CN103539644B - The preparation method of polyoxy methylene dimethyl ether - Google Patents
The preparation method of polyoxy methylene dimethyl ether Download PDFInfo
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- CN103539644B CN103539644B CN201210240010.3A CN201210240010A CN103539644B CN 103539644 B CN103539644 B CN 103539644B CN 201210240010 A CN201210240010 A CN 201210240010A CN 103539644 B CN103539644 B CN 103539644B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/14—After treatment, characterised by the effect to be obtained to alter the inside of the molecular sieve channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation method of polyoxy methylene dimethyl ether, mainly there is catalyzer in solution prior art and there is corrosive problem.The present invention is by adopting with methyl alcohol or dme and formaldehyde or trioxymethylene as raw material, methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio 1:0.1 ~ 10, it is 50 ~ 200 DEG C in temperature of reaction, reaction pressure is under 0.1 ~ 10MPa condition, and reaction raw materials and catalyst exposure generate polyoxy methylene dimethyl ether; Does catalyzer wherein used, with weight parts, comprise following component: a)? the silica alumina ratio SiO of 40 ~ 95 parts
2/ Al
2o
3be 20 ~ 300, the ZSM-11 molecular sieve of crystal grain diameter≤5 micron; B)? the binding agent of 5 ~ 60 parts; Described ZSM-11 molecular sieve at least solves this problem preferably through pickling technical scheme once, can be used in the industrial production of polyoxy methylene dimethyl ether.
Description
Technical field
The present invention relates to a kind of preparation method of polyoxy methylene dimethyl ether.
Background technology
(Chinese also can be polyoxymethylene dimethyl ether to polyoxy methylene dimethyl ether, polyoxymethylene dimethyl ethers, polymethoxy methylal, polymethoxy dimethyl ether, polymethoxy dimethyl ether, polyoxymethylene dimethyl ethers etc.), i.e. polyoxymethylenedimethylethers (PODE), it is the common name of a class material, and its molecular structural formula is CH
3o (CH
2o)
ncH
3, there is higher cetane value (cetanenumber, CN.During n=3 ~ 8, CN>76) and oxygen level (42 ~ 49%).When the value of n is 3 ~ 8, its physical and chemical performance, combustionproperty and diesel oil closely, can be used as diesel-dope, and the addition in diesel oil can reach 30% (v/v), keeps higher cetane value and combustionproperty simultaneously.The oilness of diesel oil can be improved, reduce combustion fumes and generate, diesel oil combustion position within the engine can be improved, improve thermo-efficiency, reduce the particulate matter in combustion tail gas and NO
xdischarge.Also possibility diesel oil substitute, directly as diesel-fuel.
Polyoxy methylene dimethyl ether is solve the defect that dme does the existence of derv fuel oil blend component as the main purpose that Novel clean oil dope is researched and developed.Rich coal resources in China, has strategic importance and good economic worth by coal-based methanol combined diesel oil blend component, is day by day subject to people's attention.
US2449469 disclose a kind of with methylal and paraformaldehyde for raw material, the method using sulfuric acid as the polyoxy methylene dimethyl ether of catalyst preparing n=2 ~ 4, but there is the serious problem of catalytic erosion.
WO2006/045506A1 discloses BASF AG and uses sulfuric acid or trifluoromethanesulfonic acid as catalyzer, with methyl alcohol, methylal, trioxymethylene, paraformaldehyde etc. for raw material, obtains the series product of n=1 ~ 10, there is the problem that catalytic erosion is serious equally.
US5746785 disclose a kind of with 0.1wt% formic acid for catalyzer, with methylal and paraformaldehyde or methyl alcohol and paraformaldehyde for raw material, there is the problem that catalytic erosion is serious in the series product of preparation n=1 ~ 10 equally.
CN101182367A and CN101962318A discloses and adopts acidic ion liquid as catalyzer, is the method that polyoxy methylene dimethyl ether prepared by raw material, there is the problem that catalytic erosion is serious equally by methyl alcohol and trioxymethylene.
CN101665414A discloses a kind of acidic ion liquid that adopts as catalyzer, is the method that polyoxy methylene dimethyl ether prepared by raw material, there is the problem that catalytic erosion is serious equally by methylal and trioxymethylene.
In sum, the catalyzer adopted in conventional art has corrosive shortcoming.
Summary of the invention
Technical problem to be solved by this invention there is catalyzer in conventional art to have corrosive problem, provides a kind of preparation method of new polyoxy methylene dimethyl ether.The method has the free from corrosion advantage of catalyzer.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of polyoxy methylene dimethyl ether, with methyl alcohol or dme and formaldehyde or trioxymethylene for raw material, methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio 1:0.1 ~ 10, it is 50 ~ 200 DEG C in temperature of reaction, reaction pressure is under 0.1 ~ 10MPa condition, and reaction raw materials and catalyst exposure generate polyoxy methylene dimethyl ether; Catalyst levels is 0.01 ~ 15% of reaction raw materials weight; Catalyzer wherein used, with weight parts, comprises following component:
A) the silica alumina ratio SiO of 40 ~ 95 parts
2/ Al
2o
3be 20 ~ 300, the ZSM-11 molecular sieve of crystal grain diameter≤5 micron;
B) binding agent of 5 ~ 60 parts;
Described ZSM-11 molecular sieve concentration is that the acid of 0.1 ~ 2 mol/L processes at least one times under 70 ~ 90 DEG C of conditions, each acid treatment time is 2 ~ 10 hours, wherein acid is 1 ~ 20 with the weight ratio of ZSM-11 molecular sieve, and acid is selected from least one in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid or citric acid.
In technique scheme, the crystal grain diameter preferable range of ZSM-11 molecular sieve is 0.1 ~ 5, and more preferably scope is 0.1 ~ 2 micron.The silica alumina ratio SiO of ZSM-11 molecular sieve
2/ Al
2o
3preferable range is 40 ~ 150.Described binding agent preferred version is be selected from least one in aluminum oxide or boehmite.Described ZSM-11 molecular sieve preferred version is synthesized by following method: with water glass, at least one in silicon sol or White Carbon black is silicon source, with sodium metaaluminate, at least one in Tai-Ace S 150 or aluminum nitrate is aluminium source, with Tetrabutyl amonium bromide, tetrabutylammonium chloride, at least one in tetrabutylammonium iodide or TBAH is template, with sodium hydroxide, at least one in potassium hydroxide or ammoniacal liquor is alkali source, with at least one in sodium-chlor or Repone K for metal-salt, by silicon source, aluminium source, alkali source, template, metal-salt and water mixing plastic, reaction mixture with molar ratio computing is: SiO
2/ Al
2o
3=20 ~ 300, H
2o/SiO
2=10 ~ 150, Cl
-/ SiO
2=0.01 ~ 5, OH
-/ SiO
2=0.001 ~ 1, template/SiO
2=0.01 ~ 1, under crystallization temperature 100 ~ 200 DEG C of conditions, crystallization 0.5 ~ 16 day, crystallized product after filtration, washing, namely obtain described ZSM-11 molecular sieve after drying.The constitutive molar ratio preferable range of reaction mixture is SiO
2/ Al
2o
3=40 ~ 150, H
2o/SiO
2=30 ~ 80, Cl
-/ SiO
2=0.1 ~ 1, OH
-/ SiO
2=0.05 ~ 0.5, template/SiO
2=0.1 ~ 0.5.Crystallization temperature preferable range is 120 ~ 180 DEG C, and crystallization time preferable range is 1 ~ 10 day.
Methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio preferable range are 1:0.5 ~ 6.Formaldehyde can be the formaldehyde solution of 10 ~ 80wt%, or paraformaldehyde or trioxymethylene.Catalyst levels is the preferable range of reaction raw materials weight is 0.1 ~ 10%.Temperature of reaction preferable range is 70 ~ 150 DEG C, and reaction pressure preferable range is 0.5 ~ 6MPa.
The preparation method of catalyzer in the present invention: by the acid treatment of ZSM-11 molecular sieve at least one times, dry rear and binding agent mixing moulding, then 80 ~ 150 DEG C of dryings 5 ~ 24 hours, 400 ~ 700 DEG C of roastings 3 ~ 10 hours, namely pelletizing obtains the catalyzer of preparation polyoxy methylene dimethyl ether.
ZSM-11 molecular sieve is a member in high-silicon ZSM-5 series, form oval ten-ring two-dimensional direct duct (0.51 × 0.55nm) intersecting, belong to micro-pore zeolite, because it does not have cage, so in catalytic process not easily carbon distribution, and have fabulous thermostability, acid resistance, shape selectivity, water vapor stability and hydrophobicity.The present invention is by adopting the active ingredient of fine grain ZSM-5-11 molecular sieve as catalyzer of crystal grain diameter≤5 micron, ZSM-11 molecular sieve due to little crystal grain is compared conventional ZSM-11 molecular sieve and is had the higher micropore diffusion speed of larger Extra specific surface area sum, improve catalyzer utilization ratio, strengthen macromole conversion capability, reduce deep reaction, improve selectivity and reduce in coking and deactivation etc. and all show superior performance.In addition, in the present invention, use acid to process ZSM-11 molecular sieve at 70 ~ 90 DEG C, certain regulating effect can be played to the distribution of the Acidity of molecular sieve catalyst, B acid, the sour and strong and weak acid of L on the one hand; Amorphous substance can be removed on the other hand in molecular sieve pore passage or removes the materials such as the non-framework aluminum got off from framework of molecular sieve, make originally fully to be exposed by amorphous active centre of waiting material to cover in molecular sieve pore passage, play the modification to molecular sieve pore passage, activity of molecular sieve catalysts is increased to some extent, the burnt ability of appearance of catalyzer improves greatly, and activity stability has had very large improvement.In addition, acid treatment also can reduce the sodium content of catalyzer further, to improving the activity of catalyzer and stability is useful.The present inventor finds uncannily, adopt the inventive method, under temperature 130 DEG C, pressure 6MPa react 2 hours, n be 3 ~ 8 product can reach 32.2% in products distribution; The most important thing is that catalyzer non-corrosiveness achieves good technique effect.
Accompanying drawing explanation
The XRD spectra of fine grain ZSM-5-11 molecular sieve that Fig. 1 synthesizes for [embodiment 1].
The SEM photo of fine grain ZSM-5-11 molecular sieve that Fig. 2 synthesizes for [embodiment 1].
In Fig. 1, X-ray diffracting spectrum has strong diffraction peak at 23.0,23.9,7.9,8.8 and 45.1 degree of places, illustrates that this zeolite has MEL topological framework, is ZSM-11 zeolite.
In Fig. 2, as can be seen from SEM photo, the average crystal grain diameter of this ZSM-11 zeolite is 0.5 micron.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
40% silicon sol, sodium metaaluminate, Tetrabutyl amonium bromide, sodium-chlor, sodium hydroxide and water are mixed, stirs 20 minutes, in loading reactor, 170 DEG C of crystallization 1 day.Crystallization product chilling, to filter, be washed to pH value be 8, dries 12 hours in 120 DEG C, and obtained ZSM-11 molecular screen primary powder, XRD spectra is shown in Fig. 1, and Fig. 2 is shown in by SEM photo, and crystal grain diameter is 0.5 micron.In reaction mixture, the mol ratio of each raw material is: SiO
2/ Al
2o
3=149.3, H
2o/SiO
2=32.8, NaCl/SiO
2=0.6, NaOH/SiO
2=0.08, TBABr/SiO
2=0.12.
The ZSM-11 molecular screen primary powder of synthesis 0.3 mol/L nitric acid is processed 4 hours at 80 DEG C, continuous 3 times, obtain HZSM-11.
Mixed with boehmite, field mountain valley with clumps of trees and bamboo powder, 0.3 mol/L nitric acid by HZSM-11, the weight ratio of each raw material is ZSM-11/Al
2o
3/ field mountain valley with clumps of trees and bamboo powder=1:1:0.1, extruded moulding, dries 12 hours in 120 DEG C, and 550 DEG C of roastings 5 hours, pelletizing, obtains shaping catalyzer.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 2 grams of catalyzer, 100 grams of methyl alcohol, 100 grams of trioxymethylenes, at 130 DEG C with react 2 hours made pressure be 6MPa by inflated with nitrogen under, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the mixture of acquisition composition is as table 1.
[embodiment 2]
40% silicon sol, sodium metaaluminate, Tetrabutyl amonium bromide, sodium-chlor, sodium hydroxide and water are mixed, stirs 20 minutes, in loading reactor, 170 DEG C of crystallization 1 day.Crystallization product chilling, to filter, be washed to pH value be 8, dries 12 hours in 120 DEG C, and obtained ZSM-11 molecular screen primary powder, crystal grain diameter is 0.5 micron.In reaction mixture, the mol ratio of each raw material is: SiO
2/ Al
2o
3=149.3, H
2o/SiO
2=32.8, NaCl/SiO
2=0.6, NaOH/SiO
2=0.08, TBABr/SiO
2=0.12.
The ZSM-11 molecular screen primary powder of synthesis 0.3 mol/L hydrochloric acid is processed 4 hours at 80 DEG C, continuous 3 times, obtain HZSM-11.
Mixed with boehmite, field mountain valley with clumps of trees and bamboo powder, 0.3 mol/L nitric acid by HZSM-11, the weight ratio of each raw material is HZSM-11/Al
2o
3/ field mountain valley with clumps of trees and bamboo powder=1:1:0.1, extruded moulding, dries 12 hours in 120 DEG C, and 550 DEG C of roastings 5 hours, pelletizing, obtains shaping catalyzer.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 1.5 grams of catalyzer, 80 grams of dme, 100 grams of trioxymethylenes, at 110 DEG C with react 4 hours made pressure be 4MPa by inflated with nitrogen under, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the mixture of acquisition composition is as table 1.
[embodiment 3]
By each Step By Condition of [embodiment 2], just SiO in synthesizing formula
2/ Al
2o
3=52, template adopts TBAH, and crystallization temperature 120 DEG C of crystallization 8 days, the ZSM-11 molecular screen primary powder crystal grain diameter of synthesis is 1 micron.10 hours are exchanged at 80 DEG C with 1.0 mol/L citric acids.Obtain catalyzer.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.1.2 grams of catalyzer are added, 50 grams of methyl alcohol, 50 grams of dme in autoclave, 100 grams of trioxymethylenes, 100 DEG C and made pressure be 1MPa by inflated with nitrogen under react 5 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the mixture composition of acquisition is as table 1.
[embodiment 4]
By each Step By Condition of [embodiment 2], just synthesizing formula Raw, batching proportioning difference.Aluminium source is Tai-Ace S 150, and silicon source is water glass, and template is TBAH.In reaction mixture, the mol ratio of each raw material is: SiO
2/ Al
2o
3=80.9, H
2o/SiO
2=58.5, NaCl/SiO
2=0.80, NaOH/SiO
2=0.30, TBAOH/SiO
2=0.19.Obtained ZSM-11 molecular screen primary powder crystal grain diameter is 0.8 micron.Obtain catalyzer.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 1 gram of catalyzer, 100 grams of dme, 90 grams of formaldehyde, at 80 DEG C with react 5 hours made pressure be 2MPa by inflated with nitrogen under, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the mixture of acquisition composition is as table 1.
[comparative example 1]
By each Step By Condition of [embodiment 1], just do not add NaCl.Obtained ZSM-11 molecular screen primary powder average crystal grain diameter is 11 microns.Obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction result is in table 1.
[comparative example 2]
By each Step By Condition of [comparative example 1], acid treatment is with [embodiment 3].Obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction result is in table 1.
[comparative example 3]
Adopt the former powder of certain industrial ZSM-5, its average crystal grain diameter is 10 microns, obtains catalyzer by after the method process in [embodiment 2].
By the performance of each step evaluate catalysts of [embodiment 1], reaction result is in table 1.
Table 1
Claims (6)
1. the preparation method of a polyoxy methylene dimethyl ether, with methyl alcohol or dme and formaldehyde or trioxymethylene for raw material, methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio 1:0.1 ~ 10, it is 70 ~ 150 DEG C in temperature of reaction, reaction pressure is under 0.5 ~ 6MPa condition, and reaction raw materials and catalyst exposure generate polyoxy methylene dimethyl ether; Catalyst levels is 0.1 ~ 10% of reaction raw materials weight; Catalyzer wherein used, with weight parts, comprises following component:
A) the silica alumina ratio SiO of 40 ~ 95 parts
2/ Al
2o
3be 20 ~ 300, the ZSM-11 molecular sieve of crystal grain diameter≤5 micron;
B) binding agent of 5 ~ 60 parts;
Described ZSM-11 molecular sieve concentration is that the acid of 0.1 ~ 2 mol/L processes at least one times under 70 ~ 90 DEG C of conditions, each acid treatment time is 2 ~ 10 hours, wherein acid is 1 ~ 20 with the weight ratio of ZSM-11 molecular sieve, and acid is selected from least one in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid or citric acid;
Described ZSM-11 molecular sieve is synthesized by following method: with water glass, at least one in silicon sol or White Carbon black is silicon source, with sodium metaaluminate, at least one in Tai-Ace S 150 or aluminum nitrate is aluminium source, with Tetrabutyl amonium bromide, tetrabutylammonium chloride, at least one in tetrabutylammonium iodide or TBAH is template, with sodium hydroxide, at least one in potassium hydroxide or ammoniacal liquor is alkali source, with at least one in sodium-chlor or Repone K for metal-salt, by silicon source, aluminium source, alkali source, template, metal-salt and water mixing plastic, reaction mixture with molar ratio computing is: SiO
2/ Al
2o
3=20 ~ 300, H
2o/SiO
2=10 ~ 150, Cl
-/ SiO
2=0.01 ~ 5, OH
-/ SiO
2=0.001 ~ 1, template/SiO
2=0.01 ~ 1, under crystallization temperature 100 ~ 200 DEG C of conditions, crystallization 0.5 ~ 16 day, crystallized product after filtration, washing, namely obtain described ZSM-11 molecular sieve after drying.
2. the preparation method of polyoxy methylene dimethyl ether according to claim 1, is characterized in that the crystal grain diameter of ZSM-11 molecular sieve is 0.1 ~ 5 micron.
3. the preparation method of polyoxy methylene dimethyl ether according to claim 2, is characterized in that the crystal grain diameter of ZSM-11 molecular sieve is 0.1 ~ 2 micron.
4. the preparation method of polyoxy methylene dimethyl ether according to claim 1, is characterized in that described binding agent is selected from least one in aluminum oxide or boehmite.
5. the preparation method of polyoxy methylene dimethyl ether according to claim 1, is characterized in that the silica alumina ratio SiO of ZSM-11 molecular sieve
2/ Al
2o
3be 40 ~ 150.
6. the preparation method of polyoxy methylene dimethyl ether according to claim 1, is characterized in that methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio 1:0.5 ~ 6.
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| CN103772166A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of polyoxymethylene dimethyl ethers |
| CN105032473B (en) * | 2015-06-29 | 2017-06-16 | 南京林业大学 | A kind of method using the sulfuric acid modified catalyst preparation dialkoxy methanes for the treatment of nanoscale HZSM 5 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768058A (en) * | 2009-01-07 | 2010-07-07 | 中国石油化工股份有限公司 | Method for preparing polyoxymethylene dimethyl ether |
| CN101993356A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for preparing daicel dimethyl ether |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768058A (en) * | 2009-01-07 | 2010-07-07 | 中国石油化工股份有限公司 | Method for preparing polyoxymethylene dimethyl ether |
| CN101993356A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for preparing daicel dimethyl ether |
Non-Patent Citations (1)
| Title |
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| 无粘结剂ZSM-5沸石催化剂骨架脱铝改性的研究;程晓维 等;《化学学报》;20081231;第66卷(第19期);2009-2106 * |
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