters, and the solid filtered out is through reusing as catalyzer in 009 Returning reactor R002; The product reacting generation in reaction member R002 enters separating unit rectifying tower SP001 through pipeline 006, methyl alcohol a small amount of in light constituent, formaldehyde and DMM and DMM2 isolate from tower top, and be back to reactor R001, heavy constituent is from discharging at the bottom of tower and through pipeline 005 discharging, isolated DMM3-8 is product.
12.2kg methylal, 7.2kg paraformaldehyde and 0.2kg ionic liquid [1-butyl-3-fourth sulfonic group glyoxaline cation] [trifluoromethanesulfonic acid root negatively charged ion] join in the stainless steel cauldron of continuously stirring by embodiment 3, and to compress N
2to 2.0MPa, temperature 120 DEG C, enter into stop 30min in reactor after in next stainless steel cauldron, there is the SO of 0.6kg inside
4 2-/ TiO
2catalyzer, keep pressure 1.8MPa, temperature 80 DEG C, after rapid stirring material stops 30min in reactor.Now recording outlet methylal transformation efficiency is 55%, and paraformaldehyde transformation efficiency is 76%, DMM
3-8selectivity is 62%.
Wherein, methylal transformation efficiency Conv1 calculation formula is:
The methylal quality X 100% of the methylal quality that Conv1=has transformed/feed intake.
Wherein, trioxymethylene transformation efficiency Conv2 calculation formula is:
The trioxymethylene quality X 100% of the trioxymethylene quality that Conv2=has transformed/feed intake.
Wherein DMM
3-8selectivity S
3-8for calculation formula is:
S
3-8dMM in=product
3-8dMM in quality/product
2-nquality X 100%.
12.2kg methylal, 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 of continuously stirring by embodiment 4, and to compress N
2to 1.0MPa, temperature 110 DEG C, enter into stop 30min in reactor after in next stainless steel cauldron, there is the SO of 0.2kg inside
4 2-/ ZrO
2catalyzer, keep pressure 0.8MPa, temperature 85 DEG C, after rapid stirring material stops 60min in reactor.Now recording outlet methylal transformation efficiency is 56%, and paraformaldehyde transformation efficiency is 78%, DMM
3-8selectivity is 62%.
12.2kg methylal, 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 of continuously stirring by embodiment 5, and to compress N
2be pressurized to 8.0MPa, temperature 130 DEG C, enter into stop 60min in reactor after in next stainless steel cauldron, there is the SO of 0.5kg inside
4 2-/ Fe
2o
3-SiO
2catalyzer, keep pressure 7.8MPa, temperature 50 C, after rapid stirring material stops 60min in reactor.Now recording outlet methylal transformation efficiency is 51%, and paraformaldehyde transformation efficiency is 55%, DMM
3-8selectivity is 52%.
12.2kg methylal, 7.2kg paraformaldehyde and 2.0kg ionic liquid [fourth sulfonic group pyridylium] [trifluoromethanesulfonic acid root negatively charged ion] join in the stainless steel cauldron of continuously stirring by embodiment 6, and to compress N
2be pressurized to 3.0MPa, temperature 100 DEG C, enter into stop 40min in reactor after in next stainless steel cauldron, there is the Cl of 0.02kg inside
-/ ZrO
2-SiO
2catalyzer, keep pressure 2.8MPa, temperature 35 DEG C, after under agitation material stops 120min in reactor.Now recording outlet methylal transformation efficiency is 52%, and paraformaldehyde transformation efficiency is 59%, DMM
3-8selectivity is 55%.
12.2kg methylal, 7.2kg paraformaldehyde and 6.0kg ionic liquid [1,1'-fourth sulfonic group-4,4'-bipyridine cation] [tosic acid negatively charged ion] join in the stainless steel cauldron of continuously stirring by embodiment 7, and to compress N
2be pressurized to 3.0MPa, temperature 80 DEG C, enter into stop 30min in reactor after in next stainless steel fixed-bed reactor, there is the S of 10kg inside
2o
8 2-/ TiO
2-SiO
2beds, keep pressure 2.8MPa, temperature 35 DEG C, after rapid stirring material stops 10min in reactor.Now recording outlet methylal transformation efficiency is 49%, and paraformaldehyde transformation efficiency is 48%, DMM
3-8selectivity is 43%.
12.2kg methylal, 7.2kg paraformaldehyde and 0.8kg ionic liquid [1-decyl-3-fourth sulfonic group glyoxaline cation] [trifluoromethanesulfonic acid root negatively charged ion] join in the stainless steel cauldron of continuously stirring by embodiment 8, and to compress N
2be pressurized to 8.0MPa, temperature 150 DEG C, enter into stop 30min in reactor after in next stainless steel cauldron, there is the SO of 0.8kg inside
4 2-/ Fe
2o
3beds, keep pressure 7.8MPa, temperature 65 DEG C, after rapid stirring material stops 30min in reactor.Now recording outlet methylal transformation efficiency is 58%, and paraformaldehyde transformation efficiency is 85%, DMM
3-8selectivity is 65%.
13.9kg methylal, 5.4kg paraformaldehyde and 0.4kg ionic liquid [1-methyl-3-fourth sulfonic group glyoxaline cation] [tosic acid negatively charged ion] join in the stainless steel cauldron of continuously stirring by embodiment 9, and to compress N
2to 2.0MPa, temperature 120 DEG C, enter into stop 30min in reactor after in next stainless steel cauldron, there is the S of 0.4kg inside
2o
8 2-/ TiO
2-Al
2o
3catalyzer, keep pressure 1.8MPa, temperature 110 DEG C, after rapid stirring material stops 15min in reactor.Now recording outlet methylal transformation efficiency is 42%, and paraformaldehyde transformation efficiency is 95%, DMM3-8 selectivity is 58%.
8.88kg methylal, 10.5kg paraformaldehyde and 0.4kg ionic liquid [1-methyl-3-fourth sulfonic group glyoxaline cation] [chlorion] join in the stainless steel cauldron of continuously stirring by embodiment 10, and to compress N
2to 2.0MPa, temperature 120 DEG C, enter into stop 30min in reactor after in next stainless steel cauldron, there is the S of 0.4kg inside
2o
8 2-/ Fe
2o
3-SiO
2catalyzer, keep pressure 1.8MPa, temperature 110 DEG C, after rapid stirring material stops 15min in reactor.Now recording outlet methylal transformation efficiency is 83%, and paraformaldehyde transformation efficiency is 64%, DMM3-8 selectivity is 77%.
15.0kg methylal, 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 of continuously stirring by embodiment 11, and with N
2after displaced air, setting pressure is 0.1MPa, temperature 100 DEG C, and enter into stop 30min in reactor after in next stainless steel cauldron, there is the SO of 0.4kg inside
4 2-/ TiO
2-ZrO
2-SiO
2catalyzer, keep temperature 0.1MPa, temperature 110 DEG C, after rapid stirring material stops 15min in reactor.Now recording outlet methylal transformation efficiency is 24%, and paraformaldehyde transformation efficiency is 98%, DMM3-8 selectivity is 43%.
12.2kg methylal, 7.2kg paraformaldehyde and 0.6kg ionic liquid [1-butyl-3-fourth sulfonic group glyoxaline cation] [trifluoromethanesulfonic acid root negatively charged ion] join in the stainless steel cauldron of continuously stirring by embodiment 12 (reference examples), and to compress N
2to 2.0MPa, temperature 120 DEG C, stops 60min in reactor.Now recording outlet methylal transformation efficiency is 53%, and paraformaldehyde transformation efficiency is 60%, DMM
3-8selectivity is 57%.
Embodiment 13 (reference examples) is by 12.2kg methylal, 7.2kg paraformaldehyde and 0.6kg SO
4 2-/ TiO
2catalyzer joins in stainless steel cauldron, and keep pressure 1.8MPa, temperature 80 DEG C, after under rapid mixing conditions, material stops 60min in reactor.Now recording outlet methylal transformation efficiency is 0.8%, and paraformaldehyde transformation efficiency is 0.6%, DMM
3-8selectivity is 13%.
Embodiment 14 (reference examples) is by 12.2kg methylal, 7.2kg paraformaldehyde and 0.6kg SO
4 2-/ ZrO
2catalyzer joins in stainless steel cauldron, and keep pressure 2.8MPa, temperature 110 DEG C, after under rapid mixing conditions, material stops 60min in reactor.Now recording outlet methylal transformation efficiency is 5%, and paraformaldehyde transformation efficiency is 7%, DMM
3-8selectivity is 22%.
Comparing embodiment 3 and embodiment 12, embodiment 13, embodiment 14 find, the reaction solution containing paraformaldehyde reacts with solid acid after ionic liquid first activates again, and can obtain higher transformation efficiency and target product selectivity.And under approximate condition simple using ionic liquid as catalyzer time effect slightly poor.And during merely using solid acid as catalyzer, then less than 110 DEG C are reacted hardly, and target selectivity is also poor.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit of the present invention or essential characteristic, the present invention can be realized in other specific forms.Therefore, no matter from which point, all should embodiment be regarded as exemplary, and be nonrestrictive, scope of the present invention is limited by claims instead of above-mentioned explanation, and all changes be therefore intended in the implication of the equivalency by dropping on claim and scope are included in the present invention.
In addition, be to be understood that, although this specification sheets is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets is only for clarity sake, those skilled in the art should by specification sheets integrally, and the technical scheme in each embodiment also through appropriately combined, can form other embodiments that it will be appreciated by those skilled in the art that.
Claims (10)
1. double-reactor produces a method for polymethoxy dimethyl ether, it is characterized in that comprising:
(1) reaction raw materials is inputted the first reaction member, using ionic liquid as catalyzer, it is 80 ~ 150 DEG C in temperature, pressure is carry out initial reaction under the condition of 0.1 ~ 8.0MPa, wherein said reaction raw materials comprises paraformaldehyde, methylal, and ionic liquid accounts for 0.1 ~ 30wt% of total reaction material;
(2) removing step (1) after the catalyzer of winning the first place in reaction solution, input the second reaction member again, and using superpower solid acid as catalyzer, it is 35 ~ 110 DEG C in temperature, pressure is carry out secondary reaction under the condition of 0.1 ~ 8.0MPa, obtains the second reaction solution comprising polymethoxy dimethyl ether.
2. double-reactor according to claim 1 produces the method for polymethoxy dimethyl ether, characterized by further comprising: by the second reaction solution input separating unit, to isolate target polymethoxy dimethyl ether wherein, described separating unit comprises rectifying tower.
3. double-reactor according to claim 1 and 2 produces the method for polymethoxy dimethyl ether, characterized by further comprising: unreacted reaction raw materials in described second reaction solution is re-entered the first reaction member and again participate in reaction.
4. double-reactor according to claim 1 produces the method for polymethoxy dimethyl ether, characterized by further comprising: input the first reactor to major general's part second reaction solution and again participate in reaction.
5. double-reactor according to claim 1 produces the method for polymethoxy dimethyl ether, it is characterized in that the condition of initial reaction in step (1) comprises: temperature is 90 ~ 130 DEG C, pressure is 0.5 ~ 3.0MPa, and ionic liquid accounts for 0.1 ~ 5wt% of total reaction material.
6. the double-reactor according to any one of claim 1,5 produces the method for polymethoxy dimethyl ether, it is characterized in that described ionic liquid has structure shown in formula (I):
Wherein, R is H or CH
3-(CH
2)
n-, n=0 ~ 10; X
-for CF
3sO
3 -, tetrafluoro boron F
4 -, HSO
4 -or tosic acid negatively charged ion;
Preferably, described ionic liquid has structure shown in formula (II):
Wherein, X
-for CF
3sO
3 -, HSO
4 -, tetrafluoro boron F
4 -or tosic acid negatively charged ion;
More preferred, described ionic liquid has structure shown in formula (III):
Wherein, X
-for CF
3sO
3 -, HSO
4 -, tetrafluoro boron F
4 -or tosic acid negatively charged ion.
7. double-reactor according to claim 1 produces the method for polymethoxy dimethyl ether, it is characterized in that the condition of secondary reaction in step (2) comprises: temperature is 50 ~ 90 DEG C, pressure is 0.5 ~ 3.0MPa, and superpower solid acid accounts for 0.05 ~ 50wt% of total reaction material.
8. the double-reactor according to any one of claim 1,7 produces the method for polymethoxy dimethyl ether, it is characterized in that described superpower solid acid is at least containing SO
4 2-, S
2o
8 2-or Cl
-sO
4 2-/ M
xo
y, S
2o
8 2-/ M
xo
yor Cl
-/ M
xo
ythe superpower solid acid of form, wherein M is at least selected from Fe, Zr, Al, Ti, Si, the span 0.2-1 of x/y;
Preferably, M in described superpower solid acid
xo
ycomprise ZrO
2, Fe
2o
3, Cl
-/ TiO
2, Al
2o
3, ZrO
2, SiO
2, Fe
3o
4in the combination of any one or more.
9. be applied to the polymethoxy dimethyl ether production system in method according to any one of claim 1-8, it is characterized in that comprising:
First reaction member, in order to make reaction raw materials under ionic liquid-catalyzed, be 80 ~ 150 DEG C in temperature, pressure is carry out initial reaction under the condition of 0.1 ~ 8.0MPa;
Second reaction member, in order to make that be removed ionic liquid, that step (1) obtains the first reaction solution under superpower solid acid catalysis, it is 35 ~ 110 DEG C in temperature, pressure is carry out secondary reaction under the condition of 0.1 ~ 8.0MPa, thus obtains the second reaction solution comprising polymethoxy dimethyl ether;
Separating unit, in order to isolate target polymethoxy dimethyl ether from the second reaction solution.
10. polymethoxy dimethyl ether production system according to claim 9, is characterized in that the material outlet of described second reaction member and/or the material outlet of separating unit are also communicated with the material inlet of the first reaction member.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510058474.6A CN104610026B (en) | 2015-02-04 | 2015-02-04 | A kind of double-reactor produces the method and system of polymethoxy dimethyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510058474.6A CN104610026B (en) | 2015-02-04 | 2015-02-04 | A kind of double-reactor produces the method and system of polymethoxy dimethyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104610026A true CN104610026A (en) | 2015-05-13 |
| CN104610026B CN104610026B (en) | 2016-08-17 |
Family
ID=53144717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510058474.6A Active CN104610026B (en) | 2015-02-04 | 2015-02-04 | A kind of double-reactor produces the method and system of polymethoxy dimethyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104610026B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106278835A (en) * | 2015-06-10 | 2017-01-04 | 中国科学院兰州化学物理研究所苏州研究院 | The method of anhydrous production polymethoxy dimethyl ether |
| CN106631721A (en) * | 2016-11-16 | 2017-05-10 | 安徽泗县新科农林开发有限公司 | Polyoxymethylene dimethyl ether synthesis device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249869A (en) * | 2010-05-18 | 2011-11-23 | 中国科学院兰州化学物理研究所 | Technical process for catalytically synthesizing polymethoxy dimethyl ether by ionic liquid |
| 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 |
| CN104119210A (en) * | 2014-06-27 | 2014-10-29 | 北京东方红升新能源应用技术研究院有限公司 | Method for preparing polymethoxy dimethyl ether by virtue of slurry bed in combination with fixed bed |
-
2015
- 2015-02-04 CN CN201510058474.6A patent/CN104610026B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249869A (en) * | 2010-05-18 | 2011-11-23 | 中国科学院兰州化学物理研究所 | Technical process for catalytically synthesizing polymethoxy dimethyl ether by ionic liquid |
| 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 |
| CN104119210A (en) * | 2014-06-27 | 2014-10-29 | 北京东方红升新能源应用技术研究院有限公司 | Method for preparing polymethoxy dimethyl ether by virtue of slurry bed in combination with fixed bed |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278835A (en) * | 2015-06-10 | 2017-01-04 | 中国科学院兰州化学物理研究所苏州研究院 | The method of anhydrous production polymethoxy dimethyl ether |
| CN106278835B (en) * | 2015-06-10 | 2019-01-11 | 中国科学院兰州化学物理研究所苏州研究院 | The method of anhydrous production polymethoxy dimethyl ether |
| 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 |
| CN106631721A (en) * | 2016-11-16 | 2017-05-10 | 安徽泗县新科农林开发有限公司 | Polyoxymethylene dimethyl ether synthesis device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104610026B (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2015101775A4 (en) | A method for producing polyoxymethylene dimethyl ethers from feedstock of concentrated formaldehyde | |
| CN103880615B (en) | Preparation process method and device of polyoxymethylene dimethyl ether | |
| CN103626640B (en) | A kind of preparation technology's device and method of polymethoxy dimethyl ether | |
| CN104725229B (en) | The method for preparing polymethoxy dimethyl ether carbonyl compound and methoxy menthyl acetate | |
| CN104725230B (en) | The method for preparing polymethoxy dimethyl ether carbonyl compound and methoxy menthyl acetate | |
| CN101962318A (en) | Method for synthesizing polymethoxy dimethyl ether under catalysis of geminal dicationic ionic liquid | |
| CN104250205B (en) | The preparation method of methyl tertiary butyl ether and device thereof | |
| CN107522602B (en) | Process and system for preparing DMM2 | |
| CN104610026A (en) | Method and system for producing polyoxymethylene dimethyl ethers (DMMn) through dual reactor | |
| CN106631720B (en) | Method for directly synthesizing polymethoxy dimethyl ether by taking dilute formaldehyde and methylal as raw materials | |
| CN106220481A (en) | A kind of technique of continuous production polyoxymethylene dimethyl ether | |
| CN105061165A (en) | Reaction apparatus for preparing polyoxymethylene dimethyl ether | |
| CN102504891B (en) | Preparation method of glyceryl biological fuel additives | |
| CN106278836A (en) | Intermediate concentration formaldehyde and the apparatus and method of methylal synthesis polymethoxy dimethyl ether | |
| CN107522601A (en) | A kind of polymethoxy dimethyl ether separator and technique | |
| CN106520180B (en) | A method of reducing catalytic cracking gasoline olefine content | |
| CN108383696A (en) | The method for preparing polymethoxy dimethyl ether | |
| CN110437044B (en) | Method and device for preparing polymethoxy dimethyl ether | |
| CN107056670A (en) | A kind of preparation method of two tertiary base peroxide | |
| CN203923060U (en) | A kind of preparation facilities of polymethoxy dimethyl ether | |
| CN204727802U (en) | Prepare the system of polymethoxy dimethyl ether | |
| CN110642687A (en) | Synthesis device and synthesis process for polymethoxy dimethyl ether | |
| CN210646336U (en) | Polyoxymethylene dimethyl ether synthesis and separation system | |
| CN102775284A (en) | Synthesis method of polyoxymethylene dimethyl ethers | |
| CN204874344U (en) | Preparation gathers reactor of methoxy dimethyl ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170203 Address after: 215000 Jiangsu Province, Suzhou City Industrial Park Jinji Lake Road No. 99 Suzhou city of nano NW-08 Patentee after: LANZHOU INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES Address before: Suzhou City, Jiangsu province 215123 Jinji Lake Avenue, Suzhou Industrial Park, No. 99 Patentee before: LANZHOU INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES Patentee before: Suzhou OST Advanced Materials Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211108 Address after: 730000, No. 18, jintianshui Middle Road, Chengguan District, Lanzhou City, Gansu Province Patentee after: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Address before: 215000 nw-08, Suzhou nano City, No. 99, Jinjihu Avenue, Suzhou Industrial Park, Jiangsu Province Patentee before: SUZHOU Research Institute LANZHOU INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES |